NANOTECHNOLOGY SCIENCE AND TECHNOLOGY SERIES

NANOTECHNOLOGY:
NANOFABRICATION, PATTERNING
AND SELF ASSEMBLY


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NANOTECHNOLOGY SCIENCE AND TECHNOLOGY SERIES








NANOTECHNOLOGY:
NANOFABRICATION, PATTERNING
AND SELF ASSEMBLY







CHARLES J. DIXON
AND
OLLIN W. CURTINES
EDITORS













Nova Science Publishers, Inc.
New York



Copyright 2010 by Nova Science Publishers, Inc.


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LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Nanotechnology : nanofabrication, patterning, and self assembly / editors, Charles J. Dixon and Ollin W.
Curtines.
p. cm.
Includes index.
ISBN 978-1-61761-771-3 (Ebook)
1. Nanostructured materials. 2. Nanotechnology. I. Dixon, Charles J. II. Curtines, Ollin W.
TA418.9.N35N3574 2009
620'.5--dc22
2009004990


Published by Nova Science Publishers, Inc. New York











CONTENTS


Preface xi

Research and Review Studies 1

Chapter 1 Electrochemical Nanofabrication 3
Di Wei

Chapter 2 Fabrication and Application of Novel Two-Dimensional
Nanowebs via Electrospinning 51
Bin Ding, Chunrong Li, Dong Wang and Seimei Shiratori

Chapter 3 Nano-scale Characterization and Spectroscopy of Strained Silicon 71
Norihiko Hayazawa and Alvarado Tarun

Chapter 4 Nanotechnologies for Cancer Diagnostics and Treatment 107
Phong Tran and Thomas J. Webster

Chapter 5 Mechanical Characterization at Nanometric Scale of Ceramic
Superconductor Composites 151
J.J. Roa, X.G. Capdevila and M. Segarra

Chapter 6 ZnO Nanowire Arrays: Template-free Assembly Growth
and Their Physical Properties 237
Bingqiang Cao and Weiping Cai

Chapter 7 Spatially Resolved Control of Electrical Resistivity in Organic
Materials Development of a New Fabrication Method of
Junction Structures 275
Toshio Naito

Chapter 8 Fabrication of Electrical Contacts on Individual Metal Oxide
Nanowires and Novel Device Architectures 293
Francisco Hernandez-Ramirez, Juan Daniel Prades,
Roman Jimenez-Diaz, Olga Casals, Albert Cirera,
Albert Romano-Rodriguez, Joan Ramon Morante,
Sven Barth and Sanjay Mathur

Contents viii
Chapter 9 Functionalization of Nanoparticles, Nanotubes and Nanowires
by Surface-Initiated Atom Transfer Radical Polymerization 309
Jinying Yuan, Mi Zhou and Yingwu Yin

Chapter 10 Synthesis and Applications of Nano-sized Ferroelectrics
via Mechanochemical Activation 331
L.B. Kong, Z. Xu and T.S. Zhang

Chapter 11 Preparation and Characterization of Monoatomic Carbon Chains:
Unraveling, Field Ion Microscopy, and Field Emission 371
Igor M. Mikhailovskij

Chapter 12 Sequential Nucleation and Growth of Complex Nanostructures
by a Two-Step Strategy 409
Li Yang, Paul W. May and Lei Yin

Chapter 13 Progress of Self-standing Diamond Film Fabricated by DC Arc Jet
Plasma CVD 435
G.C. Chen, F.X. Lu, B. Li, C.M. Li, W.Z. Tang, J.H. Song,
L.F. Hei and Y.M. Tong

Chapter 14 Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 459
Zhipeng Huang and Jing Zhu

Chapter 15 A Strategy for the Incorporation of Trivalent Lanthanide Ions
into Anatase Tio
2
Nanocrystals 479
Wenqin Luo, Chengyu Fu, Renfu Li and Xueyuan Chen

Chapter 16 Nanocrystallite Superhard Titanium Nitride Film in Multi-arc
Ion Plating 509
Xiang Yu, Chengbiao Wang, Meng Hua, Yang Liu
and Shengli Ma
Chapter 17 Embedded Optical-electrical Nanomateriales Fabricated
by Ion Implantation 525
X.T. Zu, X. Xiang, S. Zhu and L.M. Wang

Chapter 18 Structural, Dynamical and Optical Properties of Self-assembled
Porphyrins at the Mesoscopic Scale 559
Valentina Villari, Norberto Micali and Luigi Mons Scolaro

Short Communications
603

Short Communication A
The Influence of Thiophene Addition on Catalytic Pyrolysis
of Poly (Dimethyl Siloxane) 605
K.F. Cai, C.W. Zhou, A.X. Zhang and J.L. Yin





Contents ix
Short Communication B
Nanofinishing of Cotton Textiles 615
N. Vigneshwaran and Virendra Prasad

Index 621










PREFACE


This new book is dedicated to outstanding research in nanotechnology which is a catch-
all description of activities at the level of atoms and molecules that have applications in the
real world. A nanometer is a billionth of a meter, about 1/80,000 of the diameter of a human
hair, or 10 times the diameter of a hydrogen atom. Nanotechnology is now used in precision
engineering, new materials development as well as in electronics; electromechanical systems
as well as mainstream biomedical applications in areas such as gene therapy, drug delivery
and novel drug discovery techniques.
Nano- and micro-fabrications have been largely used in the applications such as
integrated circuits, micro/nano electro-mechanical systems (M/NEMS), micro-optics and
countless others. The methodology of nanofabrication can be divided into two types, top-
down and bottom-up processes, which themselves can be further divided. Top-down process
refers to approaching the nanoscale from the top (or larger dimensions), such as lithography,
nanoimprinting, scanning probe and E-beam technique etc.. In bottom-up fabrication
processes, the nanotechnology process builds nanoscale artifacts from the molecular level up,
through single molecules or collections of molecules that agglomerate or self-assemble. Using
a bottom-up approach, such as self-assembly enables scientists to create larger and more
complex systems from elementary subcomponents (e.g. atoms and molecules). In general,
top-down processes that transfer minute patterns onto material are more matured than bottom-
up processes. An exception is epitaxial processes that create layers through layer-by-layer
growth with registry at the atomic level.
Electrodeposition has actually been used for decades to form high quality, mostly
metallic, thin films. It has recently been shown that high quality copper interconnects for ultra
large scale integration chips can be formed electrochemically on Si wafer [1;2].
Electrodeposition has thus been shown compatible with state of the art semiconductor
manufacturing technology. The largest semiconductor companies, for example, IBM, Intel,
AMD, Motorola etc. are installing wafer-electroplating machines on their fabrication lines
[1]. The electrodeposition of Cu with the line width 250 nm was used in the mass-production
of micro-processor Pentium III in 1998. In 2003, the line width of the CPU was reduced to
130 nm in Pentium IV. Electrochemistry was largely used in chip fabrication [3] and the
packaging of micro-electronics [4]. However, comparing with other nanofabrication
techniques, electrochemical nanofabrication is still a maiden area which needs further
development and fulfilment.
Charles J. Dixon and Ollin W. Curtines xii
Chapter 1 summarized the most recent developments in electrochemical nanofabrications.
It includes not only the conventional technique, under potential deposition (UPD), which
deals with the deposition of a single metal-ion on a definite substrate but also some new
developments using ultrashort voltage pulsing and template methods for 3D construction of
nano-materials. Electrochemical nanofabrication is a versatile method, which includes both
top-down nanofabrication (e.g. electrochemical lithography) and bottom-up process such as
electrochemical atomic layer epitaxy (EC-ALE). Nano-templates including anodized
aluminum oxide (AAO) membranes, colloidal polystyrene (PS) latex spheres, single/aligned
carbon nanotubes, selfassembled monolayers (SAMs), blocked copolymers and cyclodextrin
molecules can be used for the preparation of various types of nanowires, nanotubes, ordered
arrays of nanoparticles and nanodots electrochemically. Combining electrochemistry with
other nanofabrication techniques such as focused ion beam (FIB) and self-assembly provides
many novel strategies in the fabrication of nanomaterials with specific design. Selective areas
in the nanoscale can be modified by electrochemical nanostructuring with metals, metal
oxides and conducting polymers using a bipolar electrochemical technique. The traditional
lithography and pattern technique is costly. In the construction of soft matters such as
conducting polymers, traditional spin casting cannot guarantee nanostructures due to the fast
speed of solvent evaporation. Electrochemical technique provides an innovative, versatile and
economic way of nanofabrication. It especially offers better alternative to construct the soft
matter nano-structures in a controllable manner.
In general, electrochemical nanofabrication offers simplicity, efficiency, low-temperature
processing, cost-effectiveness, the possibility in preparing large area deposits and precise
control of the deposit thickness, which are the essential advantages than other nanofabrication
techniques till date. Additionally, it can be used to prepare a wide range of materials
comprising the inorganic and the organic. The former includes quantum dots, metallic and
semiconducting (e.g. ZnO, TiO
2
) nanotubes and nanorods. The latter includes conducting
polymer nanotubes and nanowires.
Chapter 2 reviews our recent progress on the novel two-dimensional nanowebs by the
optimization of processing parameters during electrospinning. Using high applied voltage and
low relative humidity in chamber, the by-product of micro-sized defect films can be splitted
into nanowebs due to the fast phase separation of the charged droplets which flight with high
moving speed in electric field from capillary tip to collector. The electrospun fibers act as a
support for the fishnet-like nanowebs comprising interlinked one-dimensional nanowires.
The average diameter of the nanowires contained in typical nanowebs is about one order of
magnitude smaller than that of conventional electrospun fibers. Nanowebs together with
common electrospun nanofibers can be assembled into a three-dimensional fibrous mat. So
far, nylon-6, polyacrylic acid (PAA), poly(vinyl alcohol) (PVA)/SiO
2
nanoparticles, and
PVA/zinc acetate have been found to have the possibility forming nanowebs. The formation,
morphology, and area density of the nanowebs in electrospun fibrous mats are strongly
affected by the applied voltage, ambient relative humidity, kinds of solvents, solution
concentration and conductivity, and distance between capillary tip to collector. The expanded
applications of electrospun fibers are expected due to the formation of nanowebs, such as the
nano-sized controllable filters, high efficient catalysts, catalyst supporter, and sensors. The
preliminary data showing that the sensitivity of PAA nanowebs to ammonia is 2.5 times
higher than that of electrospun PAA nanofibers. Additionally, PAA nanowebs show much
Preface xiii
quicker absorption speed and larger capacities than that of PAA nanofibers during the
ammonia absorption test.
Strained silicon (-Si), the fundamental material of integrated circuit, is finding
tremendous attention because it boosts the speed and reduces the power consumptions of
electronic devices. However, poor homogeneity distribution of strain in -Si layers can
degrade performance of electronic devices. Raman spectroscopy is used to study strain
fluctuations in silicon because the optical phonons in Raman spectra are strongly influenced
by strain. Though silicon are Raman active devices, the Raman efficiency of a nanometer
layer of -Si is extremely weak and is often eclipsed under the Raman scattering of
underlying buffer substrates. Micro Raman measurements show only uniform features in the
nano-scale because of averaging effect from diffraction-limited spatial resolution.
In Chapter 3, the authors utilized surface enhancement in Raman scattering to overcome weak
emission problems and to suppress averaging effect. Thin -Si layers were covered with thin
Ag layer to invoke surface enhanced Raman spectroscopy (SERS). Results show that SERS
effectively enhanced the Raman signal from -Si layer and it stands distinctly apart from the
Raman signal originating from the buffer layer. This technique is promising but it lacks the
spatial resolution in the nano-scale due to diffraction limit from the probing light. In order to
achieve nano-scale spectroscopy, point-surface-enhancement was used, rather than a large
surface enhancement. The authors used a silver-coated sharp tip, just like SERS, but only the
sample region very close to the tip apex is characterized. This technique, known as the tip-
enhanced Raman spectroscopy (TERS), provides nanometric resolution in our measurement.
The authors observed localized strains by employing TERS. The TERS spectra revealed clear
nano-scale variation in Raman frequency. Now that the authors can distinctively separate -Si
from underlying buffer layer, signal-to-noise ration (SNR) needs further improvement. They
improve TERS SNR in two ways: optical field enhancement using different metallic tip and
background signals reduction arising from bulk materials. The tip-enhancement is more
important for homogenous nano-materials or for samples with very weak signals whereas the
background signal reduction is indispensable for nano-materials that consist of different thin
layers with strong signals such as -Si or samples with strong signal level. Accordingly, the
authors introduce several approaches mainly for the suppression of background signals
arising from other bulk materials. The authors will discuss the utilization of UV light source,
specialized tip, sample orientation relative to probing polarization, and depolarization
configuration to obtain high contrast Raman signal. The characterization techniques describe
above is applicable to other nano-materials.
Cancer treatment usually uses drugs (chemotherapy) to reduce tumor size, followed by
surgery to remove the tumor (if possible). Then, more chemotherapy and radiation therapy is
used to kill as many tumor cells as possible. The goal of this collective treatment is to target
and kill cancerous tissue while minimizing side effects on healthy cells. Due to their non
specificity, current cancer therapies have poor therapeutic efficacy and can also have severe
side effects on normal tissues and cells. In addition, cancer is often diagnosed and treated too
late, i.e., when the cancer cells have already invaded and metastasized (i.e. spread) to other
parts of the body. At this stage, treatment methods are highly limited in their effectiveness.
Thus, scientists have been focusing efforts into finding alternative methods to detect cancer at
earlier stages and kill such cancerous tissues more effectively. Nanoparticles (that is, particles
with at least one dimension less than 100 nm) have become very attractive for improving
Charles J. Dixon and Ollin W. Curtines xiv
cancer diagnosis and treatment due to their novel optical, magnetic and structural properties
not available in conventional (or micron) particles or bulk solids. Nanoparticles have been
extensively studied for various applications including delivering anti-cancer drugs to
tumorous tissues and/or enhancing imaging capabilities to better diagnose and treat cancer. In
Chapter 4, recent work related to the improved targeted therapy for specific cancers (whether
by developing more specific anti-cancer agents or by altering delivery methods) are
summarized. Discussions on the advantages and disadvantages of the most widely studied
nanoparticles (i.e., liposome nanoparticles, polymer-based nanoparticles, quantum dots,
nanoshells, and superparamagnetic particles) in cancer imaging followed by anti-cancer drug
delivery are highlighted. Lastly, bone cancer and current research in using nanoparticles for
treating bone cancer, with an emphasis on the novel use of selenium (a natural anti-cancer
element found in our bodies), are addressed.
The nanoindentation or indenter testing technique (ITT) is a functional and fast technique
that can give us a lot of information about the mechanical properties of different materials at
nanometric scale, from soft materials, such as copper, to brittle materials, such as ceramics.
The principle of the technique is the evaluation of the response of a material to an applied
load. In a composite material, if the size of the residual imprint resulting from a certain load is
lower than the size of the studied phase, then is possible to determine its mechanical
properties, and therefore its contribution to the global mechanical properties of the composite.
Depending on the tipped indenter used, different equations should be applied to study the
response of the material and calculate stress-strain curves and parameters such as hardness,
Youngs modulus, toughness, yield strength and shear stress. These equations are related to
the different deformation mechanisms (elastic, plastic or elastoplastic) that the material
undergoes.
In the case of most of the ceramic composites, when a spherical tipped nanoindenter is
used, elastic deformation takes place, and Hertz equations can be used to calculate the yield
stress, shear stress and the strain-stress curves. On the other hand, when a Berckovich
indenter is used, plastic deformation takes place, then Oliver and Pahrr equations must be
applied to evaluate the hardness, Youngs modulus and toughness. Nevertheless, in the
hardness study, Indentation Size Effect (ISE) must be considered.
In Chapter 5, the mechanical properties of a ceramic superconductor material have been
studied. YBa
2
Cu
3
O
7-
(YBCO or Y-123) textured by Bridgman and Top Seeding Melt
Growth (TSMG) techniques have been obtained and their mechanical properties studied by
ITT. This material presents a phase transition from tetragonal to orthorhombic that promotes a
change in its electrical properties, from insulating to superconductor, and that can be achieved
by partially oxygenating the material. On the other hand, the structure of the textured material
is heterogeneous, and two different phases are present: a Y-123 as a matrix and Y
2
BaCuO
5

(Y-211) spherical inclusions. Moreover, the texture process induces an anisotropic structure,
thus being the ab planes the ones that transport the superconductor properties while the c axis
remains insulating.
The purpose of this study is the characterization of the mechanical properties, in elastic
and plastic range, of orthorhombic phases of YBCO samples textured by Bridgman and
TSMG technique. With the ITT technique, the oxygenation process can be followed and its
kinetics established.
In Chapter 6, growth and physical properties of ZnO nanowire arrays were reviewed. It
begins with some general remarks on semiconductor nanowires and basic properties of ZnO.
Preface xv
In the second part, different kinds of growth methods that have been applied to grow ZnO
nanowires are summarized. Vapor phase methods usually based on VSL or VS mechanism,
depending on the presence or absence of a metal catalyst, were discussed in general. Typical
solution methods for growth of ZnO nanowires were discussed separately as there is no
common growth mechanism that can be applied to describe them. A new template-free
strategy based on self-assembly process to grow ZnO nanowire into arrays were emphasized
and discussed in detail. The obtained sample qualities were characterized with scanning
electron microscopy, transmission electron microscopy, X-ray diffraction and energy-
dispersive X-ray spectrum. The third part deals with the physical properties of ZnO nanowire
arrays. Raman spectrum, including resonant Raman spectrum, was applied to test the crystal
quality and phonon interaction of ZnO nanowires. Temperature-dependent
photoluminescence spectra were measured to probe the intrinsic exciton and defect-related
emission process of ZnO nanowires. Field emission properties of such ZnO nanowire arrays
were also studied in view of the possible application for flat-panel displays. Some brief
conclusions were summarized at the end.
Organic materials (OMs) are diverse and are interesting in terms of application in
electronic devices. In particular, organic charge transfer salts (OCTSs), which are typically
composed of positive and negative ionic (and often radical) organic molecules, attract
continued attention. Without carrier doping, they generally have high conductivity,
magnetism, and well-defined unique nanostructures in their crystalline form. In order to apply
the OCTSs to electronic devices, they should be made junction structures. Although there are
established ways and advanced methods for doping and fabrication of junction structures in
the current industrial techniques for the silicon devices, few of them are applicable to the
OMs due to totally different chemical and physical properties between inorganic and organic
materials. In Chapter 7, the authors would like to discuss a new method for simultaneous
realization of doping and junction structures beginning with the single crystals of the OCTSs.
The method utilizes a photo-induced chemical reaction, and produces a stable solid state
composed of well-defined different parts of different conducting/magnetic properties. With
reference to our recent and previous work as well as related studies of other groups,
discussion will briefly cover experimental methods, preparation of materials, examination of
irradiation conditions and resultant solids characterization, outline of mechanism of this
photochemical modification, and remaining problems to be explained or overcome.
Metal oxide nanowires exhibit novel properties due to their high surface-to-volume ratio
and high surface stability. For this reason, they are considered excellent candidates to be
incorporated into a new generation of devices with improved performance. Nevertheless,
reaching complete control of their physical, chemical and electrical properties is needed
before they can be widely used in our everyday life. This objective can be only fulfilled if
reproducible electrical measurements on individual nanomaterials are performed. However,
the fabrication of electrical nanocontacts in a fast and well-controlled process is still an
unsolved issue. In Chapter 8, the main nanofabrication techniques that are commonly used to
electrically access individual metal oxide nanowires, and to study their intrinsic properties are
presented. Advantages and limitations of these methodologies are discussed in detail. By
integrating bottom-up and top-down techniques, the first functional prototypes based on
individual nanowires have already been implemented, paving the way to the future
developments of nanoscale electronics, optoelectronics and chemical sensing devices.
Charles J. Dixon and Ollin W. Curtines xvi
The inorganic-polymer hybrid nanomaterials have many excellent properties. So they are
becoming increasingly important for various applications ranging from biomaterials to
semiconductors in many fields and arouse much interest of scientists all over the world.
Chapter 9 highlights the development of surface-initiated living radical polymerizations from
the inorganic materials, including nanoparticles and one-dimensional (1D) nanostructures, by
surface-initiated atom transfer radical polymerization (SI-ATRP). The emphasis is put upon
the new developments of SI-ATRP taken to prepare hybrid nanomaterials in the recent years.
Ferroelectric materials have been found to be promising candidates in applications of a
wide range of electronic devices, such as high-dielectric constant capacitors, piezoelectric
sonar or ultrasonic transducers, pyroelectric security sensors, medical diagnostic transducers,
electro-optical light valves, and ultrasonic motors, and so on. Ferroelectric materials were
conventionally fabricated via solid-state reactions at relatively and sometimes extremely high
temperatures for calcining and sintering. Due to the presence of volatile components, such as
lead (Pb), bismuth (Bi) or lithium (Li), in most ferroelectric compounds, high temperatures
processing would brought out the problems of losing of the elements, which often resulted in
the deteriorations in microstructures and thus electrical performances of the ferroelectric
materials. To reduce the fabrication temperatures of ferroelectric ceramics, it is necessary to
use ultrafine powders. High-energy mechanochemical technique, as an alternative method,
has been used to synthesize nanosized ferroelectric powders directly from their oxide and
other precursors. Chapter 10 serves as an overview of progress in the synthesis of various
ferroelectric materials by using various mechanochemical milling facilities. In addition,
applications of nanosized ferroelectric powders in materials preparation and device
fabrication will be also be included.
Linear forms of carbon are important in a wide variety of application, ranging from
highly conducting interconnects to field emission materials. By methods of field ion
microscopy (FIM) and mass-spectrometry, it was revealed the presence of linear carbon
chains at the surface of carbon fibers after high-voltage treatment. The authors present in
Chapter 11 a brief review of these research emphasizing recent developments. The carbon
chains attached to the specimen tips can be produced in situ in a field ion microscope using
low-temperature pulsed evaporation by electric fields of the order of 10
11
V/m. Atomic C-
chains are produced during the high-field unraveling of nanofibers. The experimental
procedures used in FIM carbon chains studies are reviewed and the results in relation to the
atomistics of unraveling processes are discussed. Molecular dynamics simulations and high
resolution FIM experiments are performed to assess the evaporation of atomic chains under
high-field conditions. Carbon exhibits a very rich dynamics of bond-breaking that allows
transformation from graphenes to atomic chains. High-field experiments, theories leading to
carbon chain formation, and methods to extract quantitative information on a variety of chain-
surface interactions are described in detail. Isolated atomic carbon chains can be obtained at
different temperatures, pulling speeds and forces. Current versus voltage field electron
characteristics of monoatomic carbon wires were investigated. These results lend strong
support to the conjecture of Smalley that linear carbon chains may provide the ultimate
atomic-scale field emitters.
Self-assembled nanostructures are new forms of materials which are interesting from a
fundamental scientific perspective, as well as having many potential technological
applications. As explained in Chapter 12, it is believed that the ability of nanostructures to
self-assemble with controlled crystalline orientation, size, complexity and crystal
Preface xvii
morphology, provide potential applications in data storage, functional devices,
communications and technology. Recently, a two-step strategy was successfully developed in
our lab to produce two-dimensional or three-dimensional carbon nitride well-defined
hierarchical complex structures. This strategy is a combination of a novel laser-induced
deposition technique followed by self-assembly. In the first step, a suspension of carbon
nitride nanoparticles was prepared by liquid-phase pulsed laser ablation (LP-PLA). In the
second stage, this suspension was deposited onto a silicon substrate to act as a seed layer.
Via controlling the rate of evaporation of the liquid phase part of the seed suspension, and the
size and the quantity of nanocrystals within the droplet, it was possible to create a range of
nanoscale structures, including dense nanospheres, highly-symmetric flowers, hollow core-
shell and uniform grass-like structures. The growth of such complex structures is governed by
an evaporation-driven self-assembly process. As the droplet dries, small building blocks, such
as nanoparticles (NPs) or nanorods (NRs) nucleate upon the existing crystals and template,
sharing the same edges, to form a close-packed arrangement. By varying the design of the
building blocks, materials combination, interfacial chemistry, and confining dimensions, it is
expected to extend this synthetic approach to a range of new structured materials with useful
functional properties.
Self-standing diamond films were fabricated by a 30 kW DC Arcjet CVD system. The
novel progresses, including layer-structured film (nano-/micro-crystalline layer) fabrication,
high orientated film deposition with high growth rate at very high ratio of CH
4
/H
2
, crack-free
thick and large area films growth, and single crystal fabrication, were reported.
Layer-structured self-standing films, 2- and 4-layered ones, were fabricated by
fluctuating the ratio of methane to hydrogen with deposition time. Results of scan electronic
microscopy (SEM) and Raman spectra showed that the layered films were constructed by the
micro-crystalline grains layer / nano-crystalline grains layer. The residual stress within the
films were balanced, and even diminished in the certain layer. The layer containing nano-
crystalline grains due to a plenty of secondary nucleation could weakly inherit the columnar
growth feature of the overlaid layer containing micro-crystalline grains. The grain size and
growth orientation of the layer containing micro-crystalline grains could be adjusted by
introduction a mid-layer containing nano-crystalline grains. Growth rate was over 10m/hr in
layered film fabrication.
The effect of very high concentration of CH
4
in H
2
, 10%CH
4
/H
2
25%, was studied on
the film morphology and orientation. Diamond films with morphology containing nice
faceted micro-sized grains were obtained with CH
4
/H
2
up to 17%. The film composition
change was found by Raman spectra. High (111)-oriented films were deposited under the
condition of CH
4
/H
2
=15% at the maximum growth rate about 50m/h. Deposition
temperature could influence both the morphology and orientation of the diamond films. The
higher deposition temperature, the higher CH
4
/H
2
could be allowed to deposit micro-sized
grain-containing films. However, high deposition temperature would spoil (111)-orientation.
As a consequence, (220) and (311) would be enhanced.
Crack patterns occurring in self-standing films were classified as network shape, river
shape and circle shape. The distribution and style of dominating crystalline surface was found
to influence the strength of self-standing film. The films with 60-120mm of diameter and
2mm of thickness were successfully deposited by controlling of dominating crystalline
surface in the films.
Charles J. Dixon and Ollin W. Curtines xviii
A new approach to single diamond crystal fabrication by arc jet was proposed and
discussed in Chapter 13. This method was named as stable-tip method which was applied to
overcome the morphology instability. Single crystal, 110.6mm
3
in size, was successfully
fabricated by this method. The synchrotron radiation topography was adopted to characterize
this single crystal diamond.
Low emission efficiency of silicon (Si) based light emission devices (LED) still blocks
application of Si-LED. Therefore, studies focusing on improving light emission of Si-LED
still attract researches passion. Recently, the authors have developed a new method
combining nanosphere lithography and pulsed laser deposition to fabricate Si-based arrays
nanostructures, and have obtained remarkably enhanced photoluminescence (PL) from these
structures. The Si based nanostructures are hemisphere shell arrays (HSSAs) or nanoflower
arrays assembled by silicon-germanium (SiGe) alloy. These structures include non-close-
packed and close-packed ones, single layer and multilayer ones, as well as arrays on different
substrates.
In Chapter 14, the authors investigated the photoluminescence of these arrays structures,
and found that all these structures could enhance the photoluminescence intensities. Among
them, the enhancement of light emission from SiGe double layer HSSAs (DL-HSSAs), which
is as high as 700 folds, is the highest among those of all structures.
Employing transmission electron microscopy (TEM), scanning electron microscopy
(SEM), time-resolved PL, and electromagnetic simulation etc, the authors found the
enhancement of light emission in Si based nanostructures originated mainly from the increase
of extraction efficiency of photons from the nanostructures. The electromagnetic simulation
of enhancement matched well the experiment data. The authors also found that these
enhancements are related to degree of order of arrays. In highly order arrays, the enhancement
is higher than that in other arrays.
Trivalent lanthanide (Ln
3+
) ion-doped semiconductor nanocrystals have attracted
extensive attention due to the ability to tailor their optical properties via size control and to
achieve highly efficient luminescence through sensitization by the host. To date, finding a
way to dope the undopable Ln
3+
ions into semiconductor nanomaterials via chemical
methods remains a challenge. In Chapter 15, recent progress in the doping of Ln
3+
ions in
TiO
2
nanomaterials has been reviewed. A novel sol-gel-solvothermal method has been
developed to effectively incorporate Ln
3+
ions (Eu
3+
, Er
3+
, Nd
3+
and Sm
3+
) into anatase TiO
2

nanoparticles via the self-assembly and crystallization process of previous amorphous
nanoparticles, in spite of a large mismatch in ionic radius and charge imbalance between Ln
3+

and Ti
4+
. The crystallization process of Ln
3+
doped TiO
2
nanoparticles were systematically
studied by means of thermogravimetric-differential thermal analyses (TG-DTA), powder X-
ray diffraction (XRD), and transmission electron microscope (TEM). Photoluminescence
(PL) spectra of Ln
3+
:TiO
2
samples exhibit resolved and sharp emission and excitation lines
from the intra f-f transitions of Ln
3+
ions (Ln=Nd, Sm, Eu, Er), indicating regular crystalline
surroundings of Ln
3+
ions. Multiple sites of Eu
3+
, Sm
3+
and Nd
3+
ions in anatase TiO
2
were
detected by means of high- resolution site-selective spectroscopy at 10K, whereas only single
site emission of Er
3+
in TiO
2
were observed. Very intense near-infrared luminescence around
1.53 m was also observed, which originated from the single lattice site of Er
3+
ions
incorporated in TiO
2
nanocrystals. The luminescence dynamics and CF levels of Ln
3+
at
different sites have been analyzed. Highly efficient emissions of Nd
3+
and Sm
3+
sensitized by
the TiO
2
host were observed upon the excitation above the TiO
2
band gap energy at room
Preface xix
temperature (RT), which is of particular interest for material applications. A growth
mechanism for the incorporation of Ln
3+
in the anatase lattice is also suggested.
Titanium nitride (TiN) films synthesized by multi-arc ion plating (AIP) normally have a
columnar microstructure, and are likely to induce surface defects due to the formation of
macroparticles and neutral particles in the vicinity of cathode arc sources. Hence, the
achievable microhardness of the normal AIP TiN films only ranges between 20~30 GPa. A
systematic study for fabricating an adherent nano-superhard titanium nitride (TiN) film on
M2 high speed steel substrate by a vacuum cathode multi-arc ion-plating (AIP) system was
initiated. To understand the relationship of the film processing-structure-property, their
microhardness, film-to-substrate adhesion, frictional property, and microstructure of the film
were investigated using Vickers hardometer, scratch tester, ball-on-disc tester, X-ray
diffractometer, and transmission electron microscope. Results in Chapter 16 show that: (i) the
achievable film microhardness ranges between 35 GPa and 45 GPa; (ii) the critical load (Lc)
of the superhard TiN film is at 64 N approximately; (iii) the friction coefficient, under a high-
load and a high rotating-speed, of the film is ranging from 0.5 to 0.8; and (iv) the nm scale
mean main grain-sizes of the film are approximately 12.7 nm for TiN
111
, 19.7 nm for TiN
200

and 9.6 nm for TiN
220
. The maximum achievable microhardness 45 GPa is more than twice of
the 22 GPa for standard TiN film. Such hardness enhancement is anticipated as mainly due to:
(a) the formation of nanoscaled crystalline grains; (b) the preferential orientation and growth
of grains in the close-packed plane (111); and (c) the induced residual stress within the film
by ion bombardment.
In Chapter 17, nanoparticles embedded in insulators, e.g., Al
2
O
3
, MgO, YSZ and TiO
2

single crystals, were fabricated by ion implantation and subsequent thermal annealing,
including metallic Ni, Zn and their oxides, and intermetallic nanoparticles. Optical, magnetic
and mircostructural properties of nanoparticles have been studied. The metallic nanoparticles
have surface plasmon resonance absorption, and oxide nanoparticles show good
photoluminenscence. The magnetic nanoparticles, e.g., metallic Ni and intermetallic Co
x
Ni
1-x
nanoparticles, show strong ferromagnetism behaviors. The ion fluence can affect the
concentrations and the intensities of the surface plasmon absorption of metallic nanoparticles.
Ion flux is another important parameter to fabricate nanoparticles. An example of effects of
ion flux on the nanoparticles has been presented in this data review. The relationship between
annealing temperature and optical, magnetic and microstructural properties of nanoparticles
has also been systematically studied.
Ion implantation provides a versatile and powerful technique for synthesizing nanometer-
scale clusters embedded in the near-surface region of a variety of host materials. The
embedded nanoparticles have attracted considerable attention because of their unique optical-
electrical properties that are different from those of the bulk matrix. Metallic nanoparticles
embedded in insulators have pronounced optical effects, including surface plasma resonance
(SPR) absorption, and strong third-order nonlinear optical (NLO) susceptibility. The former
suggests applications as optical filters, including eye-glass coatings. The latter has potential
application in all-optical-memory or switching devices. Oxide nanoparticles have good
photoluminescence. They have promising application in light-emitting devices. Magnetic
metallic nanoparticles often show a ferromagnetic behavior with a larger coercivity than that
of the corresponding bulk materials, which may provide potential application of the
nanocomposite as magneto-optical materials for a high density magnetic data storage device.

Charles J. Dixon and Ollin W. Curtines xx
Organized self-assembly of molecules, driven by noncovalent intermolecular interactions,
is the most versatile tool for accessing new materials with desired optical and electronic
properties. Porphyrins are particularly attractive species to incorporate into supramolecular
assemblies because their rich photochemistry may impart functionality, provide insight into
the mechanisms of biological processes such as photosynthesis, serve as probes into the
features of self-assembled structures and as models for molecular organization and
energy/electron transfer processes. The close molecular packing in a self-assembled
porphyrin aggregate leads to different electronic coupling and delocalization of the excitation
energy, which can be exploited for applications in non-linear optical devices, photoelectric
cells, recording devices. The possibility to control and tune either shape and size of the
porphyrin clusters opens the way for their use as potential nanodevices. Chapter 18 aims to
collect some recent developments in the field of porphyrin self-assembly and to frame all the
reported topics into the current theories.
The influence of thiophene addition on the pyrolysis of poly(dimethyl siloxane) catalyzed
by ferrocene at ~1050
o
C in Ar was studied in the first Short Communication. The as-
synthesized product was characterized by X-ray diffraction, scanning electron microscopy,
transmission electron microscopy and high-resolution transmission electron microscopy. The
thiophene addition caused several changes. Firstly, the yield of the product was increased by
several times and the diameters of the product were somewhat increased. Secondly, the
product was changed from only SiC/SiO
2
nanocables to a mixture of SiC/SiO
2
nanocables
and SiC-SiO
2
side-by-side nanowires. Thirdly, more Y type nanostructures were found.
Finally, the growth process of the product was altered as the nanostructures each had a
polyhedral FeS nanoparticle rather than spherical Fe nanoparticle. However, lengths of the
product were still on the millimeter scale. The promotion mechanism of thiophene addition
was also analyzed.
As discussed the second short communication, nanotechnology revolutionized every field
in science and technology. Recently, its usefulness in nanofinishing of cotton fabrics by
imparting functional properties like antimicrobial, UV-resistance, self-cleaning and drug-
delivery is well documented. In addition, enhancement in comfort properties of cotton textiles
is also being evaluated with the help of nanofinishing. With judicial use of nanomaterials,
keeping in view their bio-safety and environmental impact issues, nanofinishing will be a
great boon to the users of cotton textiles.

RESEARCH AND REVIEW STUDIES
In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 3-50 2010 Nova Science Publishers, Inc.
Chapter 1
ELECTROCHEMICAL
NANOFABRICATION
Di Wei
Nokia Research Centre, c/o Nanoscience Centre
at University of Cambridge,
11 JJ Thomson Avenue, CB3 0FF, Cambridge, UK
Abstract
Nano- and micro-fabrications have been largely used in the applications such as integrated
circuits, micro/nano electro-mechanical systems (M/NEMS), micro-optics and countless
others. The methodology of nanofabrication can be divided into two types, top-down and
bottom-up processes, which themselves can be further divided. Top-down process refers to
approaching the nanoscale from the top (or larger dimensions), such as lithography,
nanoimprinting, scanning probe and E-beam technique etc.. In bottom-up fabrication
processes, the nanotechnology process builds nanoscale artifacts from the molecular level up,
through single molecules or collections of molecules that agglomerate or self-assemble. Using
a bottom-up approach, such as self-assembly enables scientists to create larger and more
complex systems from elementary subcomponents (e.g. atoms and molecules). In general, top-
down processes that transfer minute patterns onto material are more matured than bottom-up
processes. An exception is epitaxial processes that create layers through layer-by-layer growth
with registry at the atomic level.
Electrodeposition has actually been used for decades to form high quality, mostly
metallic, thin films. It has recently been shown that high quality copper interconnects for ultra
large scale integration chips can be formed electrochemically on Si wafer [1;2].
Electrodeposition has thus been shown compatible with state of the art semiconductor
manufacturing technology. The largest semiconductor companies, for example, IBM, Intel,
AMD, Motorola etc. are installing wafer-electroplating machines on their fabrication lines
[1]. The electrodeposition of Cu with the line width 250 nm was used in the mass-production
of micro-processor Pentium III in 1998. In 2003, the line width of the CPU was reduced to
130 nm in Pentium IV. Electrochemistry was largely used in chip fabrication [3] and the
packaging of micro-electronics [4]. However, comparing with other nanofabrication
techniques, electrochemical nanofabrication is still a maiden area which needs further
development and fulfilment.
Di Wei 4
This chapter summarized the most recent developments in electrochemical
nanofabrications. It includes not only the conventional technique, under potential deposition
(UPD), which deals with the deposition of a single metal-ion on a definite substrate but also
some new developments using ultrashort voltage pulsing and template methods for 3D
construction of nano-materials. Electrochemical nanofabrication is a versatile method, which
includes both top-down nanofabrication (e.g. electrochemical lithography) and bottom-up
process such as electrochemical atomic layer epitaxy (EC-ALE). Nano-templates including
anodized aluminum oxide (AAO) membranes, colloidal polystyrene (PS) latex spheres,
single/aligned carbon nanotubes, selfassembled monolayers (SAMs), blocked copolymers and
cyclodextrin molecules can be used for the preparation of various types of nanowires,
nanotubes, ordered arrays of nanoparticles and nanodots electrochemically. Combining
electrochemistry with other nanofabrication techniques such as focused ion beam (FIB) and
self-assembly provides many novel strategies in the fabrication of nanomaterials with specific
design. Selective areas in the nanoscale can be modified by electrochemical nanostructuring
with metals, metal oxides and conducting polymers using a bipolar electrochemical technique.
The traditional lithography and pattern technique is costly. In the construction of soft matters
such as conducting polymers, traditional spin casting cannot guarantee nanostructures due to
the fast speed of solvent evaporation. Electrochemical technique provides an innovative,
versatile and economic way of nanofabrication. It especially offers better alternative to
construct the soft matter nano-structures in a controllable manner.
In general, electrochemical nanofabrication offers simplicity, efficiency, low-temperature
processing, cost-effectiveness, the possibility in preparing large area deposits and precise
control of the deposit thickness, which are the essential advantages than other nanofabrication
techniques till date. Additionally, it can be used to prepare a wide range of materials
comprising the inorganic and the organic. The former includes quantum dots, metallic and
semiconducting (e.g. ZnO, TiO
2
) nanotubes and nanorods. The latter includes conducting
polymer nanotubes and nanowires.
Electrochemical Deposition
Under Potential Deposition (UPD)
Surface limited reactions are well known in electrochemistry and are generally referred to
as under potential deposits [5;6]. Underpotential deposition (UPD) is the formation of an
atomic layer of one element on a second element at a potential under, or prior to, that needed
to deposit the element on itself. The shift in potential results from the free energy of the
surface compound formation.
;Early UPD studies were carried out mostly on polycrystalline electrode surfaces [7].
This was due, at least in part, to the difficulty of preparing and maintaining single-crystal
electrodes under well-defined (and controlled) conditions of surface structure and cleanliness
[8]. For example, cadmium (Cd) can be underpotentially deposited on Cu(111) and Cu(100)
[9]. There are a number of excellent reviews on this topic [5;6].
Electrochemical Atomic Layer Epitaxy (EC-ALE)
Electrochemical atomic layer epitaxy (EC-ALE) is the combination of UPD and ALE,
which uses UPD for the surface limited reactions in an ALE cycle [10]. Fundamental to
forming high quality structures and devices with thin films of compound semiconductors is
the concept of epitaxy. The definition of epitaxy is variable, but focuses on the formation of
Electrochemical Nanofabrication 5
single crystal films on single crystal substrates. This is different from other thin film
deposition methods where polycrystalline or amorphous film deposits are formed even on
single crystal substrates. Homoepitaxy is the formation of a compound on itself.
Heteroepitaxy is the formation of a compound on a different compound or element, and is
much more prevalent. The principle of ALE is to grow the deposit one atomic layer at a time
[11]. Surface limited reactions are developed for the deposition of each component element in
a cycle to directly form a compound via layer-by-layer growth, avoiding 3D nucleations.
With cycle, a compound monolayer is formed, and the deposit thickness is controlled by the
number of cycles. In an EC-ALE process, each reactant has its own solution and deposition
potential, and there are generally rinse solutions as well.
Control of growth at the nanoscale is a major frontier of materials science. The
manipulation of a compounds dimensions, or unit cell, at the nanoscale, can result in
materials with unique properties. By constructing superlattices, nanowires and nanoclusters or
forming nanocrystalline materials, the electronic structure (bandgap) of a semiconductor can
be engineered. EC-ALE has been developed as an electrochemical methodology to grow
compound semiconductors with nanoscale or atomic layer control. In an EC-ALE synthesis of
CdTe, for example, atomic layers of tellurium and cadmium are alternatively electrodeposited
to build up a thin layer of CdTe [12;13]. The necessary atomic level control over the
electrodeposition of these two elements is obtained by depositing both elements using UPD.
The thickness of the CdTe layer prepared by EC-ALE can be specified by controlling the
number of Cd and Te layers that are deposited.
Figure 1. Transmission electron micrograph (TEM) of a CdTe deposit formed using 200 cycle of CdTe
via EC-ALE [14]. Reproduced by the kind permission from the publisher.
Di Wei 6
Fig. 1 shows the TEM figure of the CdTe usng EC-ALE with 200 cycles [14]. The
regular layered structure, parallel with the substrate Au lattice planes, suggests the epitaxial
nature of the deposit. There are a number of ways to introduce dopants into an EC-ALE
deposit and they can be introduced homogeneously throughout the deposit. Initial doping
studies of ZnS were run with the idea of forming phosphor screens for flat panel display
applications [15].
Electrochemical Deposition Methods for Semiconducting Nanocompounds
Electrodeposition normally leads to small particle size, largely because it is a low
temperature technique, thereby minimizing grain growth. It, however, possesses the
additional feature of a very high degree of control over the amount of deposited material
through Faradays law, which relates the amount of material deposited to the deposition
charge. This feature is particularly desirable when isolated nanocrystals are to be deposited on
a substrate.
Several methods and variations have been developed to electrodeposit compounds.
Oxides are probably the largest group of electrodeposited compounds (for example,
aluminium anodization). The electrodeposition of II-VI compounds has been extensively
studied and is well reviewed in a number of articles [16-18]. A number of reviews of
semiconductor electrodeposition also exist which describe the various methods used [19;20].
The most prominent electrodeposition methods for semiconducting compounds include:
codeposition, precipitation and various two-stage techniques.
Semiconductor film can be electrodeposited either by EC-ALE or by co-deposition
[21]. The most successful methodology to form II-VI compounds has been codeposition
[22-26], where both elements are deposited at the same time from the same solution.
Stoichiometry is maintained by having the more inactive element as the limiting reagent,
and poising the potential where the less noble element will underpotentially deposit only on
the more noble element. The classic example is CdTe formation [22], where the solution
contains Cd
2+
and HTeO
2+
, usually at pH 2. The potential is set to reduce HTeO
2+
to Te on
the surface at a limiting rate, while Cd
2+
is reduced on the Te at an under potential, a
potential where no bulk Cd is formed. Cd
2+
ions are present in a large excess, to deposit
quantitatively on Te as it is formed, resulting in stoichiometric CdTe. Although the
structure and morphology of codeposited compounds are variable, some having been
described as cauliflower like, high quality deposits have been formed [27]. There are a
number of papers in the literature concerning the formation of compound semiconductor
diodes by electrodeposition, the most popular structure being a CdS-CdTe based
photovoltaic. CdS was generally deposited first on an ITO/glass substrate, followed by a
layer of CdTe, usually by codeposition [28-34]. Sailor and Martin et al. grew an array of
CdSe-CdTe nano-diodes in 200 nm pore alumite [35-37], using a compound
electrodeposition methodology called sequential monolayer electrodeposition [38]. A
commercial process is being developed by BP Solar to form CdTe based photovoltaics
using codeposition. Relatively rapid deposition rate has been achieved by codeposition and
it is presently the most practical compound semiconductor electrodepostion methodology.
Codeposition holds great promise if greater control can be achieved. At present the main
parameters of control are solution composition and the deposition potential. There have
Electrochemical Nanofabrication 7
been a number of attempts to improve the process by using variations in reactant
concentration, pH [39;40], and the potential program [38;41-45]. In most cases, the deposits
are improved by annealing. In the application of photovoltaic applications, annealing is
used to convert CdTe from the as-deposited n-type material to the desired p-type [34;46].
Semiconductors such as polycrystalline ITO on glass have been used to form deposits of
ZnS with no obvious problems [15]. Ideally lattice matched semiconductor substrates
could be used to form deposits. For instance, InSb is lattice matched with CdTe and could
be used as a substrate. Good quality deposits of CdSe have been formed on InP and GaAs
substrates using codeposition by Maurin and Froment et al. [47;48]. Their work clearly
show the applicability of high quality commercial compound semiconductors wafers as
substrates for compounds electrodeposition.
The precipitation method involves electrochemical generation of a precursor to one of the
constituent elements, in a solution containing precursors to the other elements [49-52]. The
reaction is essentially homogeneous, but as one reactant is formed at the electrode surface,
most of the product precipitates on the surface. This method resembles passive oxide film
formation on reactive metals, where metal ions react with the solvent, oxygen or hydroxide.
The film thickness is controlled by the amount of electrogenerated precursor. However, as the
method resembles precipitation, the quality of the resulting deposit is questionable, and the
process is difficult to control. Film thickness is necessarily limited by the need for precursor
transport through the deposit. A classic example is the formation of CdS by oxidizing a Cd
electrode in a sulphide solution [49;53-57].
Two stage methods are where thin films of the compound element, or an alloy, are first
deposited, at least one by electrodeposition [58]. A second stage, annealing, then results in
inter-diffusion and reaction of the elements to form the compound. The deposits are annealed
in air, inert gas, or a gaseous precursor to one of the compounds component elements. For
instance, electrodeposited CuIn alloys have been annealed in H
2
S to form CuInS
2
[59]. Given
the need for annealing, this methodology has limitations for the formation of more involved
device structures. In general, annealing has been used to either form or improve the structures
of compound films formed by the electrodeposition methods described above. The primary
tool for understanding compound electrodeposition and for improving control over the
process has been the methodology of EC-ALE [60;61].
Electrochemical Synthesis of Quantum Dots
Quantum dots are semiconductor particles having diameters that are smaller than about
10 nm. Such semiconductor nanoparticles exhibit a bandgap that depends on the particle
diameter: the smaller nanoparticle, the larger the bandgap. Because quantum dots possess a
size-tunable bandgap, these diminutive particles have potential applications in detectors,
light emitting diodes, electroluminescent devices, and lasers.
Electrochemical methods can synthesize size-monodisperse quantum dots on graphite
surfaces, which provide an electrical connection to the graphite in situ. The essential features
of these methods can be depicted as in Fig. 2.
Di Wei 8
Figure 2. The electrochemical and chemical method to synthesize the quantum dots and other
semiconductor nanocrystals on graphite.
The first step involves the electrodeposition of metal nanoparticles onto a graphite
surface from a solution containing the corresponding metal ions. The metal nanoparticles are
electrochemically oxidized to yield a metal oxide (MO), in which the oxidation state of the
metal matches the oxidation state in the final product. Finally metal oxide nanoparticles are
converted into nanoparticles of a semiconducting salt (MX) via a displacement reaction in
which oxide or hydroxide is replaced by the desired anions (X). Examples of using these
methods can be shown in the synthesis of CuI [62], CdS [63] and ZnO [64] quantum dots.
Ultrathin films of quantum dots with deposits of non-connected nanocrystals and thick films
of more than 10 nm in average thickness can be made by electrochemical methods [65-67].
Electrochemical Deposition Methods for Metallic Nanostructures
Inorganic nanoparticles can be fabricated by many different techniques. Electrochemical
and wet-chemical methods are demonstrated to be effective approaches to make metal
nanostructures under control without addition of a reducing agent or protecting agent. An in
situ electrochemical reduction method for fabricating metal nanoparticles on carbon
substrates simultaneously assembling into ordered functional nanostructures was developed
[68]. Ag
+
was adsorbed on a highly oriented pyrolytic graphite surface modified by 4-
aminophenyl monolayer with coordination interaction, and then homogeneously dispersed Ag
nanoparticles could be obtained through pulsed potentiostatic reduction. Multilayered metal
nanostructures on glassy carbon electrodes have been obtained by extending this method
[69;70]. The larger electrochemical window of ionic liquids in comparison of aqueous
electrolytes enables the investigation of electrodeposition of metal and semi-conductor
elements and compounds in nanoscale. Nanoscale electrocrystallization of metals such as Ni,
Co and the electrodeposition of semiconductors (Ge) on Au (111) and Si (111):H have been
studied in the underpotential and overpotential range from ionic liquids [71]. For example, 3D
growth in Co electrodeposition on Au (111) from ionic liquids based on imidazolium cations
starts at potentials below -0.17 V vs. Co/Co(II). 3D and 2D structures of Co and Ni deposition
in the nanoscale were illustrated. In addition, nanocrystalline aluminium can be obtained by
electrodeposition from ionic liquids containing imidazolium cations without additives[72].
Electrochemical Nanofabrication 9
The crystal refinement is due to a cathodic decomposition of the imidazolium ions to a certain
extent giving rise to nanocrystalline aluminium.
Metal nanowires can be obtained using solution phase reduction [73], template synthesis
[74-77], and physical vapour deposition (PVD) [78] onto carbon nanotubes. Metal wires with
widths down to 20 nm and lengths of millimetres can be prepared on silicon surface using
electron beam lithography [79] or by PVD [80]. However, none of these methods are useful
to prepare free-standing metal nanowires that are longer than 20 m. Penner et al. [81] have
used the step edge defects on single crystal surfaces as templates to form metal nanowires by
electrochemical step edge decoration. Metallic molybdenum (Mo) wires with diameters
ranging from 15 nm to 1 m and lengths of up to 500 m were prepared in a two-step
procedure on freshly cleaved graphite surfaces [82]. Molybdenum oxide wires were
electrodeposited selectively at step edges at -0.75 V
SCE
and then reduced in hydrogen gas at
500 C to yield Mo metal. Such nanowires can be obtained size selectively because the mean
wire diameter was directly proportional to the square root of the electrolysis time.
Parrallel arrays of long (> 500 m), dimensionally uniform nanowires composed of
molybdenum, copper, nickel, gold, and palladium can also be electrodeposited by the same
strategy [81]. They were firstly prepared by electrodepositing nanowires of a conductive
metal oxide such as NiO, Cu
2
O or MoO
2
. Nanowires of the parent metal were then obtained
by reducing the metal oxide nanowires in hydrogen at elevated temperature. Nanowires with
diameters in the range from 15 nm to 750 nm were obtained by electrodeposition onto the
step edges present on the surface of highly oriented pyrolytic graphite electrode. After
embedding the nanowires in a polymer film, arrays of nanowires could be lifted off the
graphite surface thereby facilitating the incorporation of these arrays in devices such as
sensors. Vertical arrays of metal nanowire hold promise for making chemical and biological
sensors in addition to electron emitters in field-emission displays. But the difficulty of
growing well-defined arrays has kept these technologies at bay. Electrochemical
nanofabrication using crystalline protein masks solved this problem [83]. A simple and robust
method was developed to fabricate nanoarrays of metals and metal oxides over macroscopic
substrates using the crystalline surface layer (S-layer) protein of deinococcus radiodurans as
an electrodeposition mask. Substrates are coated by adsorption of the S-layer from a
detergent-stabilized aqueous protein extract, producing insulating masks with 2-3 nm
diameter solvent-accessible openings to the deposition substrate. The coating process can be
controlled to achieve complete or fractional surface coverage. The general applicability of the
technique was demonstrated by forming arrays of Cu
2
O, Ni, Pt, Pd, and Co exhibiting long-
range order with the 18 nm hexagonal periodicity of the protein openings. This protein-based
approach to electrochemical nanofabrication should permit the creation of a wide variety of
two-dimensional inorganic structures.
Electrochemical Nanolithography
In addition to its well-known capabilities in imaging and spectroscopy, scanning probe
microscopy (SPM) has shown great potentials for patterning of material structures in
nanoscales with precise control of the structure and location. Electrochemical
nanolithography using SPM, which includes scanning tunnelling microscopy (STM) and
atomic force microscope (AFM), has been used to fabricate of patterned metal structures
Di Wei 10
[84-87], semiconductors [87;88] and soft matters such as conducting polymers [89;90]. The
electrochemical processing of material surfaces at nanoscale both laterally and vertically can
be conducted by scanning probe anodization/cathodization, which used the tip-sample
junction of a scanning probe microscope connected with an adsorbed water column as a
minute electrochemical cell. A review on nanofabrication by scanning probe microscope
lithography examines various applications of SPM in modification, deposition, removal, and
manipulation of materials for nanoscale fabrication [91]. Comprehensive reviews of SPM-
related lithography can be found in the literature [92].
STM has a tremendous potential in metal deposition studies. The initial stages of metal
deposition and the Ag adlayer on Au (111) have been studied by Kolb et al. [93].The inherent
nature of the deposition process which is strongly influenced by the defect structure of the
substrate, providing nucleation centres, requires imaging in real space for a detailed picture of
the initial stage. This is possible with an STM, the atomic resolution helps to understand these
processes on a truly atomistic level. The following figure demonstrates wealth of structural
detail supplied by STM. In situ STM investigations for Ag UPD on Au (111) in the potential
range from 600 to 200 mV vs. Ag/Ag
+
were carried out [93]. Underpotentially deposited Ag
revealed a series of ordered adlayer structures with an increasing density of adatoms when
decreasing applied potentials.
Nanostructuring can be also achieved by involving electrochemical processes into the
overall procedures. For example, Li et al. [94;95] deposited Ag and Pt clusters on a graphite
surface by applying positive voltage pulses to the STM tip in a solution containing the
respective metal cations. This effect was attributed to nucleation within holes which were
created on the graphite substrate surface by the voltage pulses. Kolb et al. [96], on the other
hand, were able to detach Cu clusters from a tip, where they had been previously deposited
electrochemically, onto a Au substrate by mechanical contact. However, all these techniques
suffer from restrictions, which could be largely avoided if controlled nanostructuring could be
achieved by a direct local electrochemical reaction on the substrate, with the geometry being
determined by the location of the tip which acts as a local counter electrode. By applying
ultrashort voltage pulses ( 100ns), holes of about 5 nm in diameter and 0.3 to 1 nm depth on
Au substrate can be created by local anodic dissolution, while cathodic polarization led to the
deposition of small Cu clusters [97]. The development of allowing the generation of small
metal clusters, with the help of an STM tip, and placing them at will onto single crystal
electrode surfaces was reported [96;98]. This so-called tip-induced metal deposition involves
conventional electrolytic deposition of a metal onto the tip of an STM, followed by a
controlled tip approach during which metal is transferred from the tip to the surface (so-called
jump-to-contact [99]). Small copper clusters, typically two to four atomic layers in height,
were precisely positioned on a Au(111) electrode by a process in which copper was first
deposited onto the tip of the STM, which then acted as a reservoir from which copper could
be transferred to the surface during an appropriate approach of the tip to the surface [100].
Tip approach and position were controlled externally by a microprocessor unit, allowing the
fabrication of various patterns, cluster arrays, and ''conducting wires'' in a very flexible and
convenient manner [96]. The formation of such clusters with the tip of a STM is simulated by
atom dynamics and subsequently the stability of these clusters is investigated by Monte-Carlo
simulations in a grand-canonical ensemble. It leads to the conclusion that optimal systems for
nanostructuring are those where the metals participating have similar cohesive energies and
Electrochemical Nanofabrication 11
negative heats of alloy formation. In this respect, the system Cu-Pd(111) is predicted as a
good candidate for the formation of stable clusters [101].
In addition to producing the metal nano-clusters, STMs can also be applied to form
nanoscale pits in thin conducting films of thallium (III) oxide [102] as well as to write stable
features on an atomically flat Au (111) surface [103]. Pit formation was only observed when
the process was performed in humid ambient conditions. The mechanism involved in pit
formation was attributed to localized electrochemical etching reactions beneath the STM tip.
By applying voltage pulses (close to 3 V) across the tunnelling junction in controlled
atmosphere with the presence of water or ethanol vapour, nano-hole can be produced. The
smallest hole formed is 3 nm in diameter and 0.24 nm in depth. This nano-hole represents the
loss of about 100 Au atoms in the top atomic layer of gold surface, there is no atomic
perturbation seen inside and outside the nano-hole. Different nanostructures (lattice of dots,
legends, map, etc.) can also be fabricated. The threshold voltage for the formation of a nano-
hole depends on the relative humidity, however, the relationship between the threshold
voltage and the relative humidity is basically independent of the tip material.
The application of conducting AFM probe anodization to nanolithography was also used
in the fabrication and patterning of materials in a similar manner as STM probes. AFM-tip-
induced and current-induced local oxidation of silicon and metals were reported and this
novel local oxidation process can be used to generate thin oxide tunneling barriers of 10-50
nm.[88]. The direct modification of silicon and other semiconductor and metal surfaces by the
process of anodization using the electric field from a SPM is one promising method of
accomplishing direct-writing lithography for the electron device fabrication. This technique
involves the application of an electrical bias to both the conducting probe and the sample
substrate to locally oxidize selected regions of a sample surface. Since most of lithographic
works with organic resists have been exclusively carried out on silicon surface for practical
application, so several organic resists with different function groups have been studied in
order to investigate the surface group effect on the anodic anodization using AFM.
Silicon (Si) samples whose surfaces were terminated with hydrogen (Si-H samples) or
covered with an organosilane monolayer were generally used to deposit metallic and/or
semiconductor nanomaterials [86]. Silicon oxide (SiO
2
) patterns can be prepared on the Si-H
sample surfaces by the use of anodization of Si, while in the second case the organosilane
layer was selectively degraded by anodic corrosion. Furthermore, pattern transfer processes
that fabricated metal nanostructures using these patterned SiO
2
or organosilane layers as
templates were developed. These processes are based on area-selective electroless plating
where selectivity depends on the difference in the chemical reactivity between the surface
modified by scanning probe anodization and the unmodified surface. Nanostructures down to
a few ten nanometers in size have been fabricated with LangmuirBlodgett (LB) films and
self-assembled monolayers (SAMs) using SPM lithography [104]. The SAMs can be
prepared with organosilane etc. as ultrathin resists on Si substrate. The effect of such
functional groups of molecules on the AFM anodization, which was performed under contact
mode has been studied in the optimized process conditions. Applied voltage between the
AFM tip and sample, the scanning speed and the relative humidity in air are also important
factors for nanometer-scale lithography of the ultrathin films. The high structural orderness
and perfect thickness of ultrathin organic molecular assemblies are the major advantages as
required for nanoscale lithography.
Di Wei 12
Cleaned p-type Si (100) wafer was firstly oxidized by piranha solution (3:1 mixture of
sulfuric acid and 30% hydrogen peroxide) to make the surface hydrophilic. The
octadecyldimethylmethoxysilane (ODMS) molecules react with OH groups on a silicon oxide
surface resulting in the formation of a SAM in a thickness of 1.7 nm. The local degradation of
the monolayer on selected area where the probe tip of the AFM was scanned with a bias
voltage occurred due to the anodic reaction. The degraded regions became hydrophilic
indicating that the ODMS molecules were decomposed and replaced with OH groups as a
result of the probe scan. AFM images showed that the tip scanned regions were protruded
compared to the surrounding regions as Fig.3 shows. This is due to volume expansion
resulting from anodization of the Si substrate, which immediately followed the tip-induced
degradation of the SAM.
Figure 3. Anodized pattern formation on Si-wafer. Si wafer was firstly oxidized to form hydrophilic
oxide layer for the selfassembly of ODMS. ODMS SAMs act as the resist. Reproduced by the kind
permission from the publisher.
Figure 4. The AFM image of ODMS monolayer after AFM anodization at the different applied currents
[104]. Reproduced by the kind permission from the publisher.
Fig. 4 shows the AFM image of ODMS monolayer after AFM anodization at the different
current conditions. Typically with ODMS monolayers, protruded patterns are fabricated with
line-width of 70 nm at a scan rate of 120200 m/s and an applied voltage of 2025 V. The
Electrochemical Nanofabrication 13
height of protruded lines can be controlled by changing the current between the tip and
substrate. When the applied current was 57 nA, the height of protruded line was 1.0 nm.
With increasing the current up to 2023 nA, the anodized height increased to 3.0 nm. Thus,
the height of the protruded lines increases due to the effective electric field strength for a
given applied voltage and a scan rate. The electric field plays an important role in the
formation of protrusion. AFM anodization was successfully carried out with SAMs on the
silicon substrate. Applied voltage between the AFM tip and sample, the scanning speed,
surface group, and the relative humidity in the laboratory are very important factors for
nanometer-scale lithography of the ultrathin films. The high structural orderness and perfect
thickness of ultrathin organic molecular assemblies are the major advantages as required for
nanoscale SPM lithography.
Soft matters such as conducting polymers can also be patterned in the nanoscale by such
lithographic method. Cai et al. described the first observation of localized
electropolymerization of pyrrole and aniline on highly oriented pyrolytic graphite (HOPG)
substrates under AFM tip-sample interactions [89]. A scanning or oscillating AFM tip,
providing the horizontal scratching force and the vertical tapping force, is essential as the
driving force for the surface modification with the conducting polymer. It was shown that
under the AFM tip interaction, the electropolymerization can be blocked on the bare HOPG
substrate or enhanced on the as-polymerized film. The localized electropolymerization in
selected surface areas enables the nanomodification of lines, square platforms, or hollows of
polypyrrole and polyaniline on the substrates. The result indicates that AFM can be used as a
unique tool for nanofabrication of conducting polymers.
Nano-writing of intrinsically conducting polymer was also achieved via a novel
electrochemical nanolithographic technique using tapping mode electrochemical AFM.
Conducting polymer (polythiophene derivatives) nanolines as small as 58 nm in width were
obtained and the line width is controlled as a function of the writing speed and writing
potential [90].
Figure 5. Electrochemical nanolithography [90]. Reproduced by the kind permission from the publisher.
Di Wei 14
The electrochemical nanolithography process is shown in Fig. 5. Conductive AFM
probes, gold coated silicon nitride (SiN
4
) are used as working electrode. Silver wire and
platinum wire were used as reference electrode and counter electrode, respectively. Higher
writing potential and slower writing speed produce wider conducting polymer nanolines due
to enhanced propagation. The great benefit of this method lies in no specific restriction in the
choice of substrates and the ease of controlling feature size, which is expected to facilitate to
fabrication of all plastic nanoelectronic devices.
As stated previously, many SPM lithography techniques based on anodization of Si
surfaces [88], electrochemical reactions in solution using electrochemical STM tips [96;98]
and electrochemical decomposition of self-assembled monolayers [104] have been developed
in the past decade. More recently, a dippen nanolithography (DPN) method was invented
that uses an AFM tip as a nib to directly deliver organic molecules onto suitable substrate
surfaces, such as Au [105-107]. When AFM is used in air to image a surface, the narrow gap
between the tip and surface behaves as a tiny capillary that condenses water from the air. This
tiny water meniscus is actually an important factor that has limited the resolution of AFM in
air. Dip-pen AFM lithography uses the water meniscus to transport organic molecules from
tip to surface. By using this technique, organic monolayers can be directly written on the
surface with no additional steps, and multiple inks can be used to write different molecules on
the same surface. By coupling electrochemical techniques, the DPN are not limited to deliver
organic molecules to the surface. Electrochemical dip-pen nanolithography (EC-DPN)
technique can be used to directly fabricate metal and semiconductor nanostructures on
surfaces.
Figure 6. Schematic sketch of the EC-DPN experimental setup [108]. Reproduced by the kind
permission from the publisher.
The tiny water meniscus on the AFM tip was used as a nano-sized electrochemical cell,
in which metal salts can be dissolved, reduced into metals electrochemically and deposit on
the surface as shown in Fig. 6. In a typical experiment, an ultrasharp silicon cantilever coated
with H
2
PtCl
6
is scanned on a cleaned p-type Si (100) surface with a positive DC bias applied
on the tip. During this lithographic process, H
2
PtCl
6
dissolved in the water meniscus is
electrochemically reduced from Pt(IV) to Pt(0) metal at the cathodic silicon surface and
deposits as Pt nano-features as shown in the result below [108].
Electrochemical Nanofabrication 15
Figure 7. AFM image and height profile of two Pt lines drawn at different scan speed. a) line at 10 nm/s
and b) line at 20 nm/s. The voltage applied at the tip is 3V for both lines and the relative humidity is
43% [108]. Reproduced by the kind permission from the publisher.
Electrochemical AFM "dip-pen'' nanolithography has significantly expanded the scope
where DPN nanofabrication can be applied. It combines the versatility of electrochemistry
with the simplicity and power of the DPN method to produce nanostructures with high
resolution. Electrochemical STM-based methods require that the substrates be metallic, but
substrates used in EC-DPN do not have to be metallic since the control feedback of the AFM
does not rely on the current between the tip and surface. Si wafers coated with native oxide
provides enough conductivity for the reduction of the precursor ions. This development
significantly expands the scope of DPN lithography, making it a more general
nanofabrication technique that not only can be used to deliver organic molecules to surfaces
but is also capable of fabricating metallic and semiconducting structures with precise control
over location and geometry.
Local electrochemical deposition of freestanding vertically grown platinum nanowires
was demonstrated with a similar approach, electrochemical fountain pen nanofabrication (EC-
FPN) [109]. The EC-FPN exploits the meniscus formed between an electrolyte-filled
nanopipette ('the fountain pen') and a conductive substrate to serve as a confined
electrochemical cell for reducing and depositing metal ions. Freestanding Pt nanowires were
continuously grown off the substrate by moving the nanopipette away from the substrate
while maintaining a stable meniscus between the nanopipette and the nanowire growth front.
High quality and high aspect-ratio polycrystalline Pt nanowires with diameter of similar to
150 nm and length over 30 m were locally grown with EC-FPN. The EC-FPN technique is
shown to be an efficient and clean technique for localized fabrication of a variety of vertically
grown metal nanowires and can potentially be used for fabricating freeform 3D
nanostructures.
Di Wei 16
3D Electrochemical Nanoconstruction
In combination with lithographic patterns, electrochemistry has taken a key position in
products and manufacturing processes of microtechnology, which has established a multi-
billion dollar market with applications in information, entertainment, medical, automotive,
telecom and many other technologies such as lab on a chip etc. [110]. Different strategies and
techniques such as electrochemical etching, LIGA and ultrashort voltage pulsing, which have
been used in microtechnology, were also applied to construct 3D structures in the nanoscale.
Electrochemical EtchingandLIGA Technique
Electrochemical etching with ultra-short voltage pulses allows to dissolve
electrochemically active materials within an extremely narrow volume and to manufacture
three dimentional (3D) microstructures. Micro- and nanoporous silicon can be generated by
anodization of silicon wafers in hydrofluoric acid. Since etching proceeds preferably in the
(100) direction of the single-crystalline silicon wafer, the pore shape is nearly straight and the
depth is equal for all pores. The pores start to grow on a polished wafer in a random pattern,
and their arrangement is usually defined by transferring a suitable lithographic pattern and
generating a corresponding pattern of pits by alkaline etching as shows in Fig. 8. The pattern
of the deep pores generated subsequently by the electrochemical etching process corresponds
to the pattern of the shallow starter pits. The cross section of the pores is usually square with
rounded corners and their size can be varied by changing the etching current. More complex
cross sections can be generated by overlapping of pores using additional etching steps and
corresponding pattern definition (e.g. by means of lithography).
Figure 8. Macroporous silicon structure generated by means of electrochemical etching of single-
crystalline silicon (Source: V. Lehmann, Siemens AG) [110]. Reproduced by the kind permission from
the publisher.
Electrochemical Nanofabrication 17
The macroporous silicon structure generated by means of electrochemical etching of
single-crystalline silicon was demonstrated above. In the electrochemical set-up, hydrofluoric
acid (HF), with or without ethanol and/or water is used as electrolyte and platinum is the
standard cathode. The etch rate of ca. 1 m/min is observed. Both electro-polishing and pore
formation take place in the anodic regime. Depending on current density, silicon can be
etched in such two different modes: pore formation and electro-polishing. In pore formation,
etching proceeds vertically downwards, leaving a silicon skeleton with up to 80% empty
space, whereas in electropolishing, the whole surface is being etched. Pore formation starts at
the wafer surface from a defect or an intentional initial pit. Electronic holes from the bulk
silicon are transported to the surface, and they react at the defect or pit. Further etching occurs
at the newly formed pore tips, because they attract more holes due to higher electric field
strength, and the process leads to a uniform porous layer depth as the holes are consumed by
the growing tips and other surfaces are depleted of holes. This etching mode takes place under
low hole concentration and it is limited by hole diffusion, and not by mass transfer in the
electrolyte cell. If hole density increases, some holes reach the surface and react there, leading
to surface smoothing. This is the electro-polishing regime, in which ionic transfer from the
electrolyte plays a role. Illumination contributes to hole concentration in n-type silicon (but
not in p-type silicon) and the anodic etching of n-type silicon happens under illumination
whilst p-type silicon etches in dark. A very wide range of pore size from 0 to 20 m can be
etched by varying electrolyte concentration, current density and illumination [111]. As a rule
of thumb, pore diameter in micrometre is half the resistivity in ohm/cm: for 1 um pore, 2
ohm/cm n-type silicon is suitable. For small pores, low resistivity is needed; for large pores,
high resistivity material has to be used. If pore formation starts from an unobstructed surface,
a random pore array results. If initial pits are prepared by lithography and etching, pores can
be arranged at will [112]. When an n-type silicon wafer is an anode in an alkaline etching
solution (e.g. KOH) biased positively above passivation potential, the surface will be
oxidized, which stops silicon dissolution whilst p-type silicon was etched. The n-type layer of
a p/n-structure can similarly be protected. Etching of p-type silicon continues until the diode
is destroyed, and n-type silicon is then passivated. The confined etchant layer technique has
been applied to achieve effective three-dimensional (3D) micromachining on n-GaAs and p-
Si. This technique operates via an indirect electrochemical process and is a maskless, low-
cost technique for microfabrication of arbitrary 3D structures in a single step [113]. It has also
been presented that free-standing Si quantum wire arrays can be fabricated without the use of
epitaxial deposition or lithography by electrochemical and chemical dissolution of wafers
[114]. This novel approach uses electrochemical and chemical dissolution steps to define
networks of isolated wires out of bulk wafers.
Electrochemical methods, either alone or in combination with other techniques, have
been developed for shaping materials. 3D microstructures with extremely high precision and
aspects ratio can be manufactured by means of LIGA technology, which combines deep
lithography, electrodeposition and moulding process steps. The acronym LIGA is derived
from the German expressions for these manufacturing steps and offer high potential regarding
miniaturization, freedom of design and mass production. Micro-gear system produced from a
nickel iron alloy by means of LIGA was shown in Fig. 9.
Di Wei 18
Figure 9. Micro-gear system produced from a nickel iron alloy by means of LIGA technology (Source:
Micromotion, IMM) [110]. Reproduced by the kind permission from the publisher.
However, the ultra precise microstructures with extreme aspect ratio could only be
generated by deep X-ray lithography. Difficulties, for example, the access to synchrotron
radiation facilities have limited the commercialization of LIGA technique in mass fabrication.
Micro- and Nano-machining by Ultrashort Voltage Pulsing Technique
The application of electrochemistry in micro-machining can be found in book [115]. In
contrast to the conventional processes of electrochemical micromachining, where the gap
between the electrodes is usually 0.1 mm and direct current is applied, a novel
electrochemical micofabrication method using a gap in m range and very short voltage
pulses of some tens of nanoseconds was developed. The short pulse confines electrochemical
processes correspondingly, removal of material to a very narrow volume to enable a precise
nanomachining. Ultrashort pulses can be employed to machine conducting materials with
lithographic precision [116]. Resolution can be improved significantly through the use of
ultrashort voltage pulses comparing to the use of conventional direct current anodization.
Three dimensional complex nanostructures, lines, curved features, and arrays can be
machined in substrates in single-step processing.
The method is based on the application of ultrashort voltage pulses of nanosecond
duration, which leads to the spatial confinement of electrochemical reactions, e.g. dissolution
of material. The electrochemical dissolution rate of the material has to be intentionally varied
over the workpiece surface by applying inhomogeneous current density distribution in the
electrolyte and at the workpiece surface. This can be achieved by the geometric shape of the
tool, locally very small tool-workpiece distances, partial insulation of the tool or workpiece,
and high overall current densities etc. This situation is illustrated in Fig 10. The workpiece is
preferentially etched within the gap region between the front face of the tool and the
workpiece surface. This approach for local confinement of electrochemical reactions is based
on the local charging of the electrochemical double layer (DL) and the resulting direct
influence on the electrochemical reaction rates.
Electrochemical Nanofabrication 19
Figure 10. Sketch of the experimental setup and principle of electrochemical micromachining with
ultrashort pulses. RE and CE are abbreviates of reference and counter electrode.
The potentials of the workpiece and tool are controlled by the low-frequency
bipotentiostat. The voltage pulses are supplied by the high frequency pulse generator. An
ultrashort voltage pulse limits the charging of double layer capacitance to the vicinity of the
tool. The current distribution between the DL is also illustrated in Fig. 10. The pulsing time
constant is given by the DL capacitance multiplied by the resistance of the electrolyte along
the current path. The latter factor is locally varying, depending on the local separation of the
electrode surfaces [116]. Therefore, upon proper choice of the pulse duration, DL areas where
the tool and workpiece electrodes are in close proximity are strongly charged by the voltage
pulses, whereas at further distances the charging becomes progressively weaker. The pulse
duration provides a direct control for the setting the machining accuracy. Machining
precisions below 100 nm were achieved by the application of 500 ps voltage pulses [117].
Figure 11. Spiral trough with a depth of 5 mm, machined into a Ni sheet with a W tool in 0.2 M HCl (3
ns, 2 V pulses, 33 MHz repetition rate, workpiece -0.1 VAg/AgCl, tool -0.3 VAg/AgCl [117].
Reproduced by the kind permission from the publisher.
Di Wei 20
The application of ultrashort voltage pulses between a tool electrode and a workpiece in
an electrochemical environment allows the three-dimensional machining of conducting
materials with nanoscale precision. The principle is based on the finite time constant for DL
charging, which varies linearly with the local separation between the electrodes. During
nanosecond pulses, the electrochemical reactions are confined to electrode regions in close
proximity. The performance of electrochemical micromachining with ultra-short voltage
pulses was demonstrated in a number of experiments where microstructures were
manufactured from various materials like copper, silicon and stainless steels [116]. Three
dimentional structures with high aspect ratios can be achieved by using suitable
microelectrodes and piezo-driven micropositioning stages. The spiral shown in Fig. 11 was
manufactured by machining the Ni sheet with 3 ns pulses. Walls of similar thickness with
surface roughness and radii of curvature less than 100 nm were readily machined [117].
Figure 12. Scanning electron micrographs. (a) the tool; (b) structure in Ni substrate. Experimental
conditions: Usub=-0.35 V, Utool=-0.3 V, 2 ns pulse duration, 2.2 V amplitude, 1:10 pulse to pause
ratio, and 0.05 M HCl electrolyte. The structure was machined 400 nm into the surface in less than 2
min [118]. Reproduced by the kind permission from the publisher.
Small tools can be used to make very small features. High aspect ratio nanometre
accurate features were machined in nickel using ultrashort voltage pulse electrochemical
machining [118]. Two tools (one is the rotunda tool, presented in Fig 12a and other is 22
array of cubes, presented in Fig. 13a) were firstly fabricated by focused ion beam (FIB)
milling and then used in the machining. The potentials of the shaped tungsten tool and nickel
substrate electrodes were controlled with a bipotentiosts which kept the potentials of the tool
and substrate constant versus an Ag/AgCl reference electrode by applying a potential to Pt
counter electrode. All experiments were conducted in an aqueous HCl solution with various
concentrations. Supplementary circuitry was present to allow the additional of ultrashort
(order of 1 ns) pulses to the potential of the tool electrode. The separation of the tool and the
substrate workpiece electrodes was controlled with piezoactuators and the tool was fed into
the workpiece with a constant feeding speed, avoiding mechanical contact between the
electrodes by monitoring the dc current between tool and workpiece. Structures with 90 nm
widths were made by applying 2ns voltage pulses for the parallel lines in the centre of the
structure in Fig 12b. To reach a depth of 400 nm, total electrochemical machining time of 1
Electrochemical Nanofabrication 21
min 45s was applied. Examples of patterns made with the 22 array of cubes tool are shown
in Fig. 13b. It indicates that the feature resolution improves with decrease in pulse duration.
Figure 13. Scanning electron micrographs. (a) Tungsten tool; (b) machined Ni substrate. Experimental
conditions: U
sub
=-1.7 V, U
tool
=-1.0 V, pulse duration indicated, 2 V amplitude, 1:10 pulse to pause ratio,
and 0.2 M HCl electrolyte. Feature resolution and edge sharpness increased as pulse duration decreased
[118]. Reproduced by the kind permission from the publisher.
Three-dimensional machining of electrochemically active materials including
construction of unconventional island patterns on a surface with nanoscale resolution was
realized by this method [97;119-121]. Thus, electrochemical machining can be applied to
microelectro-mechanical systems (MEMS) [122], and even in the nanoelectro-mechanical
systems (NEMS).
Electrochemical methods can realize the nanofabrication in a selective place and make
the complicated 3D nanostructures. Conducting polymers can also be made in this way.
Similar to the electrochemical machining, by application of short voltage pulses to the tool
electrode in the vicinity of the workpiece electrode, the electropolymerization of pyrrole can
be locally confined with micrometre precision [123]. As the produced nuclei of conducting
polymers will grow preferentially vertically to the surface, fibre-like morphologies were
found in the local polypyrrole electrosynthesis with short voltage pulses. A polypyrrole ring
with needle-like feature can be selectively nanofabricated, which was grown with 1 s pulses
in 0.2 M H
2
SO
4
/0.2M Pyrrole. To obtain such structure, a 50 m diameter flattened
cylindrical Pt wire tool was brought to a distance of 1 m from the workpiece substrate before
applying the pulses. The small distance between tool and the substrate strongly hinders the
supply of monomer at the reaction site. The consequent relatively low supersaturation leads to
a low density of nuclei, which grow and form isolated polypyrrole fibres. With the increase of
the distance, a more compact ring-like structure can be obtained.
Di Wei 22
Template Free Methods for Conducting Polymer Nano-architecture
Although oriented carbon nanotubes, oriented metal and semiconductor nanowires have
attracted wide attention, there have been few reports on oriented polymer nanostructures such
as nanowires. The assembly of large arrays of oriented nanowires containing molecularly
aligned conducting polymers without using a porous membrane template to support the
polymer was reported recently [124]. The uniform oriented nanowires were prepared through
controlled nucleation and growth during a stepwise electrochemical galvanostastic deposition
process, in which a large number of nuclei were first deposited on the substrate using a large
current density. After the initial nucleation, the current density was reduced stepwise in order
to grow the oriented nanowires from the nucleation sites created in the first step. The
usefulness of these new polymer structures is demonstrated with a chemical sensor device for
H
2
O
2
, the detection of which is widely investigated for biosensors. It offers a general
approach to control nucleation and and has potential for growing oriented nanostructures of
other materials.
Fig. 14 demonstrates the steps to electrochemically fabricate arrays of oriented
conducting polyaniline (PANI) nanowires by well controlled nucleation and growth without
templates. After initiating the nucleation of the conducting polymer at high current densities
the current density is reduced to avoid formation of further nuclei. The existing nuclei grew
preferentially vertically to the surface. A typical procedure involves electrochemical
deposition in an aniline-containing electrolyte solution, by using the substrate as the working
electrode. This process involves: 0.08 mAcm
-2
for 0.5 h, followed by 0.04 mAcm
-2
for 3 h,
which was then followed by another 3 h at 0.02 mAcm
-2
. The stepwise growth produced
uniform, oriented nanowires on a variety of flat and rough surfaces as Fig. 15 shows.
Figure 14. Schematic drawing of the steps for growing oriented polymer nanowires. a) Schematics of
the reactions in the electrochemical cell. b) Schematics of the nucleation and growth.[124]. Reproduced
by the kind permission from the publisher.
Electrochemical Nanofabrication 23
Figure 15. SEM micrographs of oriented polyaniline on Pt. a) Low magnification face-on. b) High
magnification face-on. c) Tilted view, low magnification. d) Tilted view, high magnification. The insert
in Figure 3 a is the image of the oriented nanowires on Si substrate[124]. Reproduced by the kind
permission from the publisher.
The PANI films prepared by the above method appear to be fairly uniform with the diameters
of the tips ranging from 50 nm to 70 nm. The direct electrochemical synthesis of large arrays
of uniform and oriented nanowires of conducting polymers with a diameter much smaller
than 100 nm, on a variety of substrates (Pt, Si, Au, carbon, silica), without using a supporting
template was thoroughly studied [125]. Ordered PANI nanowires tailored by such stepwise
electrochemical depositions showed remarkably enhanced capacitance [126]. The superior
capacitive behaviors of PANI nanowires show great potential in the application of
supercapacitors and rechargeable batteries. Conducting polymer nanowires are also promising
one-dimensional nanostructured materials for application in nanoelectronic devices and
sensors [127;128] due to their light weights, large surface areas, chemical specificies, easy
processing with low costs and adjustable transport properties. The electrochemical growth of
nanowire devices using e-beam-patterned electrolyte channels potentially enables the
controlled fabrication of individually addressable sensor arrays [128]. This approach should
be highly efficient and scalable, while meeting the current requirements for nanoelectronics
technologies, i.e., an integration of bottom up production methods (electropolymerization of
the nanoframeworks) and top-down fabrication (lithographic fabrication of Pt electrodes in
array).
The same galvanostastic template free, site specific electrochemical method was
developed to precisely fabricate individual and addressable conducting polymer nanowires on
electrode junctions in a parallel-oriented array [129]. Electrochemical polymerization at low
and constant current levels was used to fabricate 10 nano-framework-electrode junctions
simultaneously with uniform diameter (ca. 40 to 80 nm) PANI nanowires interwined to
nanoframeworks. Electropolymerization was carried in an aqueous solution containing 0.5 M
Di Wei 24
aniline and 1.0 M HCl. Firstly, a constant current (50 nA) was applied for ca. 30 min to
introduce the PANI nuclei onto the Pt working junction electrodes. The current was then
reduced to 25 nA for 180 min. The PANI nanoframeworks begin to propagate from the
working junction electrodes to the other set of the junction electrodes. In the last step, the
current was decreased to 12 nA for 180 min, and the 10 polyaniline nano-framework-
electrode junctions were obtained simultaneously with each PANI nanoframe work positioned
precisely within the 2 m gap between its electrodes. All these nanoframe work electrode
junctions can be covered by such conducting polymer wires simultaneously and site-
specifically in a parallel fashion. This device can be used as miniaturated resistive sensors for
real-time detection of NH3 and HCl gases. Such two-terminal devices can be easily converted
to three-terminal transistors by simply immersing it into an electrolyte solution along with a
gate electrode. Electrolyte-gated transistors based on conducting polymer nanowires junction
arrays was developed and the field induced modulation can be applied for signal
amplification to enhance the device performance [130]. Conducting polymer nanowires
including PANI (ca. 50-80 nm), PPy (ca. 60-120 nm) and PEDOT(ca. 80-150 nm) were
introduced to the 10 paralleled 2m-wide gaps by the template free electropolymerization
method. The preparation of electrolyte gated transistors can be completed simply immersing
the conducting polymer nanowire-based two-terminal resistive device along with a gate
electrode (a Pt wire or Ag/AgCl electrode) into a buffered electrolyte solutions containing
NaCl. P-channel transistor characteristics at pH7 and n-type behaviour in basic media were
observed for both PANI and PPy nanowires. Whereas PEDOT nanowire based device only
exhibit depletion mode behaviors in neutral solutions. These open new opportunities to
fabricate sensor arrays with conducting polymer nanowires to realize the ultrasensitive, real-
time and parallel detection of analytes in solutions.
Template Methods
The growth of thin films displaying special features like aligned pores perpendicularly to
the substrate surface and nano-porous structures have attracted the attention of many research
groups in the last decade and, with that aim several techniques such as ion beam lithography
have been used [131]. On the other hand, a lot of bottom up techniques, particularly those in
which, self-assembly processes play a relevant role in the growth mechanisms of that
nanostructures have been reported. Among them, electrochemical techniques constitute one of
the most used to fabricate highly ordered nanostructures to be used as templates for
replicating other nanostructured materials and for growing functionalized material arrays.
An overview on the nanofabrication techniques is done mainly of those related with the
nanostructures fabrication based on ordered and nanoporous anodic aluminium oxide
membranes (AAO), anodic titania membranes, colloidal polystyrene (PS) latex spheres.
Templates from carbon nanotubes, self-assembled monolayers (SAMs) and selfassembled
block copolymers etc. are also summarized. Template methods offer very important strategies
for complicated nano-structures.
Electrochemical Nanofabrication 25
Anodized Aluminum Oxide (AAO) Membranes
A simple and completely nonlithographic preparation technique for free-standing
nanostructured films with a close-packed hexagonal array of nanoembossments has been
developed by porous anodic aluminium oxide (AAO) membrane templates with different pore
diameters. They have been largely used to construct different free-standing inorganic and
organic nanowires [132-134], nanotubes [135] and ordered arrays of nanoparticles [136] since
invented.
Aluminium anodization provides a simple and inexpensive way to obtain nanoporous
templates with uniform and controllable pore diameters and periods over a wide range. The
usual electrochemical method for producing the AAO film is the anodization of high purity
Al plates at constant voltage (e.g. anodized at 22 V from an Al foil and detached by the
reverse-bias method) [137]. Membranes with several different pore sizes can be made, for
example, in the following electrolytes: Aqueous solutions of H
2
SO
4
at 10-20 V for pores ~10-
25 nm, H
2
C
2
O
4
at 40-80 V for pores ~40-100 nm, and H
3
PO
4
at 100-140 V for pores ~100-
170 nm. The pore diameter is linearly related to the anodizing voltage (1.2 nm/V). A voltage
reduction was done to thin the barrier layer that inhibits anodic current during
electrodeposition [138]. Other attempts have been made to create nano-porous symmetries
other than hexagonal packing [139]. Recently, a novel AAO membrane with a six-membered
ring symmetry co-existing with the usual hexagonal structure has been fabricated by constant
current anodization [140].The pore sizes of this structure can be tailored by changing the
processing conditions. Ordered arrays of nanodots with novel structure have been fabricated
by this AAO template. In the final stage, the porous alumina substrate can be removed by
etching in KOH. Moreover, one of the interesting possibilities afforded by the anodization
process is that the anodization can take place on arbitrary surfaces, such as curved surfaces.
Unique features including cessation, bending, and branching of pore channels are observed
when fabricating AAO templates on curved surfaces [141]. The new structures may open new
opportunities in optical, electronic and electrochemical applications.
Many strategies have been ingeniously implemented to fabricate complicated nano-
structures based on the AAO templates. For example, hexagonally ordered Ni nanocones have
been fabricated using an a porous AAO template where the pores are of a cone shape
[142].The conical AAO film was found to exhibit hexagonal order with a period of 100 nm.
The Ni nanocones and the surface morphology of the nano-conical film exhibit the same
periodic structure of the template as shown in Fig. 16.
The hexagonally ordered Ni nanocones and nano-conical film were produced using
anodization and metal plating techniques. The conical AAO template was produced using a
process of repeated applications of the anodization and pore-widening steps, applying the two
steps alternately. The Ni nanocones were produced by electroless Ni deposition onto the conical
AAO template, with the pores filled with Ni particles. The resulting Ni nanocones exhibit the
same ordered structure. The Ni nano-conical film was produced by detaching the deposited Ni
layer, with the surface morphology also a hexagonally ordered array with a period of 100 nm.
These nanostructures were produced using the wet-processes of anodization, a pore widening
treatment, the pulsed deposition of Pd particles and electrochemical Ni deposition. Clearly, this
complete process can produce good quality results.
A double-templating approach using simple electrochemical methods to create aligned
arrays of nanotubes on substrates was also introduced [143].
Di Wei 26
Figure 16. (A) Surface normal, (B) surface angled and (C) cross-section view of the hexagonally
ordered conical Ni film [142]. Reproduced by the kind permission from the publisher.
Figure 17. Schematic of method to fabricate nanotube arrays on substrates. Nanorods are
electrodeposited into nanoporous anodic alumina template films, the alumina is removed, and then the
nanorods are used as secondary templates for nanotube electrodeposition [143]. Reproduced by the
kind permission from the publisher.
Electrochemical Nanofabrication 27
The method used to fabricate nanotube arrays is shown schematically in Fig. 17. Initially,
nanorod arrays are fabricated by electrodeposition into AAO templates. By varying the
anodization conditions, the pore diameter, spacing, and height can be tuned, and the pore
ordering can also be controlled. Nickel nanorods are then electrodeposited into the pores of
the alumina. After deposition, the exposed ends of the nanorods are modified by anodization
in a dilute KOH solution. Because the anodization is performed when the alumina is still in
place, only the top ends of the nanorods are anodized. Then the alumina template is removed
by a selective chemical etch, leaving an array of nickel nanorods with anodized tips. This
nanorod array is then used for electrodeposition of gold nanotube arrays. The nanotube
material deposits uniformly across the entire surface of the nanorod arrays, except at the
anodized tips of the nanorods. Finally, the nickel nanorod array template is selectively
removed, resulting in an array of open-ended nanotubes on the substrate. This approach
allows both fabricate and organize nanostructures over large areas on substrates in the same
process. This method is demonstrated to prepare arrays of electrodeposited, open-ended
nanotubes aligned vertically on substrates. The nanotube inner diameter, spacing, and height
are determined by the nanorod dimensions, which in turn correspond to the alumina film
characteristics. The nanotube morphology and wall thickness can be controlled by the
electrodeposition parameters.
Utilizing electrochemically prepared textured aluminum sheets as a replication master in
conjunction with electrochemical deposition of metals revealed a highly facile and
economical way for the production of periodic metallic nanostructures in a large area with
high fidelity in pattern transfer as well as with a good degree of flexibility in materials [144].
The growth of metal nanowires using AAO membranes as hard templates has been reviewed
[145]. These kinds of metal nanowires can be applied to superconductivity, optical
spectroscopy, sensing, and catalytic conversion, and energy harvesting. The AAO template
method provides access to arrays of single-crystal metal nanowires and to quasi-one-
dimensional metal nanostructures with controlled compositional variation along their length.
Important semiconductors such as ZnO and TiO2 with nanostructures can also be
manufactured in such template or related anodization techniques.
Zinc Oxide (ZnO)
ZnO exhibits many unusual properties including uniaxial piezoelectric response and n-
type semiconductor characteristics. Such properties can be used in applications such as field-
emission materials [146], light emitting diodes (LEDs) [147], solar cells [148] and gas
sensors [149].
Electrodeposition of ZnO films has been reported by several groups and used in
fabrication of oriented nanowire and nanorod arrays [150-155]. ZnO films can be
electrodeposited cathodically in aqueous chloride solutions using dissolved oxygen as a
precursor. The deposition reaction in the electrolyte is:
ZnO e 2 O
2
1
Zn
2
2
+ +
+
. The
deposition mechanism was analyzed in terms of electrochemical induced surface precipitation
due to an increase of local pH resulting from the oxygen reduction reaction. A dramatic effect
of temperature on the formation of ZnO was observed. When the temperature increases
(T
transition
50C), a transition between amorphous insulating zinc oxyhydroxide (ZnO
x
(OH)
y
)
to well-crystallized and conducting ZnO happens [156]. The dimensions and the deposition
Di Wei 28
rate of electrodeposited ZnO nanowire arrays can be controlled by changing the chemical
nature of the anions in solution. A significant variation of the diameter (65 to 110 nm) and
length (1.0 to 3.4 m) of the nanowires can be obtained by changing only the nature of the
anions in solution [157].
Recently, large-scale, single-crystalline ZnO nanotube arrays were directly fabricated onto
F-doped SnO2 (TCO) glass substrate via an electrochemical deposition method from an
aqueous solution [158]. The tubes had a preferential orientation along the [0001] direction and
hexagon-shaped cross sections. The novel nanostructure could be easily fabricated without a
prepared layer of seeds on the substrate. The surface condition of substrate material and the
experimental conditions played a key role in the nanotube formation. The growth of ZnO arrays
and the deposition reaction take place by applying a cathodic potential (-0.7 V vs. SCE) to the
TCO substrate at 80C. The dissolved oxygen serves as the oxygen source for the growth of
ZnO arrays in the electrolyte. SEM image of the result ZnO nanotubes are shown in Fig. 18.
The electrochemically deposited single crystalline ZnO nanowires can be applied in
LEDs [154;155].The ZnO nanowire films can be embedded in an insulating spin-coated
polystyrene layer. The spin-coating parameters are carefully finetuned to completely fill out
the space between the ZnO nanowires and produce only a very thin coverage of the nanowire
tips. The polystyrene layer thickness at the tips can be further reduced by the plasma etching
treatment to make the n-type ZnO tip junctions outside. A top contact consisting of a thin p-
type poly(3,4-ethylene dioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layer and an
evaporated Au film are provided to serve as the hole injection anode in the LED. A flexible
LED can be realized when electrochemical depositing the ZnO nanowire on flexible
transparent polymer substrates (e.g. polyethylene terephtalate, PET) coated with indium-tin-
oxide (ITO) [147]. The infrastructure of such flexible LED is illustrated in Fig. 19.
Figure 18. SEM image of the ZnO nanotube film [158]. Reproduced by the kind permission from the
publisher.
Electrochemical Nanofabrication 29
Figure 19. Design scheme for a flexible LED structure consisting of vertically oriented single
crystalline nanowires grown electrochemically on a polymeric ITO-coated substrate. The top contact
consists of p-type polymer (PEDOT:PSS) and an evaporated Au layer. Light is emitted through the
transparent polymer [147]. Reproduced by the kind permission from the publisher.
This device exhibits electroluminescence over most of the visible spectrum at moderate
forward bias.
Titanium Dioxide (TiO
2
)
Another semiconductor which has similar bandgap with ZnO, titanium dioxide (TiO
2
)
thin films have been widely exploited in many applications such as microelectronics [159],
highly efficient catalysts [160], microorganism photolysis [161], antifogging and self-
cleaning coatings [162], biosensors [163], gate oxides in metal-oxide-semiconductor field
effect transistors (MOSFET) [164] and more recently in dye-sensitized solar cells (DSSCs)
[165].
The geometry of anodic TiO
2
nanotubes can be controlled over a wide range by the
applied potential in H
3
PO
4
/HF aqueous electrolytes in contrast to other electrolytes. It was
found that for potentials between 1 and 25 V, tubes could be grown with any desired diameter
ranging from 15 to 120 nm combined with tube length from 20 nm to 1 m. The diameter and
the length depend linearly on the voltage [166]. Aqueous HCl electrolyte can be used as an
alternative to fluoride containing electrolytes to obtain the vertically oriented TiO2 nanotube
arrays by anodization of titanium thin films [167]. Nanotube arrays upto 300 nm in length, 15
nm inner pore diameter and 10 nm wall thickness can be made using 3 M HCl aqueous
electrolyte for anodization potentials between 10 and 13 V.
A highly ordered TiO
2
nanotube array with a unique surface morphology can be
fabricated by electrochemical anodization of titanium in an organic electrolyte (e.g. 1:1
mixture of DMSO and ethanol) containing 4% HF. The TiO
2
nanotube arrays with improved
Di Wei 30
photochemical response can be obtained using electrochemical anodization of titanium in
fluorinated organic electrolytes by optimizing etching time, applied potential, solvents and the
HF concentration [168]. Using an electrochemical approach in organic electrolytes, the
growth of more than 250 m thick self-organized TiO
2
nanotube layers is possible [169].
Combining the electrochemical parameters in an optimal way, ordered TiO
2
nanotube layers
with a length of over 250 m have been obtained at 120 V with 0.2 M HF. The tubes can
grow as a hexagonal close packed pore array. Although the TiO
2
nanotubes fabricated in
organic solution have the longest length and the largest surface area, its conductivity may be
lower than the one synthesized in aqueous solutions [163]. Crucial parameters that decide on
the dimensions are the fluoride ion concentration, the voltage and the anodization time. The
different length of TiO
2
nanotubes synthesized by electrochemical anodization can be
controlled, and is shown in Fig. 20.
Figure 20. SEM images of TiO
2
nanotubes prepared in (A) 0.1M HF acid solution at 20 V (B) 1.0M
NaHSO4 containing 0.1M KF at 20 V and (C) ethylene glycol containing 0.25% NH4F at 60 V for 1 h
[163]. Reproduced by the kind permission from the publisher.
Highly ordered transparent TiO
2
nanotube arrays produced by electrochemical
anodization have been used in DSSCs. It suggests superior electron transport in nanotubular
TiO
2
based DSSCs [170]. Remarkable photoconversion efficiencies were expected to be
obtained with increase in the length of the nanotube arrays. Carboxylated polythiophene
derivatives can be selfassembled onto the TiO
2
arrays produced by anodizing titanium foils in
Electrochemical Nanofabrication 31
ethylene glycol based electrolytes [171]. Such self-assembled hybrid polymer-TiO
2
nanotube
array heterojunction solar cells can yield power efficiency of 2.1% under AM 1.5 without
dyes. It was found that the formation mechanism of TiO
2
nanotubes is similar to the porous
alumina case under high electrical field. TiO
2
nanotube arrays can be fabricated by anodic
oxidation of titanium foil in different electrolytes. The produced TiO
2
nanotube arrays
possess large surface area and good uniformity and are ready for enzyme immobilization
[172-174], which can be used as biosensors. Furthermore, different length of TiO
2
nanotube
arrays fabricated by anodic oxidation in different electrolytes were studied for their
sensitivities to hydrogen peroxide after co-immobilized horseradish peroxidase (HRP) and
thionine chloride. The nanotube arrays fabricated in potassium fluoride solution has the best
sensitivity to H
2
O
2
with a detection range from 10
-5
to 310
-3
M [163].
With the use of the template of an AAO, TiO
2
nanowires can be obtained by cathodic
electrodeposition [175;176] where the metallic ions are attracted to the AAO cathode
electrode and reduced to metallic form. For example, in a typical process, the
electrodeposition is carried out in 0.2 M TiCl
3
solution with pH=2 with a pulsed
electrodeposition approach, and titanium and/or its compound are deposited into the pores of
the AAO. By heating the above deposited template at 500 C for 4 hours and removing the
template, pure anatase TiO
2
nanowires can be obtained. Highly ordered TiO
2
single
crystalline (pure anatase) nanowire arrays can also be fabricated within the pores of anodic
aluminum oxide (AAO) template by a cathodically induced sol-gel method [177]. During this
electrochemically induced sol-gel process, both the formation of sol particles and the gelation
process take place in the AAO pores. Therefore, TiO
2
nanowires with very small diameters
(less than 20 nm or even smaller) can be obtained by this technique. In addition, the length of
the nanowires can be well controlled by varying the deposition time and potential of the
working electrode.
Electrochemical Fabrication of Soft Matters in Nanoscale
Nanofiber, nanospheres and other nanoscale of soft matters such as conducting polymers
have been fabricated in traditional chemistry way and/or via selfassembly [178-187].
Basically, 1D conducting polymer nanostructures can also be synthesized chemically or
electrochemically by using hard and soft template methods. Obviously, the hard-template
method (e.g. AAO) is an effective and straightforward route for fabricating conducting
polymer nanostructures with diameters determined by the diameter of the pores in the
template. Controlled conducting poly(aniline) nanotubes and nanofibers have been fabricated
in the AAO templates and find promising applications in lithium/poly(aniline) rechargeable
batteries [188]. Nanotubes and nanowires of conducting polymers including polypyrrole
(PPy), polyaniline (PANI) and poly(3,4-ethylenedioxythiophene) (PEDOT), can be
synthesized by electrochemical methods using the AAO templates [189]. By changing the
doping level, dopant and template-dissolving solvents, the electrical and optical properties of
the nanotubes and nanowires can be controlled. The diameter of the conducting polymer
nanotubes and nanowires are in the range from 100 to 200 nm, depending on the diameter if
the nanoporous template used. It was found that the polymerization was initiated from the
wall-side of the AAO template. The synthesized nanotubes have an open end at the top with
the filled end at the bottom. As polymerization time increased, the nanotubes will be filled
and nanowires will be formed with the length increased. For example, PPy nanotube can be
Di Wei 32
synthesized by applying current of 2-3 mA for 1 min. When the time is increased to 15-40
mins, PPy nanowires will be produced. Conducting polymer nanotube and nanowires
prepared by this electrochemical method using AAO templates can be applied in field
emitting applications [190;191]. Fig. 21 below shows an uniform of polyaniline nanowires
produced at constant potential at 1.0 V for 10 min through the AAO template [192].
PPy nanotubes and nanowires can be also electrochemically synthesized through
nanoporous AAO template in ionic liquids[193]. The electrolyte consisted of pyrrole
monomer, solvent, and ionic liquid dopant such as 1-butyl-3-methyl imidazolium
tetrafluoroborate (BMIMBF
4
) or 1-butyl-3-methyl imidazolium hexafluorophosphate
(BMIMPF
6
), which is stable in air and moisture. The length and diameter of PPy nanotubes
and nanowires were determined by the synthetic conditions such as polymerization time,
current, and dopant. The formation of nanotube and nanowire of PPy sample was confirmed
by using field emission scanning electron microscope and transmission electron microscope.
Formation of PANI nanotubules in room temperature ionic liquids by means of
electrochemical polymerization without any template has also been reported [194]. PANI
nanotubules were synthesized electrochemically on a modified ITO glass in BMIMPF
6
containing 1M trifluoroacetic acid. Tubular structures of PANI with the diameter of ca.120
nm were shown by scanning electron microscopy.
Figure 21. SEM of electrochemically synthesized (a) PANI nanowires and (b) composite nanowires in
AAO membranes (etched with NaOH) [192]. Reproduced by the kind permission from the publisher.
Electrochemical Nanofabrication 33
Variable inorganic nanoparticles of different sizes can be combined with conducting
polymers, giving rise to a novel composite material with interesting physicochemical
properties and possibilities for important applications. Electrochemical methods have proved
to be effective in incorporating metal nanoparticles in either pre-deposited polymers or in
growing polymer films. Metals can be electrodeposited at conducting polymer electrodes
[195]. Nanocables consisting of Ag nanowires sheathed by polyaniline were fabricated in
porous AAO template [192]. Silver/polyaniline (Ag/PANI) nanowires were prepared by
simultaneous oxidative electropolymerization of aniline and reduction of Ag+ in porous AAO
from an acidic electrolyte containing Ag+ and aniline. One-step electrochemical fabrication
of devices based on such inorganic-organic hybrid materials offers a new strategy to make
electronic devices. Electrochemical fabrication of non-volatile memory device based on
polyaniline and gold particles was reported [196]. Au nanoparticles are synthesized and
embedded into the PANI polymer matrix simultaneously during the electropolymerization.
The impedance states of the PANI:Au composite films are nonvolatile in nature and can be
read and switched several times with minimal degradation in air. Such electrochemical
fabrication method can produce multi-stable nonvolatile memory device in one step, which
simplifies fabrication of the memory device significantly.
Carbon Nanotube Templates
Carbon nanotubes (CNTs) can be used as templates for soft matters such as conducting
polymers. Composite films of CNTs with PANI, PPy or PEDOT were prepared via
electrochemical co-deposition from solutions containing acid treated CNTs and the
corresponding monomer. The capacitance of such composite was studied [197].
Figure 22. Continued on next page.
Di Wei 34
Figure 22. SEM image of (a) modified ITO glass surface (MITO); (b) purified SWNTs; (c) SWNT
modified with PANI (electropolymerization for 50 cycles); (d) SWNT modified with PANI
(electropolymerization for 300 cycles); (e) bare ITO glass surface [198]. Reproduced by the kind
permission from the publisher.
Electrochemical functionalization of single walled carbon nanotubes (SWNTs) with
PANI has also been done in ionic liquids [198]. SWNTs are covalently functionalized during
the electropolymerization of aniline in ionic liquids. This methodology provides a novel way
by which large amount of SWNTs (15 mg/ml) can be modified by aniline electrochemically.
Fig. 22 shows the processes of coating CNTs with PANI by increasing the scan cycles during
cyclic voltammetry from 50 cycles (Fig. 22c) to 300 cycles (Fig. 22d).
Electrochemical synthesis of PPy/CNT nanoscale composites using well aligned carbon
nanotube arrays was reported [199]. The thickness of the PPy film can be easily controlled by
the value of the film-formation charge. Aligned coaxial nanowires of carbon nanotubes can be
sheathed with conducting polymers shown in the following figures (Fig. 23 and Fig. 24)
[200]. In addition, the aligned MWNT electrode arrays can be given additional robustness by
electrodepositing conducting polymer around the tubes and then employing them as enzyme
sensors. Nanostructuring electrodes with carbon nanotubes for its sensing applications have
been reviewed [201]. Glucose oxidase, the most popular oxidase enzyme can be immobilized
onto CNTs by electrodeposition within conducting polymers [202].
Figue 23. Continued on next page.
Electrochemical Nanofabrication 35
Figure 23. SEM images of a) aligned nanotunes after transfer onto a gold foil (a small piece of the as-
synthesized aligned nanotue film is inlded at the bottom-left corner to show the amorphous carbon
layeras well) and b) the CP-NT coaxial nanowires produced by cyclic voltammetry (25 mV/s) on the
aligned carbon nanotube electrode in an aqueous solution of 0.1M NaClO4 containing 0.1 M pyrrole
[200]. Reproduced by the kind permission from the publisher.
Figure 24. TEM images of the CP-CNT coaxal nanowire formed from the cyclic voltammetry method.
The images are in the tip region (left) and on the wall (right) [200] Reproduced by the kind permission
from the publisher.
Colloidal Polystyrene (PS) Latex Templates
In nanoelectrodeposition, the aim is to place only a single layer or more of coverage on a
surface in a very controlled way. Colloidal crystal such as polystyrene (PS) latex templates
have been widely used to synthesise highly ordered macroporous ceramics [203], metals
[204] and polymers [205;206] where a particular interest has been in the optical, magnetic
and photonic band gap properties of the resultant structures. Studies of the magnetic
properties of the macroporous films show a large coercivity enhancement in comparison to
Di Wei 36
the corresponding plain films and it was found that the coercive field gradually increases as
the diameter of the spherical voids decreases for films of a constant thickness [207].
PS latex nanospheres can be self-assembled on hydrophobic surfaces such as unoxidised
silicon or gold and used as templates [207;208]. Two or three dimensional highly ordered
macroporous cobalt, iron, nickel, gold, platinum and palladium films containing close packed
arrays of spherical holes of uniform size (an inverse opal structure) can be prepared by such
simple and versatile template technique [207-209]. The films were prepared by
electrochemical reduction of metal cations (e.g. gold ions) dissolved in aqueous solution
within the interstitial spaces of pre-assembled colloidal templates assembled on gold surfaces.
The templates were assembled from colloidal polystyrene latex spheres assembled onto gold
electrode surfaces from aqueous solution by slow evaporation. The aqueous layer was
allowed to evaporate naturally so that the PS nanospheres assemble by capillary force on the
substrate surface. Following the electrochemical deposition of the metal films, the
polystyrene templates were removed by dissolution in toluene. The resulting films will show
well-formed two or three dimensional porous structures consisting of interconnected
hexagonal close packed arrays of spherical voids. The diameter of the spherical voids within
the structures can be varied by changing the diameter of the PS latex spheres used to form the
template. The thickness of the films is controlled by varying the charge passed in their
deposition.
Figure 25. SEM images of regions of macroporous gold films grown with a thickness gradient by
electrochemical deposition through templates assembled from either 750 nm-diameter polystyrene
spheres [209]. is the diameter of the sphere on top layer. The three dotted circle lines represent the
spheres beneath. Reproduced by the kind permission from the publisher.
Electrochemical deposition is ideal for the production of thin supported layers for
applications such as photonic mirrors, because the surface of the electrochemically deposited
Electrochemical Nanofabrication 37
film can be very uniform. Electrochemical deposition occurs from the electrode surface out
through the overlying template, the first layer of templated material, deposited out to a
thickness comparable with the diameter of the template spheres used, has a different structure
from subsequent layers. The subsequent growth of the film by electrodeposition out through
the template leads to a modulation of the surface topography of the film in a regular manner
that will depend on the precise choice of deposition bath and deposition conditions. This is
clearly shown in the following figure if more than one layer of PS is used in templates.
The electrodeposition was performed at a potential of -0.90 V
SCE
. The SEM image shows
that the spherical voids left in the gold films after the removal of the PS spheres are arranged
in well-ordered, single domain, close-packed structures. Fig. 25 gives an image for a
macroporous gold film prepared through a template of 750 nm diameter spheres in a region
where more than one layer of PS is selfassembled. Within each hemispherical void in the top
layer there are again three smaller dark circles (diameter ca.100 nm). These correspond to the
interconnections to the three spherical voids in the layer below (marked as dotted circles in
Fig. 25) that are left around the regions where the original polystyrene spheres in the two
layers were in contact. Nanostructured macroporous semiconductors such as PbO
2
can also be
electropolymerized by such template methods [211]. Other nanostructured patterns such as
nanodots can also be synthesized by this template method. Highly ordered magnetic nano-
scale dot arrays of Ni can be fabricated from double-templated electrodeposition [212;213].
Patterns of ordered arrays of spheres with controlled spacing can be electrochemical
deposited by two steps. The double templates were firstly prepared by selfassembly of PS
latex spheres on a gold coated glass substrate. This primary template was used for the
electrodeposition of the conducting polymer resulting in a macroporous polymer template.
After the deposition of PPy, the PS spheres were dissolved in toluene leaving a secondary
polymer template. The PPy was then converted into an insulator either by over-oxidation or
by undoping at a sufficiently negative potential. This insulating structure was used as the
template for electrochemical deposition of magnetic material such as Ni. Electrodeposition of
magnetic materials gradually fills the spherical cavities of the polypyrrole template. Ordered
arrays of Ni dots with quasi-spherical geometry can be fabricated by this way and the
diameter of the dots can be set from 20 nm [213].
Ordered 3D arrays of polyaniline (PANI) inverse opals can also fabricated via
electrochemical methods by using colloidal crystals of polystyrene beads as sacrificial
templates as shown in Fig. 26 [214].
Figure 26. Schematic illustration of the procedure used for fabricating PANI inverse opals. Reproduced
by the kind permission from the publisher.
Fig. 27 shows the PANI inverse opals prepared by cyclic voltammetry in 3D PS colloidal
crystal template. Compared with films obtained by chemical synthesis, the inverse opaline
samples obtained by electrochemistry had a much higher structural quality.
Di Wei 38
Figure 27. SEM images of PANI inverse opals prepared via cyclic voltammetry, at low (A) and higher
(B) magnification. scan rate 20 mV/s, 10 scan cycles [214]. Reproduced by the kind permission from
the publisher.
PANI inverse opals were also prepared by a galvanostatic method at a current density
0.05 mA/cm
2
. By adjusting the polymerization time and applied current, this method allows
for the exact control over the structure formation and film thickness of the obtained PANI
inverse opline films. To explore potential biosensing applications, PANI composite inverse
opals were fabricated by modifying the structure with different dopants, such as poly(acrylic
acid) (PAA) and poly(styrene sulfonate) (PSS). It was found that these dopants had a
significant effect on the structure and the mechanical stabilities of the obtained opaline films.
With selection of suitable dopants, PANI composite inverse opals could be fabricated with
very high quality. The obtained films remained electroactive in buffer solutions of neutral pH.
Together with their huge surface area, they would be ideal candidates for biosensing
applications. Such macroporous structures were used as electrocatalysts for the oxidation of
reduced -nicotinamide adenine dinucleotide (NADH). It showed that the electrocatalytic
efficiency of the inverse opline film was much higher compared with that of an unpatterned
film.
Using such templates is a clear example to show the significant advantages of
electrochemical deposition methods. It produces a high density deposited material and no
shrinkage of the material takes place when the template is removed. Also it can be used to
prepare a wide range of materials and allows fine control over the thickness of the resulting
macroporous film through control of the total charge passed to deposit the film.
Electrochemistry and Self-assembled Monolayers (SAMs)
Electron transfer cannot occur in blocking films. However, for very thin self assembled
monolayers (SAMs) of alkane thiols or oxide films, electrons can tunnel through the film and
cause Faradaic reactions. Monolayer of alkane thiols can form spontaneously ordered
adlayers on substrate like Au(111) due to a strong interaction between the sulphur of the thiol
and the gold substrate. These SAMs have received tremendous attention in recent years
[215;216].
Electrochemical deposition onto self-assembled monolayers gives new insights into
nanofabrication [217]. Pattern transfer with high resolution is a frontier topic in the emerging
Electrochemical Nanofabrication 39
field of nanotechnologies. Electrochemical molding is a possible route for nanopatterning
metal, alloys and oxide surfaces with high resolution in a simple and inexpensive way. This
method involves electrodeposition onto a conducting master covered by a alkanethiolate
SAMs. This molecular film enables direct surface-relief pattern transfer from the conducting
master to the inner face of the electrodeposit, and also allows an easy release of the
electrodeposited film due their excellent anti-adherent properties. Replicas of the original
conductive master can be also obtained by a simple two-step procedure. SAM quality and
stability under electrodeposition conditions combined with the formation of smooth
electrodeposits are crucial to obtain high-quality pattern transfer with sub-50 nm resolution.
Fig. 28 demonstrated the steps involved in metal electrodeposition on SAMs covered
substrates. Further in-depth investigations are required for improving SAM quality reducing
the defect size and density, and accordingly increasing the lateral resolution of the method.
Figure 28. Scheme showing the steps involved in metal electrodeposition on SAMs covered substrates.
a) Defective sites at SAMs (the molecules are indicated in black); b) nucleation and growth of the metal
(grey) within the SAM; c) three dimensional growth outside the SAM; d) formation of a continuous
metallic film on the SAM [217]. Reproduced by the kind permission from the publisher.
Electrochemical work comprised mainly copper deposition onto alkanethiol SAMs.
Under UPD, Cu would go down on the bare substrate only [218]. The chain length of the
alkane thiol on gold has an influence on the deposition over potential [219]. The long hain
alkane thio (C18) on Au (111) is demonstrated to have a high blocking power [220].
However, it appears to remain one of the challenges for the near future to find the
experimental conditions, under which metal can be deposited on top of a SAM, preferably as
a 2D overlayer.
Di Wei 40
On the other hand, electrochemistry can induce self-assembly of surface-templated
(organo)silica thin films on various conducting supports, with mesopore channels oriented
perpendicular to the solid surface over wide areas [221]. This method is intrinsically simple,
very fast and does not require any pre-treatment of the support. It consists of combining the
electrochemically driven self-assembly of surfactants at solid-liquid interfaces and an
electroassisted generation methods to produce sol-gel films. The method of electrochemically
assisted self-assembly of mesoporous silica thin films involves the application of a suitable
cathodic potential to an electrode immersed in a surfactant-containing hydrolysed sol solution
to generate the hydroxyl ions that are necessary to catalyse polycondensation of the
precursors and self-assembly of hexagonally packed one-dimentional channels that grow
perpendicularly to the electrode surface. The method opens the way to electrochemically
driven nanolithography for designing complex patterns of widely accessible meso-structured
materials.
Other Template Methods
Molecular templates such as modified cyclodextrin have been used for electrochemical
nanofabrication. Conducting polymer nanowires and nanorings can be electrochemically
synthesized using the molecular templates (thiolated cyclodextrins) on gold [222]. The
strategy is to apply electrochemical growth on gold electrodes modified with SAMs of well-
separated thiolated cyclodextrins in an alkanethiol forest. Thiolated aniline monomer is
anchored to the surface within the cyclodextrin cavity and forms an initiation point for
polymer wire growth. Nanosized conducting polymer wires several tens of nanometer thick
and a few micrometers long can be synthesized electrochemically by this template. Even
though the polymer wires appear to be made of numerous single strands, it was the first time
that a single nanowire thread of a conducting polymer has been isolated.
Block copolymers are a class of materials that selfassemble on macromolecular
dimensions and have enormous potential in nanoscale patterning and nanofabrication as
templates [223;224]. Some complicated nanoporous structures can be replicated by
electrochemical deposition with the help of selfassembly of block-copolymers, for example,
poly(4-fluorostyrene)-b-poly(D,L-lactide) [PFSPLA] [225]. By this means, very large arrays
of possible materials can be manufactured. Free standing nanowires were obtained after
removal of the block copolymer template by either dissolution or by UV irridation. Such mild
etch method is generally useful to the nanostructures that are sensitive to more aggressive
template removal processes. Furthermore, the electrochemical deposition method guaranties a
conformable and stable interface between the electrode and the electrodeposited materials.
PPy nanotubules have been chemically and electrochemically synthesized inside the pores of
nanoporous polycarbonate (PC) particle track-etched membranes (nano-PTM) [226]. Other
templates to produce the nano-structured conducting polymers such as DNA [227] and living
neural tissue [228] have been reported for its potential applications in biosensors.
Nanofabrication technologies are useful for developing highly sensitive, reproducible
nanobiosensors. A nanometric system that is composed of well-oriented nanowell arrays can
be used for highly sensitive electrochemical DNA detection, it obtained a two-orders-of-
magnitude enhancement in sensitivity [229].
Electrochemical Nanofabrication 41
The step edge defects on single crystal surfaces can be also used as templates to form
conducting polymer nanostructures. Polypyrrole nanostructures with diameters less than or
equal to 10 nm have been electropolymerized using step and pit defects on highly ordered
pyrolytic graphite (HOPG) as templates for electropolymerization [230]. Step defects were
naturally occurring, and pits were formed via oxidation of freshly cleaved surfaces of an
HOPG wafer by heating at similar to 640 C. Underpotential deposition of approximately
similar to 80 mV caused polypyrrole to form only on the step and pit edges of HOPG at and
not on the basal plane. The size of these nanostructures could be controlled by limiting the
pyrrole polymerization time at anodic potentials. Recent modeling results allow the
morphology of the deposition to be inferred, and the wire-shaped growth is up to 30 s at
constant potential, after which the growth changes morphology. Scanning tunneling
microscopy data confirm this result. These polypyrrole nanostructures can be removed by
sonication.
Others
Nanoscale Electrochemistry
Individual carbon nanotubes have been modified selectively on one end with metal using
a bipolar electrochemical technique [231]. A stable suspension of nanotube was introduced in
a capillary containing 10 mM HAuCl
4
aqueous electrolyte, and a high electric field is applied
to orientate and polarize the individual tubes. During their transport through the capillary
under sufficient polarization (30 kV), each nanotube is the site of water oxidation on one end
and the site of metal ion reduction on the other end with the size of the formed metal cluster
being proportional to the potential drop along the nanotube.
Bipolar electrochemistry occurs when an external electrical field polarizes an object that
is not physically connected to the electrodes and thus generates an anodic and a cathodic area
on the same object. The substrate can be any kind of material, but its conductivity must be
higher than that of the surrounding medium. The induced potential difference between the
two extremities of the object, and therefore the kinetics of the associated redox reactions, is
directly proportional to the particles effective length [232]. When the capillary is exposed to
a high electric field (10-30 kV), an electroosmotic flow is generated inside the capillary,
transporting the CNT/AuCl
4
suspension from the anodic capillary inlet towards the cathodic
compartment. A 1 mm long carbon fiber was inserted into a glass capillary connected to two
reservoirs filled with HAuCl4 electrolyte. The fiber was observed under the microscope
during the application of different potential values. It was found that potentials higher than 40
V are needed to generate a visible metal deposit on the cathodic side of the fiber. After less
than 5 min, a visible gold deposit was clearly formed on the negativel polarized end of the
fiber. In the course of 1 h, the metal continued growing and its morphology, as revealed by
SEM, was dominated by an agglomeration of small crystallites. The Au particle formed after
45min was illustrated in Fig 29.
Di Wei 42
Figure 29. Capillary filled with an aqueous CNT/AuCl
4
suspension dipping in the two reservoirs of a
capillary lectrophoresis setup. A high electric field is applied, leading to the polarization of the
individual nanotubes, thus triggering different electrochemical reactions on either end. Optical
micrographs of a carbon fiber inside a glass capillary during dissymmetric gold deposition by bipolar
electrochemistry. The applied voltage was 70 V for a capillary with a length of 10 cm, filled with 10
mM HAuCl
4
aqueous electrolyte [231]. Reproduced by the kind permission from the publisher.
Looking to the future, this capillary assisted bipolar electrodeposition can be generalized
to other types of nano-objects and also deposits of a very different nature such as other
metals, semiconductors, or polymers. The approach therefore opens up the way to a whole
new family of experiments leading to complex nano-objects with an increasingly
sophisticated design allowing original applications.
Sonoelectrochemistry
Single crystalline CdSe nanotubes have been successfully synthesized by a
sonoelectrochemical route in aqueous solution at room temperature [233]. The
sonoelectrochemical method is accomplished by applying an electric current pulse to nucleate
and perform the electrodeposit, followed by a burst of ultrasonic energy that removes the
products from the sonic probe cathode [234;235]. The growth progress suggested that the
CdSe nanotubes were fabricated by sonication-induced rolling-up of CdSe nanosheets and the
resulting CdSe products are in tubular structure. This method is simple, convenient and
environmentally benign. The sonoelectrochemical synthesis of other nanomaterials is being
investigated currently.
In addition, traditional top-down nanofabrication methods such as focused ion beam
(FIB), can be used to fabricate nanopore array electrodes [236]. FIB milling thus represents a
simple and convenient method for fabrication of prototype nanopore electrode arrays. These
electrode nano-arrays can be used in electrochemical nanofabrication for applications in
sensing and fundamental electrochemical studies.
Various organic and inorganic materials with nanoscale architectures can be fabricated by
electrochemical nanofabrication. It is a versatile method for fabricating nanostructures with
its simplicity, low-temperature processing, low equipment cost and precise control of the
deposit thickness through control of the total charge passed. It is an exciting era to witness the
Electrochemical Nanofabrication 43
emerging of nanotechnology. Electrochemistry will definitely contribute to its development
independently and interdisciplinarily with other nanofabrication methods.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 51-69 2010 Nova Science Publishers, Inc.
Chapter 2
FABRICATION AND APPLICATION OF NOVEL
TWO-DIMENSIONAL NANOWEBS
VIA ELECTROSPINNING
Bin Ding
*,1
, Chunrong Li
2
, Dong Wang
3
and Seimei Shiratori
2
1
Modern Textile Institute, Donghua University, Shanghai 200051, China
2
SNT Co. Ltd., Kawasaki 212-0054, Japan
3
Fiber and Polymer Science, University of California, Davis, CA 95616, USA
Abstract
This chapter reviews our recent progress on the novel two-dimensional nanowebs by the
optimization of processing parameters during electrospinning. Using high applied voltage and
low relative humidity in chamber, the by-product of micro-sized defect films can be splitted
into nanowebs due to the fast phase separation of the charged droplets which flight with high
moving speed in electric field from capillary tip to collector. The electrospun fibers act as a
support for the fishnet-like nanowebs comprising interlinked one-dimensional nanowires.
The average diameter of the nanowires contained in typical nanowebs is about one order of
magnitude smaller than that of conventional electrospun fibers. Nanowebs together with
common electrospun nanofibers can be assembled into a three-dimensional fibrous mat. So
far, nylon-6, polyacrylic acid (PAA), poly(vinyl alcohol) (PVA)/SiO
2
nanoparticles, and
PVA/zinc acetate have been found to have the possibility forming nanowebs. The formation,
morphology, and area density of the nanowebs in electrospun fibrous mats are strongly
affected by the applied voltage, ambient relative humidity, kinds of solvents, solution
concentration and conductivity, and distance between capillary tip to collector. The expanded
applications of electrospun fibers are expected due to the formation of nanowebs, such as the
nano-sized controllable filters, high efficient catalysts, catalyst supporter, and sensors. The
preliminary data showing that the sensitivity of PAA nanowebs to ammonia is 2.5 times
higher than that of electrospun PAA nanofibers. Additionally, PAA nanowebs show much
quicker absorption speed and larger capacities than that of PAA nanofibers during the
ammonia absorption test.

*
E-mail address: binding75@yahoo.com (B. Ding) Tel & Fax: +86-21-62378392; Corresponding author.
Bin Ding, Chunrong Li, Dong Wang et al. 52
Introduction
The process of electrospinning was first studied by Zeleny [1] in 1914 and patented by
Formhals [2] in 1934. In the past decade, this technique regained a great deal of attention due
to a surging interest in nanotechnology as continuous ultra-fine fibers or fibrous structures of
various polymers with diameters in the range from several micrometers down to tens of
nanometers [3-6]. The ultra-fine fibers can be easily fabricated under the driving force of an
external electric field imposed on a polymer solution or melt.
Electrospinning can be considered as a special case of electrospray process which uses
electrostatic fields to form and accelerate liquid jet from the tip of a capillary [1,7]. The
surface of a hemispherical liquid drop suspended in equilibrium at the end of a capillary will
be distorted into a conical shape in the presence of an external electric field. This distortion is
caused by a balancing of the repulsive force resulting from the induced charge distribution on
surface of droplet with the surface tension of liquid [8]. Taylor showed that at a critical
voltage, the equilibrium shape of the suspended meniscus was a cone with a semi-vertical
angle of 49.3
o
[7]. A stable jet of liquid could be ejected and accelerated if the applied voltage
exceeded this critical voltage. The jet breaks up into small droplets as a result of the
longitudinal Rayleigh instability caused by surface tension in the case of low viscosity
liquids. This process is known as electrospray for applications to obtain aerosols composed of
sub-micron droplets with narrow distribution [9,10]. For high viscosity liquids, polymer
solutions or melts, the jet does not break up, but travels as a jet to the grounded collector. The
transverse instability or splaying of the jet into two or more smaller jets is observed due to the
radial charge repulsion [11]. This process is termed as electrospinning and it produces the
polymer fibers with diameter in sub-micron scale [8].
The experimental observation of micro-sized films among the electrospun fibers has been
reported [8, 12, 13]. The sub-micron or micron sized droplets, which produced by the high
electrically driven instability of the liquid droplet suspended at the tip of capillary, was
considered to form micro-sized films among the electrospun fibers. These unexpected micro-
sized films with uncompleted solvent evaporation led the melt of their covered dry fibers, and
destroyed the uniformity of fibers. Therefore, they were called defect films. The variation in
frequency of defect films formation, size and area density of defect films could be controlled
by adjusting the processing parameters during electrospinning. The defect film density
increases with increasing instability of the jet at the capillary tip.
The one-dimensional (1D) electrospun fibers has a typical length > 100 m and diameters
in the range of 30-2000 nm [3]. The three-dimensional (3D) non-woven mats composed of
electrospun fibers are considered to be have a larger surface-to-volume ratio and smaller pore
size compared to commercial textiles, making them excellent candidates for applications in
sensor system [14-16], filtration [17,18], tissue engineering [19-21], dye-sensitized solar cells
[22, 23], super-hydrophobic surfaces [24-28], etc. Considerable recent progress in
electrospinning were made that are expected to have lasting impact on the quality and scope
of the applications, such as the alignment of electrospun fibers [29-31], fabrication of
continuous carbon [32], polyoxometalate [33, 34], ceramic [35-37], coated [38-41], and
hollow [34, 42, 43] fibers. Additionally, Yu et al. reported two major strategies to decrease
the fiber diameter from the low concentration of polymer in solution and the high charge-
carrying capacity of solution [44]. However, the reduction of electrospun fiber diameter is
Fabrication and Application of Novel Two-Dimensional Nanowebs 53
still a serious challenge. Electrospun fibers with average diameters below 50 nm are still
difficult to be produced repeatedly and uniformly for most materials with electrospinnability
until now.
This chapter reviews our recent new observation of nanowebs, which widely distributed
among electrospun fibers during electrospinning with optimized processing parameters. The
nanowires within a nanoweb, not electrospun fibers, can be easily fabricated with diameters
below 50 nm. Poly(acrylic acid) (PAA) and nylon-6 are selected as a template material for
demonstration of the nanoweb formation process and a typical nanoweb-rich example,
respectively. Additionally, other solution systems such as poly(vinyl alcohol) (PVA)/ZnO and
PVA/SiO
2
also formed the nanowebs after electrospinning. Preliminary comparative study of
PAA nanofibers and nanowebs was carried out by ammonia gas absorption and detection.
Experimental
Preparation of Polymer Solutions for Electrospinning
The starting materials included PAA (M
w
250 000, Wako), Nylon-6 (Aldrich), PVA (M
n
66 000, Wako), zinc acetate (Wako), SiO
2
nanoparticles (12 nm), ethanol (Wako), distilled
water, and formic acid (Wako). Four kinds of polymer solutions were prepared as the
following procedures.
PAA powder was dissolved in H
2
O, ethanol, and their blends, respectively, with
concentrations of 6, 8, and 10 wt%. Nylon-6 was dissolved in formic acid with concentration
of 10, 15, 20, and 25 wt%.
A 10 wt% PVA solution was prepared from PVA powder and distilled water at 80
o
C
with vigorous stirring. The electrospinning PVA/ZnO solution can be obtained by blending
10 g PVA solution, 1 g zinc acetate, and 1 g distilled water at room temperature under stirring
for 6 h. 0.2 g SiO
2
nanopartilces was blended with 10 g PVA solution (10 wt%) under
vigorous stirring and ultrasonic treatment.
The viscosity and conductivity of blend solutions were measured by a viscotester (6L/R,
Hakke, USA) and electric conductivity meter (CM-40G, TOADKK Co., Japan), respectively.
Fabrication of Nanofibrous Membranes via Electrospinning
The polymer solutions were loaded into plastic capillaries which immersed with a copper
wire. The copper wire was connected to a high voltage power supply (FC30P4, Glassman
High Voltage Inc., USA) that was capable of generating DC voltage up to 30 kV. The
ambient relative humidity was used as 20, 45, and 75 %, respectively. The spinning distance
was regulated in the range of 5-25 cm. Various samples were obtained by adjusting the
processing parameters during electrospinning. The fibrous samples can be deposited on Al
foil and quartz crystal microbalance (QCM, 10 MHz, AT-cut quartz crystal with Ag
electrodes) electrodes.
The resultant samples were conducted by 5 s of Os coating under vacuum using an Os
coater (HPC-1S, Vacuum Device Ltd., Japan). The thickness of Os coating layer on samples
was less than 2 nm. Morphological observations of samples were made by scanning electron
Bin Ding, Chunrong Li, Dong Wang et al. 54
microscopy (SEM) (S-4700, Hitachi Ltd., Japan). The diameters of samples were measured
using image analyzer (Adobe Photoshop 7.0).
Results and Discussion
Finding of Nanowebs in Electrospun Fibrous Membranes
SEM images of PAA samples produced with concentration of 6 wt%, voltage of 30 kV,
distance of 15 cm, and relative humidity of 20 % as a function of kinds of solvents are shown
in Figure 1. As shown in Figures 1A and B, several discontinuous irregular defect films with
maximum length up to 20 m were found among the electrospun PAA fibers, which were
spun from the solvent of H
2
O and H
2
O/ethanol = 3/1 (w/w). The same phenomenon for
observation of defect films was reported with electrospinning of other materials [8,12,13].
The defect films were formed from the charged droplets which originated from the jet at the
capillary tip with increased instability. However, the defect films were partly split into webs
when the PAA spun from volatile solvent of H
2
O/ethanol = 1/1 and ethanol (Figures 1C and
D). The formation of webs from films was considered due to the fast phase separation of
polymer and solvent in charged droplet caused by solvent evaporation during the flight in
high electric field [45,46]. PAA has a relatively faster phase separation with ethanol than with
H
2
O because of the low boiling point of ethanol [47].
(A)

(B)
(C)

(D)
Figure 1. Continued on next page.
Fabrication and Application of Novel Two-Dimensional Nanowebs 55
(E)
Figure 1. SEM images of PAA fibers produced with PAA solution concentration of 6 wt%, voltage of
30 kV, distance of 15 cm, and relative humidity of 20 % as a function of kinds of solvents: (A) H
2
O;
(B) H
2
O/ethanol = 3/1; (C) H
2
O/ethanol = 1/1; and (D) ethanol. (E) High magnification SEM image
taken from the sample shown in D.
Figure 1E showed the high magnification SEM image of sample, which spun from ethanol.
The strong bonding between nanowebs and electrospun fibers was found. The trace solvent left
in the nanowebs caused by the uncompleted solvent evaporation led the bonding between
nanowebs and electrospun fibers. Additionally, the nanowebs that covered on electrospun fibers
still kept the morphology of nanoweb to form a porous surface on fibers indicating the
formation of the nanowebs was performed during the flight before reaching collector.
Relative Humidity Effect on PAA Nanoweb Formation
The ambient relative humidity in electrospinning chamber was important to affect the
evaporation speed of solvent in charged droplets during the flight [48]. As the relative humidity
increased to 45% and 75 %, the PAA fibers (Figures 2A and B) showed a relatively larger fiber
diameter than that of fibers produced under a low relative humidity of 20 % (Figure 1D). And
the adjacent fibers stuck together to form a porous film without the appearance of nanowebs.
(A)

(B)
Figure 2. SEM images of PAA fibers formed with PAA solution concentration of 6 wt%, voltage of 30
kV, distance of 15 cm, solvent of ethanol, and relative humidity of 45% (A) and 75 % (B).
Bin Ding, Chunrong Li, Dong Wang et al. 56
The high relative humidity retarded the evaporation of solvents from jets which led an
increased fiber diameter and the wet fibers linked together on collector.
Effect of Applied Voltage on PAA Nanoweb Formation
Another processing parameter which affected the PAA nanoweb formation was the
applied voltage. As shown in Figure 3, there were no nanowebs for the sample produced with
the applied voltage of 20 kV. As reported by Deitzel [8], the applied voltage was one of the
key parameters to initial the bead defect formation. In this study, the applied voltage was
further proved to be one of the key parameters to affect the formation of nanowebs.
Figure 3. SEM image of PAA fibers formed with PAA solution concentration of 6 wt%, voltage of 20
kV, distance of 15 cm, relative humidity of 20 %, and solvent of ethanol.
Proposed Mechanism
The forces acting on the charged droplet which flight with a high moving speed in
electric field are shown in Figure 4A. The forces included electrostatic force, drag force,
gravity, coulombic repulsion force, surface tension and viscoelastic force. The electrostatic
force carried the charged droplet from capillary tip to collector. The drag force happened
between the surrounding air and charged droplet with high moving speed. And the drag force
was attributed to deforming the droplets into films. The coulombic repulsion force tried to
expand the droplet. The surface tension and viscoelastic forces led the contraction of charged
droplet [49]. The electric field could be increased on increasing the applied voltage with a
constant distance. Consequently, the electrostatic and coulombic repulsion forces of charged
droplet were reinforced with increasing of electric field. The increased electrostatic force
further accelerated the moving of charged droplet, which led an increased drag force. The
distortion and expand of charged droplet from spherical-like to spindle-like in electric field
during electrospraying was reported by Grimm and Beauchamp [50]. The further expand
could happened when the electric field increased to form thin films from droplets with the
effect of increased coulombic repulsion and drag forces. Moreover, the increased radial
charge repulsion force also has trend to expand the charged films. As a result, the deformation
of charged droplet was strongly affected by the electric field.
Fabrication and Application of Novel Two-Dimensional Nanowebs 57
(A)
(B)
Figure 4. (A) Forces acting on the charged droplet. (B) Schematic diagram illustrating the possible
mechanism of nanoweb formation during electrospinning.
The schematic diagram illustrating the possible mechanism of nanoweb formation during
electrospining was shown in Figure 4B. Due to the high viscosity of polymer solutions, the
major jets ejected from the tip could be continuous (as in conventional electrospinning). We
considered that the defect films or nanowebs were not formed from the charged droplets
which were obtained by breaking jets (as in electrospraying). The defect films or nanowebs
just could be regarded as a by-product caused by a high electric field induced instability of
suspended charged droplets during electrospinning [8]. The microsized charged droplets [51]
could be initialed together with the common electrospun fibers from the electrospining tip
with a high instability. During the flight of charged droplet from capillary tip to collector, the
charged droplet bore the comprehensive effects of the forces acting on it. On increasing the
moving distance, the droplet was distorted and expanded into thin film by the coulombic
repulsion and drag forces in the strong electric field. The splitting of thin film into nanoweb
performed due to the fast phase separation between polymer and solvent which caused by the
fast solvent evaporation under a low relative humidity. The fast phase separation led the
Bin Ding, Chunrong Li, Dong Wang et al. 58
spinodal or binodal types of phase morphologies within the fibers and the solvent rich regions
were apparently transformed into pores [45]. As the electrospun fibers and nanowebs were
formed at the same time, the 2D nanowebs stacked into 3D fibrous mats in a layer-by-layer
structure as same as 1D electrospun fibers. The increasing of formation frequency and area
density of nanowebs could be realized with increasing the instability of droplet at the
electrospinning tip, such as increasing the applied voltage [8, 52].
PAA Solution Concentration Effect
The morphologies of PAA nanowebs produced with various concentrations of PAA
solution are shown in Figure 5. It could be observed that all the samples showed the
uncompleted splitting of defect films. As shown in Figures 5A and B, the nanowebs produced
with 6 wt% of PAA showed the largest average hole diameter and diameter deviation of
nanowebs among three samples. As the PAA concentration increased to 8 wt% (Figures 5C
and D), the hole diameter and shape of nanoweb became uniform and the average hole
diameter reduced compared with the sample in Figures 5A and B. Moreover, as shown in
Figures 5B and D, the shapes of holes in nanowebs included round, triangle, quadrangle,
pentagon, and hexagon. Figures 5E and F showed the nanowebs produced with 10 wt% of
PAA. The nanowebs showed almost only round shape of holes with the smallest average hole
diameter among three samples. As a result, the shape, diameter, and uniformity of holes in
PAA nanowebs could be adjusted by changing the solution concentrations.
(A)

(B)
(C)

(D)
Figure 5. Continued on next page.
Fabrication and Application of Novel Two-Dimensional Nanowebs 59

Figure 5. SEM images of PAA fibers produced with applied voltage of 30 kV, distance of 15 cm,
relative humidity of 20 %, and solvent of ethanol as a function of PAA concentrations: (A) 6 wt%; (C)
8 wt%; and (E) 10 wt%. (B, D, and F) High magnification SEM images taken from the sample shown
in A, C, and E, respectively.
Effect of Voltage and Relative Humidity on Nylon-6 Nanoweb Formation
The example for relatively completed splitting of films into nanowebs was demonstrated
using nylon-6 dissolved in formic acid. As the key parameter for the formation of nanowebs,
the influence of applied voltage was investigated during fabrication of nylon-6 nanowebs.
When the applied voltage was 10 kV (Figure 6A), a web comprising several ultrathin nylon-6
nanowires appeared in a small region. As the voltage increased gradually from 15 to 25 kV
(Figures 6B to D), the 2D web comprising many interlinked 1D nanowires appeared. The
nanowebs almost covered all the regions in SEM image when the applied voltage was 30 kV
(Figure 6E). It was found that the area density of nanowebs in fabric was sharply increased
with increasing the applied voltage. This result was identical to the increase of bead defect
density [8] with increasing the applied voltage.
(A)

(B)
Figure 6. Continued on next page.
(E) (F)
Bin Ding, Chunrong Li, Dong Wang et al. 60
(C)

(D)

(E)
Figure 6. SEM images of nylon-6 fibers formed with nylon-6 solution concentration of 15 wt%,
distance of 15 cm, and relative humidity of 20 % as a function of applied voltage: (A) 10 kV; (B) 15
kV; (C) 20 kV; (D) 25 kV; and (E) 30 kV.
Unlike the PAA, the nylon-6 nanowebs could be fabricated under a high relative
humidity of 75 % (Figure 7). This was attributed to the nylon-6 has faster solidification [53]
speed than that of PAA [45]. Despite the observation of nylon-6 nanowebs under the high
relative humidity of 75%, the area density of nylon-6 nanowebs was largely decreased
compared with the sample fabricated under the low relative humidity of 20 % (Figure 6E).
Figure 7. SEM image of nylon-6 fibers formed with nylon-6 solution concentration of 15 wt%, voltage
of 30 kV, distance of 15 cm, and relative humidity of 75 %.
Fabrication and Application of Novel Two-Dimensional Nanowebs 61
Effect of Distance
Figure 8 showed the influence of electrospinning distance to the morphology of nylon-6
nanowebs. As shown in Figure 8A (distance of 5 cm) and 8C (distance of 25 cm), the 2D
nanowebs distributed randomly among electrospun fibers as the way that electrospun fibers
stacked. The electrospun fibers acted as supporter to support the nanowebs. From the high
magnification SEM image (Figure 8B), the short distance (5 cm) led a relatively larger wire
diameter about 30-50 nm in nanowebs because of the uncompleted expand of the nanowebs.
Meanwhile, the strong bonding between electrospun fibers and nanowebs was found due to
the uncompleted solvent evaporation in this short spinning distance. As the distance increased
to 25 cm (Figure 8D), the thinner wire diameter about 10-20 nm in nanowebs was found due
to the relatively sufficient expand of nanowebs in this long spinning distance. As a result, the
nanowire diameter in nanowebs and bonding between fibers and nanowebs were strongly
affected by spinning distance.
(A)

(B)
(C)

(D)
Figure 8. SEM images of nylon-6 fibers formed with nylon-6 solution concentration of 15 wt%, voltage
of 25 kV, relative humidity of 20 %, and distance of (A) 5 and (C) 25 cm. (B and D) High
magnification SEM images taken from the samples shown in A and B, respectively.
Nylon-6 Solution Concentration Effect
Figure 9 showed the SEM images of nylon-6 samples produced from various
concentrations. At 10 wt% (Figure 9A), the electrospun fibers have the thinnest mean fiber
Bin Ding, Chunrong Li, Dong Wang et al. 62
diameter of 66 nm (Figure 10A) and a few nanowebs appeared. On increasing the
concentration from 10 to 20 wt% (Figures 9A to C), the fiber diameter increased gradually up
to 184 nm (Figures 10A to C) as well as increased the area density of nanowebs. However, at
25 wt%, the fiber diameter was sharply increased to 1 m and the area density of nanowebs
decreased (Figures 9D and 10D).

(A)

(B)

(C)

(D)
Figure 9. SEM images of nylon-6 fibers produced with applied voltage of 25 kV, distance of 15 cm,
and relative humidity of 20 % as a function of nylon-6 concentrations: (A) 10 wt%; (B) 15wt%; (C) 20
wt%; and (D) 25 wt%.

0 25 50 75 100 125 150 175 200 225 250
0
10
20
30
40
50
60
70
80
90
100


F
r
e
q
u
e
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c
y

d
i
s
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o
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(
%
)
Fiber diameter (nm)
Average diameter: 66 nm
Standard deviation: 14 nm
(A)

0 25 50 75 100 125 150 175 200 225 250
0
10
20
30
40
50
60
70
80
90
100


F
r
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s
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r
i
b
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t
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o
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(
%
)
Fiber diameter (nm)
Average diameter: 106 nm
Standard deviation: 17 nm
(B)
Figure 10. Continued on next page.
Fabrication and Application of Novel Two-Dimensional Nanowebs 63

0 25 50 75 100 125 150 175 200 225 250
0
10
20
30
40
50
60
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80
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r
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c
y

d
i
s
t
r
i
b
u
t
i
o
n

(
%
)
Fiber diameter (nm)
Average diameter: 184 nm
Standard deviation: 14 nm
(C)

0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
0
10
20
30
40
50
60
70
80
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100


F
r
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q
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e
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c
y

d
i
s
t
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i
b
u
t
i
o
n

(
%
)
Fiber diameter (m)
Average diameter: 1.06 m
Standard deviation: 0.22 m
(D)
Figure 10. Diameter distributions of nylon-6 fibers produced with applied voltage of 25 kV, distance of
15 cm, and relative humidity of 20 % as a function of nylon-6 concentrations: (A) 10 wt%; (B) 15wt%;
(C) 20 wt%; and (D) 25 wt%.
The typical nanoweb-rich example of nylon-6 (shown in Figure 9C) formed from 20 wt%
of nylon-6 solution were found like fishing net to cover the electrospun fibers completely and
to form strong bonding with electrospun fibers. The high magnification of same sample was
shown in Figure 11A. The dense nylon-6 nanowebs with uniform pore were formed. The pore
diameter of nanowebs was in the range of 10-80 nm, which was much less than that of pores
among electrospun fibers. The nanowire diameter distribution of nylon-6 nanowebs was
shown in Figure 11B. The major distribution region (over 80 %) of nanowire diameters was
10-20 nm with average diameter of 17 nm. The standard deviation of the wire diameters in
nanowebs was 5 nm. The average diameter of nanowires was one order of magnitude smaller
than that of common electrospun fibers. Therefore, the surface-to-volume ratio of fibrous
mats was expected to be increased with the appearance of nanowebs [36].

(A)
Figure 11. (A) High magnification SEM images of nylon-6 nanowebs formed with solution
concentration of 20 wt%, voltage of 25 kV, distance of 15 cm, and relative humidity of 20 %. (B)
Histogram showing the diameter distribution of nanowires shown in A.
Bin Ding, Chunrong Li, Dong Wang et al. 64
Gas Absorption and Sensing Properties of PAA Nanofibers and Nanowebs
The gas absorption test was carried out in a closed box (9 L) which installed a fan (Figure
12A). Each 0.25 g fibrous PAA sample was examined with 10.5 ppm ammonia gas. The
remaining concentration of ammonia was determined by ammonia gas testing tube. Figure
12B presents the ammonia gas absorption by PAA fibers and nanowebs. Due to the higher
surface area of PAA nanowebs, the nanowebs showed the faster absorption speed and higher
absorption ability than those of nanofibers. After 55 min absorption, the concentration of
ammonia decreased from 10.5 ppm to 3.5 and 1.0 ppm for nanofibers and nanowebs,
respectively.
(A)
(B)
Figure 12. (A) Schematic of gas absorption system. (B) Gas absorption efficiency of PAA fibers and
PAA webs.
Fabrication and Application of Novel Two-Dimensional Nanowebs 65
(A)
(B)
Figure 13. (A) Schematic of a gas testing system for NH
3
detection. (B) Response of sensors containing
PAA nanofibers and nanowebs exposed to 1 ppm NH
3
at the relative humidity of 30 %.
Nanofibrous membranes were incontinuously collected on the surface of QCM until the
required frequency shift (coating load) was got. The resonance frequencies were measured by
a frequency counter (Hewlett Packard 53131 A). Then, the nanofibrous membranes coated
QCMs were dried at 80
o
C in vacuum for 2 h to remove the trace solvent prior to the
subsequent characterizations. The QCM frequency shifts caused by the deposition of PAA
fiber and nanowebs were 28 000 and 22 000 Hz, respectively. In the current work, the
Sauerbrey equation for used QCM can be drawn as f = m/0.9610
-9
. It means that the
frequency is decreased for 1 Hz in the case of 0.96 ng of gas molecules were absorbed. The
flow-type experimental setup for measuring the sensing properties of sensors is shown in
Figure 13A. The sensor was installed in the chamber which kept with constant temperature
(25
o
C) and relative humidity (30%). The N
2
was used as carrier gas. The flow rates of dry
N
2
, wet N
2
, and target gases were kept constant by mass flow controllers (MFCs, Estec, SEC-
Bin Ding, Chunrong Li, Dong Wang et al. 66
400 MK3). During the measurement, the concentration of NH
3
was regulated at 1 ppm and
the absorption time was 30 min. The sensor responses to target gases were examined by
measuring the resonance frequency shifts of QCM which due to the additional mass loading.
The resonance frequencies were measured by the frequency counter. The data from the
sensors were recorded by a personal computer.
After stabilization in N
2
at relative humidity of 30%, both samples showed the response
the 1 ppm ammonia gas (Figure 13B). The PAA nanofibers showed the maximum 6 Hz
frequency shift for 30 min ammonia absorption and returned to the original frequency after
the ammonia gas desorption. For nanoweb sample, it showed the faster response speed and
higher maximum frequency shift of 15 Hz to 1 ppm ammonia gas, 2.5 times higher than that
of nanofibers. However, it needs more time to get the maximum frequency shift and desorb
the ammonia gas. As the nanofiber sensor already showed much higher sensitivity than flat
sensing films [15,16], the nanoweb structure would be the better candidate for the future
highly sensitive material mode.
Formation of Nanowebs in Other Solution Systems
Figure 14 showed the morphology of the electrospun pure PVA fibrous films. As a
typical electrospun fibrous film, the PVA fibers were randomly oriented as a porous film with
a wide fiber diameter distribution. The PVA fiber was straight with an average fiber diameter
of 239 nm.

(A)

(B)
Figure 14. SEM images of pure PVA electrospun nanofibers.
The SEM images of composite PVA/ZnO fibrous membranes are shown in Figure 15. It
can be observed that the composite fibers have many junctions among the fibers, showing a
poor fiber uniformity compared with the pure PVA fibers. The average diameter of PVA/ZnO
fibers (258 nm) was larger than that (239 nm) of pure PVA fibers due to its increased
viscosity (Table 1). It is well known that the morphology and properties of electrospun
nanofibers are strongly influenced by the solution properties such as viscosity and
conductivity [54]. Table 1 shows the viscosity and conductivity of the electrospinning
solutions. Additionally, in Figure 15, the formation of nanowebs was observed among the
fibers. The electrospun PVA/ZnO fibers acted as a support for the fishnet-like nanowebs
comprising interlinked one-dimensional nanowires. The average diameter of the PVA/ZnO
Fabrication and Application of Novel Two-Dimensional Nanowebs 67
nanowires (10 nm) contained in this nanoweb was about one order magnitude less than that of
conventional electrospun fibers. The formation of the nanowebs was considered to be due to
the electrically forced fast phase separation of the charged droplets which move at high speed
between capillary tip and the collector. The phenomenon of nanoweb formation has been
reported in our previous study [55]. Here, the observation of PVA/ZnO nanowebs was
ascribed to the sharply increased conductivity from 0.019 to 0.712 S/m (Table 1).

(A)

Figure 15. SEM images of composite PVA/ZnO electrospun nanofibers.
Table 1. Properties of PVA and PVA/zinc acetate solutions
Sample Viscosity (centipoises) Conductivity (S/m)
PVA 420 0.019
PVA/zinc acetate 600 0.712
Another example for nanoweb formation is the PVA/SiO
2
nanowebs by electrospinning
the suspension of PVA and SiO
2
nanoparticles. SEM images of PVA/SiO
2
nanowebs are
shown in Figure 16. The formation of nanowebs probably was due to the increased instability
by blending the high content nanoparticles in polymer solution.

(A)

(B)
Figure 16. SEM images of composite PVA/SiO
2
electrospun nanofibers.
(B)
Bin Ding, Chunrong Li, Dong Wang et al. 68
Concusion
In this chapter, we have reviewed the fabrication of PAA, nylon-6, PVA/ZnO, and
PVA/SiO
2
nanowebs that stacked as layer-by-layer and widely distributed in the 3D structure
of fibrous mats. The development of PAA nanowebs indicated the formation process of
nanowebs. The splitting of defect films into nanowebs occurred under the extreme processing
conditions, such as the high applied voltage, low relative humidity, and fast phase separation
between polymers and solvents. Meanwhile, the morphology and area density of nanowebs
were found to be the comprehensive effect of various electrospinning processing parameters
of relative humidity, applied voltage, kinds of solvents, distance, and solution concentration.
The typical nanoweb-rich sample nylon-6 showed that the nanowire diameter in nanowebs
was one tenth of common electrospun fibers. As the formation of defect films was usual
phenomenon during electrospinning, other materials with electrospinability also have the
possibilities to form nanowebs. Additionally, the PAA nanowebs showed the larger gas
absorption capacity and higher sensitivity to ammonia compared with PAA nanofibers due to
its relatively high specific surface. This review collected some data from our previous
publication of reference 55.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 71-105 2010 Nova Science Publishers, Inc.
Chapter 3
NANO-SCALE CHARACTERIZATION
AND SPECTROSCOPY OF STRAINED SILICON
Norihiko Hayazawa
*
and Alvarado Tarun
Nanophotonics Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Abstract
Strained silicon (-Si), the fundamental material of integrated circuit, is finding tremendous
attention because it boosts the speed and reduces the power consumptions of electronic
devices. However, poor homogeneity distribution of strain in -Si layers can degrade
performance of electronic devices. Raman spectroscopy is used to study strain fluctuations in
silicon because the optical phonons in Raman spectra are strongly influenced by strain.
Though silicon are Raman active devices, the Raman efficiency of a nanometer layer of -Si is
extremely weak and is often eclipsed under the Raman scattering of underlying buffer
substrates. Micro Raman measurements show only uniform features in the nano-scale because
of averaging effect from diffraction-limited spatial resolution. Here, we utilized surface
enhancement in Raman scattering to overcome weak emission problems and to suppress
averaging effect. Thin -Si layers were covered with thin Ag layer to invoke surface enhanced
Raman spectroscopy (SERS). Results show that SERS effectively enhanced the Raman signal
from -Si layer and it stands distinctly apart from the Raman signal originating from the
buffer layer. This technique is promising but it lacks the spatial resolution in the nano-scale
due to diffraction limit from the probing light. In order to achieve nano-scale spectroscopy,
point-surface-enhancement was used, rather than a large surface enhancement. We used a
silver-coated sharp tip, just like SERS, but only the sample region very close to the tip apex is
characterized. This technique, known as the tip-enhanced Raman spectroscopy (TERS),
provides nanometric resolution in our measurement. We observed localized strains by
employing TERS. The TERS spectra revealed clear nano-scale variation in Raman frequency.
Now that we can distinctively separate -Si from underlying buffer layer, signal-to-noise
ration (SNR) needs further improvement. We improve TERS SNR in two ways: optical field
enhancement using different metallic tip and background signals reduction arising from bulk
materials. The tip-enhancement is more important for homogenous nano-materials or for
samples with very weak signals whereas the background signal reduction is indispensable for
nano-materials that consist of different thin layers with strong signals such as -Si or samples

*
E-mail address: hayazawa@riken.jp. phone: +81-48-467-9339, fax: +81-48-467-9170. (Author for
Correspondence)
Norihiko Hayazawa and Alvarado Tarun 72
with strong signal level. Accordingly, we introduce several approaches mainly for the
suppression of background signals arising from other bulk materials. We will discuss the
utilization of UV light source, specialized tip, sample orientation relative to probing
polarization, and depolarization configuration to obtain high contrast Raman signal. The
characterization techniques describe above is applicable to other nano-materials.
1. Introduction
Strained Si (-Si) on silicon germanium (Si
1-x
Ge
x
) substrate has now been widely used in
state of the art electronic devices such as Intel dual core products primarily due to the
mobility enhancement of electrons and holes in the -Si layer [1,2]. As -Si technologies
become more complicated and transistors become smaller, in the order of nanometer
(~45nm), issues involving strain defects and the characterization of key properties in silicon
substrates are expected to increase. Thus, development of advanced technique for nanoscale
characterization and investigation of localized strain in the -Si substrate are important in the
current semiconductor technology. Raman spectroscopy has been widely used for the
investigations of strain in semiconductors [3-5] because of its nondestructive capability to
observe lattice vibrations sensitive to strains. However, due to the low Raman scattering
efficiency, it becomes difficult to observe the localized strain in nanometer scale. Moreover,
in case of thin -Si layer fabricated on Si
1-x
Ge
x
substrate, the Raman scattering of Si-Si
vibrational mode from Si
1-x
Ge
x
buffer layer can easily eclipse the vibrational signals
originating from the -Si layer. Because of these two difficulties, conventional Raman
scattering is not suitable for strain measurements in these thin samples. Nanometer scale and
surface selective sensitivities are required, and hence surface enhanced Raman scattering
(SERS) [6] and tip-enhanced Raman spectroscopy (TERS) [7-13] turn out to be exceptionally
promising spectroscopic techniques. In this chapter, we demonstrate how effectively and
selectively enhance the Raman signal from the thin -Si layer on a thick underlying Si
1-x
Ge
x
layer using SERS. We show that the proposed technique can be straightforwardly used for
TERS microscopy to investigate localized nano-scaled strain in -Si. In section 2, we discuss
SERS from the thin -Si covered with thin Ag layer. Results show that SERS effectively
enhanced the Raman signal originating from -Si layer and it stands distinctly apart from the
Raman signal originating from the buffer layer. This technique is promising but it lacks the
spatial resolution in the nano-scale due to diffraction limit from the probing light. In section
3, in order to achieve nano-scale spectroscopy, point-surface-enhancement was used, rather
than a large surface enhancement. We used a sharp Ag-coated tip placed over the -Si and
only the sample region very close to the tip apex is characterized. This technique, known as
the tip-enhanced Raman spectroscopy (TERS), provides nanometric resolution in our
measurement. We observed localized strains by employing TERS. The TERS spectra
revealed clear nano-scale variation in the Raman frequency. Now that we can distinctively
separate -Si from underlying buffer layer, signal-to-noise ration (SNR) needs further
improvement. We improve TERS SNR in two ways: optical field enhancement using
different metallic tip and background signals reduction arising from bulk materials. The tip-
enhancement is more important for homogenous nano-materials or for samples with very
weak signals whereas the background signal reduction is indispensable for nano-materials
that consist of different thin layers with strong signals such as -Si or samples with strong
Nano-scale Characterization and Spectroscopy of Strained Silicon 73
Raman signal level. Accordingly, we introduce several approaches mainly for the suppression
of background signals arising from other bulk materials. We will discuss the utilization of UV
light source and specialized tip in section 4 and then introduce depolarization configuration in
TERS for the efficient suppression of background signals in section 5.
2. Surface Sensitive Detection by Surface Enhanced Raman
Scattering (SERS)
Recent developments in surface enhanced Raman scattering (SERS) has gained attention
not only due to enormous (10
14
) level of Raman enhancement capable of single-molecule
detection but also for surface sensitive characterization of nanometer structured surfaces. It
was observed that huge increase in the Raman cross section was result of excitation of surface
plasmon in metals. The most popular metal used in SERS studies is Ag due to intense
plasmon resonance excitation produced by nanometer sized Ag in the visible wavelength. In
this section, we utilize SERS to obtain strain information in a thin layer, ~30nm, of -Si over
silicon germanium substrate.
2.1. Experimental Configuration for SERS
Figure 1 illustrates the concept of the SERS experimental system for highly sensitive
detection of strain in the -Si surface. The substrate used for growing -Si layer was prepared
by doping Ge in a pure 100 oriented silicon substrate. The concentration of Ge in the host Si
lattice was gradually increased up to 25 % to expand the lattice constant of the host Si lattice.
In order to minimize inhomogeneous strain, a layer with 1.0 m thick Si
1-x
Ge
x
buffer layer
was grown on the prepared substrate at constant 25% Ge concentration. Finally, a 30-nm-
thick Si layer was epitaxially grown on the buffer layer to fabricate -Si. The crystal face for
both the buffer and silicon layer was maintained at 100. Due to lattice parameter mismatch
at the interface, the thin Si layer was under a constant strain. The thickness of this -Si layer
has to be low otherwise the induced strain could be gradually relaxed with increasing the
thickness. To detect Raman from a very thin layer, we invoked SERS effects by evaporating
Ag with 8-10 nm thickness on the -Si layer under vacuum (~10
-6
Torr). The topographic
image is shown in the inset of Fig. 1. This image was obtained by contact-mode atomic force
microscope (AFM) using a silicon cantilever (Nanosensor ATEC-CONT). The Ag film
consists of plenty of Ag grains, with typical grain size of 20~40 nm in diameter and 10 nm in
height. These fractal-like "pancake structures of Ag grains provide almost uniform surface
enhancement factor averaged within the diffraction limited focused spot of micro-Raman
experiments. A CW blue laser (wavelength: 488 nm, power: 9 mW) was focused by an oil-
immersion high numerical aperture (NA) objective lens (NA=1.4; 100x). The gap of Ag film
layer and the sample was filled with oil that has a matching refractive index (1.515) as the
objective lens. The Raman and SERS signals from the sample were collected by the same
objective lens and detected by confocal Raman microscope (pinhole: 30 m), in which the
spectrometer (focal length: 560 mm, 1800 grooves/mm, blaze wavelength: 500 nm) was
equipped with both, a cooled charge coupled device (CCD) camera for Raman spectra
Norihiko Hayazawa and Alvarado Tarun 74
measurements (such as the results in Fig. 2), and an avalanche photodiode for Raman image
acquisitions (such as in Fig. 3).
Figure 1. Schematic of SERS microscopy for -Si and AFM topographic image of the Ag island film
coated on the -Si.
2.2. Comparison of Raman and SERS Spectra
Vibrational modes located at the center of the Brillouin zone can only be observed in the
first-order Raman scattering due to the momentum conservation. Further, the selection rules
for the 100 oriented Si crystal in backscattering geometry allow only LO phonon to be
Raman active. Therefore, we expect to observe only LO phonon in first-order Raman
scattering experiments, which should appear at 520 cm
-1
for an unstrained or pure Si crystal.
Since the sample consists of a -Si layer above Ge-doped Si buffer layer, we expect shift from
the original frequency of LO phonon in both layers. The LO phonons in doped crystals can be
easily modified depending on the atomic mass as well as the amount of the dopant. In Ge-
doped Si crystal, the LO phonon can have three different vibrations, namely the Si-Si mode
arising from the vibrations of neighboring Si atoms, the Ge-Ge mode arising from the
vibrations of neighboring Ge atoms, and the Si-Ge mode arising from the vibrations involving
the bonds between a Si and a Ge atom. Since the amount of Ge is much smaller than the
amount of Si in our samples, the LO mode corresponding to the Si-Si vibration is dominant.
We need to concentrate only on Si-Si mode because it interferes with the Si-Si vibration
coming from the thin -Si layer in the experiments and we will be discussed throughout the
chapter. The vibrational frequency of this mode decreases almost linearly with increasing Ge
concentration [14]. The bonds between two neighboring Si atoms are stretched when Ge is
doped introducing strain in the lattice. This strain is responsible for the shift of LO mode
frequency originating from the Si-Si vibration in the buffer layer. Similarly, when a thin Si
layer is grown on Si
1-x
Ge
x
buffer layer, the Si-Si bonds in Si layer are stretched due to the
lattice mismatch at the interface. If the thickness of the layer is not too large, the strain
produced in the Si layer is transferred vertically throughout the surface. The amount of
Nano-scale Characterization and Spectroscopy of Strained Silicon 75
developed strain at surface can be different from that of the strain in the buffer layer even if
the strain in both layers is caused by the presence of Ge atoms in the buffer layer.
The penetration depth of blue-green probing light in Si is much larger than the thickness
of the -Si layer in our sample [15]. Therefore, in Raman scattering experiments, the probing
laser penetrates deep through the buffer layer. As a result, Raman scattering in the buffer
layer is strongly excited. The intensity of LO phonon mode coming from the buffer layer is
much more strong than the one coming from the -Si layer. This is a problem if the
vibrational frequencies of the two phonons are close to each other. It becomes difficult to
clearly observe the LO phonon corresponding to the -Si layer. To overcome this problem, we
used the SERS technique to selectively enhance Raman at the surface and compared the
results from those obtained by normal Raman spectroscopy. Figure 2 shows SERS (with a Ag
film deposited on -Si layer) and Raman spectra (without a Ag film) of the sample. Both
spectra were fitted by double Lorentzian functions as shown by dashed lines. The lower and
higher Raman modes in both spectra are the LO phonon modes arising from the Si-Si
vibration in Si
1-x
Ge
x
(x=0.25) and in -Si, respectively. The Raman spectrum is dominated by
a strong peak at 504.9 cm
-1
, corresponding to the background LO phonon signal from Si
1-x
Ge
x
substrate, together with a very weak shoulder at 513.8 cm
-1
that arise from the LO phonon in
-Si [16-20]. Since the Raman signal from the -Si is very close to the Si
1-x
Ge
x
buffer layer
and considering 30 nm thickness of the -Si layer, the Raman signal from -Si is almost
overwhelmed by the signal from the Si
1-x
Ge
x
layer. On the other hand, in SERS spectrum, the
Raman signal from -Si is remarkably enhanced. The signal becomes even stronger than the
Si
1-x
Ge
x
buffer layer due to the SERS effect. Even though the -Si Raman signal in SERS is
enhanced relative to the signal from the buffer layer, we noticed reduction in the scattering
efficiency in SERS with a signal bias of ~20000 counts/60s compared to the Raman
spectrum. The reduction in overall scattering efficiency is due to the lower transmission of the
probing light caused by Ag island film whereas the bias signal is due to the white continuum
emission from the Ag island film, which is often accompanied in SERS measurements [21].
Figure 2. SERS (with Ag film) and Raman (without Ag film) spectra of -Si. Both spectra are fitted by
double Lorentzian functions representing Raman modes of Si
1-x
Ge
x
(lower frequency) and -Si (higher
frequency). The meshed areas are used for Raman imaging in Fig. 3.
As seen from Fig. 2, we resolved Raman signal from the -Si in SERS. This suggests that
SERS effect is very powerful to observe the surface condition of the thin -Si layer. Both
SERS and Raman measurements were done in the same condition except the existence of Ag
Norihiko Hayazawa and Alvarado Tarun 76
island film to invoke SERS. It should be noted here that we did not use any analyzer for
polarization dependent detection in either SERS or Raman detection. The ratio of the
intensities between Si
1-x
Ge
x
and -Si would change when measured through an analyzer,
which will be discussed later in Section 5.
2.3. Comparison of Raman and SERS Images
Next, we carried out confocal micro-Raman imaging of the same sample at specific
vibrational modes from Si
1-x
Ge
x
and -Si. Figure 3(a) shows the reflection confocal image of
the sample from a region close to the edge of the evaporated Ag film. As expected, the Ag
covered layer appears to be brighter in the reflection image. Figure 3(b) was obtained by
setting the spectrometer at the lower frequency in Fig. 2, so that the avalanche diode detects
only the Raman signal from Si
1-x
Ge
x
buffer layer. Since the intensities level of SERS and
Raman from Si
1-x
Ge
x
buffer layer is almost similar from Fig. 2, Raman image in Fig. 3(b)
also reflects low contrast between Ag coated and uncoated area. However, when the
spectrometer is set to detect only the higher frequency shift arising from -Si (see Fig. 2), the
enhanced Raman signal from Ag coated -Si has high contrast as depicted in Fig. 3(c). Fig.
3(c) does not reflect any particular information about the possible nanometric strain
distribution in -Si, which could be varying within areas smaller than the focal spot. This is
because the enhanced scattering signal in this experiment is averaged within the diffraction
Figure 3. (a) A reflection confocal and Raman images obtained at Raman shift of (b) Si
1-x
Ge
x
and (c) -
Si as indicated by meshed area in Fig. 2. (d) is obtained at Raman shift of -Si, the same as (c) but with
different polarization of excitation light. An arrow in the figure indicates polarization of an excitation
light in each image. The dimension of each image is 45 m by 45 m consisting of 100 pixels by 100
pixels.
Nano-scale Characterization and Spectroscopy of Strained Silicon 77
limited focused spot. Accordingly, when polarization of the excitation light is rotated 90 from
the previous polarization as indicated in the Fig 3(d), no significant change in the contrast
could be observed. The entire signal level in Fig. 3 (d) is decreased compared to that in Fig
3(c) due to the polarization dependence of crystalline silicon 100 facet [22,23] and also due
to the different detection efficiency of the experimental system. Here, we note that the
temperature dependence of Raman scattering in silicon [24] is not observed in our
experiments under room temperature conditions. However, the temperature dependence is
also an important factor that can influences the properties of -Si substrates and could be
observed under the experimental conditions of SERS.
3. Surface Sensitive and High Spatially Resolved Detection by
Tip-Enhanced Raman Scattering (TERS)
In SERS measurement, high surface sensitivity and signal enhancement was successfully
achieved, however, the spatial resolution is still diffraction limited. Moreover, SERS is an
irreversible or destructive detection process because it requires Ag coating on the sample. For
non-destructive and higher spatial resolution measurement capable of detecting localized
nanometric strain, a sharpened metallic tip [25-27] can be utilized instead of Ag island film.
In this section we introduce the use of tip-enhancement instead of surface enhancement
to go beyond the diffraction limit of probing light. The concept of TERS is rather
straightforward that can be understood by considering the sharp apex of a metallic tip as a
point source surface enhancer [7-10].
3.1. Experimental Configuration of Reflection-Mode TERS
Figure 4 shows the concept of reflection mode TERS microscopy [28-31] for opaque
sample such as -Si layer assembled on thick substrate. There are generally two
configurations for TERS, transmission mode and reflection mode. In transmission mode [7-
13,32], the metallic probe tip is illuminated through the sample using objective lens. This
configuration has been widely used in TERS because of its high efficiency in both
illumination and collection, especially when using a high numerical aperture (NA) objective
lens. However, transmission mode TERS cannot be used for opaque or thick samples. In
reflection mode TERS [28-31], the tip is illuminated from the same side in which it is
approached towards the sample (Fig. 4). This is advantageous and promising for observing
opaque samples such as silicon substrates.
A schematic of the experimental configuration is shown in Fig. 5 [33,34]. An incident
CW YAG laser (532 nm, JDS Uniphase) is directed to the optical set-up through a single
mode optical fiber. The light coming out of fiber is set to p-polarization, parallel to the tip
axis, for optimum tip-enhancement [28] from the combination of a half-waveplate and a
polarizer. The beam diameter of the laser is then expanded to ~10 mm. This expanded and
polarized light is focused on the tip and sample using a long-working-distance (LWD)
objective lens (Mitsutoyo, NA=0.28, 20x, WD=30.5 mm). The illumination optics mentioned
above, including the LWD objective lens, is precisely positioned by three-axis actuators (New
Focus Inc. Picomotor, accuracy <30nm). The apex of the cantilever (Nanosensor ATEC-
Norihiko Hayazawa and Alvarado Tarun 78
Figure 4. Schematic of reflection-mode TERS.
Figure 5. Experimental setup of reflection-mode TERS. The inset shows the structure of -Si on Si
1-
x
Ge
x
(x = 0.25).
CONT) is adjusted onto the focused spot using the same principle as a contact-mode
operation of AFM. The power of the incident laser light is set to deliver 1 mW on the sample.
The same LWD objective lens collects the TERS signal. A dichroic mirror (or a non-
polarized beam splitter cube) directs the output Raman signal via a multimode optical fiber to
a spectrometer (Photon Design PPDT3-640). The spectrum is detected using a liquid
nitrogen-cooled CCD camera (Princeton Instruments). Raman signal was obtained with an
Nano-scale Characterization and Spectroscopy of Strained Silicon 79
integration time of 120 seconds. To attain an efficient tip-enhancement effect in the
reflection-mode TERS, the probe tip is prepared by depositing Ag on commercially available
silicon cantilever used for AFM. This is done by two-step thermal evaporation process. First,
a 5-nm-thick gold palladium alloy (AuPd) is deposited on a tip to modify the surface of
silicon, and then Ag is evaporated with the thickness of 30~50 nm at a rate of 0.5 /sec.
3.2. Comparison of Raman and TERS Spectra
The reflection mode TERS described above has been successfully applied to nanoscale
localization of -Si using dichroic mirror and Ag coated Si-tips with an excitation laser
wavelength of 532nm [33]. Figure 6(a) shows the Raman signal from 532nm probing light
under Ag coated Si-tip (Nanosensor, ATEC-CONT-20). Figure 6(b) shows the background
corrected signal, which is the difference between the TERS and far-field (tip withdrawn)
Figure 6. (a) TERS (red) and far-field (blue) spectra of -Si obtained using 532nm probing light with
Ag coated Si-tip. (b) Background corrected near-field spectrum that is broken down into three
Lorentzian curves for band peak identification. The peaks at 503, 514, and 520 cm
-1
are assigned to
phonon modes from SiGe layer, -Si layer and Si-tip, respectively.
Norihiko Hayazawa and Alvarado Tarun 80
Raman signal. In order to determine the Raman peaks, we decomposed the corrected
spectrum in Fig. 6(b), into three Lorentzian functions. The three peaks are assigned to Si-Si
vibrations in the SiGe (503 cm
-1
) bulk layer, Si-Si phonon mode in -Si (514 cm
-1
) layer and
Si-Si in Si-tip (520 cm
-1
). The corrected spectrum does not contain the peaks around 480 cm
-
1
, which was later found to be coming from PC monitor. This background corrected TERS
spectrum shown by the spectrum in Fig. 6(b), contains nanometer scale information of
localized strains. In the far-field spectrum, the -Si peak is recognized only as a shoulder of
the strong background signal generated from the underlying Si
1-x
Ge
x
(x=0.25) layer. The
TERS spectrum, however, shows a clear and distinct peak owing to tip-enhancement. Since
the -Si layer is in the order of several tens of nanometers, a sufficient amount of incident
light penetrates into the Si
1-x
Ge
x
buffer layer, and hence the background signal from the
underlying buffer layer is still significant. The shift of LO phonon mode originating from the
-Si with respect to the original position of the LO phonon for an unstrained Si (520 cm
-1
) [3]
provides us with plenty of information, such as the local strain in the layer [35-38]. The
estimated enhancement factor for -Si is 2.2 x 10
4
[33], which is calculated by considering the
size of the diffraction limited focused spot (: 3 m) and the enhanced electric field
corresponding to the tip diameter (: 40 nm).
3.3. TERS Spectra Mapping
Nanoscale lateral heterogeneity of strain in -Si / Si
1-x
Ge
x
structures is a serious problem
in fabrication of high-mobility electronic devices. Therefore, it is necessary to investigate the
heterogeneity of strain at nanoscale. A position dependent TERS measurement can be used
for a detailed characterization. Figure 7(a) shows the bright-field microscopic image of the -
Si surface. The crosshatch patterns induced by lattice-mismatch are seen on the epitaxial
surface of the -Si. Fig. 7(b) illustrates the contact AFM image (3 m x 3 m) of the
crosshatch pattern. The six red crosses indicate positions where the tip-enhanced
measurements were carried out. Fig. 7(c) shows near-field (TERS) spectra of -Si extracted
by Lorentzian curve fitting. From Fig. 7(c), we can observe that the peak position and the
intensity of the -Si change. The changes are due to variations in thickness of the -Si layer
based on an underlying surface topography in Fig. 7(b). Fig. 7(d) corresponds to the Si
1-x
Ge
x
Raman spectra. The spectral pattern in the Si
1-x
Ge
x
under layer depends both on the Ge
concentration and presence of any residual defects in the Si
1-x
Ge
x
due to lattice mismatch
during heteroepitaxial growth[36,37]. The dark areas, c and b have lower -Si intensity
compared to bright areas, a, d, e, and f, in the AFM image. If the intensity of -Si (Fig. 7(c))
is weak, the intensity of Si
1-x
Ge
x
(Fig. 7(d)) is strong. From the cross sectional view of Fig.
7(b), the step height between the bright to the dark area is ~16 nm. Figure 7(c) also illustrates
the slight shift (~ 2 cm
-1
)

of the -Si peaks. While the average deviation of the peak of the
silicon tip stays within a range 520 0.04 cm
-1
(data not shown), its value in the -Si
spectrum is 514 0.8 cm
-1
. Raman shift of Si-Si vibration basically provides a measure of the
inter-atomic Si-Si spacing in the -Si layer. This spacing causes fluctuation of channel strains,
and subsequently affects the performance of the device. It has been reported that lateral strain
variations is mostly associated with the crosshatched pattern and its variation is in the order of
Nano-scale Characterization and Spectroscopy of Strained Silicon 81
~1 cm
-1
[36]. Calculated from the shift in Raman peaks, the strain imposed on the capped -Si
layer is about 1.5 0.2 GPa [37].
Figure 7. (a) Reflection microscopic image of the -Si surface. (b) AFM image of the -Si surface. Red
crosses indicate the tip positions where TERS mapping was carried out. (c) and (d) are Lorentzian
fitting results of position dependent TERS spectra of -Si and Si
1-x
Ge
x
, respectively. a-f correspond to
the positions shown in (b).
Figure 7(d) shows the subtracted near-field spectrum for the LO phonon mode arising
from Si
1-x
Ge
x
buffer layer. The LO phonon mode in the underlying Si
1-x
Ge
x
layer did not
show much spectral shift during the spectra mapping except a slight shift observed in the
spectrum d. This can be attributed to the local density of doped Ge, which could be higher
around the position d. This is also evident from Fig 7(c) point d, which exhibits the highest
spectral shift for the LO phonon mode in -Si layer. The nearby spectra obtained at c and e
also have slight spectral shifts. This means that, at position d, we have high concentration of
defects associated to the heterogeneity in the Ge-concentration in the underlying layer. This is
the direct evidence of the fact that the Si-Si bond length in -Si is affected by the crystalline
structures and concentration of Ge in the underlying Si
1-x
Ge
x
layer on nanoscale. However,
the observed spectral shifts in the -Si (~2 cm
-1
) are higher than those in the Si
1-x
Ge
x
layer (~1
cm
-1
). This is understandable, because even though the strains in both layers are caused by the
presence of Ge atoms in the buffer layer, the amount of strain may not be the same.
All these observed nanometer scale information on localized strain cannot be detectable
by micro SERS experiments due to averaging effect within a diffraction limited focused spot
Norihiko Hayazawa and Alvarado Tarun 82
[34]. Using TERS, however, we could successfully reveal the localized strain hidden in
nanometer scale.
4. Managing the Excitation Wavelength and the Tip Material for
TERS
So far, we have demonstrated selective enhancement of LO phonon signals arising from
the thin -Si layer by SERS and TERS in the presence of strong background scattering from
Si
1-x
Ge
x
buffer layer to distinctly observe Raman signal and successfully revealed localized
strain in nanometer scale using TERS. However, as can be seen from Fig. 6, the LO phonon
from the -Si layer is sandwiched between two comparatively strong unwanted peaks arising
from the Si
1-x
Ge
x
buffer layer and Si-tip material. In order to have higher sensitivity and to
obtain high contrast image of the strain distribution in silicon layer by TERS, it is important
to get rid of these two unwanted background scattering modes. We address this by using
shorter wavelength and using different tip material.
4.1. Ultraviolet Light Excitation for Background Suppression from
Underlayers
Since the strong scattering from the buffer layer is excited due to the longer penetration
depth of the probing light, this problem can be overcome only if the penetration depth of the
probing light in silicon can be reduced. It has been reported [15] that by varying the excitation
wavelength from 532 to 351 nm, the penetration depth of the probing light in silicon can be
changed from 400 to 5 nm. For example, the penetration depth is 5 nm, 47 nm, 108 nm, 241
nm, and 406 nm for the excitation wavelength at 351 nm, 405 nm, 442 nm, 488 nm, and 532
nm, respectively [39]. Moreover, resonant Raman scattering in Si has been reported [40] for
excitation around 365 nm (3.4 eV). Thus, an increase in the phonon intensity due to the
resonance effect can also be observed for lower excitation wavelengths, which is an
additional advantage in using the lower excitation wavelengths. However, the use of Ag-
coated tip in TERS limits the wavelength that can be effectively used for enhancement. This
is because the field enhancement near the tip apex comes from the plasmon resonance within
the Ag layer coated on the tip [41]. By reducing the excitation wavelength, we move away
from the plasmon resonance of the tip, and hence lose the enhancement of the field at the tip
apex. Therefore, for an efficient TERS detection from the thin layer of -Si, we need to find a
compromise between the two opposite effects of reducing the excitation wavelength. One, a
positive effect by reducing the penetration depth together with increasing Raman efficiency
due to resonance Raman effect, and the other, a negative effect by reducing the field
enhancement at the tip apex. To compromise for the negative effect of using shorter
wavelength, we performed far-field Raman measurements in different excitation wavelength.
Figure 8(a) shows the far-field Raman spectra (without tip) obtained from sample. Each
spectrum is normalized and then decomposed into two Lorentzian function (dashed lines) for
peak intensity analysis. The relative intensity of the Si-Si in -Si relative the Si-Si in Si
1-x
Ge
x
buffer layer increases with decreasing wavelength. The total intensity for each phonon mode
Nano-scale Characterization and Spectroscopy of Strained Silicon 83
Figure 8. (a) Far-field Raman intensity of -Si layer grown in the SiGe layer at different wavelength.
The Lorentzian functions under Si-Si in Si
1-x
Ge
x
(x=0.25) peaks at 502.6, 503.4 and 502.6 cm
-1
, which
corresponds to phonon modes from 442nm, 488nm and 532nm, respectively. (b) Total Raman intensity
ratio (blue) between -Si and SiGe and penetration depth (red) as a function of excitation wavelength.
The Raman intensity ratios were obtained by calculating the area under the Lorentzian curves.
in Si
1-x
Ge
x
and -Si were obtained by calculating the area under the two Lorenztian curves.
The relative intensity of the LO phonon mode arising from -Si layer is increased by
shortening the excitation wavelength. Figure 8(b) shows the total Raman intensity ratio of -
Si over the Si
1-x
Ge
x
at varying wavelengths. The secondary y-axis in Fig. 8(b) is the
calculated penetration depth for each excitation wavelength used. As the penetration depth
decreases with decreasing wavelength, the total Raman intensity ratio between -Si and Si
1-
x
Ge
x
increases. At 442nm excitation wavelength, the penetration is ~108nm and still bigger
than the 30nm thickness of -Si sample. A laser with 405nm excitation wavelength may be a
good candidate because the penetration is ~47nm and near the 30nm -Si thickness. At
442nm, the Raman intensity from -Si is increased to half the intensity of Si
1-x
Ge
x
. This is a
significant improvement compared to 532nm light where only a small -Si Raman signal is
observed (see Fig. 6). The incurred loss in enhancement due to shorter wavelength was offset
Norihiko Hayazawa and Alvarado Tarun 84
by the gain in the ratio between -Si and SiGe signal. Reducing the excitation wavelength
allows us to obtain effectively background-free scattering signal from the -Si layer, leading
to a feasible imaging of strain in -Si substrates. The field enhancement at the tip apex is still
reasonable for the He-Cd laser with excitation wavelength of 441.6 nm (data not shown here),
so we selected this wavelength in further TERS aimed towards higher sensitivity detections.
4.2. Selection of Tips for Background Suppression from Silicon Tips
In order to further improve the sensitivity in TERS, we still need to address the other
problem arising from the presence of the LO phonon mode from the tip itself. Since the tip is
made of silicon and coated with Ag, it works as a perfect enhancer for the Si-Si scattering in
the tip itself. This is because all the silicon atoms are adsorbed in the enhanced field created at
the tip apex. Hence, it is impossible to suppress the scattering from the tip. The best way
address the unwanted peak arising from Si-Si vibration mode in the Si-tip that interferes with
the Raman signal from -Si layer, is to change the tip material. We need to select a material
that will not interfere with sample vibrations. Unfortunately, most of the commercially
available AFM cantilever tips are made of silicon, which is not a good tip-material for
detecting TERS from silicon samples. However, cantilever tips made of silicon nitride (Si
3
N
4
)
are now commercially available. The Raman vibrational modes of Si
3
N
4
are distinctly
separated from those of Si, which is a good tip-material for observing TERS from Si samples.
Aside from Si
3
N
4
tips, oxidized silicon tips [42,43] or silicon dioxide (SiO
2
) tips such as a
tapered optical fiber probes can be also useful for the base material for metallized tips. If all
Si atoms of the tip are oxidized, Raman vibration of Si from the tip can be completely
suppressed, and hence this tip can be effectively use. It has been recently reported [44] that
tips made of materials with lower refractive index, such as Si
3
N
4
(n=2.05) or SiO
2
(n=1.5)
could show higher enhancement factors especially in shorter wavelength region.
Figure 9. A TEM image of an oxidized silicon cantilever tip.
Figure 9 shows the transmission electron microscope (TEM) image of the thermally
oxidized silicon cantilever probes at 1100C temperature under steam atmosphere for 3
Nano-scale Characterization and Spectroscopy of Strained Silicon 85
minutes. As seen in the figure, SiO
2
layer with a thickness of ~100 nm is formed on a silicon-
based tip without degrading the original sharpness. This oxidized silicon tips is also
promising for tuning the plasmon resonance of metals coated on the tip by controlling the
thickness of the SiO
2
layer. Instead, for our experiments, we utilized the commercially
available Si
3
N
4
cantilever tips, after coating them with Ag. Figure 10 shows the SEM image
of the Si
3
N
4
tip (Budget Sensors, BS-SiNi) coated with 50-nm-thick Ag layer by thermal
evaporation process. The diameter of the tip apex after Ag coating was about 30 nm, which is
relatively smaller than the 50nm thickness of coated Ag because of the very sharp tip shape.
Fig. 10 (b) is the SEM image (bottom view) of the cantilever. In order to illuminate the tip by
a LWD objective lens with the angle of 30 degrees, part of the cantilever is removed by
focused ion beam (FIB), otherwise it creates an unwanted shadow on the sample [28]. This
was not necessary for the previous silicon tip, because the shapes of the bottom structures for
the Si and Si
3
N
4
tips are different. Even after chopping off a part of the tip, some shadow of
the tip still existed for Si
3
N
4
tips. It was impossible to reduce this shadow any further, so the
overall intensity of Raman scattering was slightly reduced for TERS compared to the far-field
measurements in the TERS experiments involving Si
3
N
4
. For reflection mode TERS, the
geometrical accessibility of the tip for illumination should also be taken into consideration to
minimize excitation power loss and fake scattering signals from the protruding parts of most
commercially available tips.
Figure 10. SEM images of Ag coated Si
3
N
4
tip. The area surrounded by dashed lines is removed by FIB
for an efficient light delivery onto the tip by a LWD objective lens.
4.3. TERS Imaging
In this section, we demonstrate TERS imaging on -Si layer using He-Cd laser with 441.6
nm wavelength and Ag coated Si
3
N
4
cantilever tip. Figure 11 (a) shows the comparison
between TERS (with a tip) and far-field Raman spectrum (without a tip). As expected, the Si-
Si background signal seen from the tip at 520 cm
-1
in Fig. 6 is completely eradicated.
Furthermore, the penetration depth of the excitation light at 441.6 nm in the underlying Si
1-
x
Ge
x
layer is drastically reduced compared with that at 532 nm. The far field Raman signal
Norihiko Hayazawa and Alvarado Tarun 86
Figure 11. (a) Comparison of TERS and far-field Raman spectra, (b) Comparison of SERS and far-field
Raman spectra.
from the thin -Si layer is relatively increased to the half of the intensity of the background
signal from the Si
1-x
Ge
x
layer. This is a significant change compared to the Fig. 6(a), which
uses 532nm, where only a small shoulder corresponding to the LO phonon arising from the -
Si layer was observed. In the TERS spectrum in Fig. 11 (a), the background signal from Si
1-
x
Ge
x
layer is slightly reduced because of the shadowing effect of the tip. Even with
shadowing effect by the tip, the signal from the -Si layer is increased because of the efficient
tip-enhancement effect. In addition, Fig. 11 (b) shows the comparison between SERS (with
Ag film; thickness ~ 8nm) and far-field Raman spectrum (without Ag film). The Raman
spectrum without Ag film is the same without Ag tip in Fig. 11 (a). The presence of thin Ag
layer reduces the intensity of excitation light reaching the sample due to absorption. This
explains the reduction of the overall intensity of the Raman scattering in SERS spectrum
compared to the far-field Raman spectrum. However, in the SERS spectrum, the relative
intensity of the LO phonon arising from the -Si layer compared to the LO phonon intensity
of the buffer layer is increased. This is once again a good demonstration of selective
Nano-scale Characterization and Spectroscopy of Strained Silicon 87
enhancement of the LO phonon vibration arising from the -Si layer. Comparing the
experimental results of TERS and SERS in Fig. 11, the enhancement in the relative intensity
of -Si with respect to the scattering from Si
1-x
Ge
x
buffer layer achieves almost same value.
But, the scattering volume involved in TERS (about the same size as tip apex) is much
smaller than that in SERS (same as the diffraction limited focused spot), which suggests that
tip-enhancement with a Ag coated Si
3
N
4
tip at 442 nm excitation works much more
efficiently compared with surface enhancement at the same wavelength.
Since the combination of a Si
3
N
4
tip and 442 nm excitation shows much higher
sensitivity in TERS measurements compared to the previous experiments using 532nm and Si
tip, we employed this combination to image the nano-scale strain distribution on the surface
of the -Si layer through near-field Raman imaging. In order to realize the nano distribution
of the strain, the near-field Raman image was also compared with a far-field image from the
same area of the sample. Figure 12(a) shows a topographic image (128 pixels by 128 pixels)
and Figs. 12(b), and 12(c) show the strain images extracted from near-field and far-field
Raman spectra, respectively, obtained from the same position (32 pixels by 32 pixels). In
order to obtain these Raman images, the LO phonon modes from each position where fitted
with Lorentzian functions, and then the peak positions were estimated from the fittings, which
were plotted with respect to the position. The near-field image was constructed by the above-
mentioned process applied to the subtracted near-field spectra obtained by moving the tip at
different positions. The far-field image on the other hand was constructed by applying the
process to the far-field spectra by moving the center of the focused laser spot at different
positions. Since the shift in the frequency position of the LO phonon mode is a direct
reflection of the local strain, the images shown in Fig. 12(b) and 12(c) correspond to the
distribution of the local strain in the sample. The near-field image clearly reveals strain
embedded in nanoscale, which cannot be seen in the far-field image that shows almost
uniform contrast. This confirms that there is nanometric distribution of the local strain in the
sample, which could not be seen by the far-field imaging. Figures 12(d) and 12(e) show the
plots of the number of pixels as a function of Raman peak position for the near-field image in
Fig. 12(b) and for the far-field image in Fig. 12(c), respectively. Narrow Gaussian distribution
produced in the far-field image is due to averaging effect within the diffraction limit while the
widely broadened distribution in the near-field image is due to the observation of nano-scale
strain distribution. This meets our expectation simply because near-field image in Fig. 12(b)
shows large fluctuation of contrast compared to Fig. 12(c). It would be important to point out
that the LO phonon peak positions in Fig. 12(d) is distributed in lower Raman shifts
compared to Fig. 12(e), as can be seen from the shift of the Gaussian distributions in the two
figures. There are two possible mechanisms for this effect; one is related to the chemical
effects taking place between the Ag atoms of the coated tip and silicon atoms of the strained
layer, and the other, due to the local pressure applied on the sample by the tip. Further
investigation is required for confirmation. A careful observation of SERS spectrum in Fig. 11
reveals that there was a small downshift of Raman mode in SERS compared to far-field
spectrum. It is also well know that Raman modes in SERS measurements are often
downshifted [45-48]. The primary reason for such a shift is the chemical bonding between the
Ag atoms and the sample atoms, which effectively modifies Raman vibrations. This can also
happen for TERS, when Ag molecules of a coated tip come in close contact with the sample
molecules. Since we used the contact mode operation of AFM to control the tip position in
Norihiko Hayazawa and Alvarado Tarun 88
TERS experiment, the tip can apply a unidirectional force on the sample at the contact point.
Even though the value of this force is not large, the resultant pressure per atom could be large
enough due to the nano-sized of the tip apex. This effect was recently observed in various
nanomaterials [45,49,50] under controlled application of pressure using tip. In our case, the
tip applied pressure works in a direction perpendicular to sample surface. In the equilibrium
condition, we can expect that the pressure to increase the bond lengths in the direction parallel
to the sample surface. As a result, it adds to the strain present in the silicon layer due to the
lattice mismatch between the silicon and the buffer layers. Hence, Raman modes are further
shifted to the lower frequencies. For detailed characterization of strain distribution, some
analytical investigations such as finite element method (FEM) are also very important factors
together with the development of experimental system.
Figure 12. (a) topographic image and strain images of (b) near-field and (c) far-field, respectively. (d)
and (e) are Raman peak distributions in (b) and (c), respectively.
5. Controlling the Polarization in Detection
At this point, we tried to improve sensitivity by modifying the tip material, using shorter
wavelength to reduce penetration depth and focus spot, and manipulating the well-defined
polarization of crystalline sample along with the polarization conditions of probing light. The
key issue is how to improve the sensitivity of the weak near-field signal at the nanoscale level
to be detectable from the strong background coming from the total illuminated area. Most of
the research works done have focused on electric field enhancement, either by Ag coated Si
and Si
3
N
4
tip or by pure metallic tip [11,29,32,51,52]. Various arguments were made
Nano-scale Characterization and Spectroscopy of Strained Silicon 89
regarding tip form and material [53-55] and the control of polarized excitation light [56,57].
Recently, researchers started working on reducing the far-field background signal without
comprising the field enhancement to obtain high contrast near-field Raman image. One way is
manipulating the well-defined polarization properties of crystalline sample relative to the
polarization and propagation of the incident light. Ossikovski et al, proposed a simple model
that describe polarized TERS to characterize tip-enhancement process [58]. The model is
based on tip-amplification tensor describing the interaction of tip on both the incident and
scattered optical field. From their results, by appropriately setting the polarizer and analyzer
relative to the material crystalline axis, far-field signal can be reduced. Poborchii et al,
proposed far-field suppression by depolarization configuration [59]. In this configuration, the
tip depolarizes the incident beam from p-polarized light to s-polarized light or vise versa. The
resulting depolarized light will incur depolarized Raman signal that can be detected through
an analyzer while blocking the Raman signal from the originally polarized light to minimize
the far-field Raman signals [60]. Sokolovs group optimizes this depolarization configuration
to obtain high contrasts Raman image on silicon material with lateral resolution of 20nm [61].
However, the authors noted that the optimum polarizer and analyzer condition, which gives
highest contrast, changes with the morphology and geometry at the tip end.
In this section, we used the silicon Raman tensors to estimate at which combination of
incident polarization and sample orientation will offer minimum far-field Raman intensity.
We also introduce different analyzer setting to further reduce the far-field background by
taking into account the depolarization effect mentioned above. We performed SERS
experiment to validate the numerical results and we found good agreement with the Raman
tensor calculation. The configuration that gives minimum far-field background signals with
high contrast in SERS was utilized in TERS experiment to obtain high contrast near-field
Raman signal. In this approach, we fixed the polarizer and analyzer along with sample
orientation based on SERS to ease the difficulty of optimizing the polarizer and analyzer
setting for different tip geometry. Both the field enhancement effect and depolarized detection
were considered to obtain a high signal-to-noise TERS signal. We found out that for Raman
active thin samples assembled in bulk crystalline materials, depolarization effect outweighs
the field enhancement effect in getting high-contrast Raman signal.
5.1. Theoretical Calculation of Raman Intensity by Side Illumination Optics
The geometrical model used in the Raman intensity calculation is shown in Figure 13.
This model was formulated for reflection-mode TERS system where a metallic tip is placed in
contact with the -Si sample. There are two Cartesian coordinate systems, the sample (xyz)
and the light (xyz). The laser beam is introduced at =60 degrees

relative to the sample
normal (z-axis). The sample rotation angle (azimuth) is denoted as . The sample azimuth is
varied to obtain the maximum and minimum Raman intensity level for both p- and s-
polarization of incident light.
Norihiko Hayazawa and Alvarado Tarun 90
Figure 13. Schematic of reflection-mode TERS. TERS were defined with two Cartesian coordinate
systems, the sample (xyz) and the light (xyz) reference frames. Laser beam is introduced at

relative
to the samples normal (z-axis) and denotes the rotation angle (azimuth). The thickness of the
strained Si is ~30nm. Electron micrograph of the Ag coated tip shows a tip-diameter of ~30nm.
The far-field Raman scattering intensity I is generally expressed as [22,62]:
I e
s
T
R
j
e
i
j

2
(eq.1)
where R is Raman tensor for any j active phonon, and e
i
, e
s
are the unit vector of incident and
scattered electric field, respectively. The superscript T denotes transpose of the scattered
electric field vector. The derivation of Raman tensor R for c-silicon in the (100) plane by
back-scattering geometry (normal incidence) is discussed in detail by R. Loudon [22]. The c-
silicon Raman tensor for the phonon modes in the sample reference frame (xyz) is:
TO
1
R
1
=
0 0 0
0 0 d
0 d 0










, TO
2
R
2
=
0 0 d
0 0 0
d 0 0










, LO R
3
=
0 d 0
d 0 0
0 0 0










(eq.2)
in which R
1
, R
2
, and R
3
are respectively, the TO
1
, TO
2
, and LO, phonon modes of c-silicon
and d is the constant that is dependent on the Raman polarizability of the sample. Note that in
Raman spectra of Si there is only one very strong one-phonon peak at 519 cm
-1
(at 305 K),
corresponding to the zone-center optical phonons in Si, in which the TO and LO phonons are
degenerate at zone center in diamond-type crystals [63]. The d value for the c-silicon can be
different from -Si but for qualitative Raman intensity analysis, using c-silicon Raman tensor
can provide a good approximation. Nevertheless, the Raman tensor of unstrained silicon
expressed in eq. 2 is different from -Si because of the inhomogeneous tensile stress induced
in the -Si layer. The amount of strain is maximized at the boundary of SiGe layer and -Si
layer, then and gradually decreases and minimized at the surface layer of -Si. In order to
Nano-scale Characterization and Spectroscopy of Strained Silicon 91
obtain the qualitative comparison of Raman intensity in -Si at different incident and
scattered polarizations with sample azimuth, we simply employ the Raman tensor of
unstrained Si. To utilize the Raman tensors and scattered Raman intensity in eq.1 in
reflection-mode TERS studies, the Raman tensors must be transformed to the laser
illumination reference frame (xyz) at angle . This is because the Raman tensors in eq. 2
were obtained in normal incidence. First, we need to rotate the sample azimuth about its
normal (along the z-axis) in the xyz coordinate, and then formalize the z-component of the
transformation matrix, T
z
(). The Raman polarizability tensor of the sample rotated by an
angle would become,

R
j

( ) = T
z
T
( )R
j
T
z
( ) (eq.3)
where, T
z
() is the rotational matrix for a sample and given by,

T
z
() =
cos() sin() 0
sin() cos() 0
0 0 1










(eq.4)
Next step is to transform the Raman tensor in the xyz reference frame. In this case,
rotation is done along the z-axis. The transformed Raman tensor R''(, ) of the sample in the
(xyz) reference frame at an angle is given by

R
j

( , ) = T
x
T
( )R
j

( )T
x
( ) (eq.5)
where, T
x
() is the x-component of the rotational matrix converting (xyz) to (xyz) and
expressed as


T
x
( ) =
1 0 0
0 cos() sin()
0 sin() cos()










(eq.6)
Consequently, the transformed scattering intensity I for the transformed Raman tensor in
far-field takes the form similar to (eq.1) as
I e
s
T
R
j

(,)e
i
j

2
(eq.7)
Another factor, that we need to consider, is the change in amplitude of the electric field at
the surface, such as air/-Si and strained Si/SiGe interfaces. The transmission and reflection
Norihiko Hayazawa and Alvarado Tarun 92
coefficients for the p- and s-polarized light at different media of known refractive index can
be easily be derived from Snells law and Fresnel equations given as

[64]:
n
1
sin
1
= n
2
sin
2
(eq.8)
n
1
and n
2
are refractive indexes.

and

are the angle of incidence and refraction of light,

respectively.

T
p
=
n
2
cos
2
n
1
cos
1
t
p
2

t
p
=
2n
1
cos
1
n
2
cos
1
+ n
1
cos
2
(eq.9)

R
p
= r
p
2

r
p
=
n
1
cos
1
n
2
cos
1
n
1
cos
2
+ n
2
cos
1
(eq.10)

T
s
=
n
2
cos
2
n
1
cos
1
t
s
2

t
s
=
2n
1
cos
1
n
1
cos
1
+ n
2
cos
2
(eq.11)

R
s
= r
s
2

r
s
=
n
1
cos
2
n
2
cos
2
n
1
cos
1
+ n
2
cos
2
(eq.12)
Figure 14. Schematic of transmittance and reflectance ratio in -Si. T
p
, T
s
are transmission coefficient
for p and s polarization at =60. R
p
, R
s
are reflection coefficient for p and s polarization at =60. The
index of refraction n
1
, n
2
and n
3
are for air, -Si and SiGe, respectively. Index of refraction values were
obtained in Ref.65,66.
The summary of the transmittance (T
p
, T
s
) and reflectance (R
p
, R
s
) obtained from the
calculation are illustrated in Figure 14. Refractive indexes of n
2
(Si) and n
3
(SiGe) were
quoted from reference [65,66]. However, the strain is gradually relaxed from the boundary of
Nano-scale Characterization and Spectroscopy of Strained Silicon 93
strained Si/SiGe to strained Si/air. Thus, the strain at the surface is minimum and is very close
to ordinary silicon, which means that the refractive index of -Si approximately equal to
unstrained Si. Detailed characterization of the refractive index can be analyzed by
ellipsometry. It should be noted that when the incident angle
1
is 60 degrees, the angle of
incidence inside underneath the -Si layer,
2
, is 10.5 degrees. This fact should be taken into
account when calculating the far-field Raman contributions inside the material. Taking into
account all the factors above, the dependence of the far-field Raman intensities with sample
azimuth was calculated at four combinations of polarizer and analyzer. The four combinations
are P-P-, P-S-, S-P-, and S-S-, which represent the polarizer-analyzer-sample azimuth
in degrees, respectively. In the next section, numerical results will be compared with SERS
experimental data.
5.2. Sample Azimuth Dependence of Polarization Raman Measurement :
Depolarization Effect in SERS
The left most part in Figure 15(a)P-P- (b)P-S-, (c)S-P- and (d)S-S- shows the
calculated normalized far-field Raman intensities as a function of sample azimuth relative to
y-axis using c-silicon Raman tensor at different polarization states of polarizer and analyzer.
Fig. 15(e)P-P-0, (i)P-P-45, (f)P-S-0 (j)P-S-45, (g)S-P-0, (k)S-P-45, (h)S-S-0, and (l)S-S-
45 are the experimental results of the far-field Raman and SERS spectra at 0 and 45 degrees
sample azimuth, which indicate the minimum or maximum far-field Raman intensity for (a)P-
P-, (b)P-S-, (c)S-P- and (d)S-S-. All the spectra in Fig. 15 were obtained with the
same exposure time of 10 minutes and laser power of 9.8 mW before the objective lens
(NA:0.28) in a side illumination optics oriented at an angle
1
=60 degrees from the sample
normal. The CCD dark counts are subtracted from all the spectra. For SERS spectroscopy, a
10 nm thick Ag film is evaporated at the rate of ~0.7m/s on the -Si surface under the ~10
-6
Torr vacuum pressure. The SiGe Raman peak intensities at ~503 cm
-1
in SERS (with Ag) are
reduced to almost half of the far-field (without Ag) Raman intensity. This is because the
illumination light has to transmit through the Ag films, in turn losing some probing power.
Besides, no surface enhancement effect is expected to reach the underlying SiGe layers
because the enhanced field decays strongly and is localized within ~20 nm from the surface
[30,67]. From the calculation results, the amplitude of sinusoidal Raman intensities in (a)P-P-
is to found to be greater than (b)P-S-, (c)S-P- and (d)S-S-. Fig. 15 (b)P-S- and
(c)S-P- have the same amplitude. This amplitude of the Raman intensity is dependent on
the excitation transmittance at the sample surface, e.g., the detection efficiency of P-P- is 67
% (0.82 x 0.82: incident x scattered), P-S-and S-P- is 28% (0.82 x 0.34=0.34 x 0.82), and
S-S- is 12% (0.34 x 0.34). The detection efficiency was summarized in Fig. 14. In the P-P
polarizer-analyzer setting in Fig. 15, the far-field Raman intensity level of (e)P-P-0 can be
suppressed down to 1/4 when compared to the (i)P-P-45 where sample is rotated 45 degrees.
This observation is consistent with the calculation result wherein the ratio of the maximum
amplitude intensity over the minimum amplitude intensity is eight because the offset intensity
marked in the red circle in Fig. 15(a) is ~0.12. Note that this discrepancy between
experiments and calculations is because experimental results are obtained as an average of
wide variety of incident angles using an objective lens. The offset of ~0.12, marked in the red
Norihiko Hayazawa and Alvarado Tarun 94
circle in Fig. 15(a), is the sample azimuth where Raman intensity was obtained in (e)P-P-0
setting. However, in (j)P-S-45, (k)S-P-45 and (h)S-S-0 cases, the far-field Raman intensity
offset available for detections is suppressed down to almost zero. The reason why there exists
a strong Raman background signals in (e)P-P-0 measured in side illumination, can be
justified from the contributions of R
1
(TO
1
), R
2
(TO
2
), and R
3
(LO) to the total detected
Raman intensity. However, when measured by backscattering illumination optics with normal
incidence (=0; normal incidence optics), only R
3
(LO) becomes Raman active and can be
totally suppressed by an analyzer [23]. On the other hand, at incident light angle of 0 (side
illumination optics), both R
1
(TO
1
) and R
2
(TO
2
) also becomes Raman active and contributes
to the total Raman intensity because its not suppressed by the analyzer. In other words,
Raman signal of (e)P-P-0 are mainly coming from TO phonon modes but not from the LO
phonon modes.
Figure 15. (a-d) Calculated Raman intensity as a function of sample azimuth at a fixed polarizer and
analyzer setting using the transformed silicon Raman tensor. (e-l) Comparison of far field and SERS
Raman spectra at various combinations of polarizer, analyzer and sample azimuth. The black line
spectra are far field Raman spectra, and the red line spectra are SERS spectra. Dashed lines are fitted
Lorentz function spectra for Raman intensity analysis. SERS contrast value at each combination was
obtained and indicated. (i) and (k) shaded with gray are the two conditions used in the TERS
experiment. Red circles in the (a-d) indicate the sample angle at which minimum Raman intensity is
observed.
Nano-scale Characterization and Spectroscopy of Strained Silicon 95
Strictly, the TO modes may not be overlapped with the stretched LO phonon mode. For
example, in Fig. 15(e), Raman peak of -Si is observed at 511.1 cm
-1
, which is mainly due to
the TO modes, while SERS peak of -Si is slightly shifted and observed at 509.4 cm
-1
, which
is due to stretched LO mode. These facts suggest that the TO modes are considered as
background signal for LO mode in our experiment and should be suppressed for higher
sensitivity. Total intensities from TO and LO phonon modes are plotted in Fig. 15, (a)P-P-,
(b)P-S-, (c)S-P- and (d)S-S-. To clearly understand the origin of background Raman
signal, Figure 16 shows the calculated Raman intensities at each LO, TO
1
, and TO
2
phonon
mode in both normal and side illumination optics. Fig. 16(a) shows the normal incidence and
Fig. 16(b), (c), and (d) correspond to P-P-, P-S- (or S-P-), and S-S- in the side
illumination optics tilted at
1
=60 degrees incidence, respectively. When the incident angle is
0 degree (normal incidence), the minimum intensity of LO phonon mode is zero at the sample
azimuth of 0 and multiples of 90 degrees (see inset in Fig. 16(a)), while the maximum
intensity occurs at 45, 135, 225 and 315 degrees because the TO phonon mode is not active at
all. However, in cases of (b) and (c), the TO phonon modes at the minimum LO phonon mode
is not zero. This is because the two TO phonon modes are 90 degrees out of phase, making
the sum a non-zero constant value at minimum LO phonon mode sample azimuth. Only in the
case of (d), the TO phonon modes are not active. This suggests that selective LO phonon
mode measurement is feasible. The issue is that (d)S-S- in Fig. 15 is not optimal situation
for spectroscopy. In particular, for microscopic image acquisition the Raman signal level is
extremely weak. According to the individual Raman intensities assigned to LO, TO
1
and TO
2
phonon modes shown in Fig. 16, the residual (offset) far-field Raman intensities of (e)P-P-0,
(j)P-S-45 and (k)S-P-45, red circles in Fig. 15, are all due to TO phonon modes because LO
phonon modes are completely rejected by the analyzer. On the contrary, far-field Raman
intensity of S-S-0 should not have a contribution from the TO phonon modes, however, the
far-field Raman spectrum in Fig. 15 (h)S-S-0 has the signal intensity similar to the (j)P-S-45
and (k)S-P-45. This residual far-field Raman signal observed in (h)S-S-0 is experimentally
due to the wide variation of the incident angle and depolarization effect of the objective lens
itself; the background signal level becomes almost the same as (k)S-P-45. In this sense, S-S-
0 is not advantageous over S-P-45. Using this polarization dependence, we suggest a
method to collect the near-field Raman signals with high efficiency in P-P-0, P-S-45, and S-
P-45 by tip-depolarization effect [59-61]. The far-field Raman signal that comes from the
large focused spot is linearly polarized while the near-field Raman signal that comes from the
proximity of the tip can be depolarized by the tip geometry. The depolarized near-field
Raman signal can pass through the analyzer by choosing proper conditions of incident angle,
polarizer, analyzer, and sample azimuth. Therefore, SERS spectra were studied first by
coating 8nm thickness Ag film on surface of -Si before TERS. The depolarization effect in
SERS occurs at the entire focused spot with the aid of roughened Ag thin films. In TERS, the
depolarization is localized and takes place at the tip apex while in SERS, the depolarization
occurs at the entire focus. Hence, the main difference in the depolarization effect is the
scattering volume. The SERS and far field Raman spectra are shown in Fig. 15(e)P-P-0, (i)P-
P-45, (f)P-S-0, (j)P-S-45, (g)S-P-0, (k)S-P-45, (h)S-S-0, and (l)S-S-45 which correspond
to either minimum or maximum conditions for each polarizer-analyzer set.
Norihiko Hayazawa and Alvarado Tarun 96
Figure 16. Raman intensity dependence of different Raman modes, LO (red) and TO (blue), as a
function of sample azimuth at different polarizer and analyzer setting. (a) Normal incidence at P-P, P-S,
S-P and S-S polarizer-analyzer polarization setting and side illumination (oblique incidence) (b)P-P,
(c)P-S and S-P, (d)S-S polarizer-analyzer polarization configuration. Solid and dashed blue lines are
Raman signal intensity of TO
1
and TO
2
phonon modes, respectively. Red solid line is Raman signal
intensity from LO phonon mode. Black line is total Raman signal intensity. (inset: zoomed plot
showing the zero Raman intensity)
Based on the SERS spectra, the Raman intensities of -Si is higher compared to their far-
field Raman intensities at (e)P-P-0, (j)P-S-45, (k)S-P-45, and (h)S-S-0 conditions. The
reason is that, at these conditions, the far-field Raman is at minimum intensity as indicated by
red circles in the calculation results of Fig. 15 and both depolarization and surface
enhancement effect works efficiently with Ag film. To quantify the improvement, we
calculated the parameter, contrast that is defined as the ratio of near-field signal intensity I
near
to the far-field signal intensity I
far
expressed as [61]:
Nano-scale Characterization and Spectroscopy of Strained Silicon 97

Contrast=
I
near
I
far
=
I
total
I
far
1








I
total
is the measured intensity that is the sum of far-field and near-field Raman intensities.
Since the Raman signal from the sample consists of both the target -Si layer and the
underlying SiGe layer, which generates strong Raman signal as background component, we
focused on the relative intensity (I(-Si /SiGe)) between -Si and SiGe layer. In this case, the
contrast can be expressed as:

Contrast=
I
total
I
far
1








=
I
SERS
(
- Si
SiGe
)
I
far
(
- Si
SiGe
)
1










Since the Raman signal from the sample consists of both the target -Si layer and the
underlying SiGe layer, which generates strong Raman signal as background component, we
focused on the relative intensity (I(-Si /SiGe)) between -Si and SiGe layer. The Raman
spectra were break down into Lorentz function spectra for peak intensity analysis. The total
intensity for each peak, -Si and SiGe, were obtained from the area under the fitted Lorentz
function spectrum. The calculated contrasts for each combination of polarizer, analyzer and
sample azimuth are labeled in the experimental results of Fig. 15. The highest contrast (~3.7)
is obtained in the (j)P-S-45 and (k)S-P-45 conditions. We can expect the same effect in
TERS experiment. Following the SERS experiments, in order to show that the background
suppression is more important than electromagnetic field enhancement for contrast
improvement in Raman active and bulk crystalline materials such as silicon, we performed
TERS measurement under the conditions in P-P-45 and S-P-45 (shaded with gray in Fig.
15). In the former case, P-P-45, Raman signal level is strongest because tip-enhancement
effect is expected in both for the incident and scattered light. In the latter case, S-P-45,
background signal is well suppressed due to the s-polarized incident light. Moreover, tip-
enhancement effect is not expected to happen in S-P-45 configuration because the incident
light is s-polarized. However, tip-enhancement is expected for the scattered light. It is
important to point out that the only difference between P-P-45 and S-P-45 is the incident
polarization and the other parameters, analyzer and sample azimuth, are the same. These facts
suggest that S-P-45 benefits on the tip-enhancement effect from the scattered light whereas
P-P-45 utilizes tip-enhancement effect also from the incident light. This is because it is
generally accepted that p-polarized illumination is better for the efficient incident tip-
enhancement effect

[28,55]. Besides, the S-S-0 condition actually showed the best
background suppression in the calculation, however, we exclude the use of S-S-0 in TERS
because as discussed above the observed residual far-field Raman signal in S-S-0 is mainly
due to the wide variation of the incident angle and depolarization effect caused by the
objective lens itself. In this context, S-S-0 is not advantageous over S-P-45.
Norihiko Hayazawa and Alvarado Tarun 98
5.3. Experimental Observation of Depolarization Effect in TERS
In order to compare contributions of field enhancement and depolarization effect
included in P-P-45 and S-P-45 spectra, TERS measurements were carried out with and
without Ag coated Si
3
N
4
tip. In pure Si
3
N
4
tip (without Ag), field enhancement is lower when
compared to Ag coated Si
3
N
4
tip that is expected to have higher field enhancement. The
TERS result obtained from the Ag coated Si
3
N
4
tip is shown in Figure 17. In the P-P-45
condition, the far-field Raman signals from LO phonon mode can efficiently pass through the
analyzer. The decrease in the peak Raman intensity of SiGe when Ag coated tip is in contact
can be attributed to the depolarization effect and the incident intensity loss caused by
shadowing effect

[28,61] in the tip. The influence of the shadowing due to tip insertion is
almost negligible because tip diameter (~30nm) is much smaller than the area of an
ellipsoidal focused spot (~2.6 x 1.5m
2
) generated by LWD objective lens. The Raman
intensity loss in SiGe associated with depolarization effect is the dominant factor because the
Raman signal from LO phonon mode arising from the depolarized incident light, s-polarized
in the P-P-45 case, is blocked by the analyzer. In order to accurately analyze the field
enhancement and the depolarization effect, the discussion below are based on the following
assumptions: (1) the diameter of the near-field scattering volume resulting from field
enhancement is comparable to the tip diameter (~30nm) and the same as the thickness of the
-Si layer (~30 nm), (2) the tip-enhancement factor for SiGe layer is negligible

[68] because
the thickness of -Si is 30 nm and set to 1x. Next, the 0.89x TERS depolarization effect was
derived from simple intensity ratio between with Ag and without Ag coated tip in Fig. 17(a).
This is because the reductions in SiGe Raman signal level is mainly attributed to the
depolarization effect. These values are summarized in Fig. 17(c). On the other hand, the -Si
Raman intensity exhibits a signal increment. Since depolarization effect was observed for
SiGe layer, it should be also applicable to -Si layer in the same manner because both layers
have the same facet (100). The depolarization effect factor on -Si is set to 0.89x in Fig.
17(c). The ratio of the total TERS intensity from -Si with Ag tip is 1.64 times higher than
without Ag coated tip. The tip-enhancement factor is set to 1.84x in Fig. 17(c), and was
calculated from 1.64/0.89. This fact supports that the tip actually enhanced the incident
electric field intensity. Due to the existence of high background Raman signals from the
entire focused spot, the estimated tip-enhancement contribution is small, ~1.84x. It should be
noted that only the surface (-Si) is selectively enhanced and SiGe signal is reduced. This
signifies that the result is not based on the signal enhancement from the multiple reflections,
which is necessary in evaluating field enhancement on multilayered sample as discussed in C.
Georgi et al, studies

[69]. In the case of S-P-45, the obtained depolarization effect value is
1.34x. The reason why the value turned-out to be more than one (signal is increased) is based
on the fact that the polarized LO phonon (background) signals were rejected by the analyzer
and the depolarized LO phonon signals by the tip passed through the analyzer efficiently.
Using the value of the depolarization effect, tip-enhancement value can be also calculated in
the same way we calculate for P-P-45. Results are tabulated in Fig. 17(d). In S-P-45, the tip-
enhancement is very large, ~11.7x, compared to P-P-45, ~1.84x, despite the s-polarized
incident polarization and p-polarized scattered light detection. In this case, tip-enhancement is
expected to occur only on the Raman signal at the detection. These results strongly suggest
that for bulk sample and Raman active crystals with well-defined crystalline polarization such
Nano-scale Characterization and Spectroscopy of Strained Silicon 99
as silicon, far-field (background) Raman signal suppression, which is likely to happen in s-
polarized illumination, is more important and should be carefully considered in improving the
signal-to-noise ratio (SNR) in TERS experiment. For microscopic application and for faster
data acquisitions, P-P-45 is recommended because of higher Raman signal level. The Raman
signal from thin -Si layer was detected with much higher SNR in S-P-45 than the case in P-
P-45 in the presence of strong background signals from the thick underlying SiGe layer.
Figure 17. TERS (red) and far field (blue) Raman spectra with Ag coated silicon nitride (Si
3
N
4
) tip at
(a)P-P-45 and (b)S-P-45 polarizer-analyzer-sample azimuth setting. (c) and (d) tabulates the
calculated values for tip enhancement and depolarized effect contribution coming from P-P-45 and S-
P-45 setting, respectively.
To further demonstrate the importance of depolarization effect, TERS using pure Si
3
N
4
tips (without Ag) was carried out and the results are shown in Figure 18. The far-field Raman
spectra in Fig. 18(a) and (b) and the ones of Fig. 17 (a) and (b) are the same. The summary of
enhancement factors induced by depolarization effect and tip-enhancement effect are listed in
Fig. 18(c) and (d). Depolarization effect by the Si
3
N
4
tip in P-P-45 case also caused
reduction in the SiGe Raman intensity. This time, the depolarization effect is a bit higher,
~0.97x in Fig. 18(c) compared to 0.89x from the previous TERS experiment using Ag coated
tip in Fig. 17(c). This could be due to the slight difference in the tip geometry between Ag
coated Si
3
N
4
tips and uncoated Si
3
N
4
tips. On the other hand, the field enhancement value at
the -Si is 1.24x, smaller than TERS with Ag coated tip. This means that tip-enhancement is
still present even without the Ag coating. This can be due to the large contribution of an
image dipole (the polarizability of image dipole: =(
s
-1)/(
s
+1),
s
: dielectric constant of
material

[70]) and efficient gap mode formed by a high refractive-index sample, in this study,
-Si. Furthermore, in S-P-45, the depolarization effect value (2.60x) is larger than Ag coated
tip. This can be again due to difference in the tip geometry discussed above. The tip-
enhancement value is 2.61x and smaller than the case with Ag coated tip, but it is more than
Norihiko Hayazawa and Alvarado Tarun 100
twice as high as Fig. 18 (a)P-P-45 with an uncoated tip. Even with uncoated Si
3
N
4
tip and s-
polarization incidence, the -Si signal level got almost the same signal level as SiGe by the
depolarization effect, and the SNR is much better than Fig. 17 (a) P-P-45 with a Ag coated
tip.
Figure 18. TERS (red) and far field (blue) Raman spectra with pure silicon nitride (Si
3
N
4
) tip at (a)P-P-
45 and (b)S-P-45 polarizer-analyzer-sample azimuth setting. The tip enhancement and depolarized
effect contributions in the P-P-45 and S-P-45 setting are listed in (c) and (d), respectively.
6. Conclusion
We introduced the utilization SERS to selectively enhance the LO phonon vibrations
originating from a thin silicon layer, which is under strain due to lattice mismatch with
underlying Ge-doped silicon buffer layer. The selective enhancement makes it possible to
efficiently detect the weak Raman signal originating from a thin layer, in the presence of a
strong background signal originating from comparatively thick buffer layer. This selective
enhancement could be localized to nanometric scale by utilizing TERS, where a metal-coated
sharp tip is used for point-surface enhancement, which turned out to be an effective tool to
investigate the nanometric variation of strain within the -Si layer. Further, we suggested
some optimization and improvements in TERS for a higher sensitivity of the measurements.
This included the selection of shorter wavelength for excitation, proper selection of tip
material, and consideration of tip-originated effects, such as the tip-applied pressure that can
add up in the local strain of the sample. In order to further improve the signal-to-noise ratio,
we calculated the far-field Raman intensity of -Si (100) based on Raman tensor, Snells law,
and Fresnels equations with the incident angle of 0 (normal incidence) and 60 degrees.
Numerical results suggest that for normal incidence, only LO phonon mode is observed while
in side illumination, incidence angle of 60 degrees, both TO and LO phonon modes are also
Nano-scale Characterization and Spectroscopy of Strained Silicon 101
observed. Because of TO phonon modes contributions, background Raman signal cannot be
completely suppressed in cross-polarized configuration. However, LO phonon mode can be
suppressed. SERS experiments suggest that P-P-45 gives the highest signal intensity and
good for faster data acquisition in microscopic Raman studies. The P-S-45 and S-P-45 show
the highest contrast between -Si and SiGe layers. In order to demonstrate the importance of
background signal reduction for TERS, we compared experimentally the TERS spectra
between P-P-45 and S-P-45 whose only difference is the incident polarization. Results show
that S-P-45 condition strongly reduces the background signal but also reduces the tip-
enhancement effect. However, much higher signal contrast is observed between near field and
far field compared to P-P-45 condition where high tip-enhancement effect is higher but also
with strong far field background. Hence, for imaging Raman active and bulk crystalline
materials such as silicon, background signal suppression (s-illumination) needs to be carefully
considered as well as the field enhancement with strong far field Raman signal level (p-
polarization). Accordingly, depending on the specific geometry of each tip, which affects
both depolarization effect and field enhancement effect, the proper combination of s- and p-
illuminations show the highest contrast in the experiments while minimizing the background
contributions from the sum of TO
1
, TO
2
, and LO modes through optimize analyzer and
sample azimuth setting.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 107-150 2010 Nova Science Publishers, Inc.
Chapter 4
NANOTECHNOLOGIES FOR CANCER DIAGNOSTICS
AND TREATMENT
Phong Tran
1
and Thomas J. Webster
2,*
1
Physics Department, Brown University, Providence, RI 02912
2
Division of Engineering and Department of Orthopedic Surgery,
Brown University, Providence, RI 02912
Abstract
Cancer treatment usually uses drugs (chemotherapy) to reduce tumor size, followed by
surgery to remove the tumor (if possible). Then, more chemotherapy and radiation therapy is
used to kill as many tumor cells as possible. The goal of this collective treatment is to target
and kill cancerous tissue while minimizing side effects on healthy cells. Due to their non
specificity, current cancer therapies have poor therapeutic efficacy and can also have severe
side effects on normal tissues and cells. In addition, cancer is often diagnosed and treated too
late, i.e., when the cancer cells have already invaded and metastasized (i.e. spread) to other
parts of the body. At this stage, treatment methods are highly limited in their effectiveness.
Thus, scientists have been focusing efforts into finding alternative methods to detect cancer at
earlier stages and kill such cancerous tissues more effectively. Nanoparticles (that is, particles
with at least one dimension less than 100 nm) have become very attractive for improving
cancer diagnosis and treatment due to their novel optical, magnetic and structural properties
not available in conventional (or micron) particles or bulk solids. Nanoparticles have been
extensively studied for various applications including delivering anti-cancer drugs to
tumorous tissues and/or enhancing imaging capabilities to better diagnose and treat cancer. In
this review, recent work related to the improved targeted therapy for specific cancers (whether
by developing more specific anti-cancer agents or by altering delivery methods) are
summarized. Discussions on the advantages and disadvantages of the most widely studied
nanoparticles (i.e., liposome nanoparticles, polymer-based nanoparticles, quantum dots,
nanoshells, and superparamagnetic particles) in cancer imaging followed by anti-cancer drug
delivery are highlighted. Lastly, bone cancer and current research in using nanoparticles for
treating bone cancer, with an emphasis on the novel use of selenium (a natural anti-cancer
element found in our bodies), are addressed.

* E-mail address: Thomas_Webster@brown.edu (Webster TJ). Tel.: +1-401-863- 2318. (Corresponding author)
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and Thomas J. Webster 108
1. Introduction
Nanotechnology is an exciting multidisciplinary field that involves designing and
engineering of materials and systems whose structures and components are less than 100 nm
in at least one dimension [Ferrari 2005]. At this nanometer scale, the properties of objects
(such as electrical, optical, mechanical, etc.) significantly differ from those at larger scales
such as the micrometer scale [Klabunde 1996, Wu 1996, Baraton 1997 and Siegel 1995].
Having the ability to create new products with new characteristics and properties which
were not available before, nanotechnology has shown great potential in a wide range of
applications (such as information and communication technology [Heath 1998, Akyildiz
2008], biology [Giaever 2006, Saini 2006], and medicine [Silva 2004, Jain 2003, and West
2003], etc.). One of the most exciting contributions nanotechnology has made is in medicine
and medical research to improve human health. Novel nanometer scale drug delivery systems
and nano-tools have been developed to aid in disease detection of higher accuracy at earlier
stages to treat such diseases more effectively [Park 2007, Orive 2005, Kong 2005, Jain 2003,
and Shantesh 2006].
Of the tools that nanotechnology has created, nanoparticles have emerged over the last
decade as the most promising for disease treatment and management, especially for
diagnosing and treating cancer. Nanoparticles have unique properties that allow them to
specifically target and deeply penetrate tumors. In addition, some nanoparticles (such as
quantum dots, superparamagnetic nanoparticles) also have superior imaging capabilities
allowing for a highly sensitive diagnosis of cancer [Shantesh 2006, Brannon-Peppas 2004,
and Brigger 2002]. (See Table 1 for a summary of the advantages and disadvantages of the
nanoparticles used in cancer diagnosis and treatment that will be discussed in the chapter).
Among many kinds of cancer, bone cancer has been the subject of numerous studies due to its
complexity.
It is estimated that 2,380 individuals (1,270 men and 1,110 women) will be diagnosed
with bone and joint cancers and 1,470 individuals will die from primary bone and joint
cancers in 2008 in the United States [ACS 2008]. Primary bone cancer is rare as usually bone
cancer is a result of the spread of cancer from other organs (such as the lungs, breasts and the
prostate [Millier 2007]). Because many deaths are officially attributed to the original cancer
source, the true numbers of bone cancer related deaths have been underreported. A common
technique to treat bone cancer is the surgical removal of the cancerous tissue followed by
insertion of an orthopedic implant to restore patient function. However, it is not always
possible to remove all cancerous cells and therefore the remaining tumor cells can redevelop
cancer. In these cases, it would be beneficial to have implants specifically designed to prevent
the reoccurrence of bone cancer and simultaneously promote healthy bone tissue growth. This
same argument can be made for numerous tissues (such as the lung, breast, etc.). This can be
achieved by imparting conventional implant materials (such as titanium, stainless steel, etc.)
with an anti-cancer chemistry. To promote healthy bone tissue growth, nano-feature surfacing
can be used since studies have shown that osteoblast (bone-forming cells) function (including
adhesion, proliferation, and the deposition of calcium containing minerals) is greater on nano-
structured compared to current implant surfaces (which are micron-scale rough and nano-
scale smooth) [Webster 1999, Webster 2000a, Webster 2000b, Webster 2001, Webster 2004,
Perla 2005].
Nanotechnologies for Cancer Diagnostics and Treatment 109
This chapter will first give a brief introduction to the development and characteristics of
cancerous tumors, different cancer targeting strategies, and then discuss the emerging roles of
nanoparticles (including liposomes, quantum dots, nanoshells, superparamagnetic
nanoparticles, and polymeric nanoparticles) in cancer imaging and therapeutics. Finally, this
chapter will focus on the novel use of selenium nanoclusters as anti-cancer coatings for
orthopedic applications.
Table 1. Summary of advantages and disadvantages of the use of nanoparticles for
cancer treatment to be discussed
Type of
nanoparticle
Advantages Disadvantages References
Liposomes Biocompatible; biodegradable; non-
immunogenic; amphiphilic; size,
charge and surface properties of
liposomes can be easily changed
Poor control over leakage of
drugs; low encapsulation
efficacy; poor stability
during storage; poor
manufacturability at the
industrial scale
Torchilin 2005
Tiwari 2006
Soppimath 2001
Hans 2002
Quantum dots Fluorescently bright; large
extinction coefficients; high
quantum yields; absorption
coefficients across a wide spectral
range; highly resistant to
photobleaching
Composition includes heavy
metals which are toxic
Gao 2004a
Dubertret 2002
Ballou 2004
Reiss 2002
Niemeyer 2001
Alivisatos 1996
Nanoshells Fine-tunable optical response in a
broad region of the spectrum from
the near-UV to the mid-infrared;
can be designed to strongly absorb
or strongly scatter light in the NIR
region; gold shell is biocompatible
and rigid
Little-known fate following
introduction to human
bodies
Loo 2004
Loo 2005
Oldenburg 1999
Hirsch 2003
Superparamagnetic
nanoparticles
Controllable nano size;
magnetic properties; easy to be
directed using external magnetic
fields; have controllable, specific
Curie temperatures which allow
for self regulated hyperthermia
Hard to be directed to
tumors which have a large
distance to possible position
of magnets;
occlusion of blood vessels
can occur in the target
regions; possible toxic
responses to human bodies
Mornet 2004,
Wang 2001,
Jordan 1996,
Wust 2002,
Falk 2001, Kapp
2000, Gerner
2000, Alexiou
2000
Polymeric
nanoparticles
Tailorability of polymer;
biocompatibility;degradability;
various nanoparticle synthesis
methods; versatility of drug loading
techniques; controllable drug
release characteristics
Some preparation methods
use toxic organic solvents;
poor drug encapsulation for
certain hydrophilic drugs
and possibility of drug
leakage
Hans 2002
Anderson 1997
Brigger 2002
Soppimath 2001
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and Thomas J. Webster 110
2. Growth and Other Characteristics of Tumors
2.1. Introduction to Tumors
A tumor starts with a single or a couple of mutated cancerous cells surrounded by
healthy, normal cells. As the cancerous cells replicate, due to its modified DNA, they
generally develop at a higher speed than normal cells [Brannon-Peppas2004]. The term in
situ cancer refers to the earliest detectable cancer cell mass [Rudon 1987]. In situ cancers are
small lesions (a few millimeters in diameter) localized within normal tissues. These small
tumors are avascular, i.e., they do not have their own network of blood vessels to supply
oxygen and nutrients. Avascular tumors depend on diffusion of nutrition from pre-existing
blood vessels and therefore grow slowly. As the cancerous cells develop further, surrounding
normal tissue will not be able to compete for nutrition. Because of the insufficient nutrient
supply, some tumor cells also die especially those located deep inside the tumors. Compared
to cancer cells at the edge of the tumor, deep-located cancer cells rely entirely on diffusion to
receive nutrients and to eliminate waste products. The cancerous cells will continue to
duplicate and displace surrounding healthy cells until they reach a diffusion-limited maximal
size where tumor cell growth rate is equal tumor cell death rate [Brannon-Peppas2004].
Unless there is more nutrients supplied from blood, tumors can not grow beyond this
diffusion-limited maximal size (which is around 2 millimeters

in most tumors [Brannon-
Peppas2004, Grossfeld 2002, and Jones 1998]). Tumors stay in this stage for years until they
initiate the formation of blood vessels (the process known as angiogenesis).
In order to continue growing, tumors need to be establish their own blood vessels through
a process known as vascularization which is stimulated by angiogenesis factors (such as the
vascular endothelial growth factor family, transforming growth factor , ephrins, cadherin 5-
type 2, etc.). The vascularized tumors begin to grow more as nutrition supply is established.
Clinically detectable tumors (approximately 10
9
cells, about one gram mass) can be found
within a few months or years, depending on cell type [Ruddon 1987]. By that time, the tumor
will have already gone through about 30 doublings, approximately two-thirds of its lifetime.
If the tumor is not detected, a tumor mass of 32 gram can be achieved after five more
population doublings (approximately 2 days for bone cancer cells (osteosarcoma)). More
seriously, the tumor compresses surrounding tissues, invades basement membranes, and
spread to other organs in the bodies (the process called metastasis) [Ruddon 1987]. This
exponential growth of tumors and their abilities to metastasize are the reason why early
cancer detection is extremely important.
2.2. Vascularization Process in Tumors (Angiogenesis)
Angiogenesis is the process in which new blood vessels grow from pre-existing blood
vessels. Angiogenesis can come from circulating endothelial precursors, shed from the vessel
wall or mobilized from the bone marrow [Carmeliet 2000]. Angiogenesis starts with
retraction of pericytes (vascular cells that wrap around blood capillaries) from the abluminal
surface of capillaries. After that, endothelial cells release and activate proteases (such as
urokinase (uPA), progelatinase A, progelatinase B, etc.) that degrade the extra-cellular matrix
surrounding the existing capillaries. Endothelial cells then migrate, proliferate and align to
Nanotechnologies for Cancer Diagnostics and Treatment 111
form tube-like structures, which eventually join together to form new capillaries [Eatock
2000]. All of these stages can be the targets for cancer diagnosis and treatment.
2.3. Characteristics of Tumor Vascular Structures
Blood vessels of tumors are very different from those of normal tissues [Carmeliet 2000].
Tumor vessels have uneven diameters, more branching and especially, a lot of openings. The
reason for this irregular structure may be the imbalance of factors involved in angiogenesis,
such as vascular endothelial growth factor (VEGF) and angiopoietins. Tumor vessels may
also not have mechanisms to protect themselves from changes in oxygen, hormonal or
metabolic balance. Abnormal vascular structure of tumors also have chaotic blood flow that
results in insufficient blood supply in some areas. There areas, having not enough oxygen
supplied from blood, become hypoxic (oxygen-starved) and acidic [Helmlinger 1997].
Hypoxic tumors are difficult to treat for traditional treatment such as drug delivery through
blood stream or radiation therapy.
Tumorous tissues not only have higher vascular density than normal tissues, but the
structure of tumor vessels is also different [Carmeliet 2000]. For example, there are many
openings on the walls of the vessels, the inter-endothelial junctions are wider, the basement
membrane is discontinuous or absent, and the shapes of endothelial cells are also abnormal.
Tumor vessels, therefore, are leakier than those of healthy, normal tissues. Rapid
vascularization also leads to impaired lymphatic drainage systems in tumor tissue. The high
vascular density of tumors, their leaky vessels and impaired lymphatic drainage in the tumor
tissues creates the so-called enhanced permeation and retention (EPR) effects which the
anti-cancer treatment methods can exploit [Sledge 2003, Teicher 2000].
3. Tumor Targeting Methods
3.1. Passive Targeting
Passive targeting is a methodology that increases the target/non-target ratio of the
amounts of delivered drugs primarily by minimizing non-specific interactions with non-target
organs, tissues, and cells [Yokoyama 2005]. Nanoparticles are good candidates for this
targeting strategy as they can be designed to have various size, surface charge, and
hydrophobicity/hodrophilicity properties that subsequently affect the uptake of the particles
by organs, tissues and cells. For example, particles with more hydrophobic surfaces (such as
poly(propylene oxide), poly(methyl methacrylate), etc.) are taken up more by the liver than
by the spleen and lungs [Brigger 2002]. To maximize circulation time and targeting ability,
the nanoparticle size should be less than 100 nm (in diameter) and the surface should be
hydrophilic to avoid clearance by macrophages. This goal can be achieved by coating
nanoparticles with hydrophilic coatings (such as poly(ethylene glycol) (PEG), poloxamines,
or poloxamers [Storm 1995, Brannon-Peppas 2004]. The enhanced permeability and retention
(EPR) effect creates opportunities to increase the transport of drugs from blood vessels into
tumor tissues and retain the drugs inside tumor tissues. Specifically, drugs can be designed to
have sizes larger than the pore size of blood vessels in healthy tissues (from 2 nm-6 nm) but
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and Thomas J. Webster 112
smaller than the pore size of blood vessels in tumor tissues (ranging from 100 nm to 780 nm)
[Yuan 1995, Hobbs 1998]. The drugs therefore, will accumulate preferably at the tumor site
and side effects of the drug on healthy tissue will be minimized. Moreover, due to the
impaired drainage lymphatic system at tumor sites, the drugs can stay in the tumor longer,
therefore increasing treatment effectiveness.
3.2. Active Targeting
Active targeting is the method in which the therapeutic agent is delivered to tumors by
attaching it to a ligand that binds to specific receptors that are over-expressed on target cells
[Marcucci 2004]. Upon binding to the receptors on the target, the particle-ligand conjugates
could be internalized into the cell (internalizing ligand) or only the particle is internalized
(non-internalizing ligand) [Marcucci 2004]. The receptors that are over-expressed on target
cells can be divided into the following groups [Marcucci 2004]: (i) receptors that are over
expressed on endothelial cells in tumor blood vessels (such as integrin-v3 and negatively
charged phospholipids) [Hood 2002, Ran 2002] and (ii) receptors that are over-expressed on
tumor cells (such as HER2 and disialoganglioside (GD2)) [Park 2002, Pastorino 2003]).
Figure 1. EPR effects and targeting nanoparticles to the tumor. Nanoparticles with diameters between
50 nm and 100 nm can avoid entering normal tissue but can extravagate into tumors and target the
tumor cells by ligand-receptor methods and release anti-cancer drugs to kill the tumor cells.
In active targeting strategy, sizes of drug carriers are also very critical. One needs the
drugs to be transported by blood to the desired site (i.e. tumor) to be taken up by the tumor
cells. As mentioned in section 3.1, blood vessels in most healthy tissues have a pore size from
2 nm to 6 nm while tumor vasculature has pore sizes ranging usually from 100 nm to 780 nm.
Nanotechnologies for Cancer Diagnostics and Treatment 113
Therefore, as illustrated in Figure 1, drug-nanoparticle conjugates of 50 nm to 100 nm size
can enter the tumor from tumor blood vessels but cannot get into healthy tissue from healthy
blood vessels [Marcucci 2004, Drummond 1999].
Figure 2 gives an example of doxorubicin-loaded liposomes with phospholipid-anchored
folic acidPEG conjugates (FTL-Dox) accumulated inside KB-HiFR tumor cells in vitro
[Gabizon 2004]. Phospholipid-anchored folic acid is the ligand to target folate receptors over
expressed on KB-HiFR tumor cells. The doxorubicin fluorescence (orange) is clearly seen in
the nucleus.
Reprinted with permission from [Gabizon 2004].
Figure 2. Confocal fluorescence microscope picture of KB-HiFR tumor cells after two hours of in vitro
exposure to 10 M FTL-Dox.
Clearly, the above choice of nanoparticle size is part of passive targeting when one tries
to avoid the uptake of drugs from healthy tissues. The passive component of drug targeting is
important in active targeting systems and should not be over looked because the majority of a
living body is non-target sites. For example, liver which is one of the largest drug targets
comprises only 2% of the body weight. The rest of the body, which is 98% of the weight, can
be considered to be a non-target site in this case [Yokoyama 1996]. Furthermore, before
specific ligand-receptor interactions take place in active targeting, the drug-carrier-ligand
complex has to be transferred through many other tissues since most targets are located in the
extravascular space [Yokoyama 1996].
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and Thomas J. Webster 114
After reaching the tumor site, the drugs will be internalized (i.e., enter tumor cells) with
or without internalization of the carrier, i.e. nanoparticles. In the latter, nanoparticles will stay
localized in the interstitium surrounding the tumor cells, while the drug, after being released
from the drug-nanoparticle conjugate degradation, will enter tumor cells through diffusion or
active transport [Marcucci 2004]. According to Marcucci and co-workers [Marcucci 2004],
the factors that accelerate this degradation to release drugs are possibly the irregular condition
of the tumor environment (such as acidic pH, enzymes and oxidizing agents [Drummond
1999]). Many methods have exploited these factors to design particulates that preferentially
disintegrate at acidic pH or elevated temperature [Kirpotin 1996]. If the nanoparticles are also
internalized along with the drugs, the internal environment of lysosomes will be the factors
that disintegrate the nanoparticles and the drug can then diffuse out of the lysosomes.
Between these two strategies of internalizing drugs, the methods that also internalize carrier
particles have higher delivery efficacy.
4. Liposome Nanoparticles
4.1. Liposomes and their Advantages in Drug Delivery
Liposomes are spherical vesicles formed by one or several concentric lipid bilayers with
an aqueous phase inside and between the lipid bilayers (Figure 3A) [Torchilin]. Therefore,
liposomes usually have hydrophilic outer surfaces, hydrophilic inner cores and hydrophobic
matrices in between. Figure 3B gives an example of a transmission electron microscopy
(TEM) image of liposomes (adapted with permission from [Ran 2003]).
Adapted with permission from [Ran 2003].
Figure 3. Schematic structure of a liposome with both water-soluble and water-insoluble encapsulated
drugs (A) and a TEM image of the liposome (B).
Liposomes have several advantages in drug delivery for cancer treatment [Torchilin
2005]. They are highly biocompatible, biodegradable and non-immunogenic. These properties
are attributed to their composition of naturally occurring lipids. Second, the size, charge and
surface properties of liposomes can be easily changed by adding new ingredients to the lipid
mixture before their preparation. For example, small unilamellar liposomes formed by a
single bilayer can be around 100 nm in size, larger unilamellar vesicles have sizes ranging
Nanotechnologies for Cancer Diagnostics and Treatment 115
from 200 nm to 800 nm and multilamellar vesicles can be as large as 5,000 nm and consist of
several concentric bilayers.
Maybe the biggest advantage of using liposomes for drug delivery is their amphiphilicity
(i.e., having both hydrophilic and hydrophobic properties) that allows for conjugations with
both hydrophilic and hydrophobic therapeutic agents. Water-soluble (hydrophilic) drugs can
be encapsulated in the aqueous core of liposomes and water-insoluble (hydrophobic) drugs
can be entrapped within the lipid membrane [Torchilin 2005, Tiwari 2006]. Liposomes can
also fuse with cell membranes and transfer drugs in the liposome to inside the cells
[Chatterjee 2007]. There are two main mechanisms of liposomes releasing encapsulated drugs
[Jesorka 2008]. One mechanism is based on the development of an affinity reaction [Gmez-
Hens 2006]. In this release mechanism, liposomes are fabricated to contain some component
of affinity interaction (such as antigens, antibodies, enzymes, receptors) which interact with
complementary affinity component at the targeted site and release the loaded drugs in situ. In
the other mechanism, the triggered-release mechanism, liposomes are synthesized to contain
some ingredients that are sensitive to external stimulus leading to changes in the membrane
when an appropriate external stimulus is applied. Examples of this triggered-release
liposomes include pH sensitive [Hafez 2000, Mizoue 2002, Reddy 2000, Yamada 2005],
thermosensitive [Anyarambhatla 1999, Liu 2004], light sensitive [Benkoski 2006] or
ultrasound sensitive[Huang 2004] liposomes. Membrane integrity of liposomes is lost under
effects of the external stimulus leading to the release of entrapped compounds.
4.2. Passive Targeting Liposomes with PEG Coatings
Liposome particles have several disadvantages when used as carriers for drug delivery.
They are very quickly captured by the RES (half-life is less than 30 minutes). They are also
instable, therefore, can not be used as a delivery agent without modification [Torchilin 2005].
PEG coatings, as seen in Figure 4, can prolong the circulation time of liposomes in the
bloodstream (half-life can be increased to 5 hours [Klibanov 1990]) and PEG-coated
liposomes can also be targeted to tumors by the EPR effect [Yokoyama 2005].
PEG is a hydrophilic, nonionic polymer commonly used as coatings on nanoparticles.
PEG molecules have good biocompatibility properties and can be covalent bonded, absorbed
to surface of particles or can be mixed with other ingredients to form particles during
preparation process [Hans 2002]. It has been proposed that there are two main factors that
affect the affinity of liposomes to the RES [Lee 1999]. Nonspecific hydrophobic interactions
of liposomes with RES cells, and a specific opsonization reaction involving some blood
component(s) such as immunoglobulin, complement proteins, apolipoproteins, and fetuin
[Moghimi 2001]. Hydrophilic PEG coating can make liposomes become more hydrophilic
therefore their nonspecific interactions with RES cells decrease. Specific interactions with
opsonizing proteins are also reduced with PEG coatings because these coating layers may act
as a brush shielding liposomes from the proteins [Drummond 1999]. More interestingly,
coating liposomes with PEG can also be designed so that after the PEG coated liposomes
reach the tumor site through EPR effect, the local conditions of tumor tissues (e.g. acidic pH
in tumors) will make the PEG coating detached, promoting intracellular delivery of drugs
[Immordino 2006].
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and Thomas J. Webster 116
Figure 4. Schematic illustration of a PEG-coated, drug loaded liposome nanoparticle.
4.3. Active Targeting with Liposomes
Besides passive targeting of liposomes to the solid tumor site as mentioned above,
liposomes can also be conjugated with ligands for active targeting. One of the examples is the
incorporation of a ligand of folate receptors (FR) to liposomes. FR is over-expressed on many
cancer cells compared to their healthy, normal counterparts. For instance, the folate receptor
is over-expressed in ovarian (52 of 56 cases tested), endometrial (10 of 11), colorectal (6 of
27), breast (11 of 53), lung (6 of 18), renal cell (9 of 18) carcinomas, brain metastases derived
from epithelial cancers (4 of 5), and neuroendocrine carcinomas (3 of 21) [Sudimack 2000,
Garin-Chesa 1993]
In experiments by Pan and co-workers [Pan 2003], nanometer liposome particles with
diameters of 100 nm, loaded with doxorubicin (DOX) and covalently attached with folate,
were effectively delivered to KB xenograft tumors in mice and inhibited tumor growth,
resulting in a 31% higher (p <0.01) increase in the lifespan of the tumor bearing mice
compared to those that received liposomes loaded with DOX only.
4.4. Disadvantages of Liposomes
Despite many advantages of liposomes, they still have some disadvantages in drug
delivery applications [Bhojani 2007]. One of the disadvantages is leakage of the encapsulated
drugs from liposomes into the blood before the drug-liposome conjugates can reach the
targeted sites. Other limitations include low drug encapsulation efficacy and poor stability of
liposomes during storage and manufacturability at the industrial scale [Soppimath 2001, Hans
2002].
Nanotechnologies for Cancer Diagnostics and Treatment 117
5. Quantum Dots
5.1. Properties of Quantum Dots
Quantum dots (QDs) are nanocrystalline semiconductors consisted of an inorganic core
(e.g., cadmium, mercury, cadmium selenite, etc.) with a metal shell (e.g., ZnS) that shields the
core and provides biocompatibilities. QDs have diameters ranging from 2-10 nm (for core-
shell QDs) and 5-20 nm after surface modifications (core-shell-conjugate QDs) (Figure 5A,
5B). QDs have unique optical and electrical properties (such as their fluorescence emission)
and can be tuned from visible to infrared wavelengths depending on their size and
composition. Especially, QDs can have large absorption coefficients across a wide range of
spectrum and are very bright and photostable, making them ideal candidates for various
imaging applications in vivo [Gao 2004a, Niemeyer 2001, Alivisatos 1996].

Adapted with permission from [Kim 2003].
Figure 5. Schematic quantum dot (QD) structures (A) and a TEM image of CdTe core - CdSe shell QDs
in water (B).
The light-emitting properties of QDs are attributed to the quantum effects that are due to
(i) their nanoscale structures and (ii) the quantum confinement phenomenon. Quantum
confinement is a quantum effect in which the energy levels of a small nanocrystal (smaller
than the Bohr exciton radius, about a few nanometers) are quantized with values directly
related to the size of the crystal [Alivisatos 1996]. When exposed to light sources, the cores of
QDs absorb incident photons and generate electron-hole pairs (characterized by a long
lifetime, greater than 10 nanoseconds [Michalet 2005, Efros 2000]). The pair then recombines
and emits a photon in a narrow, symmetric energy band (full width at half maximum is
typically from 30 to 50 nm) [Michalet 2005]. The emitted light has wavelength ranging from
400 to 1350 nm (for QDs with sizes from 2 to 9.5 nm not including functional layers)
[Michalet 2005]. In comparison with current organic fluorophores, QD nanoparticles have
more desirable properties, therefore offering exciting new opportunities for in vivo imaging,
especially in cancer diagnostics and management [Michalte 2005, Larson 2003].
First, fluorescence emitted by QDs is brighter than that of current organic dyes. Single
QDs is from 10 to 20 times brighter than organic dyes [Gao 2004a]. QDs have very large
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and Thomas J. Webster 118
extinction coefficients (around an order of magnitude larger than those of most dyes) that
make them absorb more incoming light per unit concentration of dye [Michalte 2005,
Dubertret 2002, Ballou 2004]. They also have high quantum yields (close to 90% [Reiss
2002, Bailey 2003]), meaning a high amount of light emitted over that absorbed.
Second, QDs have properties that allow for multiple and simultaneous labeling of
biological targets [Lee 2007]. Large absorption coefficients of QDs in a wide range of
wavelength [Niemeyer 2001, Alivisatos 1996, Gao 2004a] enable one to simultaneously
excite multiple QDs of different emissions with a single excitation wavelength. Furthermore,
their emission spectra have very distinct and narrow wavelengths, therefore, allowing
independent labeling and identification of numerous biological targets [Han 2001, Gao 2003,
Gao 2004b]. This feature is very useful in studying tumor physiology which requires one be
able to distinguish and monitor each component of the tumor microenvironment under
dynamic conditions [Stroh 2005]. For example, researchers have used two-photon microscopy
to image blood vessels within a tumorous tissue using PEG coated QDs [Stroh 2005]. As seen
in Figure 6B, compared to Figure 6A, there was a good contrast between cells, matrix and the
leaky vascular.
Reprinted with permission from [Stroh 2005].
Figure 6. (A) Concurrent imaging of both QDs with a 470 nm emission maximum and green
fluorescent protein (GFP) (indicated in green) provides clear separation of the vessel from GFP-
expressing perivascular cells and (B) and vessels highlighted with a deep red (QDs with a 660 nm
emission maximum) micelle preparation were imaged simultaneously with the second harmonic
generation signal (indicated in blue); the image represents a projection of a stack of 20 images at an
interval of 2 micrometers per slice. Bars = 50m.
Nanotechnologies for Cancer Diagnostics and Treatment 119
This experiment demonstrates the potential of QDs as a fluorescence contrast agent for
noninvasive diagnostics and imaging of human tumors.
Another advantage of QDs is that they have very high resistance to photobleaching. This
feature is extremely important for in vivo imaging where fluorescent agents are constantly
photobleached during image acquisition. For example, Dubertret and colleagues showed that,
after 80 minutes of constant illumination, QDs fluorescence intensity remained unchanged
while the dextran molecules were photobleached [Dubertret 2002].
5.2. Quantum Dots in Cancer Imaging and Treatment
5.2.1. Active and Passive Targeting for QDs
Having superior light emitting properties, QDs are excellent candidates for tumor
imaging if they can be effectively delivered to tumor sites. Both passive and active targeting
mechanisms are being aggressively pursued in order to achieve this goal. Researchers have
been working to increase circulation time of QDs in the blood and target QDs to cancerous
tissues [Gao 2004a, kerman 2002, Rosenthal 2002]. Coating QDs with polymers (such as
PEG) to avoid uptake by the RES, thereby, improving circulation time is an attractive
approach being actively studied. For example, PEG coated CdSe-ZnS (core-shell) QDs have
shown prolonged circulation in the mouse blood stream (half life more than 3 hours)
compared to organic dyes which were cleared from circulation within minutes after injection
[Gao 2005, Ballou 2004]. These PEG coated QDs were also shown to remain fluorescent after
at least four months in vivo. It is believed that these PEG coated QDs are in an intermediate
size range in which they are small and hydrophilic enough to reduce opsonization (that is, the
alteration of a particles surface either by the attachment of complement proteins or
antibodies specific for the antigen, so that the particle can be ingested (phagocytosed) by
phagocytes, macrophages and/or neutrophils) and decrease uptake of RES, but they are still
large enough so that renal filtration is minimized [Gao 2005].
Taking this design a step further, some researchers have conjugated PEG-coated QDs
with ligands that can recognize cell membrane receptors (such as HER2, FR) that are over-
expressed on cancer cells or on endothelia cells in cancer blood vessels. Specifically, a new
class of QD conjugates containing an amphiphilic triblock copolymer for in vivo protection,
targeting-ligands for tumor antigen recognition and multiple PEG molecules for improved
biocompatibility and circulation have been developed [Gao 2004a]. In this study, researchers
prepared CdSe-ZnS (Core-Shell) QDs encapsulated in a copolymer layer, tri-n-
octylphosphine oxide (TOPO), coated with PEG and conjugated to a prostate-specific
membrane antigen monoclonal antibody (PSMA). PSMA is a cell surface marker for prostate
epithelial cells and neovascular endothelial cells [Chang 2001] and has become a target for
both imaging and targeted treating of prostate cancer [Gao 2005]. The QD conjugates have
been successfully targeted to tumor sites in mice through both active and passive targeting
mechanisms and have enhanced fluorescent imaging ability.
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and Thomas J. Webster 120
5.2.2. QDs in Drug Delivery and Therapy for Cancers
In addition to using QDs in imaging, there is a growing interest in using QDs for drug
delivery and therapy. The size of QDs can be readily controlled, allowing for the evaluation
of the size effect on the delivery efficiency and specificity, and therefore, the optimal size of
drug carriers can be determined. High surface-to-volume ratios of QDs allow scientists to
impart multiple functionalities on a single QD to develop a multi functional vehicle while
keeping the overall size within the optimal range. For example, by coating a QD with an
amphiphilic polymer layer (such as poly(maleic anhydride-alt-1-octadecene) (PMAO),
octylamine-modified poly(acrylic acid), etc.), hydrophilic therapeutic agents and targeting
biomolecules (such as antibodies, peptides), can be immobilized onto the hydrophilic side of
the amphiphilic polymer and small molecule hydrophobic drugs can be entrapped in the
matrix between the inorganic core and the amphiphilic polymer coating layer as illustrated in
Figure 7A. Figure 7B shows an image of fixed breast cancer SK-BR-3 cells incubated with
monoclonal anti-Her2 antibody (which was used to bind to the external domain of Her2) and
goat anti-mouse IgG conjugated to QDs with an emission maximum at 630 nm (QD 630-
IgG). Her2 was clearly labeled with QD 630IgG (shown in the red color).
Adapted with permission from [Wu 2002].
Figure 7. (A) Schematic of QDs fabricated to carry drugs and targeting ligand and (B) Fixed breast
cancer SK-BR-3 cells incubated with monoclonal anti-Her2 antibody and goat anti-mouse IgG
conjugated to QDs with an emission maximum at 630 nm (QD 630-IgG). Her2 was clearly labeled with
QD 630IgG (shown in the red color). The nuclei were counterstained with Hoechst 33342 (blue). Bar
= 10 m.
This integrated nanoparticle may serve as a multi-functional vector that not only
specifically bind to and destroy tumor cells, but also emit detectable signals for real-time
monitoring of its path.
5.3. Disadvantages of QDs
The main disadvantage of QDs is due to their composition of heavy metals in the cores
(e.g. Cd, Pb and Se which are known to be toxic to vertebrate systems at parts-per-million
Nanotechnologies for Cancer Diagnostics and Treatment 121
concentrations [Hardman 2006]) and the instability of uncoated QDs when exposed to UV
radiation which leads to the release of heavy metal ions. For example, free cadmium in
solution can bind to sulfhydryl groups of mitochondrial proteins [Wang 2008]. Thiol group
inactivation then leads to oxidative stress and mitochondrial dysfunction [Notas 2006]. The
instability of QDs under UV exposure is due to the fact that the energy of UV radiation is
close to that of covalent chemical bonds [Smith 2006]. Therefore, UV exposure can dissolve
the semiconductor particles through a photolysis process and toxic ions (such as cadmium
ions) are released [Gao 2005]. For example, under exposure to air (30 min) or long exposure
to UV (28 h), QDs at a concentration of 0.0625 mg/mL are already found to be extremely
toxic [Ozkan 2004, Derfus 2004].
Generally, QD toxicity depends on the affects of multiple factors from both individual
QD physicochemical properties and environmental conditions [Hardman 2006]. It has been
shown that toxicity of QD depends on size, charge, concentration, outer coating bioactivity
(i.e., capping material, functional groups, etc.), and oxidative, photolytic as well as
mechanical stability of QDs [Hardman 2006]. For example, Derfus and co-workers found that
the toxicity of CdSe QDs in liver cultures was influenced by different factors such as
synthesis parameters, exposure to ultraviolet (UV) light and surface coatings [Derfus 2004].
They found CdSe (core only, no shell) QDs non cytotoxic under standard conditions of
synthesis and water-solubilization with mercaptoacetic acid (MAA). However, TOPO-coated
QDs which were first exposed to air for 30 min then modified with MAA, showed a dose-
dependent cytotoxicity toward primary hepatocyte cells (viability decreased from 98% to
21% at a QD concentration of 62.5 microgram/mL). They also coated CdSe QDs with layers
of ZnS to study the effect of capping on cytotoxicity. They found ZnS capping eliminated
cytotoxicity caused by air oxidation but ZnS capping did not eliminate cytotoxicity induced
by UV exposure.
To overcome the cytotoxicity problems, researchers have coated QDs with PEG or
encapsulated them in micelles (that is, vesicles formed by the aggregation of surfactant
molecules dispersed in a liquid colloid) which can limit the release of toxic metals induced by
UV exposure [Cuenca 2006, Gao 2004a, Dubertret 2002, Stroh 2005, Gao 2005]. More work
is still needed to develop optimal coatings and, thus, encapsulation that prevents the release of
heavy ions from QDs.
6. Nanoshells
6.1. Structure of Nanoshells
Metal nanoshells are spherical nanoparticles consisting of a dielectric core (such as silica)
coated with a thin layer of metal (typically gold) (Figure 8). Gold nanoshells have optical
properties similar to colloidal gold nanoparticles (such as strong optical absorption due to the
collective electronic response of metal to light) [Loo 2004]. However, gold nanoshells show a
strong dependence of optical response on the relative size of the core and the shells
thickness. By varying the core size and the thickness of the gold layer, the color of these
nanoparticles can be fine tuned across a wide spectral range spanning the visible and near
infrared regions. Therefore, nanoshells show great promise in biomedical imaging and
therapeutic applications in general and cancer imaging and treatment in particular [Loo 2005,
Phong Tran

and Thomas J. Webster 122
Hirsch 2003, Chen 2001]. In addition, as with other types of nanoparticles, especially gold
nanoparticles, drugs can be conjugated to nanoshells for drug delivery to tumors as seen in
Figure 8.

Reprinted with permission from [Oldenburg 1998].
Figure 8. (Left) Schematic illustration of a nanoshell. Polymers (PEG) can be coated onto a nanoshell
surface and drug molecules can be entrapped within the polymer matrix. (Middle and Right) (a)(f)
TEM images of nanoshell growth on 120 nm diameter silica dielectric nanoparticle. (a) Initial gold
colloid-decorated silica nanoparticle. (b)(e) Gradual growth and coalescence of gold colloid on silica
nanoparticle surface. (f) Completed growth of metallic nanoshell.
The optical properties of nanoshells are attributed to the plasmon resonance at the
dielectric-metal interface [Hirsch 2003]. Plasmon resonance is the phenomenon in which light
induces collective oscillations of conductive metal electrons at the dielectric-metal interface.
The absorbing and scattering properties of the particle will be influenced by the particles
plasmon resonance. Depending on the relative thickness of the core and shell layers of a
nanoshell, its plasmon resonance and hence, the optical absorption can be tuned across a wide
range of the spectrum from the near-UV to the mid-infrared. Of particular interest in this
spectral range is the near infrared region (NIR) [Oldenburg 1999] in which the transmittivity
of tissues is high and adsorption is low. The NIR is very important in tissue imaging
[Weissleder 2001].
The sensitive dependence of optical properties on the core diameter-shell thickness ratio
can be understood by the hybridization model of Prodan et al. [Prodan 2003] in which
plasmon resonance of a nanoshell is considered as the result of the interaction between the
nanosphere plasmon and cavity plasmon which are electromagnetic excitations that induce
surface charges at the outer and inner interfaces of the metal shell, respectively [Prodan
2003]. The sphere plasmon depends on the diameter of the sphere and the cavity plasmon
depends on the inner and outer radius of the metallic shell [Aden 1951]. In addition, the
Nanotechnologies for Cancer Diagnostics and Treatment 123
interaction of the sphere and cavity plasmons depends on the thickness of the shell layer
[Prodan 2003].
6.2. Optical Properties of Gold Nanoshells
As previously stated, the optical response of nanoshells strongly depends on the relative
size of the dielectric core and thickness of the metal layer. The ability to fine tune nanoshells
to have optical resonance which varies over a broad region ranging from the near-UV to the
mid-infrared is very important for tissue imaging. It has been demonstrated that nanoshells
can be developed to highly scatter light within this spectral region as would be desired for
many imaging applications; alternatively, nanoshells may be engineered to function as highly
effective NIR absorbers permitting photothermal-based therapy applications as well [Loo
2004]; dual scattering/absorbing nanoshells can also be fabricated [Loo 2005]. For instance,
the conventional NIR dye indocyanine green has an absorption cross section of 10
-20
m
2
at
~800 nm while the cross-section of absorbing nanoshells can be as high as 4 10
-14
m
2
[Hirsch 2003]. This comparison indicates that those nanoshells are over a million fold more
(compared to the conventional dye) likely to encounter an absorbing event and convert that
light into thermal energy which can be used to kill cancer cells or improve chemotherapy and
radiotherapy efficiency [Hirsch 2003].
6.3. Nanoshells in Cancer Diagnostics and Treatment
Gold nanoshells, having attractive optical properties as discussed above, offer promises
for biomedical sensing and therapeutic applications, especially in cancer diagnosis and
treatment [Loo 2005]. In addition to attractive optical properties, nanoshells also have rigid
structures due to metallic shells, therefore offering improved stability. Therapeutic agents and
other targeting molecules can be readily conjugated to the surface of nanoshells to
specifically target and destroy cancer cells [Loo 2004]. To enhance biocompatibility and
improve blood circulation, nanoshells are usually coated with stealthing polymers (such as
PEG) even though the gold surfaces of nanoshells are generally considered to be
biocompatible [Tang 1998].
Researchers have developed a novel approach to combine cancer diagnostics and
therapeutics based on the use of gold nanoshells as near-infrared (NIR) absorbers. Loo and
co-workers [Loo 2004] fabricated silica-gold nanoshells of 3 different sizes (core radius/shell
thickness): 120nm/35nm, 100nm/20nm and 60nm/10nm. These nanoshells have strong
optical scattering and absorption coefficients in the NIR region (wavelength around 800nm)
and were used for imaging (by both dark field scattering and optical coherence tomography)
and killing (by photothermal therapy) cancer cells (SKBr3 breast cancer cells). In order to
specifically target cancer cells, anti-HER2 was conjugated onto the nanoshells to deliver the
bioconjugates (i.e., anti-HER2- nanoshells) to SKBr3 breast adenocarcinoma cells which
overexpress HER2. Compared to the control groups (cells cultured with nanoshells alone),
cells cultured with targeted nanoshells were imaged with increased contrast. Cells were
exposed to NIR irradiation (820 nm, 0.008 W/m
2
for 7 min) to test photothermal therapy
concepts. Cell death was observed only in the SKBr3 breast cancer cells incubated with anti-
Phong Tran

and Thomas J. Webster 124
HER2 nanoshells. Cell death was not observed in cells treated with either nanoshells alone or
exposed to NIR light alone.
In vivo studies have also shown promising initial results for the use of gold nanoshells for
cancer detection and treatment. In one study [Hirsch 2003], investigators fabricated
nanoshells of 110 +/- 11-nm diameter core and a 10 nm thick gold shell. These gold
nanoshells had a peak absorbance at 820 nm. A monolayer of PEG was assembled onto the
gold nanoshell surfaces to stabilize them. The nanoshells were injected interstitially ~5 mm
into a solid tumor volume in immunodeficiency (SCID) mice. From 5 to 30 minutes after
nanoshell injection, tumors were exposed to NIR light (820 nm, 4 W/cm
2
, 5 mm spot
diameter, <6 min). It was demonstrated that tumors injected with nanoshells had an average
temperature elevation of T = 37.4 6.6 C within 4-6 minutes after light radiation. The
increased temperature resulted in tumorous tissue damage indicated by coagulation, cell
shrinkage, and loss of nuclear staining. In contrast, control cells which were injected with
saline had significantly reduced average temperature increase after exposure to the same NIR
treatment (T < 10 C) and showed no tissue damage.
6.4. Disadvantages of Nanoshells
Although nanoshells with attractive optical properties which can be readily fine tuned
offer great promises in cancer detection and treatment, limitations still exist. The biggest
disadvantage of nanoshells is probably their little-known fate following introduction to
human bodies. These particles, having a very small size might present some potential
undesired effects on the organs and tissues in our bodies. More intensive in vivo animal
studies are currently being completed in order to investigate both applications and limitations
of nanoshells in cancer imaging and treatment.
7. Superparamagnetic Nanoparticles
Superparamagnetic nanoparticles (SPMNPs) have been extensively studied in
biomedicine applications and, in particular, cancer diagnostics and treatment [Mornet 2004,
Wang 2001, Jordan 1996, Wust 2002, Falk 2001, Kapp 2000, Gerner 2000, Alexiou 2000].
They have attractive properties that are desired in tumor imaging and treatment. First, they
have a controllable nano size. Second, they possess magnetic properties that make them
excellent candidates in magnetic-based imaging techniques and magnetic-based treatment
methods. For example, SPMNPs can be conjugated with drugs, targeted to tumors using
magnets. They can then absorb energy from a time-varying magnetic field to be heated up and
result in the release of drugs while the heat can also make chemotherapy and radiation
therapy more effective or can directly destroy tumor tissues. In this section, we will review
the use of SPMNPs in magnetic resonance imaging (MRI), hyperthermia treatment and
magnetic-based drug delivery.
Nanotechnologies for Cancer Diagnostics and Treatment 125
7.1. SPMNPs used as Magnetic Contrast Agents in MRI
MRI works by the dual applications of an external magnetic field B
o
(up to 2 Tesla) and a
transverse (i.e. transverse to B
o
) radio frequency (RF) pulse on protons which are present in
large amounts in biological tissues (for example in water molecules, membrane lipids,
proteins, etc.) [Mornet 2004]. Each proton has a small magnetic moment that can be aligned
by applying an external magnetic field. The external magnetic field first applies to align a
magnetic moment of each proton. The RF pulse is then directed to the region of interest and
the protons absorb energy from the pulse and spin in a direction different than the direction of
the external field. The RF pulse then will be turned off, the protons now begin to return to
their original alignment with the external magnetic field and release excess stored energy
through a process called relaxation. When this happens, a signal will be given off and the
MRI system can detect this signal and process it to transform it into images of the tissue area
of interest.
Relaxation can be divided into two independent processes [Mornet 2004]: (i) longitudinal
relaxation in which the longitudinal component of the protons magnetic moment returns to
align with an external field B
o
(called T
1
-recovery); and (ii) transverse relaxation, in which
the transverse (i.e. transverse to B
o
) component of the protons magnetic moment vanishes
(called T2-recovery). Different tissues have different T
1
and T
2
values, therefore, they can be
differentiated by MRI scanning. Both T
1
and T
2
can be shortened by the use of magnetic
contrast agents. Magnetic contrast agents work by altering local magnetic moments in the
region of interest, therefore, relaxation signals can be enhanced. For example, T
2
can be
shortened according to the equation (1) [Pankhurst 2003]:
1/T
2
* = 1/T
2
+ B
o
/2 (1)
Where B
o
is the change in the magnetic field caused by variations in the local magnetic
field inhomogenity or local magnetic susceptibility of the system due to the presence of
magnetic enhance agents [Leach 1988, Browne 1999]. Figure 9 shows TEM images of Fe
3
O
4
SPMNPs and schematically illustrates how SPMNPs can affect T
2
recovery time.
Compared to traditional MR contrast agents (such as gadolinium), SPMNPs have several
advantages. First, SPMNPs are in the size range in which they can be delivered to the desired
tissues more effectively. They are often composed of a superparamagnetic core composed of
iron oxides such as magnetite Fe
3
O
4
, maghemite (-Fe
2
O
3
) or other insoluble ferrites
(generally from 3 to 10 nm in diameter) with or without polymer coatings such as dextran
[Sahoo 2003]. In particular, in the case of MRI for tumor imaging, SPMNPs can be delivered
to tumors using passive targeting methods based on EPR effects. Second, they have much
greater magnetic susceptibility (more than three orders of magnitude greater than traditional
gadolinium superparamagnetic particles [Kraichman 2001]), meaning they are more
responsive to an external magnetic field, than traditional MR contrast agents. For example,
superparamagnetic iron oxides are effective as T
2
relaxation enhancers due to the induction of
local magnetic field inhomogenity in the surrounding tissues leading to a stronger shortening
of the recovery time as in equation (1) [Pankhurst 2003].
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and Thomas J. Webster 126
Adapted with permission from [Sun 2004].
Figure 9. TEM bright field images of (A) 6 nm and (B) 12 nm Fe
3
O
4
SPMNPs deposited from their
hexane dispersion on an amorphous carbon-coated copper grid and dried at room temperature. (C)
Schematic illustration of SPMNPs bound to a tissue of interest, thereby, shortening T
2
recovery time
[Pankhurst 2003].
7.2. SPMNPs in Hyperthermia Treatment for Cancer
Hyperthermia is a cancer treatment method in which temperatures of certain organs or
tissues are raised to 41
o
C- 46
o
C. If the temperature is raised to above 47
o
C, tissue destruction
occurs and this process is called thermoablation [Jordan 1999, Chen 2007]. Thermoablation is
characterized by acute necrosis, coagulation or carbonization of tissue. It is clearly
undesirable in a clinical situation due to systemic side effects and further clinical
complications [Chen 2007]. Modern hyperthermia trials focus mainly on the optimization of
thermal homogeneity at moderate temperatures (42
o
C- 43
o
C) in the target volume. SPMNPs
have the potential to solve this optimizing problem.
As it is well known, tumor cells are more susceptible to heat increases than healthy,
normal cells [Chen 2007]. Cancer cells are more vulnerable to elevated temperatures
compared to normal, healthy cells because [Chen 2007]: (i) normal cells locate close to
normal blood streams which can dissipate heat more effectively compared to cancerous cells
which have abnormal blood flow and (ii) cancerous cells have a more acidic surrounding
environment, therefore, they are more susceptible to hyperthermia. Hyperthermia treatment
for cancer works by raising the tumor temperature resulting in damages in the plasma
membrane, the cytoskeleton and the cell nucleus [Shellman 2008]. In addition, some
regulatory proteins, cytokine or kinases are affected by elevated temperature, which leads to
changes in the cell cycle and can even induce apoptosis (that is, programmed, natural cell
death driven by the cell regulatory system itself) [Chen 2007, Fairbairn 1995, Sellins 1991].
Nanotechnologies for Cancer Diagnostics and Treatment 127
There are several different methods of creating local heat increase (such as using
microwave radiation, capacitive or inductive coupling of radiofrequency fields) by implanting
electrodes, by ultrasound, or by lasers [Glockl 2006]. Magnetic hyperthermia uses the losses
during the magnetization reversal process of the particles when exposed to alternating
magnetic fields to convert such losses to heat. More specifically, SPMNPs are first directed
and concentrated at the desired location using passive or active targeting methods or both. An
alternating magnetic field is then applied resulting in the magnetization reversal process of
the particles. Energy lost in this process is converted to heat.
There are many advantages of using SPMNPs in hyperthermia. First, they can be
effectively directed to tumor tissues using magnetic fields and hence can avoid heating up
normal tissues. For example, in one in vivo study, superparamagnetic magnetite
(Fe
2
O
3
/Fe
3
O
4
) particles (core size 3.1 +/- 0.7 nm) were coated with modified dextran and
intratumouraly injected and delivered using magnets to C3H mammary carcinoma in the leg
of mice. With an applied magnetic field of 50mT, the iron concentration at tumor increased
2.5 fold compared to the control in which no magnets were used for targeting [Jordan 1996].
Second, SPMNPs can be readily conjugated with therapeutic agents and delivered to tumors.
Upon reaching the tumor site, an alternating magnetic field will be applied causing the
particles to be heated, melting the thermosensitive coatings, leaking the drug at the tumor site
and, at the same time, heating the tumor [Chen 2007]. This strategy has a dual effect on
cancer treatment as researchers have shown increased chemotherapy efficacy when combined
with hyperthermia [Wust 2002, Falk 2001, Kapp 2000, Gerner 2000]. Another advantage of
SPMNPs in hyperthermia is that they have an appropriate and specific Curie temperature (T
C
)
(i.e., the temperature above which SPMNPs lose their magnetic properties and, hence, their
coupling with the external magnetic field) that limits the hyperthermia at a predetermined
temperature. For example, PEG-coated copper nickel (Cu/Ni) alloy magnetic nanoparticles
were synthesized to have a Curie temperature in the range of 4346C [Chatterjee 2005]. This
range of Curie temperature of the Cu/Ni magnetic nanoparticles is very desirable in
hyperthermia applications. Once the temperature of the magnetic nanoparticles increases to
above T
C
(from 43-46
o
C in this case), the external magnetic field will stop interacting with
the nanoparticles, therefore, further tissue heating will not occur.
7.3. Magnetic Targeting of SPMNPDrug Conjugates
A clear advantage of using SPMNPs is that they can be directed to tumor sites using an
external magnetic field. Using this method, SPMNPs conjugated with anti-cancer drugs not
only can be delivered specifically to tumors to release therapeutic agents but also the
magnetic field can keep the conjugate localized in the tumor site leading to increased drug
efficiency. For example, investigators have used 100 nm (hydrodynamic diameter) iron oxide
SPMNPs bound to mitoxantrone (that is, an agent used in the treatment of certain types of
cancer including metastasis breast cancer and acute myeloid leukemia) to target squamous
cell carcinoma in rabbits [Alexiou 2000]. A magnetic field of up to 1.7 Tesla was used to
attract SPMNPs to the tumor site. They observed a very high concentration of SPMNPs
within the tumor after intra-arterial infusion. Importantly, this treatment resulted in a
complete and permanent remission of the cancer cells compared with the control group (no
treatment) with no signs of toxicity.
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and Thomas J. Webster 128
In another example, investigators used a ferrofluid (i.e. colloidal solutions of iron oxide
SPMNPs surrounded by anhydroglucose polymers) chemically bound to epirubicin (an
antibiotic drug commonly used in chemotherapy) to treat cancer in animals [Lubbe 1996a].
The conjugating method allowed for a reversible drug-nanoparticle binding that enables drug
desorption under physiological conditions of tumors (such as osmolality, pH, temperature).
Their experiments showed for the first time, high tolerance and efficacy in mice and rats in
which no LD50 (i.e. a dose at which 50% of subjects will die) could be found for the
ferrofluid. This success led to clinical trials in humans. The ferrofluid was directed and
concentrated in the tumor site using permanent magnets that generated a magnetic field of 0.8
T in tumors located near the body surface [Lubbe 1996b]. The investigators showed that the
ferrofluid could be successfully targeted to the tumors in about half of the patients.
7.4. Disadvantages of SPMNPs
In spite of the very exciting properties SPMNPs can offer, there are still several problems
associated with using these nanoparticles in cancer diagnostics and therapeutics especially for
magnetically targeted drug delivery. The first limitation is the use of magnets for attracting
SPMNPs. When dealing with the tumors which have a large distance to possibly position the
magnets, magnetic field strength at the tumor site will not be enough to attract the SPMNPs.
Secondly, occlusion of blood vessels can occur in the target regions as due to high
accumulation of magnetic particles [Timko 2005]. In addition, toxic responses of the body to
the SPMNPs can also limit the application of such particles. All of these potential
disadvantages need to be carefully considered.
8. Polymeric Nanoparticles
Polymers have become increasingly attractive in formulating drug-loaded nanoparticles
for treating cancers due to the tailorability of polymer, biocompatibility and biodegradability
properties, various nanoparticle synthesis methods, versatility of drug loading techniques and
controllable drug release characteristics. In this section, common fabrication methods will be
briefly summarized followed by drug loading techniques to demonstrate how drug release
characteristics of polymeric nanoparticles can be manipulated.
8.1. Polymeric Nanoparticle Preparation Methods
Polymeric nanoparticles can be formulated from either preformed polymers or monomers
by a variety of methods. However, the most popular methods to prepare polymeric
nanoparticles start from biocompatible preformed polymers [Hans 2002].
8.1.1. Emulsification-Solvent Evaporation Method
The polymer is dissolved in an organic solvent first, and then the drug is dissolved into
the polymer solution to create a mixture of drugs dispersed in a polymer solution. The
polymer solution is then added with water and a surfactant to create the emulsion. The
Nanotechnologies for Cancer Diagnostics and Treatment 129
organic solvent is finally evaporated and the polymeric nanoparticles are collected by
centrifugation or lyophilization [Hans 2002, Torche 2000, Suh 1998, Song 1997, Cheng 1998,
Feng 2001]. In this method, both water soluble and water non-soluble drugs can be
incorporated into polymeric nanoparticles, however, hydrophilic drugs have showed a lower
incorporating efficiency [Hans 2002].
8.1.2. EmulsificationDiffusion Method
In this synthesis method, the solvent is chosen as a partially water soluble solvent (e.g.
acetone). The polymer and drug are dissolved in the solvent and emulsified in the aqueous
phase containing the stabilizer. The role of the stabilizer is to prevent emulsion droplets from
aggregating. Then, water is added to the emulsion so that the solvent can diffuse into the
water. The solution is stirred, resulting in the precipitation of nanoparticles which can be
collected by centrifugation [Hans 2002, Kwon 2001, Takeuchi 2001]. The problem with this
method is that water soluble drugs tend to leak out during the diffusion of the solvent [Hans
2002].
8.1.3. Nanoprecipitation Method
In this method, the polymer and drugs are dissolved in solvents (such as acetone to
prepare PLGAs) and followed by dispersing the mixture into a solution containing Pluronic
F68 which is a difunctional block copolymer surfactant terminating in primary hydroxyl
groups, a nonionic surfactant that is 100% active and relatively nontoxic. The solvent is then
evaporated under reduced pressure leaving the nanoparticles remained in the suspension
[Hans 2002].
8.1.4. Salting-Out Process
The principle of salting out process is that solubility of a certain material is affected by
concentration of salt in the solution. For example, proteins are less soluble in the more salty
solution. In salting-out method to prepare polymeric nanoparticles, an emulsion is formed
containing the polymer, acetone, magnesium acetate tetrahydrate, stabilizer, and the drugs
[Hans 2002]. Then, water is added until the volume is sufficient to allow for diffusion of the
acetone into the water, which results in the formation of nanoparticles. One limitation of this
procedure is the incompatibilities of the salts with many bioactive compounds.
As mentioned, the above methods are the most popular techniques to prepare
nanoparticles from biocompatible, preformed polymers (such as poly(lactic-co-glycolic acid)
(PLGA), poly(lactic acid), poly(hexadecylcyanoacrylate, etc.) [Hans 2002]. However,
biodegradable nanoparticles can also be made from monomer polymerization methods
[Sakuma 2001, Behan 2001]. Hydrophilic polysaccharides (like chitosan (CS)) can also be
used to make polymeric nanoparticles by spontaneous ionic gelatin process [Vila 2002, Janes
2001]. This technique is becoming attractive because it does not use harmful organic solvents
and it can formulate particles of small sizes and positive surface potentials [Hans 2002].
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and Thomas J. Webster 130
8.2. Control the Properties of Polymeric Nanoparticles
Along with various methods for forming polymeric nanoparticles is the firm control over
the properties of the nanoparticles [Hans 2002]. First, the type of polymer and its
concentration used in nanoparticle fabrications strongly affect the particle properties. The
molecular weights of polymers can influence the particle size and drug loading capacity,
specifically, smaller nanoparticles can be formulated from lower molecular weight polymers
but also have lower drug encapsulation efficiency in general [Hans 2002]. Higher polymer
concentrations and higher polymer molecular weights lead to higher encapsulation efficiency
and larger sizes of the nanoparticles [Blanco 1997, Song 1997, Kwon 2001]. For example,
Table 2 demonstrates the dependence of bovine serum albumin (BSA) capture efficiency on
molecular weights and concentrations of PLGA (PLGA nanoparticles were prepared by
emulsion-solvent evaporation).
Table 2. Effect of PLGA molecular weight (MW) and concentration on bovine serum
albumin (BSA) incorporation
MW of PLGA
Concentration of
PLGA (%)
Concentration of BSA
(%)
Efficiency of BSA
capture (%)
58000
58000
102000
102000
3.0
6.0
3.0
6.0
10.0
14.0
10.0
14.0
24.8
36.8
68.0
74.8
Adapted with permission from [Songa 1997].
As seen in Table 2, lower concentration of PLGA or lower molecular weight PLGA
resulted in particles that had lower BSA entrapment than those made from higher molecular
weight PLGA or higher PLGA concentration. Figure 10 shows the effect of PLGA
concentrations on the size of PLGA nanoparticles prepared by emulsificationdiffusion
method using poly(vinyl alcohol) (PVA) as a stabilizer [Kwon 2001]. Larger size PLGA
nanoparticles were formed with higher PLGA concentrations.
Second, the type and amount of surfactant/stabilizer are also factors that affect properties
of nanoparticles as well as drug encapsulation characteristics [Hans 2002]. For example,
dipalmitoyl-phosphatidylcholine (DPPC), a phospholipid found in cell membrane, when used
as an emulsifier to synthesis PLGA nanoparticles provided a more dense coating on the
surface of the nanoparticles resulting in a smoother surface than particles made with
traditional emulsifier, PVA [Feng 2001]. The drug loading efficiency of the PLGA
nanoparticles made with DPPC also increased compared to the particles made with PVA
using the emulsification solvent evaporation method. Another example is the case of PLGA
nanoparticle preparations. It was shown that PLGA nanoparticle sizes were smaller when
prepared using didodecyl dimethyl ammonium bromide (DMAB) than those prepared with
PVA [Kwon 2001]. In another study, PLGA nanoparticles were formulated using PVA,
chitosan or PVA-chitosan blend as different stabilizers [Ravi 2004]. It was shown (Figure 11)
in this study that the sizes and morphologies of PLGA nanoparticles were different for
different stabilizers.
Nanotechnologies for Cancer Diagnostics and Treatment 131
Reprinted with permission from [Kwon 2001].
Figure 10. Effect of PLGA concentration on the mean particle size of PLGA nanoparticles (at the
concentration of 2.5 (weigh/volume %) of poly(vinyl alcohol) (PVA)).
Adapted with permission from [Ravi 2004].
Figure 11. Atomic force microscopy images of PLGA nanoparticles: (A) PLGA nanoparticles with
PVA alone as a stabilizer, (B) with chitosan alone, and (C) with a PVA-chitosan blend. Bars represent
150 nm.
Third, the Zeta potential of polymeric nanoparticles can be controlled [Hans 2002]. Zeta
potential is an electric potential that is directly related to, and an indication of, the total charge
of a particle in a solution. Particles with more charges will have larger Zeta potential. Zeta
potential has a strong influence on the stability of nanoparticles. Strong electronic interaction
between charged particles with high Zeta potential (repulsive forces) will result in more stable
particles (leading to less aggregation) and more uniform size distribution. Surface coatings
(such as PEG) can make Zeta potential more negative (meaning, absolute value of Zeta
potential increases), increasing the nanoparticle stability [Vila 2002].
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and Thomas J. Webster 132
8.3. Drug Loading Methods
There are many places and different methods therapeutic drugs can be loaded into
polymeric nanoparticles. The drugs can be dispersed in a polymer matrix, entrapped in a
nanoparticle core, surrounded by a polymer membrane, chemically bond to the polymer, or
physically absorbed onto the particles surface [Hans 2002]. The method of drug loading can
be divided into two classes [Soppimath 2001]: (i) incorporation of the drugs during the
formulation of polymeric nanoparticles and (ii) absorption of the drugs into nanoparticles
after the formulation of the particles. It was shown that the absorption method to load drugs
after forming polymeric nanoparticles has a lower loading efficiency than incorporating the
drugs during the process of forming nanoparticles [Alenso 1991, Ueda 1998].
In the incorporation method (i.e., drug is incorporated during the synthesis of
nanoparticles), several factors can affect drug loading efficiency. The concentration of
monomer and the concentration of drugs can both determine the drug entrapment efficiency.
For example, the drug loading of doxorubicin into poly(butylcyanoacrylate) (PBCA)
nanoparticles was shown to strongly depend on the concentration of doxorubicin [Yang
2000]. Increasing the concentration of doxorubicin from 5% to 20% resulted in a decrease in
the entrapment efficiency from 24.9% to 10.5%.
In the absorption method, the surface properties of nanoparticles (such as hydrophilicity)
have a strong impact on drug loading. These surface properties, in turn, are functions of the
properties of the polymers themselves and the methods used during preparation.
8.4. Drug Release Characteristics and Drug Biodistribution Profiles
Since polymeric nanoparticles can be fabricated from various polymers by many different
methods, the release characteristics of the nanoparticles loaded with drugs can be readily
controlled [Bhojani 2007]. Prolonged release of drugs is desirable and can be achieved by
changing polymer composition of the particles and/or their surface properties [Anderson
1997]. For example, by changing the composition of polymers, the degradation of
nanoparticles varied from days to months [Brigger 2002]. For instance, PLGA nanoparticles
were formulated from PLGA- monomethoxypoly(ethyleneglycol) (mPEG) copolymers of
different compositions (i.e., different PLGA-mPEG molar ratios) and loaded with cisplatin
(that is, a drug used in treatment of various types of cancers, including sarcomas, some
carcinomas and lymphomas) [Avgoustakis 2002]. The composition of the PLGAmPEG
nanoparticles was shown to strongly affect the drug release profile, i.e. the rate of release
increased at higher content of the mPEG in composition. The Zeta potentials and
biodegradability of the PLGA-mPEG particles were also influenced by the content of mPEG
in the copolymer.
Not only does the polymeric composition of the nanoparticle determine the release profile
of the drug, but properties of the drug itself (such as molecular weight, charge, localization in
the nanospheres, drug loading method) can also strongly affect the drug distribution pattern in
the RES [Brigger 2002, Couvreur 1980]. For example, it was also demonstrated that the
incorporation of cytostatic drugs (drugs that stop cancer cells from multiplying in contrast to
cytotoxic drugs that kill cancer cells) into polymeric nanoparticles resulted in a change in the
drug distribution in animal bodies [Brigger 2002]. In one experiment in mice treated with
Nanotechnologies for Cancer Diagnostics and Treatment 133
doxorubicinloaded poly(isohexylcyanoacrylate) (PIHCA) nanoparticles, more doxorubicin
were found in the liver, spleen and lungs, as compared to the controls (i.e., mice treated with
free doxorubicin) [Verdun 1990]. In another experiment, it was demonstrated that when
actinomycin D was adsorbed on poly(methylcyanoacrylate) (PMCA) nanoparticles and
injected to rats, most of the drug was found in the lungs of the rats [Brasseur 1980]. In
contrast, actinomycin D incorporated into a more slowly biodegradable
poly(ethylcyanoacrylate) (PECA) nanoparticles, the drug was found mainly in the small
intestine of rats [Couvreur 1980]. Even with the same PECA nanoparticles, when other drug
(vinblastine, an anti-cancer drug used to treat several kinds of cancer such as Hodgkin's
lymphoma, non-small cell lung cancer, breast cancer and testicular cancer) was loaded, the
drug highly concentrated in the spleen of rats [Couvreur 1980].
8.5. Disadvantages of Polymeric Nanoparticles
Although polymeric nanoparticles have many advantages (such as various fabrication
methods, versatile drug loading and drug release methods), they still have some drawbacks.
The main limitation is that some preparation methods use toxic organic solvents that could
degrade certain drugs when they come into contact during the formulation process or could be
toxic to the environment as well as to the physiological system [Birnbaum 2000]. Other
disadvantages include poor drug encapsulation for certain hydrophilic drugs and the possible
drug leakage before reaching its target tissues and/or cells.
9. The Use of Selenium Nanoclusters as Anti-cancer Coatings for
Orthopedic Applications
9.1. Selenium as a Chemopreventive Agent
Natural materials, most notably, selenium are also being used to fight cancer. Selenium
belongs to the group of metalloids, which are neither fully metals nor non-metals but share
characteristics of both [Styblo 2001]. Selenium is naturally found in humans and animals and
selenoproteins are important in antioxidant defense systems, thyroid hormone metabolism and
redox control of cell reactions [McDowell 2003]. Animal studies have shown that selenium
intake in excess of the nutritional requirements can inhibit and/or retard carcinogenesis
[Combs 1986]. Moreover, studies have shown that people in areas of low soil selenium
(bellow 0.05 ppm) and people with decreased plasma selenium levels (bellow 128 ng/ml)
have higher cancer incidence and/or cancer mortality rates [Combs 1998, Clark 1991]. High
levels of selenium in the blood (up to 112 g/ml) have been correlated with reduced numbers
of cancers including pancreatic, gastric, lung, nasopharyngeal, breast, uterine, respiratory,
digestive, hematological and gynecological [Navarro-Alarcon 2000]. Clinical trials showed
lower incidences of total non-skin cancer, cancers of the lung, colon-rectum cancer, and
prostate cancer, as well as lower overall cancer mortality rates when a daily oral supplement
of selenium-enriched yeast (200 g selenium/day) was followed [Combs 1998]. The strongest
evidence for the effect of selenium in reducing cancers was shown for lung cancer (46%
lower incidence) [Clark 1996], esophageal and gastric-cardiac cancers [Wei 2004] and
Phong Tran

and Thomas J. Webster 134
especially prostate cancer (63% lower incidence) [Clark 1998, Rayman 2007]. The
mechanisms of selenium-based chemoprevention are complex and incompletely understood
[Combs 2001].
9.2. Selenium Nanoclusters as a Promising Anticancer Coating Material for
Orthopedic Implants
9.2.1. Method of Coating Selenium Nanoclusters on Orthopedic Implants
The colloidal synthesis of selenium nano-particles is known and yields stable dispersions
of free nano-particles in the presence of surface stabilizing agents [Kopeikin 2003, Lin 2005,
Wang 2005]. These nano-particle suspensions have also been proven to have anti-cancer
properties [Wang 2005]. In a previous study, nano-rough selenium was made by chemical
etching from selenium compacts [Perla 2005, Tran 2008]. This mode of selenium addition,
however, can limit the mechanical properties of the implant. Moreover, this methodology
does not give control over the release and the dose of selenium. Considering that selenium is
toxic at high doses [Whanger 1996], stability and control over its release would be a very
desirable attribute. In the meantime, currently used orthopedic materials (such as titanium,
stainless steel, etc.), on the one hand, show good mechanical properties to serve as bone graft
materials, but, on the other hand, do not posses any inherent mechanisms to protect cancer
from reoccurring. Therefore, it is may be a good idea to coat selenium nanoparticles on the
current orthopedic material substrates. To achieve this, colloidal synthesis of selenium
Figure 12. SEM images of titanium substrates: (A) Pure Ti (denoted pTi in later figures); (B) Titanium
with low Se coverage level (denoted Low-nSe-Ti in later figures); (C) Titanium with medium Se
coverage level (denoted Medium-nSe-Ti in later figures) and (D) Titanium with high Se coverage level
(denoted High-nSe-Ti in later figures).
Nanotechnologies for Cancer Diagnostics and Treatment 135
Figure 13. SEM images of stainless steel (SS) substrates: (A) Pure SS (denoted pSS in later figures);
(B) Substrate with low Se coverage level (denoted Low-nSe-SS in later figures); (C) Substrate with
medium Se coverage level (denoted Medium-nSe-SS in later figures) and (D) Substrate with high Se
coverage level (denote High-nSe-SS in later figures). Bars = 1m.
nanoparticles [Painter 1941, Ganther 1968] was carried out in the presence of common
orthopedic metals: titanium and stainless steel. Briefly, the cleaned and sterilized substrates
(that is, titanium and stainless steel) were placed in a beaker with the sides to be decorated
facing upward. The reduced glutathione solution was added to the beaker followed by the
sodium selenite solution. Different solution concentrations were used to achieve different
doses. After a gentle mixing of the solutions in the reaction beaker, 1M NaOH was introduced
to bring the pH into the alkaline regime in which selenium nanoparticles were released from
the solution creating selenium nanoclusters formed on the substrates.
Scanning electron microscopy (SEM) images of the titanium and stainless steel before
and after coating showed selenium nanoclusters formed on the surfaces of substrates as seen
in Figures 12 and 13. Different coating densities were also achieved by varying the
concentration of synthesis solutions.
9.2.2. Surface Characteristics of the Titanium Substrates Coated with Selenium
Nanoclusters
In order to determine the state of selenium on the substrates, X ray photoelectron
spectroscopy (XPS) was employed and the results (Figures 14 and 15) showed that selenium
present on the titanium substrates is elemental selenium. This is important since this form of
selenium (elemental) is believed to have the least toxicity among selenium and selenium
compounds.
Phong Tran

and Thomas J. Webster 136
Figure 14. XPS profiles of (A) pTi; (B) Low-nSe-Ti; (C) Medium-nSe-Ti and (D) High-nSe-Ti. The
heights and numbers of peaks indicate relative amounts of selenium.
Figure 15. Peak at 55.2 eV indicates elemental state of selenium on the titanium substrates.
XPS data (Figure 14) also quantitatively confirmed the increasing amounts of selenium
on titanium substrates as expected from increasing selenium concentrations in the synthesis
solutions.
Nanotechnologies for Cancer Diagnostics and Treatment 137
9.2.3. Enhanced Non-Cancerous Osteoblast (Bone-Forming Cells) and Inhibited
Cancerous Osteoblast Densities on Substrates Coated with Selenium
Nanoclusters
Nanomaterials have been shown to increase healthy bone tissue growth [Webster 1999,
Webster 2000a, Webster 2000b, Webster 2004, Khang 2007]. For example, increased non-
cancerous osteoblast functions (from adhesion to proliferation and calcium containing mineral
deposition) were demonstrated on nanostructured ceramic (such as alumina or titania) and
metal (such as titanium, titanium alloys) surfaces compared to microstructured, nano-smooth
surfaces [Webster 1999, Webster 2000a, Webster 2000b Webster 2001, Webster 2004, Perla
2005]. The mechanism of this increase is believed to be the increase in initial absorption of
proteins that mediate subsequent osteoblast functions (such as fibronectin and vitronectin)
[Webster 2000a, Webster 2001, Khang 2007].
A similar trend was observed for the titanium substrates coated with selenium (Figure
16). In particular, non-cancerous osteoblast densities increased on the coated titanium
substrates after one day of in vitro culture compared to the uncoated titanium substrates.
Although more investigation is needed, the nanofeatures of selenium nanoclusters are
hypothesized to increase non-cancerous osteoblast cell densities.
Figure 16. Healthy osteoblast densities after four hours ( ) and one day ( ). Increased
osteoblast densities on selenium coated titanium substrates after one day of culture. Data = mean
SEM; N=3, * p<0.05, ** p<0.1 compared to pTi. (Compared at the same time period).
Importantly, after 3 days of culture, cancerous osteoblast densities on both titanium and
stainless steel substrates coated with the highest amount of selenium were significantly
reduced in comparison to all other substrates of the same type (Figure 17 and 18).
Phong Tran

and Thomas J. Webster 138
Figure 17. Cancerous osteoblast densities decreased on selenium coated stainless steel substrates
compared to the uncoated substrates. Data = mean +/- SEM. N=3. * p <0.01 compared to pSS.
Figure 18. Decreased cancerous osteoblast densities on selenium coated titanium substrates compared
to the uncoated substrates. Data = mean +/- SEM. N=3. * p<0.01.
Selenium has been shown to have anti-cancer properties in the form of selenium
compounds such as sodium selenite, selenium-sethylselenocysteine but not in the form of
elemental selenium [Ip 1998]. It was also believed that elemental selenium has the least toxic
properties than other compound forms of selenium [Ip 1998]. The above results showed, for
the first time, that elemental selenium inhibited cancer osteoblast growth in vitro. The
Nanotechnologies for Cancer Diagnostics and Treatment 139
mechanisms of cancer-inhibiting properties of elemental selenium remain not fully
understood and are still under active investigation.
In the first step toward studying the mechanism of cancer-inhibiting properties of the
selenium nanoclusters, the titanium substrates coated with selenium nanoclusters were
immersed in cell culture media without the addition of serum for three days. The media was
exchanged after 2 days and the spent media collected for graphite furnace atomic absorption
spectroscopy (AAS). A dose dependent release of selenium from the substrates to the cell
culture medium was observed as shown in Figure 19.
Figure 19. Total selenium released into cell culture media ( ) after 2 days and ( ) after 3 days.
Data = mean SEM; N=3, * p<0.0001 compared to High-nSe-Ti. (Compared at same time period);
p<0.0001 compared to Low-nSe-Ti. (Compared at same time period).
More interestingly, approximately 5.6% of the total selenium (estimated using SEM
images) was released from the titanium coated with highest amount of selenium after 2 days.
The release then slowed greatly, with a negligible selenium release occurring on the third day.
Importantly, the concentration of selenium released into the culture media was much less than
the concentration of 3-5 ppm that was demonstrated to show chemopreventive properties [Ip
1998]. Therefore, it was hypothesized that the attached cells experienced much higher
selenium concentration in the vicinity of the coated surfaces.
In a summary, studies on the fabrication and applications of selenium nanoclusters coated
on orthopedic implant materials have yielded some preliminary results which showed
anticancer properties of elemental selenium nanoclusters. More intensive research is
underway to further study this promising material for a wide range of anticancer applications.
Phong Tran

and Thomas J. Webster 140
10. Conclusions
Over the last decade, a lot of effort has been focused on finding more sensitive diagnostic
techniques, more targeted delivery methods as well as more effective therapeutic agents.
Some advances have been used in the clinics but most of them are still under developmental
stages. The ultimate goal is to lengthen the life of cancer patients by developing the tools that
can detect cancer in early stages and treat them efficiently while keeping side effects minimal.
There is undoubtedly a lot more that needs to be studied and improved in order to use even
just some of the above-mentioned nanoparticles in a clinical setting. Understanding the
advantages and disadvantages of each type of nanoparticle, researchers are focusing on
making them more targeted and less harmful to healthy tissues while still delivering efficient
therapeutic agents and imaging capabilities.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 151-236 2010 Nova Science Publishers, Inc.
Chapter 5
MECHANICAL CHARACTERIZATION
AT NANOMETRIC SCALE OF CERAMIC
SUPERCONDUCTOR COMPOSITES
J.J. Roa
1
, X.G. Capdevila and M. Segarra
Departamento de Ciencia de los Materiales e Ingeniera Metalrgica
Facultad de Qumica, Universidad de Barcelona,
C/ Mart i Franqus, 1; 08028, Barcelona, Spain
Abstract
The nanoindentation or indenter testing technique (ITT) is a functional and fast technique that
can give us a lot of information about the mechanical properties of different materials at
nanometric scale, from soft materials, such as copper, to brittle materials, such as ceramics.
The principle of the technique is the evaluation of the response of a material to an applied
load. In a composite material, if the size of the residual imprint resulting from a certain load is
lower than the size of the studied phase, then is possible to determine its mechanical
properties, and therefore its contribution to the global mechanical properties of the composite.
Depending on the tipped indenter used, different equations should be applied to study the
response of the material and calculate stress-strain curves and parameters such as hardness,
Youngs modulus, toughness, yield strength and shear stress. These equations are related to
the different deformation mechanisms (elastic, plastic or elastoplastic) that the material
undergoes.
In the case of most of the ceramic composites, when a spherical tipped nanoindenter is
used, elastic deformation takes place, and Hertz equations can be used to calculate the yield
stress, shear stress and the strain-stress curves. On the other hand, when a Berckovich indenter
is used, plastic deformation takes place, then Oliver and Pahrr equations must be applied to
evaluate the hardness, Youngs modulus and toughness. Nevertheless, in the hardness study,
Indentation Size Effect (ISE) must be considered.
In this work, the mechanical properties of a ceramic superconductor material have been
studied. YBa
2
Cu
3
O
7-
(YBCO or Y-123) textured by Bridgman and Top Seeding Melt Growth
(TSMG) techniques have been obtained and their mechanical properties studied by ITT. This
material presents a phase transition from tetragonal to orthorhombic that promotes a change in

1
E-mail address: joanjosep_roa@ub.edu.
J.J. Roa, X.G. Capdevila and M. Segarra 152
its electrical properties, from insulating to superconductor, and that can be achieved by
partially oxygenating the material. On the other hand, the structure of the textured material is
heterogeneous, and two different phases are present: a Y-123 as a matrix and Y
2
BaCuO
5
(Y-
211) spherical inclusions. Moreover, the texture process induces an anisotropic structure, thus
being the ab planes the ones that transport the superconductor properties while the c axis
remains insulating.
The purpose of this study is the characterization of the mechanical properties, in elastic
and plastic range, of orthorhombic phases of YBCO samples textured by Bridgman and
TSMG technique. With the ITT technique, the oxygenation process can be followed and its
kinetics established.
1. Introduction
High Temperature Superconducting (HTSC) materials can be use in a wide range of
applications:
I) related to energy storage as flywheels,
II) current transport devices as cables or fault current limiters,
III) magnetic field related applications as squids, etc.
The magnetic properties of such materials are well known but the structural or
mechanical properties that will allow the construction of real devices are not still completely
described.
The purpose of this work is to determine this set of parameters and characterize the
material behaviour under determined stress conditions. This study will help us to define the
optimal dimension of the material pieces in order to resist the stress suffered during its
operating life.
1.1. High-Temperature Superconductors (HTSC)
Since about 1962 it has become universally recognized that there exists a whole new
class of superconductors, type II, which are characterized by the fact that they exhibit a new
type of reversible magnetic behaviour. This discovery has made it possible to understand
many of the previously unexplained superconducting properties of a number of elements and
alloys. Furthermore, it has led to the recognition of the existence of a new thermodynamic
state, the mixed state, which is only shown by type II superconductors. In addition to their
intrinsic scientific interest they have a technological importance: niobium-zirconium alloys
and the compound Nb
3
Sn have been used in the construction of superconducting solenoids
capable of producing steady fields of 50 or 100 kOe.
In 1986 Bednoz and Muller [1 and 2], discovered a new type of superconducting
materials, now known as high temperature superconductors (HTSCs), which drastically
improved the superconducting transition temperature (T
c
).
Further, YBa
2
Cu
3
O
7-
(YBCO or Y-123) was discovered by a group of researchers at the
University of Houston in 1987 [3]. The T
c
of YBCO material exceeded the boiling point of
liquid nitrogen (92 K vs. 77 K). As a consequence, the superconducting products were
expected to be operable using liquid nitrogen, which is cheaper and easier to handle than
Mechanical Characterization at Nanometric Scale 153
Helium; this is one of the most important advantages of HTSCs [4]. Moreover, the next year
new superconducting materials were discovered in the Bi (Pb)-Sr-Ca-Cu-O system [5] with a
T
c
of 110 K and in the Tl-Ba-Ca-Cu-O system [6] with a T
c
of 125 K. In 1993
HgBa
2
Ca
2
Cu
3
O
9
, with a T
c
of 134 K was discovered [7], and at present, T
c
has reached 164
K, under high pressure [8].
HTSC materials present structural features of ionic crystals. They contain CuO
2
planes in
their crystal structure. The layers between the CuO
2
planes are called the charge reservoir
layers. Features of the crystal structure of HTSCs include the following:
a) Crystal structure is layered and the CuO
2
layer and charge reservoir layer are stacked
periodically.
b) The parent material is the antiferromagnetic insulator. By doping electrons or holes
to the CuO
2
plane from the charge reservoir layer, the CuO
2
plane becomes metallic
and the superconductivity appears.
c) At least one CuO
2
plane, where the superconductivity current flows, must be
included in the unit cell.
d) When the superconductivity appears, the number of oxigens in the CuO
2
plane for
the number of copper ions is 0.15 to 0.20, and then the effect of the
antiferromagnetism is strongly exhibited.
The crystal structure, space group, and lattice constants of YBCO HTSC are summarized
in Table 1.
Table 1. Crystal data of YBCO HTSC [9]
Material Crystal Structure a (nm) b (nm) c (nm) Space Group
YBa
2
Cu
3
O
7-
(YBCO or Y-123)
Orthorhombic 0.38177 0.38836 1.16827 Pmmm
HTSC have unique features such as a high upper critical field, high anisotropy, and an
extremely short coherence length, , in addition to the T
c
being very high. The physical
properties of YBCO are shown in Table 2.
Melt and growth processes for producing Y-123 superconductive oxide [10, 11 and 12]
are considered to be an effective process to obtain high critical current densities. Many
investigations 13, 14 and 15] were performed to clarify the growth mechanism of Y-123
crystal from the partial molten state where Y
2
BaCuO
5
(Y-211) and liquid phase coexist.
Recently, it was found that the peritectic reaction of the Y-123 phase formation proceeded by
the solute diffusion between Y-211 particles dispersed in the liquid phase and the growing Y-
123 interface and 16]. The growth models proposed assuming the mass transfer limiting were
suggested, and the growth rate was found to be affected by an interface undercooling as the
driving force for solute diffusion, [17 and 18]. Therefore, the undercooling is a principle
parameter in controlling the growth of Y-123 single crystals.
The inclusion of Y-211 particles has several advantages to the growth and properties of
bulk YBCO superconductors:
a) Preventing the liquid flow so as to decrease the amounts of holes.
J.J. Roa, X.G. Capdevila and M. Segarra 154
b) Shorten space between the Y-211 particles to help growing the Y-123 crystal as well
as creating more Y-123/Y-211 boundaries which are the effective flux pinning site.
c) Volume fraction of Y-211 particles is approximately constant; the current density, J
c
,
value is an inverse measure of the mean size of Y-211 phase [19 and 20]. High
critical current density values can be achieved by controlling volume fraction and
particle size of the Y-211 phase.
Table 2. Physical Properties of YBCO
Material name YBCO or Y-123
Critical temperature, T
c
(K) 92
674 (//ab)
Upper critical field,
B
c2
(at 0K) [T]
122 (//c)
0.025 (//ab)
Lower critical field,
B
c1
(at 0K) [T]
0.085 (//c)
Carrier concentration n [cm
-3
] 1.510
22
1.15 (//ab)
Coherence length,

GL
(at 0K) [nm]
0.15 (//c)
142 (//ab)
Penetration depth,
(at 0K) [nm]
>700 (//c)
Recent studies of YBCO materials pointed to two major issues: creating pinning centers
and eliminating weak-lines between grain boundaries. It has been reported that some defects
may act as pinning centers. Pinning strength and critical current density were increased by the
introduction of fine Y-211 inclusions [21 and 22]. Flux pinning may be effective by two
ways: first, the defects around the Y-211/Y-123 boundary, such as dislocations or stacking
faults, and second, the magnetic pinning caused by the different induction generated in Y-123
superconducting matrix and Y-211 non-superconducting phase [23]. However, the weak-link
can be caused by impurity phases, micro-cracks, or high-angle misalignment of the crystals
[24].
Figure 1 shows the phseudoternary phase diagram of YO
1.5
-BaO-CuO system at 900C
and oxygen partial pressure of 0.21 atm.]. There are four types of quaternary compounds
YBa
2
Cu
3
O
7
(Y-123), Y
2
BaCuO
5
(Y-211), Y
2
Ba
8
Cu
6
O
18
(Y-143), YBa
6
Cu
3
O
11
(Y-163) - and
five types of ternary compounds Y
2
BaO
4
(Y-210), Y
3
Ba
3
O
9
(Y-340), Ba
2
CuO
3
(Y-021),
BaCuO
2
(Y-011), and Y
2
Cu
2
O
5
(Y-101).
Figure 2, shows the vertical cross-sectional diagram including Y-123 and Y-211
compounds]. The Y-123 phase is produced by the following ternary peritectic reaction at
1010 C:
L+Y-211+Y-143 Y-123 (1)
Mechanical Characterization at Nanometric Scale 155
Figure 1. Phseudoternary phase diagram of YO1.5-BaO-CuO system at 900C and oxygen partial pressure
of 0.21 atm (From Chemical Processing of Ceramics, Second Edition, edited by Burtrand Lee, Sridhar
komarneni; Chapter 23. Synthesis and Processing of High-Temperature Superconductors, page 604).
BaO:YO
1.5
1:5
BaO:CuO

3:5
mol% YO
1.5
Figure 2. Vertical cross-sectional diagram including Y-123 and Y-211 compounds in pseudoternary
phase diagram (From Chemical Processing of Ceramics, Second Edition, edited by Burtrand Lee,
Sridhar komarneni; Chapter 23. Synthesis and Processing of High-Temperature Superconductors, page
604).
J.J. Roa, X.G. Capdevila and M. Segarra 156
The peritectic transformation of Y-211 + L Y-123 proceeds with the solute diffusion
through liquid between Y-211 particles and Y-123 interface, and the undercooling acts as a
driving force of the diffusion and]. All texturing techniques make use of the peritectic
reaction where Y-123 phase grows from the Ba- and Cu-rich liquid (BaCuO
2
+ CuO) and the
solid Y-211 phase [25]. From the viewpoint of solute diffusion, the large amount of Y-211
phase can supply more yttrium solute to the growing interface. During heating, the YBCO
bulk to a high temperature, CuO reacts with Y-123 to form Y-211 and liquid.
CuO + Y-123 Y-211 + L (2)
The solidification temperature of the liquid is lower than that of the peritectic liquid.
Thus no Y-123 grain nucleates at the sample surfaces.
Another way to prevent the surface nucleation is to coat the bulk surface with CeO
2
powder. CeO
2
was reported to react with barium of the Y-123 phase to form BaCeO
3
[26] and
the reaction is given by:
CeO
2
+ Y-123 BaCeO
3
+ Y-211 + CuO (3)
As by-products, CuO and Y-211 form. The CuO reacts with Y-211 to produce lower
melting point liquid in the same manner as the CuO addition, and hence surface nucleation is
suppressed.
The peritectic growth of Y-123 phase at typically low growth rates, coupled with the
relatively large amount of highly reactive and viscous liquid phase generated during peritectic
decomposition, makes it difficult to support bulk samples processed by directional
solidification [27].
Melt processing technique of (RE)BCO generally involves slow solidification of a Y-211
and a Ba-Cu-O liquid phase mixture typically between 30 and 40 C below the T
p
.
A crystal that grows with faceted interfaces such as Y-123 crystal needs the driving force
of interface kinetics for growth; i.e., it needs the saturation. The saturation or the
undercooling kinetics, , can be re-written as:
( )
123 ,
123 ,

=
Y L
Y L i
C
C C
(4)
where C
i
and C
L,Y-123
are the Y-123 concentration in the growth interface and in the liquid,
respectively.
The kinetic undercooling, is the difference between the chemical potential of a crystal
and its surroundings. This concept is schematically shown in Figure 3.
The growth of atomically flat face takes place by a step flow mechanism, the so-called lateral
growth. Some probable mechanisms are schematically shown in Figure 4. The Y-211 particle
is the yttrium source for Y-123 growth, and the yttrium concentration near the particle is
higher than that near the Y-123 (Figure 3). This higher concentration near the Y-211 particle
causes the concentration on the growing interface to be higher by approaching close to the
interface and promotes the two-dimensional nucleation (Figure 4.a). The boundary between
the Y-124 crystal and the Y-211 particle on the growing interface can act as the
heterogeneous two-dimensional nucleation sites (Figure 4.b), and the entrapment of Y-211
Mechanical Characterization at Nanometric Scale 157
particle may field the misfit dislocations behind it (Figure 4.c). These nucleations and/or
dislocations act as the step sources. These sites may become dominant when more Y-211
particles are entrapped. Therefore, the undercooling dependence of growth rate of the sample
with excess Y-211 phase becomes linear.
a)
b)
Figure 3. Schematic ilustration of (a) the yttrium concentration profile between the Y-211 particle and
the Y-123 interface, and (b) the phase diagram showing the relation between the concentrations and the
undercoolings (From Nakamura et al., J. Mater. Res., Vol.11, No. 5, May 1996).

a)
c)
b)
Y-211
Y-211
Y-211
Y-123
Y-123
Y-123
Figure 4. Schematic illustration showing some possible step sources on the Y-123 interface. a) A two-
dimensional nucleation resulting from higher concentration with approaching Y-211 close to the
interface. b) Heterogeneous nucleation at the Y-211/Y-123 interface and c) A misfit dislocation caused
by the entrapment of Y-211 particle. (From Nakamura et al., J. Mater. Res., Vol.11, No. 5, May 1996).
J.J. Roa, X.G. Capdevila and M. Segarra 158
1.1.1. Solidification and Microstructure of YBCO Bulk Materials
Fabrication of single crystals usually involves the building of a structure, adding atoms
layer by layer. Techniques to produce large monodomains included slowly dragging a
rotating seed out of a molten bath of feeder material (as in Crochralski process and the
Bridgman technique).
Previously to the thermal treatment, we must to have a perform with shape and
dimensions close to the final ones. These green bodies are achieved after pressing and
sintering stages. The application of pressure varies within methods. It could be in uniaxial
form or with an isostatic pressure field, etc. By the other hand, the sintering step could be
realised previous to texturing process, such in the Bridgman technique or included in it, such
in the TSMG method.
Melt processing has been shown to be a suitable technique for the fabrication of bulk
YBCO high-temperature superconductors with good flux pinning properties and high critical
current densities [28, 29 and 30]. Several variations of melt texturing technique under a
variety of names] have been developed based on this principle with a view to improving
either features of the melt process or the quality of the product bulk material. The bulk
textured material can be produced using the top-seeded Melt-Growth (TSMG) technique and
the Bridgman technique with the purpose to obtain single crystals or monodomains. A
monodomain can be described as a monocrystal (no grain boundaries) with numerous defects
like secondary phases and mosaicity. Details on the texturation process can be found
elsewhere [31]. The final microstructure in both techniques shows a homogeneous
distribution of Y-211 particles in the textured Y-123 matrix. It is well-known that the Y-211
inclusions play an important role for the pinning of vortices].
Top-Seeded Melt-Growth (TSMG) Technique
Top-seeded melt growth (TSMG) is known as the most effective process to fabricate
block-type simples used for example in energy storage application, such a superconducting
flywheel system, and others. In this technique, too long isothermal step and so great
processing times is regarded as one of the most significant weak points. In the case of melt
texturing with a temperature gradient, processing time is shorter, but the sample shape and
size are restricted.
The TSMG technique has been widely used to grow YBa
2
Cu
3
O
X
crystals as large as
several centimeters [32], but these crystals were intended for applications such as magnetic
levitation. The size of single-domain is generally about several centimeters in diameter, and
limited to 10 cm for high quality YBCO bulk up to now, because of the grains mis-orientation
during the melt growth process [33]. The resulting cubic centimeter-size YBCO crystals are
further annealed to obtain the oxygen-ordered orthorombic phase (x = 6.5).
Uniquely, the TSMG process yield large, single grains of approximately the dimensions
of the green body [34, 35 and 36]. The TSMG technique has become the preferred method for
the fabrication of bulk (RE)BCO superconductors and is used routinely in the processing of
single-grain cylindrical/square shape samples of up to 50 mm in diameter [37].
TSMG processing is classified into two types by seeding method; cold seeding and hot
seeding. Cold and hot seeding are named for the moment when the seed crystal is placed on
the powder compact. In handling the sample, the cold seeding method is easier than hot
Mechanical Characterization at Nanometric Scale 159
seeding, because the seeding is performed at room temperature [38]. In this study the seeding
method used is cold seeding.
In order to obtain large-domain-sized YBCO and to control the growth orientation,
seeding effects should be taken into consideration sufficiently [39]. The seed should not only
have a similar structure and lattice constant to those of as-grown YBCO bulks, but also
control the orientation and ensure single-domain growth [40]. The seed crystal initiates the
nucleation and growth of the Y-123 phase in the incongruent melt, which subsequently
solidifies into a single grain during controlled cooling.
A variety of seed have so far been applied for the melt-textured (MT) growth of YBCO
bulks], which can be classified into three major categories:
Non-superconductors, such as MgO.
Bulk superconductors, such as RE123 MT bulks or single crystal, such as Nd-123,
Sm-123, and others.
RE123 thin films [41].
In principle, the seed materials should not melt during the texture process, because the
maximum process temperature is below their melting points. But the seed crystals were
observed to dissolve frequently when they were in contact with the Ba-Cu-O liquid that was
formed as a result of the incongruent melting of Y-123 compact during a high temperature
holding period [42]. As the seed dissolve during processing, it no longer acts as a seed. In the
case of dissolution formed, decreasing the levitation force and trapped magnetic field by
reducing the size of the shield current loop. For this reason, the growth mode of YBCO grains
is significantly dependent on seed thickness [43].
To obtain the green bodies, the well-mixed powder fabricated by Alcohol polyvinyl
method (PVA method) with 1 wt. % CeO
2
, was uniaxially pressed into pellets with a diameter
of 25 mm and thickness of 10-20 mm [44]. Stoichiometric quantities of the oxides and
carbonates are weighted to give 69% w/w Y-123, 30 %w/w Y-211 and 1% w/w CeO
2
. This
proportion has been demonstrated to maximize critical current density [45]. The NdBa
2
Cu
3
O
7
(NdBCO or Nd-123) single crystals were manufactured with the Bridgman technique] with a
temperature gradient 1-4 C/m in vertical direction. The (001) Nd-123 was placed on the top
of sample. The Y-123 crystal grew from the Nd-123 seed crystal epitaxially with a squared
sharp interface. The growth distance was defined as the length from the edge of the seed
crystal to the solid-liquid interface. Figure 5 shows the heat treatment pattern followed in this
study. The optimization of the temperature profile is crucial for the production of large-
single-domain YBCO monoliths. The TSMG YBCO samples were fabricated by the
following process: The YBCO samples were heated up to 1055C at a rate of 300 C/h, and
held for 2 h for homogenous melting. After that, the samples were cooled to about 1010 C at
a rate of 30 C/h, and further cooled to 1008 C at a rate of about 0.02 C/h. Then the samples
were cooled to room temperature at a rate of 300 C/h. Figure 6 shows YBCO samples with
tetragonal structure obtained with the thermal treatment explained over (figure a, shows a
single crystal and b, shows a poly-crystal). Finally, the as-grown samples were annealed at
450C for 300 h (In this step occurs the transformation from tetragonal to orthorhombic
phase).
J.J. Roa, X.G. Capdevila and M. Segarra 160

Oxigenation process Texture process
Time, h
T
e
m
p
e
r
a
t
u
r
e
,

C

Y-211 + L
T
Nucleation
= 1010C
T
f,Nucleation
= 1008 C
T
T
Oxigenation
= 450C
Figure 5. Heat pattern of the experimental procedure in the manufacture of YBCO samples by TSMG
technique.
To define the degree of undercooling, the equilibrium peritectic temperature of Y-123
phase is needed. The temperature has been reported to be 1010 10C by many researchers].
a)
1 cm
b)
1 cm
Figure 6. Photograph of the top view of the typical seeded grown sample, a) Single crystal and b) poly-
single-crystal.
During the oxygenation process, cracks in the (a,b) planes appeared as a major drawback
for the c-axis elements. The occurrence and propagation of cracks was found to be directly
related to the oxygenation of the material. The oxygen uptake results in a decrease of the cell
unit in the c-direction. The low oxygen diffusion rate yields large oxygen gradient during a
Mechanical Characterization at Nanometric Scale 161
classical annealing treatment. The cracks are then an easy diffusion path and the shrinkage of
the unit cell along the c-axis at the crack tip provides the driving force for the cracks
propagation.
Ceramic superconductors exhibit an extensive defect zonology ranging from point-like
defects of various natures, such as chain oxygen vacancies or anisette defects in some RE
substituted 123 compounds, to a variety of extended defects. In addition, 123 compounds
typically display ferroelectric transition which takes place well above room temperature and
results in extensive twin formation. Dislocations, as well as their dissociated configurations
are confined onto a prominent glide plane (001), although dislocation lines out of this plane
may be frequently found building grain boundaries or as non-assembled segments that have
climbed out the glide plane. This high anisotropy of dislocation configurations is consistent
with the anisotropy of the crystal structure, the prominent glide plane corresponding to the
largest lattice spacing.
The melt processed ceramic composites contain a dense population of fine peritectic
(non-reacted) particles, which drastically affects the microstructure acting as nucleation sites
for dislocations and stacking faults as well as microcrak stoppers thus enhancing the
mechanical toughness of the composite [46].
For TSMG techniques, under isostatic pressing conditions, plastic deformation is only
possible if there is some kind of anisotropy in the material. In melt textured Y-123
composites, two kinds of anisotropy exist: elastic anisotropy [47] in the matrix; and plastic
anisotropy between the peritectic inclusions and the matrix [48].
The main microstructural features are shown in figure 7a. The two dark areas in the left
side and the upper right corner are Y-211 peritectic inclusions. Several dislocations oriented
along (001) appear attached to the left hand side inclusions. It can be observed that the lower
dislocations (indicated by A) is decorated with stacking faults appearing at every other twin
domain. Similarly, stacking faults associated to the Y-211 particle located at the upper right
corner of the micrograph (indicated by B) are observed to expend selectively on one twin
domain. This distinction is only relevant to the orthorhombic lattice. Figures 7b and 7c are
schematic drawings of the basic mechanism associated to the observed microstructural
modifications.
Another way to obtain green bodies used for TSMG is High Oxygen Pressure Processing.
In this case, TEM observations have revealed a strong increase in the density of stacking
faults nucleated at the interface of the Y-211 particles. Typical observations are presented in
Figure 8a and 8b. The main distinguish features is the development of dendritic-like
morphologies of the stacking faults.
Bridgman Technique
The Bridgman technique is a method single crystal ingots or boules. It is a popular
method of producing certain semiconductor crystals, such as gallium arsenide, II-V Crystals
(ZnSe, CdS, CdTe) and BGO, where the Crochralski process is more difficult.
The method involves heating polycrystalline material in a container above its melting
point and slowly cooling it from one end where a seed crystal is located. Single crystal
material is progressively formed along the length of the container. The process can be carried
out in a horizontal or vertical geometry.
J.J. Roa, X.G. Capdevila and M. Segarra 162
In this study a modified Bridgman technique have been used. In this case, the sample was
introduced into the furnace at one determined thermal gradient and a external
Superconducting YBCO bars were prepared by a modified Bridgman process. After
heating the presintered YBCO bars well above the peritectic temperature, T
p
, the semisolid
bars were displaced at a constant rate of 1 or 2 mmh
-1
through a region having an axial
temperature gradient of 20 Kcm
-1
at T
p
until the full length of the bars was cooled down to
900C. Details of the sample preparation are given in [49]. The thermal treatment can be
observed in figure 9.

a)
b)
c)
Figure 7. a) TEM micrograph close to the (001)plane of a Y-123 sample submitted to CIP, showing the
selective expansion of stacking faults in a particular twin variant. Dislocation loops are indicated by
arrows. The selective dissociation of a <100> dislocation is one twin variant is indicated by A.
Selective reorganization of a partial loop orientated at the interface of a Y-211 particle is indicated by
B, b) Schematic drawing of the reorganization of a partial loop driven by CuO fluxes from twin variant
2 to twin variant 1 as indicated by arrows, and c) Interaction of a gliding perfect <100> dislocations
with a <E1-6><031> partial loop and resulting selective dissociation in twin variant 1. (From
Sandiumenge et al., Advanced Materials, 12, No.5, 2000)
Mechanical Characterization at Nanometric Scale 163

a)
b)
Y-211
Figure 8. a) Typical TEM image of dendritic-like stacking faults generated at the interface of Y-211
particles. Imaging conditions are such that the stacking faults appear dark in order to emphasize their
irregular shape. b) Enlarge view where the stacking fault contrast is avoided showing the high density
of partial dislocation associated to the Y-211 interface (From Puig et al., Applied Physics Letters, Vol.
75, No. 13, 1999, 1952-1954).
Time, h
T
e
m
p
e
r
a
t
u
e
,

C

t
o

T
o

T
1
T
2
T
p
= 1010 C
Figure 9. Thermal treatment of bulk superconductor samples textured by Bridgman technique.
J.J. Roa, X.G. Capdevila and M. Segarra 164
The two main problems found when obtaining YBCO samples with this technique are:
- The first one is related to the different liquid properties. The optimal viscosity have
to be found between minimize the sample flowing and maximize atomic diffusion.
- It is well known that the liquid phase generally migrates to the cold zone. In this
case, the bar loss the correct stochiometry and in the end of the bar have a rich Y-211
zone.
After the texture process, the YBCO bars were introduced in an oxygenation furnace at
450C for 240 h.
Figure 10 shows a schematic drawing and optical micrograph (OM) of YBCO bars
textured by Bridgman technique. By means of polarized light microscopy an initial region can
be observed where polynucleation and growth competition phenomena take place. This
competition region has a length which is inversely proportional to the processing rate, thus
indicativy that the nucleation is promoted by an enhanced undercooling [50]. In the single
domain region the c-axis of Y-123 has a tilt angle of 45 respect to the long axis of the bars.
b) a)
Syngle-Crystal
(45)
300 m
Figure 10. a) OM and b) schematic drawing showing from bottom to top, a multinucleation region, a
growth competitive region and a single domain region of a Bridgman melt-grown sample. (Figure 10.b,
from Ullrich et al., Materials Science and Engineering B, 53, 1998, page 143-148).
Mechanical Characterization at Nanometric Scale 165
Figure 11 shows a TEM micrograph of a Bridgman sample. In this picture, a high quality
dislocations can be observed in the matrix of this material. The dislocation substructure of Y-
123 is highly anisotropic, being confined to the (001) plane. Lubenets et al. reported that
strong covalent and ionic bonds create high Peierls barriers, which constrain the dislocation
mobility in YBCO single crystals [51].
The micrograph presented in Figure 12 also shows lower amounts of dislocations placed
preferentially in the grain boundary between Y-123 and Y-211. Moreover, the trajectories of
the dislocations appear to be either unaffected or changed across the twin boundaries. On the
other hand, this micrograph presented a higher amount of twins inside the precipitates. These
effects could be due to two different factors: the compressive strain during the cooling
treatment in the texture process and the different thermal expansion coefficients between the
matrix and the particles (from 20C to 900C are 1.2410
-3
K
-1
and 1.7010
-3
K
-1
for Y-211 and
Y-123, respectively]). Finally, we observe twins and residual stress inside the Y-211 particles.
Stresses associated to the Y-211/Y-123 interface can arise from two different mechanisms.
The first takes into account the thermal expansion and elastic modulus mismatch between the
two phases].Secondly, stress is thought to result from the incorporation of Y-211
decomposition products into the matrix. Below the peritectic temperature, there is a
thermodynamically driving force for solid-state dissolution of precipitates embedded in the
matrix. Under uniaxially pressing conditions, plastic deformation is only possible if there is
some kind of anisotropy in the material. In melt textured Y-123 composites, two kinds of
anisotropy exist: elastic anisotropy] in the matrix, and plastic anisotropy between the
peritectic inclusions and the matrix.

200 nm
Dislocation
Figure 11. TEM micrograph of a Bridgman sample observed of a region containing dislocations in the
maximum anisotropy plane (001 plane, ab).
J.J. Roa, X.G. Capdevila and M. Segarra 166

1 m
Twins
Res idual
Stres s
Figure 12. TEM micrograph of Bridgman sample of a region containing several precipitates with
different sizes. Note that several twins and residual stress produced during the texture process are
present into the precipitates.

Dislocation
Residual Stress
0.5 m
Figure 13. TEM micrograph of a sample textured by Bridgman technique shows a precipitate with
residual stress and dislocation. Both defects are due to the compressive strain produced during the
texture process of material.
Mechanical Characterization at Nanometric Scale 167
In Figure 13, inside the Y-211 particle a dislocation can be observed, as well as in the
middle of the particle a microcrack and a residual stress at the corners of the particle produced
during the texture process. At the grain boundary between Y-211 and Y-123 phases, a fine
dislocation line surrounding the particle can be observed. If we observe the matrix we will
find a great amount of dislocations.
1.1.2. Oxygenation Process
Although in the standard melt-grown YBCO microcracks also appear in the vicinity of Y-
211 particles due to thermal expansion difference of Y-211 and Y-123 [52], these microcraks
do not propagate across the Y-211 precipitates, and the length of such microcraks is limited.
The Y-211 particles are under compression when the material is cooled and can therefore
break the Y-123 matrix along ab-planes [53]. These are the intrinsic microcraks, which are
generated during the tetragonal-orthorombic phase transformation. Large secondary phase
inclusions (unreacted liquid and Y-211) can also create macrocraks due to thermal expansion
mismatch.
Oxygen annealing, necessary to make Y-123 samples superconducting, is reported to be
responsible for further macro and microcracking]. That is why oxygen concentration
gradients lead to large mechanical stress in the material. The oxygenation diffusion
coefficient in the ab-plane is about 10
4
-10
6
times larger than in c-direction].
Figure 14 shows a micrograph of Y-123 observed with scanning transmission electron
microscopy of a YBCO samples textured by Bridgman technique. We can observe a twin
produced during the oxygenation process.

Twin
0.2 m
Figure 14. TEM micrograph of YBCO sample textured by Bridgman technique of a twin present in the
matrix (Y-123) in the maximum anisotropy plane (001).
J.J. Roa, X.G. Capdevila and M. Segarra 168
Figure 15 shows a high resolution TEM (HRTEM) micrograph viewed along the grain
boundary between Y-123 and Y-211 phases. In this micrograph we can observe, along the
(001) plane, the transition from a well ordered region (Y-123) to a highly defective one (Y-
211). The distance between crystallographic planes is 7 . We can also observe the high
anisotropy in the Y-211 phase. In the case of growing the matrix (Y-123) on Yttrium
substrates, the copper oxide rich liquid reacts with the substrate to form precipitates of Y-211
at the enriched interface [54], such that subsequent nucleation of the Y-211 liquid interface
[55]. The mechanism would explain the anisotropic orientation distribution of Y-211
observed in figure 14. On the other hand, for Y-123 growing directionally from the melt, the
particle engulfment process is governed by the velocity of the advantaging interface, melt
viscosity and particle size. For anisotropic materials, such as Y-123 and Y-211 crystals, we
can expect the above process to be governed by a complex relation, between orientation and
size of the particle. These considerations suggest that the incorporation of Y-211 particles into
the bulk Y-123 would be favoured for particular orientations if the growth rate is parallel to
ab planes.

5 nm
Y211
Y123
Y123/Y211
Figure 15. HRTEM image of a Y-211/Y-123 interface viewed along the [001] direction showing a
transition from ordered zone (Y-123) to a highly defective zone (Y-211). Distance between
cristalographic planes in the Y-123 zone is 7 .
YBCO pellets textured with TSMG and/or Bridgman technique have different cracking
mechanisms
Mechanical Characterization at Nanometric Scale 169
a) Mechanical Stress
Macrocraks in textured pellets appear during the final cooling stage to room temperature.
Three major causes for large mechanical stresses, schematically illustrated in Figure 16, are
considered at this stage:
An increasing Y-211 concentration is observed with increasing resistance from the
seed in the c-growth sector while it remains relatively homogeneous in the ab-growth
sector. Thermal expansion coefficients (in ab- and c- direction) of an Y-123/Y-211
composite are a function of the Y-211 content. The c-axis stress due to Y-211
inhomogenities described above can reach 50-100 MPa in the center of the pellet and
will tend to open ab-plane macrocracks.
During cooling a thermal gradient builds up with a colder surface and a hotter bulk
due to relatively low thermal conductivity of Y-123.
During to cooling to room temperature it takes up oxygen mostly in ab-direction and
in vicinity of the surface.
a)
b)
c)
Figure 16. Schematic of mechanical (compressive or tensile) stresses associated with a) the Y-211
distribution into a pyramid pattern, b) thermal gradient during cooling and c) oxygen gradient ( From
Isfort et al, Physica C 390, 2003, 341-355).
J.J. Roa, X.G. Capdevila and M. Segarra 170
b) Propagation of Cracks during Oxygenation [56]
Cracking due to the oxygenation uptake of the surface does not seem to damage the
sample severely, as the crazing is limited to the surface.
The mechanism can be described as follows: In a first stage stress is building up at the
exterior surface which creates the regular crazing pattern. Oxygen will then penetrate in the
cracks and oxygenate their walls. The contraction in c-direction due to the oxygen uptake will
then create a stress field around the crack tip that tends to make the crack progress inside the
material (See Figure 17).



O
2




















Tensin
YBCO





Stress
Figure 17. Schematic of mechanism of propagation of cracks during oxygenation (From J.J. Roa et al.,
Anles de Mecnica de la Fractura, 25, 2008, Spain, ISSN-0213-3725).
1.1.3. Applications
At present, many applications using melt-textured YBCO are currently discussed [57].
The first demostrators, e.g. motors, flywheels, and others, have already been built. The HTSC
capability to transport electric current without any losses, together with low thermal
conductivity, suggest the application of HTSC for high current transport to low temperature
SC devices such as magnets. The fault current limiter (FCL) seems to be the most promising
superconducting power device that will be installed in the electric power networks. The
higher levitation force of the YBCO bulk means that it can be used for various applications,
such as non-contacted superconducting bearing [58], flywheel [59], magnetic levitation
transport system and motors [60]. The application is mainly dependent on the physical
properties of the YBCO bulk, such as levitation force and others.
Although YBCO compound is one of the most widely studied superconducting materials,
bulk YBCO superconductors are brittle and exhibit poor mechanical properties (strength and
fracture toughness) [61]. Bulk textured Y-123 has to be considered as a brittle composite
material due to the presence of micro-sized Y-211 inclusions in the Y-123 matrix.
The most important problem of the superconductor materials is their poor mechanical
properties. However, can become as important if one takes into account the stresses appearing
in practical service due to the mechanical action caused by magnetic and/or thermal cycling
Mechanical Characterization at Nanometric Scale 171
between room and liquid nitrogen temperatures [ii]. These poor and unknown mechanical
properties limit the performance of melt-textured YBCO in manufacture applications.
The purpose of this study is the characterization of the mechanical properties, in elastic
and plastic range, of orthorhombic phases of YBCO samples textured by Bridgman and
TSMG technique. With the ITT technique, the oxygenation process can be followed and its
kinetics established.
1.2. Indentation Testing Technique
Indentation or hardness testing has long been used for characterization and quality control
of materials, but the results are not absolute and depend on the test method. In general,
traditional hardness test consist of the application of a single static force and corresponding
well time with a specified tip shape and tip material, resulting in a hardness impression that
has dimensions on the order of nanometers or micrometers depending on the applied load.
The output of these hardness testers is typically a single indentation hardness value that is a
measure of the relative penetration depth of the indentation tip into the sample. Actually,
there are a lot of durometers which are used to characterize the mechanical resistance of
materials, such as in polymer materials, that have different spring constants and either a flat
conical tip, a sharp conical tip, or a spherical tip, as specified in ASTM D 2240, Standard Test
Method for Rubber Property-Durometer Hardness.
The deformation of materials occurs via two distinct processes: elastic (reversible) and
plastic (irreversible) deformation. Since elastic formation is a reversible process, and is
governed by angstrom scale (10
-10
m), interaction parameters such as the crystallographic
lattice constants, elastic deformation of materials exhibit virtually no size dependence unless
a large population of preexisting deffects is involved [62]. The plastic deformation response,
which occurs as a result of the generation, annihilation, and motion of deffects such as
dislocations, displays marked size effects when those material dimensions are in the range of
microns or below.
Instrumented indentation testing (ITT), also known as depth-sensing indentation,
continuous-recording indentation, ultra-low-load indentation, and nanoindentation, is a
relatively new form of mechanical testing that significantly expands on the capabilities of
traditional hardness testing. The past two decades, ITT employs high-resolution
instrumentation to continuously control and monitor the loads and displacements of an
indenter. The method was introduced in 1992 for measuring hardness and elastic modulus by
instrumented ITT and has widely been adopted and used in the characterization of mechanical
behaviour of materials at nanometric scales [63 and 64]. The principal advantage of this
technique is that the mechanical properties can be determined directly from indentation load
and displacement measurements or also from load-unload curves without the need to image
the hardness impression. For this reason, this method has become a primary technique for the
determination of the mechanical properties of thin films and small structural features [65, 66
and 67]. ITT provides information about composite materials when the particles in the matrix
have a lower size than the residual indentation imprints. This technique, also, permits the
study of the mechanical properties of monolithic samples .
During the past decade, ITT has introduced several important changes to the method that
both improve its accuracy and extend its real of application. The changes have been
J.J. Roa, X.G. Capdevila and M. Segarra 172
developed both through experience in testing a large number of materials and by
improvements to testing equipment and techniques. Some of this changes were [68]: new
methods for calibrating indenter area functions and load frame compliance, the measurement
of contact stiffness by dynamic techniques allowing continuous measurement of properties as
a function of depth, and others.
A nanoindenter is a type of an indentation instrument tester, which means that load and
total depth of penetration are measured as function of time during loading and unloading.
Depending on the details of the specific testing system, loads as small as 1 nN can be applied,
and displacements of 0.1 nm (1 ) can be measured. Mechanical properties, such as:
hardness, Youngs modulus, toughness, yield strength, shear stress,, can be obtained with
the load-displacement data.
The technique most frequently employed measures the hardness, and the elastic modulus
or Youngs modulus. [68 and 69]. This technique, also permits evaluating the yield stress and
strain-hardening curves of metals [70], characteristic parameters of damping and internal
friction in polymers, such as the storage and loss modulus and the activation energy and stress
exponent for creep [71 and 72].
Mechanical properties are routinately measured from submicron indentations, and with
careful technique, properties have even been determined from indentating only a few
nanometers deep.
Many ITT testing systems are equipped with automated specimen manipulation stages. In
these systems, the spatial distribution of the near-surface mechanical properties can be
mapped on a point-to-point basis along the surface in a fully automated way.
1.2.1. Testing Equipment (Instrumentation)
Many instrumented indentation systems can be generalized in terms of the schematic
illustration shown in figure 18 [73].
Load application device
Springs
Probe Tip
Displacement Sensor
Sample
Load frame
Load application device
Springs
Probe Tip
Displacement Sensor
Sample
Load frame
Figure 18. Schematic illustration of an instrumented indentation system.
Mechanical Characterization at Nanometric Scale 173
As shown in the figure, equipment for performing instrumented indentation tests consists
of three components: a) an indenter of specific geometry usually mounted to a rigid column
through which the force is transmitted, b) an actuator for applying the force, and c) a sensor
for measuring the indenter displacements.
However, to date, most ITT development has been performed using instruments
specifically designed for small-scale work. Advances in instrumentation have been driven by
technologies that demand accurate mechanical properties at the micron and submicron levels,
such as the microelectronic and magnetic storage industries.
1.2.2. Nanoindenters Tips
A variety of indenters made from a variety of materials are used in ITT testing. Diamond
is probably the most frequently used material because its high hardness and elastic modulus
minimize its contribution to the measured displacement from the indenter. Indenters can be
made of other less-stiff materials, such as sapphire, tungsten carbide, or hardened steel.
The indenters can be classificated in four different groups:
Pyramidal indenters
The most frequently sharp indenter in nanoindentation technique is the Berkovich
indenter. This indenter presents a three-sided pyramid with the same depth-to-area relation as
the four-sided Vickers pyramid used commonly in microhardness work. With this indenter
the hardness and the Youngs modulus can be determined.
Spherical indenters
For spherical indenters, the contact stress is initially small and produces only elastic
deformation. As the spherical indenter is driven into the surface, a transition from elastic to
plastic deformation occurs, which can theoretically be used to examine yielding and work
hardening, and to recreate the entire uniaxial stress-strain curve from data obtained in a single
test [74 and 75].
At the micron scale, the use of spherical indenters has been impeded by difficulties in
obtaining high-quality spheres made from hard, rigid materials.
Cube-Corner Indenters
A three-sided pyramid with mutually perpendicular faces arranged in geometry like the
corner of a cube. The center-line-to-face angle for this indenter is 34.3 whereas for the
Berkovich indenter it is 65.3.
The sharper cube corner produces much higher stress and strains in the vicinity of the
contact, which is useful, for example, in producing very small, well defined cracks around
hardness impressions in brittle materials; such cracks can be used to estimate the fracture
toughness at small scales [76]. Also, the toughness of brittle materials can be determined with
a Berkovich indenter.
Conical Indenters
J.J. Roa, X.G. Capdevila and M. Segarra 174
The conical indenter is also attractive because the complications associated with the
stress concentrations at the sharp edges of the indenter are absent. Curiously, very little ITT
testing has been conducted with cones. The main reason is that it is difficult to manufacture
conical diamonds with sharp tips, making them of little use in nanoindentation technique [77].
The most important indenters used in nanoindentation technique are the Berkovich and
Spherical indenter. It allows to characterize the plastic (hardness, Youngs modulus and
toughness fracture) and the elastic (yield strength, mean contact pressure, shear stress and
stress-strain curves) deformation. A typical Berkovich and Spherical indenter tip are shown in
figure 19.

200 m
a)

500 m
b)
Figure 19. High magnification SEM scan of the most important indenters used in nanoindentation
technique, a) Berkovich indenter and b) Spherical indenter.
Mechanical Characterization at Nanometric Scale 175
1.2.3. Good Experimental Practice
As in any experimental work, accurate measurements can be obtained only with good
experimental technique and practice. The most important factors that can be controlled in a
nanoindentation test are shown below:
a) Choosing an Appropriate Indenter
Choosing an appropriate indenter requires consideration of a number of factors. One
consideration is the strain the tip imposes on the test material. Although the indentation
process produces a complex strain field beneath the indenter, it has been proven to be useful
to quantify the field with a single quantity, often termed the characteristic strain, There are
problems, however, in obtaining accurate measurements of hardness and elastic modulus with
cube-corner indenters [78]. Although not entirely understood, the problems appear to have
two separate origins. First, as the angle of the indenter decreases, friction in the specimen-
indenter interface and its influence on the contact mechanics becomes increasingly important.
Second, the relation among the contact stiffness, contact area and effective elastic modulus.
Corrections are required, and the magnitude of the correction factor depends on the angle of
the indenter.
The spherical indenter can be used when one wishes to take advantage of the
continuously changing strain. In principle, one can determine the elastic modulus, yield stress,
and strain-hardening behaviour of a material all in one test.
b) Environmental Control
To take full advantage of the fine displacement resolution available in most ITT testing
system, several precautions must be taken in choosing and preparing the testing environment.
Uncertainties and errors in measured displacements arise from two separate environmental
sources: vibration and variation in temperature that cause thermal expansion and contraction
of the sample and testing system.
To minimize vibration, testing systems should be located on quiet, solid foundation
(ground floors) and mounted on vibration-isolation system. Thermal stability can be provided
by enclosing the testing apparatus in an insulated cabinet to thermally buffer it from its
surroundings and by controlling room temperature to within 0.5C.
c) Surface Preparation
Surface roughness is extremely important in instrumented indentation testing because the
contact areas, from which mechanical properties are deduced, and calculated from the contact
depth and area function, on the presumption that the surface roughness depends on the
anticipated magnitude of the measured displacements, and the tolerance for uncertainty in the
contact area. The greatest problems are encountered when the characteristic wavelength of the
roughness is comparable to the contact diameter.
J.J. Roa, X.G. Capdevila and M. Segarra 176
d) Testing Procedure
To avoid interference, successive indentations should be separated by at least 20 to 30
times the maximum depth when using a Berkovich or Vickers indenter. For other geometries,
the rule is 7 to 10 times the maximum contact radius. The importance of frequently testing a
standard material can not be over emphasized.
e) Detecting the Surface
One very important part of any good IIT testing procedure is accurate identification of the
location of the specimens surface. This is especially important for any small contacts, in
other words, when the applied load is very low, for which small errors in surface location can
produce relatively large errors in penetration depth.
For hard and stiff materials, such as hardened metals and ceramics, the load and/or
contact stiffness, both of which increase upon contact, are often used. However, for soft,
compliant materials, like polymers and biological tissues, the rate of increase in load and
contact stiffness is often too small to allow for accurate surface identification. In these
situations, a better method is sometimes offered by dynamic stiffness measurement
[79and 80].
1.2.4. Experimental Techniques
a) Hardness and Elastic Modulus Measurements
The analysis of force-displacement or load-unload curves produced by instrumented
indentation system is often based on work by Doerner and Nix [81] and Oliver and Pharr. The
two mechanical properties measured most frequently by ITT methods are hardness and elastic
modulus or Youngs modulus with a Berckovih indenter.
For materials that do not experience pile-up, which includes most ceramics, hard
materials, and soft metals that work harden, these mechanical properties can be determined
generally within 10 %, sometimes better.
The method was developed to measure the hardness and elastic modulus of a material
from indentation load-displacement data obtained during one cycle of loading and unloading.
Although it was originally indented for applications with sharp indenter, like Berckovich.
A schematic representation of a typical data set obtained with a Berkovich indenter can
be observed in figure 20, where P designates the load, and h the displacement relative to the
initial undeformed surface.
The load-displacement curve shows the elastic/plastic behaviour of each sample. From
the difference between total indentation depth at maximum indented load (h
t
) and depth of
residual impression upon loading (h
f
), the elastic recovery can be calculated [82].
In figure 20, there are four important quantities that must be measured:
a) the maximum load, P
max
,
b) the maximum displacement, h
max
,
c) the elastic unloading stiffness, S = dP/dh, defined as the slope of the upper portion of
the unloading curve during the initial stages of unloading. The parameter S has the
Mechanical Characterization at Nanometric Scale 177
dimensions of force per unit distance, and is known as the elastic contact stiffness, or
more simply, the contact stiffness, and
d) the final depth, h
f
.
The characteristics of figure 20 and such experimental results are summarized as follows:
- The initial load-displacement (P-h) response is elastic and can be described by
continuum level contact mechanics.
- The first departure from this elastic response occurs when the local maximum shear
stress level sustained by the indented material is on the order of the theoretical shear
strength of material.
- Subsequent to this initial plastic event, a series of similar discontinuities in the P-h
response occurs. Although the fundamental mechanisms responsible for the
experimentally observed discrete deformation processes under this nanoscale contact
are still debated in the literature.
Figure 20. Schematic illustration of indentation load-displacement data showing important measured
parameters (From J. J. Roa et al., Nanotechnology, 18, 2007, 385701/1-385701/6).
The loading response of the material will show, therefore, whether if the indentation
probe is blunt o sharp, producing an elastic initial response or an elasto-plastic response. Once
the loading is sufficiently high, both indenters will produce similar elasto-plastic response in
the material. It has to be taken into account that all real sharp indenters have a tip curvature
which translates into a blunt indentation at the initial contact depths. The analysis of the P-h
curves depends if it is a loading curve (which can be elastic or elasto-plastic) or a unloading
curve, where the material is usually deformed.
The accuracy of the mechanical properties in plastic deformation range (hardness and
Youngs modulus) depends on how well these three parameters can be experimentally
measured. The last parameter is the permanent depth of penetration after the indenter is fully
unload; in other words, with this value the plastic work necessary to deform the material of
the study can be calculated.
J.J. Roa, X.G. Capdevila and M. Segarra 178
The exact procedure used to measure H and E is based on the unloading process shown
schematically in figure 21, in which it is assumed that the behaviour of the Berckovich
indenter can be modelled by a conical indenter.
Figure 21. Schematic illustration of the unloading process showing parameters characterizing the
contact geometry (From J. J. Roa et al., Nanotechnology, 18, 2007, 385701/1-385701/6).
The fundamental relations from which hardness and Effective Youngs modulus or
reduced Youngs modulus are determined as follows:
A
P
H
max
= (5)
where P
max
is the maximum applied load and A is the projected contact area at that load.
The hardness valued is a measure of the load-bearing capacity of the contact computed by
dividing the applied load by the projected area of contact under load. This should not be
confused with the more traditional definition of hardness, the load divided by the projected
area of contact of the residual hardness impressions. These two different definitions of
hardness yield similar values when the plastic deformation process dominates and a fully
plastic permanent impression is formed. However, they give very different values when
contact is predominantly elastic, because for purely elastic contact, the residual contact is
vanishingly small, giving an infinite hardness based on the traditional definition.
The Effective Youngs modulus can be determined as a function of S, A and a constant
which depends on the geometry of the indenter.
( ) , , A S f E
eff
= (6)
Equation 6, can be re-written as:
A
S
E
eff

2
(7)
Mechanical Characterization at Nanometric Scale 179
Equation 7 is found in elastic contact theory and holds for any indenter that can be
described as a body revolution of a smooth function Because this equation was derived for an
axysimetric indenter, it formally applied only to circular contacts, for which the indenter
geometry parameter is = 1. However, it has been shown that the equation works equally
well when the geometry is not axysimetmetric, provided that different values of are used
[83, 84 and 85]. For indenters with square cross sections like the Vickers pyramid, = 1.012,
for triangular cross sections like the Berkovich and the cube-corner indenters, = 1.034 [iv].
This factor plays a very important role when accurate property measurements are desired.
This constant affects not only the elastic modulus calculated from the contact stiffness by
means of equation 7, but the hardness as well because procedures for determining the indenter
area function are also based on equation 7, and area functions can be mistaken if the wrong
value of is used.
An effective modulus, E
eff
, is used in equation 7 to account for the fact that elastic
displacements occur in both the indenter and the sample. The elastic modulus of the studied
material, E, is obtained from E
eff
, using the next equation:
i
i
eff
E E E
2 2
1 1 1
+

= (8)
where is the Poissons ratio for the test material, and E is the Youngs modulus. The
subindex i denote the values of the indenter. For diamond indenter, the elastic constants E
i
=1141 GPa and
i
= 0.07 are often used. While it may seem counterintuitive that one must
know the Poissons ratio of the studied material in order to calculate its Youngs modulus
using the equation 8, even a rough estimate, say = 0.25 0.1, produces only about a 5%
uncertainty in the calculated value of E for most materials. The most important thing is to
determine the contact stiffness and the contact area as well as possible. From equation 5 and
7, it is clear that, in order to calculate the hardness and elastic modulus of the studied material
from indentation load-displacement curves, an accurate measurement of the S and the A must
be performed. One of the main distinctions between IIT and conventional hardness testing is
the way to obtain the contact area. Rather than by imaging, the area is established from an
analysis of the indentation load-displacement data.
The analysis used to determine the hardness, H, and the elastic modulus, E, is essentially
an extension of the method proposed by Doener and Nix that accounts for the fact that
unloading curves are distinctly curved in a manner that cannot be accounted for by that flat
punch approximation. Doener and Nix consider that the contact area remains constant as the
indenter is withdraw, and the resulting unloading curve is linear. The Oliver and Pahrr
method begins by fitting the unloading portion of the load-displacement curve to the power-
law relation:
( )
m
f
h h A B P = (9)
where and m are power law fitting constants , and h
f
is the final displacement after
complete unloading, also determined from the curve fit. The S is established by analytically
J.J. Roa, X.G. Capdevila and M. Segarra 180
differentiating equation 9; and evaluating the results at the maximum depth of penetration, h
= h
max
, that is:
max h h
dh
dP
S
=
= (10)
Differentiating equation 9, the S can be obtained with the following equation:
( )
1
max

=
m
f
h h m B S (11)
It is thus prudent, when the S has been calculated with equation 11, to fit only the upper
portion of the unloading curve; moreover, the value of S determined from this fit should be
checked by comparing the curve fit to the data. Fitting the upper 25 to 50% of the data is
usually sufficient.
Now, the contact depth, h
c
, has been calculated, which for elastic contact is less than the
total depth of penetration (h
max
) as illustrated in the figure 21. The basic assumption is that the
contact periphery sinks in a manner that can be described by models of indentation of a flat
elastic half-space by rigid punches of simply geometry [86]. This assumption limits the
applicability of the method because it does not account for the pile-up of material at the
contact periphery that occurs on some elastic-plastic materials. Assuming, however, that pile-
up is negligible, the elastic models show that the amount of sink-in, h
s
, is given by the next
equation:
S
P
h
s
max
= (12)
where is a constant that depends on the geometry of the indenter. Typical values are: 0.72
for a conical punch indenter, 0.75 for a parabolic of revolution and 1 for flat punch.
From the geometry of figure 21, the depth along contact is made between the indenter
and the specimen, h
c
, can be calculated by:
s c
h h h =
max
(13)
Using equation 12 and 13, the contact between the indenter and the specimen is:
S
P
h h
c
max
max
= (14)
The projected contact area is calculated by evaluating an empirically determined indenter
area as a function of A = f (d) at the contact depth h
c
; that can be re-writen as:
( )
c
h f A = (15)
Mechanical Characterization at Nanometric Scale 181
The area function, also known as the shape function or tip function must be carefully
calibrated by independent measurements, so that deviation from non-ideal indenter geometry
are taken into account. These deviations can be quite severe near the tip of the Berkovich
indenter, where some rounding inevitably occurs during the grinding process.
b) Spherical Indentation (Determination of the Stress-Strain Curves)
In the past 20 years, instrumented nanoindentation experiments have emerged as a
powerful tool in understanding the mechanical behaviour of solids in general, and single
crystals and thin films in particular. However, since the majority of the work has been carried
out using Berkovich indenters, the emphasis has been put on extracting the hardness and the
Youngs modulus of the material .
Berkovich indenter is quite sharp and results in plastic deformation almost instantly;
consequently, much of the information about the purely elastic region and, as important, the
elastic to plastic transition is lost, a fact that has long been appreciate.
Given that the conversion of load-displacement curves to indentation stress-strain curves
is almost as old as the technique of using indentations to probe the mechanical properties of
solids, it is somewhat surprising that this conversion is not much more common than it is.
This comment notwithstanding, there have been a number of papers in which spherical
nanoindenters have been used [87]. Roughly a decade ago, Field and Swain suggested a
method to extract indentation stress-strain curves from load-displacement curves .
Before acquiring the Continuous Stiffness Measurement (CSM) option, Field and Swain
method was used to convert load-displacement results obtained on Ti
3
SiC
2
[88], and single
crystals of mica [89] and graphite [90], loaded parallel to the c-axis to indentation stress-
strain curve.
Typically, a nanoindentation test results in the load, P, and displacement into surface, h
t
,
data. Additionally, the CSM attachment provides the harmonic contact stiffness, S, values
over the entire range of loading. The elastic contact between two bodies was first described
by Hertz in 1882, and the equations describing this response are usually known as Hertzian
equations. Hertzian indentation has been applied to ceramic systems with heterogeneous
microstructures, where an intermediate form of damage is observed.
The vast majority of spherical nanoindentation analysis is based on the Hertz equation in
the elastic region
2
3
2
1
4
3
e eff
h R E P = (16)
where R is the radius of the indenter, h
e
is the elastic distance into the surface (see figure 22),
and E
eff
is the effective modulus given by equation 8.
For a rigid spherical indenter, Sneddon showed that the elastic displacements of a plane
surface above and below the contact circle are equal, and given by:
R
a
h h
t e
3
= = (17)
J.J. Roa, X.G. Capdevila and M. Segarra 182
where a is the contact radius during the indentation, see figure 22. Combining equation 16
and 17, next equation can be obtained:

=
R
a
E p
eff o
4
3
(18)
The left side of equation 18 represents the indentation stress or mean contact pressure,
also referred to as the Meyer hardness [91]. The expression in parentheses or a/R on the right
side represents the indentation strain.
Whith the spherical indenter two different mechanisms can be studied: the elastic and
elasto-plastic mechanism.
Figure 22. Schematic representation of spherical indentation (From S. Basu et al., J. Mater. Res., 2006,
Vol. 21, No. 10, page 2628-2637).
a) Elastic Regime
Both the Oliver and Pharr and Field and Swain methods use the slopes of the initial
portions of the unloading curves, dP/dh, to calculate h
e
. Differentiating equation 16 with
respect to h can yield:
2
3
2
1
2
e eff
h R E
dh
dP
= (19)
which when substituted this equation in equation 16, results in
e
h
dh
dP
P =
3
2
(20)
Therefore,
Mechanical Characterization at Nanometric Scale 183
dP
dh
P h
e
=
2
3
(21)
Since dP/dh is nothing but the stiffness, S
*
, of the system composed by the specimen and
the load frame, the stiffness of the material itself can be calculated from next equation:
f
S S S
1 1 1
*
= (22)
where S
f
is the load-frame stiffness. This value is obtained from the manufacturer of the
instrument.
b) Elasto-Plastic Regime
Again following the Oliver and Pharr and Field and Swain methods, it can be assumed
that the contact depth, h
c
, can be defined as the distance from the circle of contact to the
maximum penetration depth, see figure 22, to be given by the next equation:
2
e
t c
h
h h (23)
Combining equations 22 and 23 yields:
S
P
h h
t c
=
4
3
(24)
Equation 24, can be modified and re-written as follows:
+ =
S
P
h h
t c
4
3
(25)
where is an adjustable parameter of the order of a few nm needed to obtain the correct
elastic moduli.
Once h
c
is known, a can be calculated with the next equation:
c c c
h R h h R a = 2 2
2
(26)
Equation 26 is only valid for h
c
<<< a, and when the indenter tip is perfectly spherical.
In the purely elastic regime, h
c
= h
t
/2 = h
e
/2 and equations 17 and 23 become identical.
Note that for the most part of the plastic regime, since h
t
>> h
e
/2 it follows that h
c
h
t
(equation 23)
J.J. Roa, X.G. Capdevila and M. Segarra 184
c) Fracture Toughness Measurement
Ceramics are generally brittle and prone to generation of cracks when indented.
Toughness estimation by microfracture Vickers indentation is a well-known and broadly
employed technique in ceramic materials. This technique consist of the application of a
Vickers or Berkovich indenter at a given load to the material sufficiently high to nucleate
cracks at the corners of the imprint, and further measure the crack lengths produced at the
corners of the imprint, c, in order to evaluate the fracture toughness of the studied material.
The fracture toughness of brittle bulk materials, an important measure of the resistance of
these materials to fracture and crack propagation, can be evaluated through conventional
microindentation using a microindenter. However, because of the bluntness of the
microindenter tip, large forces are necessary to produce the cracks needed for analysis.
Hardness and modulus of thin films or particles in a matrix can not be measured with
microindentation without tedious work in correcting the substrate effect or the contribution of
the matrix on the results. So, the fracture toughness of thin film or ceramic composite, such as
YBCO, cannot be easily determined with the microindentation method.
Fracture toughness at small scales can be measured by ultra-low load indentation using
techniques similar to those developed for microindentation testing [92].
Nanoindentation can be used to evaluate the fracture toughness of material and interfaces
in a similar manner to that conventionally used in large scale testing. During loading, tensile
stresses are induced in the specimen material as the radius of the plastic zone increases. Upon
unloading, the additional stresses arise as the elastically strained material outside the plastic
zone attempts to resume its original shape but is prevented from doing so by the permanent
deformation associated with the plastic zone. There exists a large body of literature on the
subject of indentation cracking with Vickers and other sharp indenters, such as Berkovich
indenter.
Recently, several methods for fracture toughness estimation without visualization of the
crack length have been proposed, for example the works of Field et al. [93], where they relate
the crack length produced to the pop-in behaviour during loading or the work of Dahami et al.
[94] where they related the crack length with the total load penetration depth for fused silica.
Generally, there are three types of crack. A scheme of it can be observed in figure 23:
a) Radial crack are vertical half penny type cracks that occur on the surface of the
specimen outside the plastic zone and at the corners of the residual impression at the
indentation site. These radial cracks are formed by a hoop stress and extend
downward into the speciment, but are usually quite shallow. See Figure 23a.
b) Lateral cracks are horitzontal cracks that occurs beneath the surface and are symetric
with the load axis. They are produced by a tensile stress and often extend to the
surface, resulting in a surface ring that may lead to chipping of the surface of the
specimen. See Figure 23b.
c) Median cracks are vertical circular penny cracks that form beneath the surface along
the axis of symmetry and have a direction aligned with the corners of the residual
impression. Depending on the loading conditions, median cracks may extend upward
and join with surface radial cracks, thus forming two half-penny cracks that intersect
the surface. See Figure 23c.
Mechanical Characterization at Nanometric Scale 185
a)
b)
c)
Figure 23. Scheme of the different types of cracks, a) radial crack, b) lateral cracks and c) median
cracks.
In adition, other fracture events, such as delamination or radial cracking at the interface,
may be activated in case that the indentation field comprises both materials. As in the case of
radial cracking, the delamination event will only be detected in an instrumented indentation
test for certain materials.
Fracture mechanics treatment of these types of cracks seek to provide a measure of
fracture toughness based on the length of the radial surface cracks. Attention is usually given
to the length of the radial cracks as measured from the corner of the indentation and then
radially outward along the specimen surface as shown in figure 24.
J.J. Roa, X.G. Capdevila and M. Segarra 186

l
a
c
Figure 24. Crack parameters for Berkovich indenter. Crack length c is measured from the center of
contact to end of crack at the specimen surface.
Conventional indentation toughness methods were initially developed for monolithic bulk
materials tested by microindentation when well-developed radial cracks form (for example
Marshall and Lawn [95], Anstis et al. [96]). The toughness K
IC
is related to the applied load
P, H, E and the cracks dimension, c. The fracture toughness can be obtained with the next
equation:
2
3
2
1
c
P
H
E
K
IC

= (27)
where E and H are the Youngs modulus and the Hardness of the material; these values are
obtained with nanoindentation technique using the Oliver and Pahrr approach. For Berkovich
and Vickers indenters, = 0.016.
The values obtained by this method will depend on the residual stress in the coating since
equation 27 is strictly only valid in the absence of internal stresses.
At higher loads using a Berkovich indenter, two crack systems are observed [97].
Initially, radial cracks are observed along the edge of the indenter. These are followed by
picture-frame cracks at the edge of the impression once sufficient bending has occurred.
For Vickers and Berkovich indenters, cracking threshold in most ceramic materials are
about 250 mN or more [98], and since the indentation produced at these loads are relatively
large, the cracking thresholds place severe restrictions on the spatial resolution which can
potentially be achieved. It should be noted that the cracking threshold depends on the
condition of the indenter tip, generally being higher for tips that have been blunted by wear.
At a given load, the cube-corner and Berkovich diamonds should, to a first
approximation, penetrate the material to produce approximately equal projected contact areas,
such as the hardness measured with the two indenters should be about the same.
Mechanical Characterization at Nanometric Scale 187
Given that the nucleation and propagation of indentation cracks are promoted by large
stress and strains, one would then qualitatively expect a reduction in the threshold for the
sharper indenter.
1.2.5. The Effective Indenter Shape
The effective indenter shape is outlined in figure 25. The basic principles are derived
from observation gleaned from finite element simulations of indentation of elastic-plastic
materials by rigid conical indenter with a half included angle of 70.3. During the initial
loading of the indenter (figure 25a), both elastic and plastic deformation processes occur, and
the indenter conforms perfectly to the shape of the hardness impression. However, during
unloading, figure 25b, elastic recovery causes the hardness impression to change its shape. A
key observation is that the unload shape is not perfectly conical, but exhibits a subtle convex
curvature that has been exaggerated in figure 25b, the contact area increases gradually and
continuously until full load is again achieved, a process which must be the reverse of what
happens during unloading because both processes are elastic.
It is this continuous change in contact area that produces the nonlinear unloading curves.
Furthermore, the relevant elastic contact problem is not that of conical indenter on a flat
surface, but a conical indenter pressed into a surface that has been distorted by the formation
of the hardness impression.
1.2.6. Errors Due to Pile-up and Sinking-in
In an indentation into an elastic material, the surface of the specimen is typically drawn
inwards and downwards underneath the indenter, and sinking-in occurs. When the contact
involves plastic deformation, the material may either sink in, or pile up around the indenter.

P P
Z = U(r)
elastic
elastic
P
P
Elastic/
Plastic
Z
Z = U(r)
r r
Effectiv indenter shape
a) Load b) Unload c) Reload
Effective indenter
shape
r
P P
Figure 25. Concepts used to understand and define the effective indenter shape, a) loaded, b) unloaded
and c) reloaded. (From W. C. Oliver et al., J. Mater. Res., Vol. 19, No. 1, 2004, pages 3-20).
J.J. Roa, X.G. Capdevila and M. Segarra 188
In the fully plastic regime, the behaviour is seen to be dependent on the ratio E/
ys
, where
ys
is the yield strength of the material, and the strain-hardening properties of the material.
The mechanical nature of a typical specimen can be described by a conventional stress-
strain relationship that includes a strain-hardening exponent:
E
when E
ys

= (28)
E
when k
ys x

= (29)
where k is equal to:
x
ys
ys
E
k

(30)
Such a complication arises from the pile-up or sink-in of the material around the indenter,
which is primarily affected by the plastic properties of the material [99]. In a low-strain-
hardening alloy, plastically displaced material tends to flow up to (and pile-up against) the
faces of the indenter due to the incompressibility of plastic deformation. The result is a barrel-
shaped impression due to pile-up around the sharp-indenter. In high strain hardening
materials, the plasticity deformed region is pushed out from the indenter with the imprint
sinking below the initial surface level. The result is a pin-cushion like impression around the
sharp indenter, as shown in figure 26.
True contact diameter
Pile-up
Sink-in
True contact diameter
Apparent contact
diameter
Apparent contact
diameter
True contact perimeter
Indenter Side Surface
a) b)
True contact diameter
Pile-up
Sink-in
True contact diameter
Apparent contact
diameter
Apparent contact
diameter
True contact perimeter
Indenter Side Surface
a) b)
Figure 26. Schematic illustration of a) pile-up and b) sink-in around a sharp indenter.
Mechanical Characterization at Nanometric Scale 189
As a consequence of pile-up or sink-in, large differences may arise between the true
contact area and the apparent contact area which is usually observed after indentation.
One significant problem with the determination of the contact area with equations from
12 to 15, is that this method does not account for pile-up of material around the contact
impression. When pile-up occurs, the contact area is greater than that predicted by these
equations, and both the hardness estimated from equation 5 and the effective modulus from
equation 7 are overestimated, sometimes by as much as 50% [100].
Pile-up is large only when the relation between h
f
/h
max
is close to 1 and the degree of
work hardening is small. It should also be noted that when this relation is lower than 0.7, very
little pile-up can be observed no matter what the work-hardening behaviour of the material. In
this case, the contact area given by this method match very well with the true contact area
obtained.
Furthermore, when this relation is higher than 0.7, the accuracy of the method depends on
the amount of work-hardening in the material.
For Berkovich indenters, indentations with a large amount of pile-up can be identified by
the distinct bowing out at the edges of the contact impression.If pile-up is large, accurate
measurements of H and E cannot be obtained using the contact area deduced from the load-
displacement curve. In this case, the most useful method to correct these problems is known
as Cheng and Cheng method [101 and 102]. These equations are function of the total work of
indentation (W
tot
), and the work recovered during unloading (W
u
).
The method that they proposed to account for pile-up is based on the work of indentation,
which measure from the areas under indentation loading and unloading curves. The relation
proposed by Cheng and Cheng can be observed below:
eff tot
u tot
E
H
W
W W

5 1 (31)
Combining equation 5 and 7 and considering as 1. Another equation involving H and
E
eff
can be obtained:
2 2
max
4
eff
E
H
S
P
=

(32)
where W
tot
, W
u
, P
max
, and S are all measurable from load-displacement curves.
Spherical indentation differs from conical or pyramidal indentation in that there is no
elastic singularity at the tip of the indenter to produce large stresses. Stress-strain curves can
be approximated from indentation data using the classical approach of Tabor . Field and
Swain [103 and 104] have applied Tabors approach to instrumented indentation and have
developed a method that uses the indentation load-displacement data to approximate the
stress-strain curve and the work-hardening exponent The approach requires the deformation
to be fully plastic.
Pile-up geometry can change considerably during the course of spherical indentation and
it is therefore not possible to predict the pile-up based on the mechanical properties of the
material alone, even when fully plastic deformation is achieved.
J.J. Roa, X.G. Capdevila and M. Segarra 190
1.2.7. Indentation Size Effect, ISE
The indentation size effect (ISE) is extensively studied in literature and the mechanisms
driving it remain irresolute. Examples of suggested mechanisms include inadequate
measurement capabilities of extremely small indents, presence of oxides or chemical
contamination on the surface, indenter-specimen friction, and increased dominance of edge
effects with shallow indents [105]. In conclusion, ISE produces a greater hardness at a smaller
applied load [106]. Depth-sensing indentation with loads higher than 1 N was proposed to
avoid the inaccuracy due to the ISE effect [107].
The Indentation Size Effect (ISE) can be classified in two different types:
- Intrinsic: From interference of the size (or thickness) of the sample, the plastic region
of the sample, L, or the autonomous plastic regions of the structure (the grains), D,
with some of the characteristic microstructural lengths.
- Extrinsic: Associated to deformation gradients. Size effects in the resistance to
plastic flow appear in metals when the dimensions of the specimen or of the zone
subjected to plastic deformation are in the range of m. The heterogeneity of the
field of plastic deformation implies differences in the dislocation fluxes across a
crystalline volume element (internal storage of geometrically necessary
dislocations, GND). The analysis of this phenomenon is important because: i) the
crystal deformation and fracture processes take place at this length scale and ii)
implications on the development of micro-electro-mechanical systems (MEMS) and
in the micro-electronics industry.
Recently, it is has become possible to perform indentation test at dimensions of tens to
hundreds of nanometers using nano- and microindentation methods. At these small
indentations depths classic plasticity theory predicts constants hardness using a geometrically
self-similar indenter on a homogenous material. Nevertheless a strong size dependent
indentation hardness result is well known.
ISE is characterized by an increasing hardness as the indentation depth is reduced to the
order of microns or submicrons. This phenomenon was interpreted by Nix and Gao (1998)
[108], De Guzman et al. (1993) [109], Poole et al. (1996) [110], McElhaney et al. (1998)
[111] and Fleck et al. (1994) [112] who proposed a strain gradient theory to explain the
presence of the ISE. Nix and Gao showed that the ISE for crystalline materials can be
explained using the concept of geometrically necessary dislocations, which leads to a strain
gradient plasticity law. Swadener et al. [113] extended this model for the case of spherical tip
indenters.
For loads up to and exceeding that to initiate pop-in at the beginning of the elastic/plastic
part of the loading curve all indents can be described by an approximately spherical contact.
They were analyzed using the approach of Swader et al. , which proposes that spherical
indenters show a dependence of hardness on the indenter radius rather than on the depth of
the penetration.
The load dependence of the hardness is referred to as the ISE. The ISE can be seen
remarkably under extremely low loads such as nanoindentation test [114]. Up to low various
factors such as strain-hardening and friction effects have been reported to explain the
phenomenon of the ISE [115].
Mechanical Characterization at Nanometric Scale 191
This theory assumes that the stress flow of metals depends on the density of statistically
stored and geometrically necessary dislocation. The density of the statistically stored
dislocation varies with the effective strain whereas the density of the geometrically necessary
dislocations depends on the strain gradient.
In crystalline solids (such as ceramics), dislocations are responsible for sustained plastic
deformation and dislocations impedes the motion of new dislocations. Dislocations are
generated during plastic deformation (when the applied load is higher than yield strength of
the studied material). The dislocations are then moved, and stored. Storage of dislocations
abets strain hardening. It is postulated that dislocations become stored because they either
accumulate by randomly trapping each other or they are required for compatible deformation
of various parts of the material. When they randomly trap each other, they are often known as
the statistically stored dislocation , whereas when they are required for compatibility
purposes, they are often called geometrically necessary dislocation and they are related to the
gradient of plastic shear strain in a material
ISE have been observed since the early days of indentation testing [116]. In many cases,
this effect is largely due to the rising uncertainties involved in making and measuring small
indentations.
There has been voluminous literature devoted to study the origin of the ISE.
Consequently, several empirical or semi-empirical equations widely applied in ceramic
materials can be applied to solve this problem, such as Meyers law [117], the Hays-Kendall
approach [118], the elastic recovery model , the energy-balance approach [119], the
proportional specimen resistance model [120], and others, that have been proposed for
describing the variation of the indentation size with the applied test load.
a) Meyers Law
The most widely used empirical equation for describing the ISE is the Meyers law,
which correlates the test load and the resultant indentation size using a simple power law ,
n
c
h A P =
max
(33)
where A and n are constants that can be derived directly from the curve fitting of the
experimental data. n is known as Meyers index and it is usually considered as a measure of
the ISE.
To obtain the A and n values, the values obtained from the nanoindentation data are
plotted in an ln P
max
ln h
c
scale. Each set of the data shows an excellent linear relationship,
implying that the traditional Meyers law is suitable for describing the nanoindentation data.
Trough linear regresion analyses, the best fit values of the A and n were obtained.
b) Hays-Kendall Approach
When examining the ISE in the Knoop hardness testing of a number of metals, Hays and
Kendall advanced that there exists a minimum level of the applied test load, W, named the
test-speciment resistance, below which permanent deformation due to indentation does not
initiate, but only elastic deformation occurs.
J.J. Roa, X.G. Capdevila and M. Segarra 192
An effective indentation load has been introduced, P
eff
= P
max
W, and proposed the
following relationship,
W P h A P
c eff
= =
max
2
1
(34)
where W and A
1
are constants independent of the test load for a given material.
Equation 34 predicts that a plot of P
max
versus h
c
2
would yield a straight line. This
equation provides a satisfactory description of the nanoindentation data for the studied
material.
c) Elastic Recovery Model or Elastic/Plastic Deformation Model
In microhardness test, the indentation size is measured after the indenter is removed from
the specimen surface. Note that the elastic recovery would occur in the vicinity of the
remaining indentation impression after the indenter is removed so that the indentation size
would shorten to a certain degree [121]. Considering this effect, Tarkanian et al. suggested
that the measured indentation size should be corrected with a revised term in order to obtain
the true hardness. The true hardness can be calculated as follows:
( )
2
o
o
d d
P
k H
+
= (35)
where d
o
is the correction in the indentation size d due to the elastic recovery and k is a
constant dependent on the indenter geometry.
Furthermore, several authors have pointed out that, for calculating the hardness from the
recorded indentation test such as the nanoindentation, similar correction in indentation size
should be considered because of the elastic recovery associated with the new bands of plastic
deformation [122] and /or the blunting of the indenter tip [123]. Thus it is necessary to check
if equation 35 is suitable for describing the nanoindentation data obtained for ceramics.
To analyze the nanoindentation data, equation 35 may be re-written in the next form:
o c
h h P + =
2
1
2
1
2
1
max
(36)
where h
o
is the correction in h
c
and = H
o
/k is a constant related to the true hardness.
Equation 36 allows to determine h
o
and from the plots of P
max
1/2
against h
c
.
There are two ways to calculate the true hardness based on the elastic recovery model:
Directly use equation 35, or
Obtain .
d) Proportional Specimen Resistance Model or PSR Model
Proportional specimen resistance (PSR) model was proposed by Li and Bradt . This
model can be considered as a modified Hays-Kendal approach. In this model, the test-
Mechanical Characterization at Nanometric Scale 193
specimen resistance to permanent deformation is assumed not to be a constant, but this factor
increases linearly with the indentation size. This phenomena is governed by the next equation:
c
h a W =
1
(37)
To a first approximation, the equation 37 can be considered to be similar to the elastic
resistance of a spring with the opposite sign to the applied test load. The effective indentation
load and the indentation dimension can be related as follows:
2
2 1 max max c c eff
h a h a P W P P = = = (38)
where a
1
and a
2
are constants for a given material. According to the analysis of Li and Bradt ,
the parameters a
1
and a
2
can be related to the elastic and the plastic properties of the test
material. a
2
was suggested to be a measure of the socalled true hardness, H
o
. For the
nanoindentation test with a Berkovich tip indenter, H
o
can be calculated directly from a
2
with:
5 . 24 5 . 24 5 . 24
2
2
1 max
2
a
h
h a P
h
P
H
c
c
c
eff
o
=

= (39)
Equation 38 can be rearranged as;
c
c
h a a
h
P
+ =
2 1
max
(40)
which enables to determine both a
1
and a
2
from the plot of P
max
/h
c
against h
c
.
An alternative explanation for the physical meaning of equation 40 was proposed by
Flhlich et al. [124] based on energy-balanced analysis. According to the energy balance
consideration, the parameters a
1
and a
2
in equation 40 are related to the energies dissipated for
creating a new surface of a unit area and for producing the permanent deformation of a unit
volume, respectively. Also, a
2
is a measure of the true hardness.
e) The Modified PSR Model
Examining the load-dependence of the microhardness of some ceramics measured in a
wide load range, Gong et al. [125], found that the resultant P/d-d (where d is a half-length of
the Vickers indentation) curves exhibit significant nonlinearity and argued that the PSR model
mentioned above may only be used to represent the experimental data measured in a narrower
range of applied loads.
Gong et al. suggested that the PSR model should be modified as follows:
2
2 1 max c c o
h a h a a P + + = (41)
J.J. Roa, X.G. Capdevila and M. Segarra 194
where a
0
is a constant related to the surface residual stress associated with the surface
machining and polishing and a
1
and a
2
are the same parameters as those in equation 40.
An equation with the same form as 41 has been also deduced based on a modified
energy-balanced analysis
The modified PSR model provides two different ways to obtain the true-hardness:
2
1 max
1
5 . 24
c
c o
o
h
h a a P
H

= (42)
5 . 24
2
2
a
H
o
= (43)
2. Mechanical Properties
2.1. State of the Art of Mechanical Properties of YBCO Samples
The mechanical properties of YBCO samples have been studied during the last years. The
most important properties studied have been the hardness (at micrometric and nanometric
scale), the Youngs modulus and the toughness fracture. Some authors studied the mechanical
properties at room or at cryogenic temperatures also known as work temperature. The
techniques used to perform these studies have been: microindentation or nanoindentation, to
obtain the hardness of the YBCO samples; the bending, X-ray diffraction and others, to obtain
the Youngs modulus; and microhardness to obtain the toughness fracture.
Reported values of Youngs modulus, hardness and fracture toughness of YBCO
composite obtained using different experimental techniques are summarized in tables 3, 4 and
5, respectively.
Table 3. Literature values of Youngs modulus for YBCO with different techniques
Author Material Youngs modulus (GPa) Method
YBCO 110
YBCO + 5% vol. Ag 103
YBCO + 10% vol. Ag 103
Joo. et al.
YBCO + 15% vol. Ag 97
Pulse echo technique
Lucas et al. [126] Y-123 154.30 16.34 Indentation
Soifer et al. [127] YBCO film 210 Nanoindentation
YBCO polycrystalline, 50K 47.20
YBCO polycrystalline, 160K 29.63
YBCO polycrystalline, 180K 28.47
Gl et al. [128]
YBCO polycrystalline, 293K 9.39
Vickers indentation
Ledbetter et al. [129] YBCO polycrystalline 90.8-101.8 Ultrasonic
Sheahen et al.[130] Syntherized with Ag 75-120 -
Goyal et al. [131] Syngle crystal 220 20 Ultrasonic
Soifer et al. [132] Thin film 210 Nanoindentation with AFM
Goyal et al. [133] Y-211 213 Nanoindentation
Goyal et al. Texturized 182 Nanoindentation
Reddy et al. [134] Texturized 95.89 Ultrasonic
Mechanical Characterization at Nanometric Scale 195
Table 4. Literature values of Hardness for YBCO with different techniques
Author Material Hardness (GPa) Method
Lucas et al. Y-123 10.28 1.67 Indentation
YBCO, MTG-1100C, 5 min 5.4
YBCO, MTG-1100C, 10 min 5.0
YBCO, MTG-1100C, 15 min 5.1
Li et al. [135]
YBCO, Solid state reaction 4.7
Vickers indentation
Soifer et al. YBCO film 8.5 Nanoindentation
YBCO 40K 18 2.5
Yoshino et al. [136]
YBCO 293 K 5.2 0.5
Vickers indentation
YBCO polycrystalline, 50K 3.58
YBCO polycrystalline, 160K 1.03
YBCO polycrystalline, 180K 0.95
Gl et al. [137]
YBCO polycrystalline, 293K 0.53
Vickers indentation
Lim et al. [138] YBCO single crystal 7.81 0.23 Nanoindentation
Cook et al. [ YBCO 8.7 Vickers indenter
Goyal et al. Textures 6.7 Vickers indenter
Goyal et al. Textures 10.8 Nanoindentation
Soifer et al. Thin film 8.5 Indentation with AFM
Goyal et al. Y-211 14.0 Nanoindentation
Table 5. Literature values of fracture toughness for YBCO with different techniques
Author Material
Fracture Toughness
(MPam
1/2
)
Method
YBCO 1.60
YBCO + 5% vol. Ag 2.10
YBCO + 10% vol. Ag 2.50
Joo. et al. [139]
YBCO + 15% vol. Ag 2.80
Single-edge-notch
beam
YBCO 1.53 Lenblond-Harnois et al.
[140] YBCO + 5% wt Ag 1.88
Vickers indentation
method
YBCO, MTG-1100C, 5 min 1.9
YBCO, MTG-1100C, 10 min 1.7
YBCO, MTG-1100C, 15 min 1.7
Li et al.
YBCO, Solid state reaction 1.3
Vickers indentation
YBCO 40K 0.4
Yoshino et al.
YBCO 293 K 1.3
Vickers indentation
YBCO 1.6 Joo et al. [141]
YBCO + 5 vol% Ag 2.2
Single-edge-notch
beam
YBCO + 10 vol% Ag 2.6
YBCO + 30 mol% Y-211 1.01 Leenders et al [142]
YBCO + 60 mol% Y-211 1.44
Vickers indenter
Cook et al. [143] YBCO 1.1 Vickers indenter
Sheahen et al. YBCO 0.8-1.0 Bending
Sheahen et al. YBCO textured 1.6 Bending
Fujitomo et al. [144] YBCO textured 0.99-1.20 Vickers indenter
Sheahen et al. YBCO with 5, 15 and 25 % of Ag
textured
1.6 Bending
Sheahen et al. YBCO with 20% Ag 3.8 Bending
Fujitomo et al. YBCO with Ag 1.6-2.1 Vickers indenter
J.J. Roa, X.G. Capdevila and M. Segarra 196
From last tables it can be observed the high scattered differences between the different
studies carried out last century. Now, we have performed a study of the mechanical properties
of YBCO samples textured by Bridgman and TSMG techniques by Nanoindentation.
Figure 27a to 27c, a representation of Youngs modulus, Hardness and fracture toughness
respect the technique can be observed.
154,3
210
213
182
47,2
29,6
28,4
9,3
96,3
220
95,98
210
110
103 103
97
0
50
100
150
200
250
E

(
G
P
a
)
Indentacin Nanoindentacin Vickers
Ultrasonic AFM Pulse echo technique
a)
10,28
5,4
5,1
4,7
18
5,2
3,58
1,03 0,95
0,53
8,7
6,7
8,5
7,81
10,8
14
8,5
0
2
4
6
8
10
12
14
16
18
20
H

(
G
P
a
)
Indentacin Vickers Nanoindentation AFM
b)
Figure 27. Continued on next page.
Mechanical Characterization at Nanometric Scale 197
1,6
2,1
2,5
2,8
1,6
2,2
2,6
1,53
1,88
1,9
1,7 1,7
1,3
0,4
1,3
1,01
1,44
1,1
1,05
1,85
0,9
1,6 1,6
3,8
0
0,5
1
1,5
2
2,5
3
3,5
4
K
I
C

(
M
P
a

m
1
/
2
)
Single edge notch beam Vickers Bending
c)
Figure 27. Representation of the bibliographic mechanical property versus the different technique for a)
Youngs modulus, b) Hardness and c) Fracture toughness.
2.2. Mechanical Properties of YBCO Samples Textured by Bridgman and
TSMG Technique by Nanoindentation
2.2.1.Plastic Deformation
Experimental Conditions
The nanoindentation technique was performed by a Nano Indenter XP Systems
(Systems Corporation) equipped with Test Works 4 Professional level software.
Nanoindentation imprints were observed with optical microscope, with an AFM NanosCope
III-A atomic force microscope, and with a field emission Hitachi H-4100 scanning electron
microscope. The experiments were performed on the (001) plane at room temperature for the
different indenters used (Berkovich and Spherical tip indenters).
First of all, a plastic study was carried out with a Berkovich indenter. In this case, the
hardness, Youngs modulus and fracture toughness were studied at different applied loads: 5,
10, 30 and 100 mN. The loading/unloading time was selected to be constant for all
indentations: 15 s. Table 6 shows fixed test parameters to perform measurements of
nanoindentation when a Berkovich indenter was used.
The small nanoindentations were made by a three-sided pyramid Berkovich diamond
indenter, see figure 19.a. The displacement or also known as penetration depth, was
continuously monitored and load-time history of indentation recorded. Each hardness,
Youngs modulus, fracture toughness and other values listed in this section, are an average of
40 measurements performed on two different samples in order to achieve statistical
J.J. Roa, X.G. Capdevila and M. Segarra 198
significance. The values obtained by the Oliver and Pharr equation (equations 5, 7 and 8)
have been corroborated by FE-SEM.
After that, we studied the Youngs modulus evolution (from 0 to 700 mN of applied load)
with continuous stiffness measurement, CSM, and with a spherical tip indenter. CSM supplies
information about the first steps of the indentation and allows to know the evolution of the
Youngs modulus with the penetration depth. The radii of this tips was 25 m. .
Experimental Curves
The load/unload curves can give a qualitative information of the hardness of each phase
of the study when the applied load is lower than 10 mN. For these loads, the mechanical
properties of each phase can be isolated.
Table 6. Test inputs of nanoindentation
Name Value Units
Allowable drift rate 0.05 nms
-1
Load rate multiple for unload rate 1 -
Maximum load 5, 10, 30 and 100 mN
Number of times to load 5 -
Peak hold time 30 s
Per cent to unload 90 %
Time to load 15 s
Figure 28, shows the load/unload curves for YBCO samples textured by Bridgman
technique when the applied load was 5 mN.
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
0 50 100 150 200
h (nm)
P

(
m
N
)
Y-123
Y-211
Y-123/Y-211
a)
Figure 28. Continued on next page.
Mechanical Characterization at Nanometric Scale 199
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
0 50 100 150 200
h (nm)
P

(
m
N
)
Y-123
Y-211
Y-123/Y-211
b)
Figure 28. Load/Unload curves for YBCO samples when the applied load was 5 mN textured by a)
Bridgman technique and b) TSMG technique.
Figure 28a, shows the qualitative manner to predict the hardness of each phase. The
hardness of one material is a function of two different parameters, the maximum applied load
and the contact area. The last parameter is a function of contact penetration and this one of the
maximum penetration. For this reason, when one phase presents a high penetration depth, this
one has a low hardness value; one material has a high hardness value when the penetration
depth is low. From figure 28a, the distribution of hardness for each phase is: H
Y-123
< H
Y-123/Y-
211
< H
Y-211.
From figure 28b, the same effect that in the figure 28b can be observed. In this
case, the difference between the different phases is less than in the figure 28a. The YBCO
samples textured by TSMG technique present the same relation: H
Y-123
< H
Y-123/Y-211
< H
Y-211.
This technique presents a little difference in the hardness value at ultra low load such as 5
mN, because after the oxygenation process, the orthorhombic phase presents a high porosity
in the ab-plane.
Figure 29, shows the load-unload curve for YBCO samples textured by Bridgman and
TSMG technique recorded by CSM when the applied load was 700 mN.
Figure 29, shows that for the two different techniques of study the first steps of
nanoindentation present the same tendency. The scattered occurs mainly in the unload curve,
for this reason the Youngs moduli will be different.
Characterization Imprints
All imprints realise in the samples of study have been observed with Optical Microscopy
and FE-SEM. In order to know the correct value of the hardness, Youngs modulus and
fracture toughness of Y-123, Y-211 and Y-123/Y-211 in the case that the applied load permit
isolate each mechanical property.
J.J. Roa, X.G. Capdevila and M. Segarra 200
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600 700 800 900 1000 1100
h (nm)
P

(
m
N
)
Bridgman technique
TSMG technique
Figure 29. P-h curve for YBCO samples textured by Bridgman and TSMG technique recorded by CSM
when the applied load was 700 mN.
Figure 30 shows indentation imprints performed by applying 30 and 100 mN on the ab
plane of the monodomain, the Y-123 matrix and Y-211 inclusions.
50 m
a)
Figure 30. Continued on next page.
Mechanical Characterization at Nanometric Scale 201

50 m
100 mN
30 mN
b)
Figure 30. Optical microscope micrographs of nanohardness impressions developed on the surface of a
sample of YBCO orthorhombic phase (ab plane) at room temperature, a) for Bridgman textured sample
(From Roa et al. Nanotechnology, 18, 2007, page 38571-1 to 38571/1-38571/6) and b) for TSMG
textured sample, when the applied load was 30 and 100.
In this figure, the particles or inclusions can be observed homogeneously distributed in
the textured samples, so that they can be easily identified but not indented separately. It is
important to highlight that the size of Y-211 inclusions (from 1 to 5 m, approximately) is
smaller than the nanoindentation imprints performed at these loads, so that we can only
measure the mechanical properties of the composite (Y-123+Y-211) when the applied load
was higher than 10 mN.
In Figure 30b, it can be observed that the residual indentations are highly affected by the
superficial porosity. Every residual imprint shows a crack in its corner. Thus indicating, give
us that YBCO is a brittle material.
When the applied loads are higher than 10 mN (such as 30 and 100 mN), only the
mechanical properties of composite can be determined and we cannot isolate the contribution
of each phase.
Figure 31 shows Y-123, Y-211 and YBCO composite imprints for samples textured by
Bridgman technique. Figure 31b, shows propagation of the cracks following the corners of
the indentation, for Y-211 precipitate. Nanohardness of Y-211 is twice as high as the Y-123
matrix (see table 7); for this reason the Y-211 phase presents a brittle fracture. The analysis of
SEM images can be used to determine the profile impressions with nanometer resolution and
to provide information about the shape change on unloading. As can be seen in this figure, the
indentation exhibit triangular geometry.
J.J. Roa, X.G. Capdevila and M. Segarra 202

1.2 m
a)
1.2 m
b)

1.2 m
c)
Figure 31. Micrograph of nanoindentation imprints obtained by FE-SEM when the applied load was 10
mN. a) matrix Y-123; b) precipitate, Y-211 and c) Y-23/Y-211 composite (From Roa et al.
Nanotechnology, 18, 2007, page 38571/1-38571/6).
Figure 32 shows Y-123, Y-211 and YBCO composite imprints at 10 mN for samples
textured by TSMG technique.
Mechanical Characterization at Nanometric Scale 203

1.50 m
a)

1.50 m
b)

1.50 m
c)
Figure 32. Micrograph of nanoindentation imprints obtained by FE-SEM when the applied load was 10
mN. a) matrix Y-123; b) precipitated, Y-211 and c) Y-23/Y-211 composite.
In figure 32b, a crack at the corners of the imprint and another fracture mechanism
known as chipping, can be observed.
When the applied load is higher than 10 mN, the mechanical properties of each phase
cannot be isolated because the size of the residual imprint is lower than the size of Y-211.
Figure 33, shows the nanoindentation imprints obtained by FE-SEM when the applied load
was 30 and 100 mN for samples textured by Bridgman technique.
J.J. Roa, X.G. Capdevila and M. Segarra 204
2.0 m
a)

3.0

m 3.0

m 3.0
3.0
m
b)
Figure 33. Micrograph of nanoindentation imprints obtained by FE-SEM of samples textured by
Bridgman technique at applied load of, a) 30 mN, and b) 100 mN.

30 m
Figure 34. Micrograph of nanoindentation imprints obtained by FE-SEM of samples textured by TSMG
technique.
Figure 33a, shows cracks at the corners of the imprints; in this case the fracture toughness
can be calculated. Inside de imprints, a radial cracks can also be observed. The fracture
mechanism in this case will be further discussed.
Mechanical Characterization at Nanometric Scale 205
Figure 33b, also shows cracks, radial ones inside the imprint and length ones at two of the
three corners of the imprint. The missing crack at one corner has been stopped by a Y-211
particle. In this case, the fracture toughness cannot be calculated.
In the case of the samples textured by TSMG technique, when the applied load was 100
mN, we can observe a lot of porosity and sink-in besides the residual imprints (Figure 34).
Figure 35, shows residual nanoindentation imprints at applied loads of 30 and 100 mN.
When the load applied was 30 mN (figure 35a), cracks at the corners of the imprints cannot
be observed. No cracks can be observed at the corners of imprints, but only radial cracks.

2.00 m
a)

5.00 m
b)
Figure 35. Nanoindentation imprints obtained by FE-SEM of samples textured by TSMG technique, a)
30 mN of applied load and b) 100 mN of applied load.
Note that when the applied load was 100mN, all imprints show a high porosity beside the
imprint for both texturing technique, see figure 34 and 35b.
J.J. Roa, X.G. Capdevila and M. Segarra 206
Hardness
Table 7 shows the calculated nanohardness values of the orthorhombic phase of Y-123,
Y-211 and Y-123/Y-211 composite for the different monodomains samples textured by
Bridgman technique, when the applied loads were 5, 10, 30 and 100 mN.
Table 7. Nanohardness of orthorhombic phases of YBCO textured by Bridgman (From
Roa et al. Nanotechnology, 18, 2007, page 38571-1 to 38571/1-38571/-6) and TSMG
technique for applied loads of 5, 10, 30 and 100 mN
Hardness;
H (GPa) Monodomain
Applied Load
(mN)
Phase
Bridgman TSMG
Sample 1
Y 123
Y 211
Y123/Y211
composite
11.0 0.5
20.0 1.0
15.2 0.3
11.41 0.51
15.0 1.05
14.86 1.05
Sample 2
5
Y 123
Y 211
Y123/Y211
composite
9.8 0.4
18.1 0.5
14.4 0.7
10.59 0.45
15.35 0.58
14.92 0.98
Sample 1
Y 123
Y 211
Y123/Y211
composite
11.4 0.4
17.1 0.5
15.3 0.3
11.12 0.96
17.14 0.25
14.58 0.78
Sample 2
10
Y 123
Y 211
Y123/Y211
composite
11.0 0.3
16.7 0.6
14.9 0.2
9.59 0.76
16.89 0.86
14.86 0.95
Sample 1 11.2 0.3 8.71 0.95
Sample 2
30 Y123/Y211
composite
11.0 0.3 8.26 0.79
Sample 1 8.8 0.2 7.96 0.72
Sample 2
100 Y123/Y211
composite
9.1 0.1 7.88 0.89
Nanohardness and Youngs modulus of each phase (Y-123 matrix and Y-211 inclusions)
can be determined when the applied load was ultra-low (less 10 mN), each phase can be
indented and the respective mechanical properties can be isolated. For higher loads, the
mechanical properties of the interaction of both phases can be obtained the YBCO composite
or Y-123/Y-211.
Mechanical Characterization at Nanometric Scale 207
Values of Y-211 phase were higher than for Y-123 in both cases of study, for the
samples. Nanohardness of Y-211 was about twice as high as for Y-123. This fact could be
due to different reasons:
I). Ionic bond of Y-211 is stronger than the Y-123 bond,
II). High anisotropy of dislocation confined onto a (001) plane [145], and/or
III). the melt processed ceramic composites contain a dense population of fine peritectic
inclussion embebbed in a matrix, which drastically affects the microstructure acting
as nucleation sites for dislocation
When the applied load is 100 mN, overall nanohardness is very similar for both samples
(for Bridgman technique 8.90 GPa, and TSMG technique 7.92 GPa) but is lower than the
nanohardness of the Y-123 phase. Therefore, these results are in agreement with a previous
work reported by Lim and Chaudhri which studied the hardness of YBCO single crystal by
Nanoindentation technique and the hardness value obtained was 7.81 GPa. This value is in
agreement with the result obtained for samples textured by TSMG technique. On the other
hand, the hardness value obtained for samples textured by Bridgman technique is in
agreement with a previous work reported by Soifer et al. and Cook et al..
When the applied load is higher than 10 mN we are working within the microindentation
range and we can observe microcraks at the corners of imprints (see figure 33a), thus causing
the reduction of the hardness value (H
100mN
< H
30mN
). This effect is known as indentation size
effect, ISE.
Verdyan et al [146] reported a nanohardness for orthorhombic YBCO thin film can be
around 8.5 GPa, when the applied load varies between 0.1 and 9mN, which are similar values
to those found in the present study for the orthorombic phases. Values of the Youngs
modulus are also comparable to our results for the orthorhombic composite, studied at loads
of 30 and 100 mN.
If we compare our data for Hardness with data reported of YBCO (see table 7), we
conclude that the broad distribution of hardness observed in table 4 can be attributed both to
the different measuring techniques and to different quality of the studied YBCO samples
(grain structure, porosity, texturing process, etc).
Youngs Modulus
Table 8 shows the calculated nanohardness and Youngs modulus values of the
orthorhombic of Y-123, Y-211 and Y-123/Y-211 composite for the different monodomains
samples studied when the applied loads were 5, 10, 30 and 100 mN textured by TSMG
technique.
When the applied load is 100 mN, overall Youngs modulus are very similar for both
samples and techniques (for Bridgman technique 173 GPa and TSMG technique 129 GPa)
but is lower than the Youngs modulus of the Y-123 phase. Therefore, the results obtained by
Bridgman technique are in agreement with a previous work reported by Goyal et al. which
studied the Youngs modulus of texturized YBCO by Nanoindentation technique and the
Youngs modulus value obtained was 182 GPa. The Youngs modulus value obtained for
samples textured by TSMG technique is in agreement with a previous work reported by Joo et
al. which value had been obtained by pulse echo technique. Goyal et al. studied the Youngs
J.J. Roa, X.G. Capdevila and M. Segarra 208
modulus of Y-211 phase present in YBCO samples by Nanoindentation; this value was 213
GPa. This value obtained by Goya et al.] is in agreement with a value obtained by
Nanoindentaion for YBCO samples textured by TSMG technique when the applied load was
10 mN and the Y-211mechanical properties have been obtained.
Table 8. Youngs modulus of orthorhombic phases of YBCO textured by Bridgman
(From Roa et al. Nanotechnology, 18, 2007, page 38571-1 to 38571/1-38571/-6) and
TSMG technique for applied loads of 5, 10, 30 and 100 mN
Youngs modulus;
E (GPa) Monodomain
Applied Load
(mN)
Phase
Bridgman TSMG
Sample 1
Y 123
Y 211
Y123/Y211
composite
193 7.60
199 10.20
204 7.12
176.44 15.31
224.35 20.45
207.33 21.65
Sample 2
5
Y 123
Y 211
Y123/Y211
composite
200 6.53
189 8.56
198 7.02
175.89 15.39
223.54 16.23
208.26 19.52
Sample 1
Y 123
Y 211
Y123/Y211
composite
185 3.16
209 4.29
201 6.92
173.62 18.20
207.27 10.58
189.61 17.87
Sample 2
10
Y 123
Y 211
Y123/Y211
composite
192 4.21
203 3.56
206 5.49
174.59 15.35
206.58 9.59
190.12 15.2
Sample 1 179 5.49 140.09 14.21
Sample 2
30 Y123/Y211
composite
181 4.35 139.85 13.25
Sample 1 171 2.51 128.88 5.54
Sample 2
100 Y123/Y211
composite
175 3.87 130.37 5.69
Several measurements of Youngs modulus for Y-123 have resulted in values scattered
within the range E=40-200 GPa. Most probably, this scatter is caused by residual porosity and
bad contacts between the grains [147]. Sakai et al [148] reported a value of 370 GPa for 5
mm
3
cubic specimens cut from a single-crystal Y-123 prepared by TSMG using a single
domain of Sm-123 as a seed. The authors attribute the difference of Youngs modulus to the
40% excess of Y-211 phase present in the material. Obtained results of Youngs modulus are
in agreement with Johansen et al. and Alford et al [149] when the applied loads were 30 and
100 mN.
Mechanical Characterization at Nanometric Scale 209
If we compare our data for Youngs modulus with data reported for YBCO (see table 8)
we also conclude that the broad distribution of Youngs moduli observed in table 3 can be
attributed both to the different measuring techniques and to the different quality of the studied
YBCO samples (grain structure, texture, and others).
The tendency of the Youngs modulus versus penetration depth obtained with a spherical
tip indenter and CSM recorded for each one of these texturing techniques is presented in the
next figures.
0
20
40
60
80
100
120
140
160
0 100 200 300 400 500 600 700 800 900 1000 1100
h (nm)
E

(
G
P
a
)
a)
0
20
40
60
80
100
120
140
0 100 200 300 400 500 600 700 800 900 1000 1100
h (nm)
E

(
G
P
a
)
b)
Figure 36. Evolution of the Youngs modulus versus the penetration depth for YBCO samples at
maximum applied load for a spherical tip indenter for samples, a) textured by Bridgman technique and
b) textured by TSMG technique.
J.J. Roa, X.G. Capdevila and M. Segarra 210
Figure 36a, shows that the Youngs modulus increases until a constant value, which is
around 300 nm of penetration depth. When the penetration depth is lower than 300nm, the
spherical contact area could be smaller than the size of Y-211 particles. So, at first stages, we
could measure each phase or interface separately. This can explain the highly scattered values
that we can see in figure 36a. When the residual imprints are higher than the superficial
defects, the Youngs modulus value of the samples textured by Bridgman technique present
only a constant value with the penetration depth.
Figure 36b, shows two different tendencies of the Youngs modulus: until 300 nm a high
dependence of the Youngs modulus with the penetration depth can be seen. On the other
hand when the penetration depth is higher than 300 nm, this trend decreases. In this case, a
constant value of Youngs modulus cannot be achieved.
The difference sample response between Bridgman and TSMG monodomain could be
related to the fragilization of the material due to the high porosity density present in the
TSMG samples. Even for penetrations depth lower than 300 nm, we cannot isolate the
porosity effect over the Youngs modulus value. This is reflected in figure 36b by the high
homogeneity on the measurements. For higher applied loads, in the Bridgman samples with
lower porosity the Youngs modulus tends over the Y-123/Y-211 value. In TSMG samples,
the inner porosity not allows this kind of stabilization.
Table 9, shows the Youngs modulus values for the YBCO samples obtained with a
spherical tip indenter at 300 nm of penetration depth using CSM.
Table 9. Youngs modulus of YBCO samples obtained by spherical indentation at 300
nm of penetration depth using CSM
Material Technique Youngs modulus (GPa)
Bridgman 120 20
YBCO
TSMG 108 8
The Youngs modulus of YBCO samples textured by Bridgman technique obtained with
spherical tip indenter are similar to the values obtained with Berkovich indenter, see table 8.
In Figure 36 and Table 9, the values present a difference tendency before and after than 300
nm of penetration depth. When the sample was textured by TSMG technique at 300 nm of
penetration depth, the different curves of Youngs modulus versus penetration depth present a
lower scattered value. In this case, when the penetration depth is lower than 300 nm the
sample present a high homogeneity between Y-123 and Y-211 particles. For penetration
depth higher than 300 nm, the Youngs modulus does not present a constant value. In the
other hand, for samples textured by Bridgman technique when the penetration depth is lower
than 300 nm, the material presented a high interaction with the surfaces defects; for this
reason the Youngs modulus present high scattered values. For penetrations depths higher
than 300 nm, the material presents a constant value of Youngs modulus.
Indentation Size Effect
The indentation size effect is generally attributed to train gradient plasticity that generates
geometrically necessary dislocations; for ceramic compounds where the plasticity is limited
allow loads, the elastic recovery can be significant. When the indentation size is smaller, the
density of geometrically necessary dislocations decreases and, as a result, hardness becomes
Mechanical Characterization at Nanometric Scale 211
higher at small loads [150]. In fact, from the present calculations of the indentation height
before and after removal of the load, it is found that 10% of total work done during the
indentation at loads of 5, 10, 30 and 100 mN, is due to elastic deformation.
While most of the methodologies of analysis of instrumented indentation test assume that
materials are homogeneous and continuous this is not the case for real materials, as the
continuous broke at a given length (size effect).
However, nanohardness can be strongly affected by the presence of defects and
impurities that can cause almost no change in dislocation movement, which would affect the
hardness. This phenomenon is known as ISE.
Instrumented indentation is, a priori, a good technique for local evaluation of the residual
stresses, and, for that purpose, several methods have been developed, specially for metals
with relatively low yield stress and that do not work harden appreciably when indented with
sharp indenters. However, these tests work well when the measured residual stress is in the
order of magnitude of the order of the hardness of the material. In YBCO materials, this is
often the case because of the high hardness of these materials. In this material, the differences
obtained in the load-unload curve from a stressed to an unstressed material are too small to
qualitatively extract a value of residual stress.
The load-displacement curves obtained for various loads and techniques are shown in
figure 37. For each material, all the data points of ten measurements are given in this plot
when the applied load was 100 mN. The same effect also can be observed at different studied
applied loads, such as: 5, 10 and 30 mN. For YBCO samples textured by Bridgman and
TSMG techniques, slight scatters exist among the different load-displacement curves. These
scatters may be attributed to the intrinsic microstructural inhomogeneity of these two different
techniques to produce single crystals.
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800 900 1000
h (nm)
P

(
m
N
)
a)
Figure 37. Continued on next page.
J.J. Roa, X.G. Capdevila and M. Segarra 212
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800 900 1000
h (nm)
P

(
m
N
)
b)
Figure 37. Load/unload curves at 100 mN of applied load on samples textured by, a) Bridgman
technique and b) TSMG technique.
Figure 37. a and b, shows the load-unload curves for YBCO samples textured by
Bridgman and TSMG techniques at 100 mN of applied load, respectively. At this load, the
hardness and Youngs modulus of YBCO sample has been studied because the residual
indentation imprint is higher than the size of Y-211 particles. If the hardness of YBCO
sample is the same for all indentations performed on the ab-plane, then we only have to look
at one load-unload curves. Nevertheless, in this figure we can observe a high scattered load-
unload curves; this effect may be probably due to the ISE. When the applied load is increased,
their hardness value is decreasing due to the same factor. Some authors have studied the ISE
effect and proposed some equations to solve these problems, such as: Meyers lawn, Hays-
Kendall approach, elastic recovery model, proportional specimen resistance model or PSR
model and the modified PSR model (see equations 33 to 43).
Figure 38 shows the experimentally determined nanoindentation hardness, H, as a
function of the peak load, P
max
, for the tested materials. Until 30 mN of applied load, the high
tendency is due to the existence of two different phases embedded in the samples of study.
When the applied load is 10 mN lower, the mechanical properties of different phases can be
studied (Y-123, Y-211, Y-123/Y-211). In figure 38, a high dependency at low applied loads
can be observed. This effect is due to the difference between the different phases present in
YBCO samples. The ISE can be used for isotropic materials. In fact, YBCO samples present
high anisotropy properties in the ab-plane.
The different models proposed to study the ISE for ceramics, present some problems to
apply in YBCO samples, such as:
Mechanical Characterization at Nanometric Scale 213
- These approaches do not calculate or evaluate the area factor, and the contact area
can be strongly affected at low applied loads. This effect produces and overestimated
hardness value.
- The ISE is only affected by the dislocation movement. YBCO samples and a lot of
ceramic compounds, present another mechanism such as radial cracks, fracture
mechanisms, etc. If the material presents this mechanism, the equations proposed for
this study cannot be applied.
In conclusion, YBCO samples textured by Bridgman and TSMG techniques may present
ISE. These phenomenas cannot be solved because the different equations for ceramics
compounds do not a present the different fracture mechanism. If someone has to evaluate ISE
for ceramic compounds, the best thing to do is perform a high amount of nanoindentation
imprints, and apply the Weibull approach in order to have an average of measurements.
Investigations have confirmed that hardness numbers calculated with the Oliver and Pharr
method show load dependency as the manner of ISE depicted in figure 38. In order to
describe the ISE behaviour, several relationships between applied indentation test load, P, and
penetration depth, h, have been presented in the literature [151]. In the same figure it, can be
observed that at small loads (less than 10 mN), the Bridgman and TSMG samples have the
same Hardness. When the applied load increase, the difference between the two different
methods of texture increase. It is due to the high porosity present in TSMG sample, see
figure 39.
7
8
9
10
11
12
13
14
15
16
0 10 20 30 40 50 60 70 80 90 100
Peak load, P
max
(mN)
H
a
r
d
n
e
s
s
,

H

(
G
P
a
)
Bridgman technique TSMG technique
Figure 38. Variation of nanoindentation hardness with the peak load for the tested materials.
J.J. Roa, X.G. Capdevila and M. Segarra 214

2 m
Figure 39. Optical micrograph of YBCO samples textured by TSMG technique.
Table 10. Relation h
f
/h
max
for each phase, load and technique
Technique
Phase Peak load (mN)
Bridgman TSMG
Y-123 0.72 0.02 0.66 0.04
Y-211 0.65 0.02 0.63 0.02
Y-123/Y-211
5
0.69 0.01 0.65 0.01
Y-123 0.72 0.02 0.69 0.03
Y-211 0.67 0.01 0.65 0.01
Y-123/Y-211
10
0.70 0.01 0.66 0.04
Y-123/Y-211 30 0.73 0.02 0.70 0.02
Y-123/Y-211 100 0.76 0.01 0.70 0.01
D. Pile-up and Sink-in Problems
Another common problem in the determination of the hardness by Nanoindetation
technique, is the pile-up and sink-in, for more detail see figure 26. The most common effect
in YBCO samples is the sink-in effect. The pile-up or sink-in can be obtained from the rate
between the final and the maximum penetration depth. If this relation is higher than 1.0,
YBCO may present a pile-up effect. On the other hand, if the relation is lower than 1.0, the
sample could presented sink-in effect. This study has been performed in both samples
textured by these two different methods.
Next table summarizes the relation h
f
/h
max
for each phase, load and technique. Every
value presented in the table is an average of eighty indentations performed in two different
single crystals.
Mechanical Characterization at Nanometric Scale 215
When the applied load is lower than 10 mN, the relationship can be isolated for each
phase. At 5 and 10 mN of applied load, the Y-211 and Y-123/Y-211 phases do not present
pile-up effect. On the other hand, Y-123 can present sink-in effect. In this case, the area of the
residual imprint can be overestimated and produce a reduction of the hardness of these
phases; this effect strongly affected the samples textured by Bridgman technique. Whereas it
cannot be observed on samples textured by TSMG technique. In conclusion, the pile-up/sink-
in can be related to the hardness of each phase. When the applied load is higher than 10 mN,
we cannot isolate this relation for each phase present in the studied material; in this case, only
the existence of the sink-in in the Y-123/Y-211 can be determined.
When a residual imprint present pile-up or sink-in effect, principally for samples textured
by Bridgman technique, two different things can be performed:
- Observe all the residual imprints with scanning electron microscopy (SEM) and
calculate the contact area. Compare the contact area obtained with SEM and the area
supplied by the Nanoindenter. If the areas have the same value, the pile-up effect will
not exist, but a fracture mechanism takes place.
- In the case that the two areas have a high scattered value, the Cheng and Cheng
approach must be used, and the hardness corrected.
In this study the Cheng and Cheng equations have not be used to correct the contact area,
because the size of the imprints obtained by SEM are very similar to the size obtained by the
Indenter.

5.00 m
Figure 40. Sink-in effect besides a residual imprint due to the uniaxial compression focused under the
Berkovich indenter.
This effect has been widely observed in the residual imprints when the YBCO was
textured by TSMG technique and the applied load was higher than 10 mN. This will be
discussed widely under next heading related to fracture toughness.
J.J. Roa, X.G. Capdevila and M. Segarra 216
Fracture Toughness
Ceramics are generally brittle, and prone to generation of cracks when indented.
Toughness estimation by micro fracture Vickers indentation is a well-known and broadly
employed technique in ceramic materials. This technique consists of the application of a
Vickers (or Berkovich) indenter at a given load, onto the material, sufficiently high to
nucleate cracks at the corners of the imprint, and further measure the crack length produced at
the corner of the imprint, c, in order to evaluate the fracture toughness, K
IC
. In case that very
small volumes of material are going to be evaluated obtuse indenters are required (like
Berkovich), which do not produce cracks large enough for a correct estimation of toughness
fracture.
YBCO samples present different mechanisms of fracture, such as crack at the corners of
the imprints, chipping, radial cracks inside the imprint, sink-in, and others.
When the sample was textured by Bridgman technique method the following
observations have been made:
- Y-211: at applied loads lower than 10 mN, have lateral cracks producing chipping;
this effect can be observed in figure 31b.
- Y-123: when the applied load is lower than 10 mN any fracture mechanism can be
observed (see figure 31a).
- Y-123/Y-211: at 10 mN of applied load, a propagation of crack is only observed at
one of the corners; in this case, the fracture toughness cannot be calculated (see
figure 31 c).
- When the applied load was 30 mN, the toughness of YBCO samples textured by
Bridgman technique can be obtained. Figure 33a, shows a crack at the corner of the
nanoindentation imprints performed at 30 mN. With the crack length and the
Palmqvist equation (equation 27), the toughness can be calculated for an applied load
of 30 mN. The obtained value is 2.85 0.11 MPam
1/2
.
- When the applied load was 100 mN, porosity besides the imprint can be observed
due to the localized deformation during the nanoindentation test, and also radial
cracks inside the imprint (figure 33b). The radial cracks are vertically halfpenny type
cracks that occur on the surface of the specimen outside the plastic deformation zone,
and at the corners of the residual impression at the indentation site. These radial
cracks are formed by a hoop stress and extended downward into the indentation; an
example of the radial cracks can be observed in figure 33b.
When the sample was textured by TSMG technique method the following can be
observed:
- When the applied load was 10 mN, for Y-211 particles, the same fracture mechanism
has been observed. In this case, chipping is the most important mechanism but also
exists another mechanism that reduce the toughness of the studied sample; this factor
is the porosity near the imprints. For Y-123 and Y-123/Y-211 at the same load, any
fracture mechanism has been observed. At this applied load, the fracture toughness
has not been calculated (see figure 32).
Mechanical Characterization at Nanometric Scale 217
- When the applied load was 30 mN, any crack propagation have been observed; only
one fracture mechanism could be detected, in this case; in the residual imprint
internal cracks can be observed, perpendicular to the surface (see figure 32a). Figure
32a, shows that the Y-211 are harder than Y-123, it is due to Y-211 particles, which
after the unloading are not deformed.
- When the applied load was 100 mN, any crack propagation in the corners of the
imprint can be observed. In this case a sink-in and porosity near the indentation
imprint can be observed, see figure 35b. The sink-in had been predicted with the
relation between the final and the maximum penetration depth; this result is in
accordance with the value obtained and presented in table 15. Nest figure, shows
cracks inside the nanoindentation imprint, and a sin-in near the imprint.
In conclusion, YBCO samples textured by Bridgman and TSMG technique are brittle
materials. The Y-123 phase is a soft phase because absorb all the plastic deformation during
the nanoindentation imprint. On the other hand, Y-211 is a hard material and it is broken
during the indentation. When the indenter was performed at the interface, any fracture
mechanisms have been detected. When the applied load was higher than 10 mN, the fracture
toughness can be calculated for the samples textured by Bridgman technique. Nevertheless,
for TSMG technique, internal perpendicular cracks have been detected. At maximum applied
load, 100 mN, a sink-in effect is produced and porosity can be created due to it.

5.00 m
Figure 41. Residual imprint with different fracture mechanism when the applied load was 100 mN and
the material textured by TSMG technique.
The fracture toughness obtained for YBCO samples are in concordance with the values
published in the bibliography, concretely with Joo et al. for samples with 15% w/w of Ag
which value is 2.80 MPam
1/2
, or 10% w/w Ag which present a value of 2.60 MPam
1/2
. Both
values have been obtained with single-edge-notch beam. Sheahen et al. present a fracture
toughness value of 3.80 MPam
1/2
for a sample with 10% w/w Ag.
J.J. Roa, X.G. Capdevila and M. Segarra 218
2.2.2. Elastic Deformation
Experimental Conditions
The nanoindenter (XP System, MTS) used in this work was equipped with a CSM
attachment. The harmonic displacement for the CSM was 2 nm with a frequency of 45 Hz.
The test was carried out on two different samples for each technique of texture studied.
Figure 42 shows indentation imprints performed when the maximum load was 700 mN
on the ab-plane of the monodomain with a spherical tip nanoindenter. Also in this figure also,
it can be observed that the Y-211 particles are homogeneously distributed in the textured
sample, so that they can be easily identified but not indented separately. It is due to the size of
the Y-211.
Stiffness versus Displacement into Surfaces
Before plotting the indentation stress-strain curves it is crucial to determine the effective
elastic stiffness of the YBCO material examined. Plot of S versus displacement into surface,
allows to determine if the contact point indenter-sample is good or not. In that case a straight
line can be observed, whereas a non linear relation is found when the contact is not good
enough.

50 m
Figure 42. OM micrographs of residual impressions performed on the surface of YBCO orthorhombic
phase (ab-plane) at room temperature, when the applied load was 700 mN and the sample textured by
Bridgman technique.
Figure 43, shows the tendence of stiffness with the penetration depth. This figure gives us
information about which stress-strain curves will be suitable or present high scattered values.
When S versus h is a straight line, the contact point between indenter and sample is right and
therefore the stress-strain curve will be suitable. This implies that S is not affected by pop-ins
or plastic deformation. A bad contact point can give us an overestimated strain value, and
therefore inaccurate yield strength is obtained. In this case, MTS software must be used in
order to correct experimental values. Next figure shows the experimental curves and the same
corrected with MTS software, for both samples studied.
Mechanical Characterization at Nanometric Scale 219
0
250000
500000
750000
1000000
1250000
0 100 200 300 400 500 600
h (nm)
S

(
N
/
m
)
a)
0
250000
500000
750000
1000000
1250000
0 100 200 300 400 500 600
h (nm)
S

(
N
/
m
)
b)
Figure 43. Plot of harmonic stiffness versus penetration depth as determined from spherical
nanoindentation for YBCO materials textured by a) Bridgman technique and b) TSMG technique.
0
25000
50000
75000
100000
0 10 20 30 40 50 60
h (nm)
S

(
N
/
m
)
a)
Figure 44. Continued on next page.
J.J. Roa, X.G. Capdevila and M. Segarra 220
0
25000
50000
75000
100000
0 10 20 30 40 50 60
h (nm)
S

(
N
/
m
)
b)
0
25000
50000
75000
100000
0 10 20 30 40 50 60
h (nm)
S

(
N
/
m
)
c)
0
25000
50000
75000
100000
0 10 20 30 40 50 60
h (nm)
S

(
N
/
m
)
d)
Figure 44. Contact point for samples textured by, a) Bridgman technique with bad contact point, b)
TSMG technique with bad contact point, c) Bridgman technique with good contact point, and d) TSMG
technique with good contact point.
Mechanical Characterization at Nanometric Scale 221
Determination of the Elasto-Plastic Transition
In most materials, and according to the Tresca criterion, when the value of
max
reaches a
certain limit (
max
=
ys
/2, where
ys
is the yield strength of the material), the material will
start to flow and develops a permanent deformation. This criterion has been also used to
explain the nucleation of dislocations during pop-in effects [152], yielding the material to
make the transition from an elastic to an elasto-plasic response [153]. In this case, mean
contact pressure will converge on the hardness of the material.
0
5
10
15
20
25
0 20 40 60 80 100 120
Displacement (nm)
P

(
m
N
)
Figure 45. Load/depth-of-penetration results for YBCO monodomain ab-planes, with a 25 m spherical
indenter, for Bridgman technique at 100 nm of penetration depth.
Figure 46. Load/depth-of-penetration results for YBCO monodomain ab-planes, with a 25 m spherical
indenter, for Bridgman technique at 200 nm of penetration depth.
J.J. Roa, X.G. Capdevila and M. Segarra 222
However, it has to be taken into account that, if yield strength is not overcome, the slope
of the unloading curve will the same as for the loading curve, and the same equation, 16 will
hold, see figure 45.The typical load-displacement curves obtained when the YBCO ab-plane
is indented with a 25 m spherical indenter, figure 46, are characterized by the elasto-plastic
transition or commonly known as pop-in, indicated in the figure as a change in the slope of
the loading curve.
If we observe the surface of the imprints with AFM, residual imprint is found, for
penetrations depths lower than 150 nm which correlates with the change in the slope of the
loading curve (pop-in effect). For higher penetration depth, different residual imprints can be
observed by AFM (Figure 47).
During the first steps of nanoindentation (elastic regime), the load curve can be adjusted a
Hertzian contact (P = Ch
3/2
); when the applied load is higher than the elasto-plastic transition,
a residual imprint can be observed, and the load curves can be adjusted as P = Ch
2
. In both
cases, C is the slope of the load curve in each regime.

m
2.2
a)
2,2 m 2,2 m 2,2 m
b)
Figure 47. AFM image at different penetration depths for YBCO monodomains, textured by Bridgman
technique, a) 200 nm and b) 800nm.
Mechanical Characterization at Nanometric Scale 223
Stress-Strain Curves
In the case of spherical indentation, by plotting p
o
(mean contact pressure) against a/R
(contact radium/indenter radium) it is possible to determine the point at which there is the
transition from elastic to elasto-plastic regime, shown in Figure 46 as a change in the slope
for the studied samples.

0
1
2
3
4
5
6
0 0.05 0.1 0.15 0.2
Strain, a/R (Dimensionless)
S
t
r
e
s
s
,

p
o

(
G
P
a
)
Elastic (Hertzian theory)
a)

0
1
2
3
4
5
6
0 0.05 0.1 0.15 0.2
Strain, a/R (dimensionless)
S
t
r
e
s
s
,

p
o

(
G
P
a
)
Elastic (Hertz theory)
b)
Figure 48. Indentation stress/strain curves for YBCO textured by a) Bridgman, and b) TSMG
techniques.
J.J. Roa, X.G. Capdevila and M. Segarra 224
These values are around 3.5 GPa and 3.0 GPa for Bridgman and TSMG, respectively.
To obtain the yield strength, next equation has been used:
( )
o ys
p = 2 1
2
1
(44)
where,
ys
is the yield strength, is the Poisson ratio of the material and p
o
is the mean
contact pressure at the point of elastic to elasto-plastic transition (obtained from data in
Figure 48). Values obtained for Bridgman and TSMG samples are 700 MPa and 600 MPa
respectively. The difference between both techniques can be attributed to the different amount
of defects, as well as correlated to data for hardness, Youngs moduli and fracture toughness
previously reported.
2.2.3. Kinetic Study by Nanoindentation Technique of TSMG Samples along the C-
Axis At 450c
An important phenomenon in bulk superconductors obtained by TSMG, is the formation of
cracks due to the inherent brittleness of the Y-123 phase matrix. These cracks form during the
texturing of the superconducting monolite and play an important role in the limitation of
current flow. As-grown Y-123/Y-211 bulk superconductors prepared by the TSMG process
must be further oxygenated in order to transform from tetragonal to orthorhombic phase.
Oxygenation at temperatures around 400-450C could take between one to two weeks for a 2
cm diameters and 4 mm height sample. Oxygen diffuses through cracks previously formed
during cooling in the texturing process. Two types of macrocraks are formed:
I). a/b-macrocraks parallel to the a/b-plane and
II). c-macrocraks parallel to the a/c-plane.
While the a/b-macrocraks extend over almost the whole sample, the c-macrocrak length
is limited by the a/b-macrocraks spacing [154].
c-axis macrocrack network represents a mesoscopic defect in bulk superconductors
obtained by TSMG, and limits the local current density in the sample.
Reddy and Rajasekharan [155] studied the inner structure of partially oxygenated Y-123
bulk melt-textured material. During the oxygenation process microcraks parallel to the a/b-
planes (a/b-microcracks) appear in the melt processed YBCO (dark lines in Figure 49). Y-211
phase particles (dark), and twins can also be seen.
Experimental Conditions
Samples used to perform this study were obtained by the TSMG technique. A small
NdBCO melt textured grain was used to seed the melt growth process; it was placed at the
centre on top of the basal pellet surface before heating and the melt-growth process was
applied. From textured sample, a 20 mm x 20mm x 4mm monodomain was obtained that was
further cut into four pieces of 10 mm x 10 mm x 4 mm. Afterwards, these four pieces were
introduced in a horizontal furnace for an oxygen annealing (99.999% purity) at 450C for
Mechanical Characterization at Nanometric Scale 225
different oxygenation times, 24 h, 48 h, 96 h and 187 h. After oxygenation each piece has
been cut following next schema.
10m
a,b c
Figure 49. The microcracks parallel to the a/b-planes (a/b-microcracks) in the melt processed YBCO
(dark lines). Y-211 phase particles (dark) and twins can also be seen. (From Diko et al., Superconductor
Sci. Technol, 16, 2003, pages 90-93).
Figure 50. Preparation samples scheme.
The applied load used to determine the mechanical properties was 10 mN. At this load,
the mechanical properties of Y-123 can be isolated, and the hardness evolution with the
J.J. Roa, X.G. Capdevila and M. Segarra 226
oxygenation time can be obtained, as oxygen concentration gradients lead to large mechanical
stress in the material. The oxygenation diffusion coefficient in the ab-plane is about 10
4
-10
6
times larger than in c-direction [156].
The structure of all samples was observed by optical microscopy in polarized light after
polishing and etching in 1 w/w % HCl in ethyl alcohol. Nanoindentation imprints were
observed by FE-SEM.
Oxygenation Defects and Macro-microckracking in Melt-Textured YBCO Bulks
First, the c-axis section of the oxygenated samples was investigated in order to locate
regions of tetragonal phase which can be clearly distinguishable, under polarized light as
darker or brighter regions depending on the orientation of the Y-123 crystal axes to the vector
of polarized light and/or the mutual position of the analyses and polarizer [157].
The macrocracking and the porosity were the dominant structural changes in the samples
after oxygenation. Observation at optical microscope under polarized light revealed a high
density of porosity formed during the oxygenation process. Figure 51, shows the optical
micrographs of c-axis YBCO samples textured by TSMG technique at different oxygenation
times.

Figure 51. Optical micrographs of the c-axis at different oxygenation times, a) 24 h, b) 48 h, c) 96 h and
d) 187 h. O, orthorhombic phase and T, tetragonal phase.
Mechanical Characterization at Nanometric Scale 227
Different defects produced after the oxygenation process can be seen in Figure 52.

7.49 m
a)

6 6 .7 m
b)

15 m
c)
Figure 52. Defects observed by FE-SEM after the oxygenation process, a) formation of microcracks
around the porosity, b) generation of macrocracks and c) micrograph of the c-axis after oxygenation
process.
J.J. Roa, X.G. Capdevila and M. Segarra 228
If we observe in detail a porosity, we will see a microcrack (Figure 52a). Another
problem during this process is the presence of macrocracks,.that have been generated during
the cooling in the texture process due to the different expansion coefficients between Y-123
and Y-211, and that growth during the oxygenation process, see figure 52b. Both defects
produce an embrittlement of the material of study.
Macrocracks can easily form in regions with low Y-211 concentration and 158], because
the fracture toughness increases with the concentration of Y-211 particles [159 and 160].
Moreover, Y-211 phase has a lower thermal expansion coefficient than Y-123 phase in the c-
direction [161], and Y-211 is therefore under tension during cooling down, and a/b-
macrocracking in the Y-211 is enhanced.
Length and the spacing of a/b- and c-macrocracks, increase continuously with increasing
the oxygenation temperature. At higher oxygenation temperature the a/b- and especially the c-
macrocracks spacing is significantly increasing. In contrast, at lower oxygenation temperature
(such as 450C) the c-macrocracks are very fine and their density is very high.
Tensile stress in the c- and a/b- direction are induced by shrinkage of the lattice
parameters of the Y-123 phase with oxygen content. These stresses are then responsible for
a/b- and c-crack formation in the oxygenated layer.
Oxygen may then flow along the c-cracks to the a/c-surfaces, oxygenate the c-cracks
surface and c-cracks tip and further c-crack propagation. It can be observed in figure 52c,
that in the Y-123 material, the network of pores, dispersed in the Y-123/Y-211 skeleton, also
supports the orthorhombic transformation. This means that the region around the pores is
oxygenated by fast diffusion in the a/b-direction. All these microstructural items are
important during the process of oxygenation of YBCO bulk materials.
Determination of the Kinetics of Oxygenation by Nanoindentation
The hardness of YBCO bulk material has been studied from the oxygenation surface
oxygenation until the bottom of the sample along the c-axis. For this study the thickness of
the samples used were 4 mm. Figure 55, shows the different nanoindentation imprints along
the c-axis of the samples studied.
Figure 53. Nanoindentation imprints along the c-axis in YBCO samples textured by TSMG technique.
Mechanical Characterization at Nanometric Scale 229
Figure 53, shows a matrix of indentations being the distance between each are 40 m.
The representation of hardness versus the position from the upper surface of the sample, can
give us information about the oxygenation process.
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
0 500 1000 1500 2000 2500 3000 3500 4000
Height from the upper
surface along the c-axis (m)
H
a
r
d
n
e
s
s

(
G
P
a
)
24 h
48 h
96 h
187 h
Tetragonal
Orthormhombic
Figure 54. Hardness versus height for YBCO samples textured by TSMG technique.
Figure 54, shows the tetragonal-orthorhommbic transition in YBCO samples textured by
TSMG technique. In this figure, it can be observed that the transition is function of the
oxygenation time. When the sample is oxygenated during 187h, has a little portion of
tetragonal phase. The high disperssion presented in this figure is due to superficial defects
produced during the oxygenation process. At the end of oxygenation, all samples present a
tetragonal structure; in this case, the hardness value is higher than for orthorhombic structure,
which has a macro- and microcraks that produce a reduction of the hardness of the YBCO
samples. When the oxygenation time was 187h, the transformation has taken place in the first
3000 m, remaining the rest of the sample with a structure not purely tetragonal. In this case,
an interface between tetragonal and orthorhombic phase could be formed. For samples with a
height of 4 mm, the oxygenation time needed to complete the transformation is greater than
187 h.
Prediction of the Oxygenation Time in YBCO Bulk Materials
To predict the oxygenation form a bigger sample, we represent the distance from the
surface that has undergone the transition versus the time needed to achieve it.
J.J. Roa, X.G. Capdevila and M. Segarra 230
0
500
1000
1500
2000
2500
3000
3500
4000
0 50 100 150 200 250 300 350 400
time (h)
D
i
s
t
a
n
c
e

f
r
o
m

s
u
r
f
a
c
e

a
l
o
n
g

t
h
e





c
-
a
x
i
s

(
m
m
)
Figure 55. Distance from the surface along the c-axis transformed into orthorhombic phase versus time
of oxygenation for YBCO samples textured by TSMG technique.
As can be seen in this figure the time necessary to complete oxygenate a sample with a
height of 4 mm is around 380h. Moreover, figure 55 shows two different tendends, a quick
oxygenation process through macrocracks formed during cooling in the texture process, and a
slower oxygenation process that take place when microcracks are formed, induced by oxygen.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 237-274 2010 Nova Science Publishers, Inc.
Chapter 6
ZNO NANOWIRE ARRAYS: TEMPLATE-FREE
ASSEMBLY GROWTH AND THEIR PHYSICAL
PROPERTIES
Bingqiang Cao
*
and Weiping Cai
Key Laboratory of Material Physics, Institute of Solid State Physics, Chinese Academy
of Sciences, Hefei, 230031, Anhui, China
Abstract
In this chapter, growth and physical properties of ZnO nanowire arrays were reviewed. It
begins with some general remarks on semiconductor nanowires and basic properties of ZnO.
In the second part, different kinds of growth methods that have been applied to grow ZnO
nanowires are summarized. Vapor phase methods usually based on VSL or VS mechanism,
depending on the presence or absence of a metal catalyst, were discussed in general. Typical
solution methods for growth of ZnO nanowires were discussed separately as there is no
common growth mechanism that can be applied to describe them. A new template-free
strategy based on self-assembly process to grow ZnO nanowire into arrays were emphasized
and discussed in detail. The obtained sample qualities were characterized with scanning
electron microscopy, transmission electron microscopy, X-ray diffraction and energy-
dispersive X-ray spectrum. The third part deals with the physical properties of ZnO nanowire
arrays. Raman spectrum, including resonant Raman spectrum, was applied to test the crystal
quality and phonon interaction of ZnO nanowires. Temperature-dependent photoluminescence
spectra were measured to probe the intrinsic exciton and defect-related emission process of
ZnO nanowires. Field emission properties of such ZnO nanowire arrays were also studied in
view of the possible application for flat-panel displays. Some brief conclusions were
summarized at the end.

*
E-mail address: bqcao@issp.ac.cn
Bingqiang Cao and Weiping Cai 238
1. Introduction
1.1. Semiconductor Nanowires
Nanowires, including nanobelts and nanorods, represent an important and broad class of
one-dimensional (1D) nanostructures at the forefront of nanoscience and nanotechnology.
Nanowires are typically single-crystalline, highly anisotropic, semiconducting, insulating,
and/or metallic nanostructures that result from rapid growth along one direction [1]. They
usually have big aspect ratio (length/diameter) and uniform cross section. In contrast to
carbon nanotubes, which are another class of 1D nanostructure that have received
considerable attention, nanowires have some unique merits [2]. For example, the electronic
properties of nanowires can be more precisely controlled by doping, while those of carbon
nanotubes are largely determined by the clarity of the graphene layer. It is generally accepted
that 1D nanowires provide a good system to investigate the dependence of electrical and
thermal transport or mechanical properties on dimensionality and size. Nanowires are also
expected to play an important role as both interconnects and functional unit for optoelectrical
nanodevices as they represent one of best defined and controlled classes of nanoscale building
blocks.
Nanowires can be synthesized in single-crystal form by controlling the experimental
parameters during growth [3]. Moreover, growths of nanowires with precisely controlled
chemical composition, diameter, length, doping, growth direction, and surfaces properties are
also possible till now [4]. However, many experimentally achieved growths of nanowires
have not got a satisfactory elucidation of the underling mechanism. A well understanding of
their growth mechanisms can help to design the nanowire growth more rationally and
predictably. Generally speaking, the nanowires are synthesized by promoting the fast
crystallization of solid structures along one direction. There are two main reasons for such
preferential growth. One is the intrinsic crystal properties of the grown samples and another is
the optimized growth conditions. Vapor phase strategy is probably the most widely explored
methods for growths of one-dimensional nanowires, including nanorods and nanobelts,
especially for semiconductor nanowires. Numerous techniques have been developed to
prepare precursors into the gas phase for the next nanowire growth. Among all vapor-phase
methods, the so-called VLS (vapor-liquid-solid) or VS (vapor-solid) mechanism seem to be
the most successful in growing nanowires with single crystalline in large quality [5]. In
comparison with vapor-phase methods, a variety of solution-phase methods have also been
developed to grow nanowires. But, among them, there is no a general principle that could be
applied to explain the different experimentally employed chemical processes. Many different
mechanisms have been adopted in solution-phase methods, such as, the use of template with
one-dimensional channels to confine the growth of nanowire [6], the introduction of a
liquid/solid interface to introduce the symmetry of the seed [7], the use of selected capping
reagents to direct the crystal growth by preferentially absorption on special facets of a new
nuclear [8], and the self-assembly of zero-dimensional nanoparticles into 1D nanowires [9].
Although growth of nanowires has gained much intension and great success, it must be
acknowledged that such nanowires need to be organized into three dimensions or arrays for
the construction of functional nanodevices. The assembly of nanowires into designed
hierarchical structures represents a key step for creating arrays of nanodevices. Using a
ZnO Nanowire Arrays 239
patterned catalyst, nanowires can be directly grown into two-dimensional arrays on a solid
substrate by applying VLS-based vapor phase methods [10] without complicated lithography.
But it still faces many of the traditional constraints of planar growth and device fabrication.
For solution methods, electric-field has been used to attract and align nanowires dispersed in
solutions due to their highly anisotropic structure and large polarization [11]. Other
techniques, such as fluid-flow-directed pattern [12] and Langmuir-Blodgett method [13] have
also been developed to organize as-grown nanowires into hierarchical structures.
Alternatively, if the nanowires are synthesized under optimized conditions, their growth can
be organized into arrays by a self-assembly process. In the self-assembly process, atoms,
molecules, particles and other building blocks organize themselves into functional
nanostructures driven by energetics of the system [14]. Self-assembly has become a very
effective and promising approach to synthesize and assembly nanowires.
Nanowires have been widely used to construct many kinds of nanodevices based on their
intrinsic properties and nanoscale dimensionality [15]. Here we limited our discussion on
semiconductor nanowires. A prototypical kind of such devices is the nanowire field effect
transistor (FET). It has been illustrated that silicon, germanium and gallium nitride nanowire
FETs show good performance comparable to the best reported for planar devices made from
the same material [16]. Due to the large surface ratio, FETs fabricated with single nanowires
also show ultra sensitive sensor properties for detecting a wide range of gases, chemicals and
biomedical species in both commercial and research applications [17]. Nanowires also
represent very promising building blocks for active optoelectronic nanodevices, such as light-
emitting-devices (LED) [18] and lasers [19]. Moreover, complex logic gates and even
computational circuits have been illustrated and used as basic digital calculators [20].
Recently, nanogenerators that produce continuous direct-current by harvesting mechanical
energy from arrays of ZnO nanowire have also been successfully demonstrated [21].
1.2. Basic Properties of ZnO Nanowire Arrays
Zinc oxide (ZnO), a typical II-VI compound semiconductor with a direct band-gap of
3.37eV and a relatively high exciton binding energy (60 meV) at room-temperature, displays
excellent electrical, optical, catalysis and novel piezoelectric properties [22].

Table 1 gives a
summary of the basic physical properties of the ZnO. The most important characteristics of
ZnO that needs to be pointed out firstly is that it has a big exciton binding energy of 60 meV,
lager than GaN (21 meV), ZnSe (20 meV), which is also lager than the thermal energy (25
meV) at room temperature. This means that exciton emission can be obtained from ZnO
crystals more efficiently in the ultraviolet (UV) region. Therefore, ZnO is expected to be used
as a material for blue/UV optoelectronics, including LED and even laser diodes in addition to
GaN-based materials [23]. ZnO is also theoretically predicted to show magnetic properties
when it is doped with magnetic Co, Mn, Fe, V, etc. elements, which could be used for spin-
electronic devices [24]. Moreover, ZnO is also a transparent, highly conducting oxide (TCO),
when doped with Al, Ga, In, etc., and can be used as a cheaper alternative to indium doped tin
oxide [25]. Besides these, ZnO is also a radiation-hard material for electronic devices in space
area and a biocompatible material for biomedical applications without coating.
Bingqiang Cao and Weiping Cai 240
Table 1. Physical Properties of ZnO
Properties Parameters
Crystal Structure Wurtzite
Lattice Parameters
(300 K)
a0.32495 nm
c0.52069 nm
Density (300 K) 5.606 g/cm
3
Rigidity (Mohs) 5
Static dielectric coefficient
(/
o
C)
8.656
Melting point 1975
o
C
Thermal conductivity 0.6; 1-1.2 W/mK
Linear expansion coefficient
(/
o
C)
a-axis: 6.5*10
-6
/
o
C
c-axis: 3.0*10
-6
/
o
C
Refractive index 2.008, 2.029
Electron affinity 3.0 eV
Band gap (300 K) 3.37 eV (direct)
Intrinsic carrier concentration ~10
6
/cm
3
Exciton binding energy 60 meV
Effective mass
Electron: 0.24 m
0
Hole: 0.59 m
0
Electron mobility (300 K) 20~200 cm
2
VS
Hole mobility (300 K) 5-50 cm
2
VS
It is well known that ZnO is a polar crystal and has positively Zn
2+
-terminated (0001) and
negatively O
2
-terminated (000-1) polar surfaces, which induce a net dipole moment along the
c-axis. Thus the surface energy of the polar {0001} plane is higher than those of non-polar
{01-10} and {2-1-10} planes [26].

So preferential growth along the c-axis (<0001>-direction)
is energetically favorable. So, due to this structural polarity, ZnO has diverse nanostructures.
Many kinds of ZnO nanostructures, such as, one-dimensional (1D) nanowire, nanorod,
nanoring, nanohelix, and two-dimensional (2D) nanoplates with different crystal
morphologies and physical properties, have been synthesized by various methods [27].
Although many ZnO nanostructures have been reported, it is must be acknowledged that these
need to be integrated or to be arrayed in three dimensions to find their practical applications
in nanodevices. Among them, due to their structural uniformity and applications in nanoscale
devices, ZnO nanowire arrays represent an important step towards realizing nanoscale
devices. Till now, ZnO nanowire array based nanodevices, such as, room-temperature UV
lasers [28], solar cells [29], gas sensors [30]

and nanogenerators [31], have been illustrated.
The main problem now that prevents the ZnO films and nanostructures from being used
for practical devices is the lack of reproducible p-type conductivity. Despite numerous the
reports of p-type ZnO using various growth methods and different dopants (N, P, As, Sb, Li,
etc.), a reliable and reproducible high quality p-type conductivity is still lacking. In the
meanwhile the advantages of ZnO are being explored and exploited by alternative
approaches: such as heteroepitaxy in which n-type ZnO films are formed on other p-type
materials, utilizing ZnO as an active layer. Since the growth of nanowires is a strain nearly
ZnO Nanowire Arrays 241
fully-relaxed process and very high structural quality can be obtained on common substrates,
ZnO nanowires have a definite potential for achieving stable p-type doping. Primary results of
phosphorous-doped ZnO nanowires grown by chemical vapor deposition and pulsed laser
deposition methods have shown very promising p-type conductivity [32-34]. More
discussions about p-type conductivity of ZnO have been reviewed by several papers [35-37]
and will not be included in this chapter.
This chapter reviews the recent research activities of ZnO nanowire arrays, which
emphasizes the self-assembly growth and the physical properties. The first part is an
introduction on semiconductor nanowires and basic properties of ZnO. The second part
discusses different methods and concepts that have been applied to grow ZnO nanowire
arrays. The third part discusses the physical properties of ZnO nanowire arrays, such as
Raman scattering, photoluminescence, and field emissions, where the influence of
morphology and defect are emphasized. The final part summarizes this chapter with some
brief conclusions.
2. Growths of ZnO Nanowire Arrays
2.1. Growth of ZnO Nanowire Arrays by Vapor Phase Methods
Figure 1. Schematic illustration of the ZnO nanowire growth through the vapor-liquid-solid (VLS)
mechanism. (I) metal particles as catalyst; (II) alloying; (III) nucleation; (IV) axial growth.
Many methods have been developed to grow ZnO nanowire arrays by different groups. It
can be generally divided into two groups, vapor phase method and solution phase method.
Vapor phase method includes physical vapor deposition (PVD), chemical vapor deposition
(CVD), metal-organic CVD, molecular beam epitaxy (MBE), metal-organic vapor phase
epitaxy (MOVPE), pulsed laser deposition (PLD), etc. The general growth mechanism for
ZnO nanowires applied in vapor phase methods is the so-called Vapor-Liquid-Solid (VLS)
and/or Vapor-Solid (VS) processes. The VLS mechanism, first found in the early 1960s [38],
has achieved great success in recent years for the growth of different semiconductor
nanowires, including ZnO nanowire arrays. In this mechanism, the liquid metallic small
droplets act as catalysts to adsorb and dissolve reactant species and guide the growth of
nanowires. So the catalyst can be used to control the growth of nanowires in terms of
diameters and sites on substrates. Gold nanoparticles are the most frequently used catalysts. It
Bingqiang Cao and Weiping Cai 242
usually requires a high growth temperature (~ 900 C) so that zinc vapor can be dissolved into
a gold catalyst droplet to form alloy droplet. After saturation, zinc precipitates out from the
droplet and is oxidized as the ZnO nanowire grows with preferred crystallographic direction.
Another intrinsic feature of the VLS growth method is that at the tips (or bottoms) of the
nanowires there are always impurity particles that are undesirable for device fabrication.
Figure 2. (a) Gold nanoparticles arrays prepared by nanosphere lithography (NSL) method; (b) ZnO
nanowire arrays grown with pulsed laser deposition method using gold nanoparticles arrays shown in
(a) as catalyst on a- plane of sapphire substrate. [After ref. 39, Rahm, et al. Appl. Phys. A, 88, 31
(2007)].
Sometimes, it is also possible to grow ZnO nanowire arrays by VS process without using
any metal catalyst [40]. From the viewpoint of growth kinetics, the VS mechanism
emphasizes that surface diffusion of reactant species and preferential incorporation at high-
surface-energy sites feed and maintain the continuous growth of nanowires. Figure 3 shows
the scanning electron microscopy (SEM) image of ZnO nanowires grown with pulsed laser
deposition method on ZnO film coated sapphire substrate without using any catalyst. There
are clear hexagonal pyramids at the bottom of the ZnO nanowires. It indicates that the zinc
and oxygen vapor are absorbed here and diffuse to the tip of the pyramid for the continuous
ZnO Nanowire Arrays 243
wire growth. It is a typical VS growth process. In this method, usually no catalysts are needed
and, accordingly, it is not easy to control the diameter and density of the grown nanowires.
Table 1 gives some typical methods that use VLS or VS mechanism to grow ZnO nanowire
arrays.
Figure 3. ZnO nanowires grown with pulsed laser deposition method on ZnO film coated sapphire
substrate without using any catalyst. (a) tiled-view; (b) top-view.
The obtained ZnO nanowires with vapor phase methods are usually of high structural
quality. But, besides high preparation temperature and energy-consuming experiment
facilities, these vapor phase methods usually face other limitations in terms of sample
uniformity, low product yield and substrate choice. For example, some expensive and/or
insulting substrates, such as, sapphire,

gallium nitride (GaN), and titanium nitride (TiN), are
necessary for the epitaxial growth.
Bingqiang Cao and Weiping Cai 244
Table 2. Vapor phase growth methods of ZnO nanowire arrays
Method Catalyst Substrate Source Temperature Reference
PVD germanium silicon
ZnO,
carbon
900
o
C 41
CVD gold GaN ZnAs
2
600 42
MOCVD gold silicon
Diethylzinc
oxygen
800
o
C 43
MBE silver
silicon oxide
silicon nitride
Zinc
O
3
/O
2
600
o
C 44
PLD gold a, m, c-sapphire ZnO 850
o
C 45
PVD no Silicon (100) Zinc, Oxygen 500
c
C 46
MOVPE no c-sapphire
Diethylzinc
oxygen
400 ~500
o
C 47
CVD no TiN/Silicon (100)
Zn;
Oxygen
550
o
C 48
PECVD no Silicon (111)
Diethylzinc
oxygen
700
o
C 49
PLD no Silicon (100) ZnO 750
o
C 50
2.2. Growth of ZnO Nanowire Arrays by Solution Phase Methods
Table 3. Solution phase growth methods of ZnO nanowires
Growth Method Source Substrate
Resulting
Morphology
Temperature Ref.
Sol deposition
Zn(NO
3
)
2
;
ZnCl
2
;
HMT
no Nanorod
78
o
C;
100
o
C
51
Hydrothermal
Zn(NO
3
)
2;
HMT
Glass,
Silicon
Nanorod array 95
o
C 52
Sonochemical method HMT; Zinc
Silicon;
Glass; poly-
carbonate
Nanorod array Room tem. 53
Epitaxial Chemical
Deposition
Zn(NO
3
)
2
;
NaOH
ZnO film/
Glass
Nanorod
array
Room tem. 54
Electrophoretic
Deposition
Zn(OAc)
2
NaOH
Anodic
Alumina
membrane
Nanowire 50
o
C 55
Template-assisted
Electrochemical
Deposition
ZnSO
4
Anodic
Alumina
membrane
Zinc/ZnO
nanowires
30
o
C 56
Template-free
Electrochemical
Deposition
Zn(NO
3
)
2
Silicon nanowires 70
o
C 57
ZnO Nanowire Arrays 245
In comparison with the vapor phase methods mentioned above, another kind of
techniques that have been widely used to grow ZnO nanostructures could be generally named
as solution method, including hydrothermal method, sol-gel method, chemical bath
deposition, hydrolysis method, and electrochemical deposition method (ECD), which are also
attractive due to their low cost and high yield. Many groups have adapted different solution
strategies to grow different ZnO nanostructures. Among them, nanowire array is also an
important kind nanostructure that has been widely studied. Table 3 summarizes some typical
solution methods that have been reported to grow ZnO nanowire arrays. For solution
methods, it is more flexible and powerful to control the resulting morphologies and properties
of the final samples by changing their growth conditions. In this part, we will review and
compare some typical solution methods that have been well developed to synthesis ZnO
nanowire arrays.
2.2.1. Hydrolysis Growth
The first aqueous solution growth of rod-like ZnO crystals was reported in 1990 by
Verges et al. [51], where zinc nitride and zinc chloride solutions were hydrolyzed in the
presence of hexamethyltetramine (HMT), respectively. Now it is the most successful route
that has been widely adopted to synthesis ZnO films and nanostructures with a solution
consisting of Zn(NO
3
)
2
and HMT or dimethylamineborane (DMAB). From the viewpoint of
chemical reactions, hydroxide ions are formed by the decomposition of HMT or DMAB, and
they react with the zinc ions to form ZnO after dehydration. The hydrolysis and condensation
reactions of zinc salts can result in 1D ZnO crystals under a wide variety of conditions. In
general, low-temperature (< 300 C) nanowires (or nanorods) growth is possible in slightly
basic conditions as divalent metal ions do not readily hydrolyze in acidic media. It has been
suggested [58] that these additives (e.g. HMT, DMAB) function, in part, by decomposing
during the reaction and increasing the pH to a basic value. The crystal morphology can be
controlled by various species in the solution, which act as promoters or inhibitors for
nucleation and growth. These species can include the zinc counterion, additives such as
amines, and acids and bases. It has been demonstrated that [59], by changing the DMAB
concentration, the ZnO morphology evolves from 1D nanorods to two-dimensional
nanoplates. ZnO nanorods grow fast along c-axis direction due to the high surface energy of
the polar {0001}- plane when the concentration of OH
-
ions produced by hydrolysis of
DMAB is low. While, when the OH
-
concentration is increased, more OH
-
ions preferably
adsorb on the (0001) plane of ZnO and the growth of the ZnO nanocrystallite along c-axis is
partially suppressed. But they can still grow sideways along <2-1-10> directions. So with the
OH
-
concentration increased, the average aspect ratio (high/width) of ZnO nanorods is
decreased. Finally, two-dimensional ZnO nanoplates are formed. In this case, the OH
-
ions act
as both precursor and inhibitor for the crystal growth. Although pH may play an important
role in this case, it is shown that the species in solution can have a strong effect on the
resulting morphology. In general, the obtained ZnO nanowires deposit randomly on the
bottom of the reaction vessel or on the immersed substrate, as shown in Figure 4.
Bingqiang Cao and Weiping Cai 246

Figure 4. ZnO nanorods and nanoplates grown through hydrolysis method with Zn(NO
3
)
2
(0.5 M for
nanorods and 0.1 for nanoplates) and DMAB (0.05 M) as precursor solutions. [After ref. 59, Cao, et al.
J. Phys. Chem. C, 112, 680 (2008)].
Later, Vayssieres et al. [60] developed this method and succeeded in growing ZnO
nanowire arrays through monitoring of the nucleation, growth, and aging process by means of
chemical and electrostatic control of the interfacial free energy. In most cases, homogeneous
nucleation of solid phases requires a higher activation energy barrier, and therefore,
heteronucleation is easier and energetically more favorable. Indeed, the interfacial energy
between crystals and substrates is usually smaller than the interfacial energy between crystals
and solutions. Consequently, nucleation takes place at a lower saturation ratio onto a substrate
than in homogeneous solution. Epitaxial crystal growth occurs from substrate-generated
nuclei along the preferential direction of crystallization, and if the concentration of precursors
is high, a condensed phase of single-crystalline rods perpendicular to the substrate is
obtained. According to this strategy, ZnO nanorod arrays were obtained on different
substrates, such as glass and silicon wafer, with precursor composed of equimolar (0.1 M)
zinc nitride and HMT aqueous solution. Moreover, by decreasing the concentration of the
precursors while keeping the same 1:1 ratio, the diameter of the obtained ZnO nanorods also
decrease likewise by about an order of magnitude, due to the critical diffusion of the
monomers and the subsequent limited growth. Microrods with diameter of 1-2 m were
grown at a concentration of 0.1 M zinc nitride and DMAB. While nanorods of 100-200 nm in
diameter were grown at 0.01 M. Greene et al. [61] also reported the growth of ZnO nanowire
arrays on ZnO nanocrystals coated silicon substrates. They firstly spin-coated a 150-nm-thick
ZnO crystal seeds on silicon substrate, which is composed of ZnO nanocrystals with an
average size of 5-10 nm. Then ZnO nanorod arrays were grown on such substrate with
precursor solution composed of NaOH (0.3 M) and zinc acetate dihydrate (0.01 M). It is also
possible to control the aspect ratio of the nanorod by changing the precursor concentration.
2.2.2. Template-Assisted Electrochemical Deposition
Recent advances have made electrodeposition an attractive approach for preparation of
nanomaterials [62]. When a metallic salt is dissolved into water or other solution it dissociates
to form positively charged ions. The solution that contains these charged ions is called as an
electrolyte. By passing a sufficient amount of electric current through this electrolyte, one can
ZnO Nanowire Arrays 247
reduce the metal ions to form solid metals or compounds on electrodes. Especially, if the
metals are oxidized again when they are deposited, oxide compound will be acquired instead
of pure metals. This process is referred in literature to electrochemical deposition (ECD). In
common with other relatively low temperature solution synthesis techniques, ECD of
semiconductors typically results in a small crystal size. This is clearly advantageous when the
goal is formation of nanostructured materials [63]. There are many different ways of
electrodepositing semiconductors and different tactics to control crystal size and
nanostructure of the resulting samples. Electrodeposition is usually carried out in a three
electrode electrochemical cell that contains a working electrode, a reference electrode, and a
counter electrode.
ECD has some advantages over physical vapor phase deposition methods for growth of
nanostructures [64]. (a) Electrochemical reaction usually takes place close to the electrode
within the electric double layer, which has a very high potential gradient of 10
5
Vcm
-1
. Under
these conditions, the reactions often lead to products which cannot be obtained in an ordinary
chemical synthesis. (b) The samples are deposited on the electrode, which is also the substrate
for the sample growth. So the sample morphologies can be influenced by the nature of the
substrate, especially for the interface between the substrate and electrolyte. (c) Growth
kinetics can be controlled by the deposition current passed through the cell, while growth
thermodynamics control can be excised by the applied potential. (d) The sample composition
can be tuned by varying the composition of the electrolyte. (e) ECD is fast and usually
performed at low temperature (< 100
o
C). (f) The experimental instruments are not complex
and inexpensive therefore well-suited for large-scale production.
Growth of ZnO polycrystalline films by ECD method was firstly illustrated by Lincot et
al. [65] and Izaki et al. [66], respectively, in 1996. As for the growth mechanism, the one-step
ECD reactions using Zn(ON
3
)
2
as electrolyte have been generally proposed and widely
adopted [67]. The reduction of the nitrate (

3
NO to

2
NO ) in mild acid solution of Zn
2+
,
which results in increase of the pH value near the electrode surface, is crucial. With the
increasing concentration of OH
-
, Zn(OH)
2
will form and deposit on the cathode electrode.
The deposited Zn(OH)
2
will subsequently be decomposed and form ZnO on the substrate at
the temperature of 70
o
C. Another electrochemical route that has also been used to grow ZnO
is the oxidation of the zinc ions by introducing oxygen gas when the electrodeposition is
performed [68]. An historic overview of work carried out in this field has been summarized
elsewhere [69]. Here we limit the present discussion on the ECD growth of ZnO nanowires.
Although rod-like films were firstly reported by epitaxial ECD growth of ZnO on GaN
[70] and single crystal gold substrates [71], growth of ZnO nanowire arrays by the template-
assisted method is the most direct route, where the nanochannels of the template, such as
anodic aluminum oxide (AAO) membrane, were filled by electrochemical deposition. In
2002, Li et al. [56] firstly developed a two-step template-assisted ECD method to grow ZnO
nanowires. They prepared zinc nanowires by filling the AAO channels with ECD from zinc
electrolyte. Then the zinc nanowires were annealed in air. As a result, ZnO nanowire arrays
were formed by oxidation of the zinc metal nanowires. The acquired ZnO nanowires were
typically polycrystalline and only the typical defect-related green emission were observed
from the ZnO nanowires.
Bingqiang Cao and Weiping Cai 248
Figure 5. PL spectra of the as-prepared ZnO nanowires (a) and annealed samples (c-d) grown with
template-assisted ECD method. (Inset) TEM images of such ZnO nanowires embedded in AAO
template. [After ref. 56, Li, et al. Appl. Phys. Lett. 76, 2011 (2002)].
Later, Zheng et al. [72] adopted the one-step electrochemical method to grow ZnO
nanowires into the AAO template. The prepared ZnO nanowires are also of low crystal and
optical qualities. Another question about the AAO template-assisted growth method is that
when the nanowire/AAO composite is dissolved to remove the template, the ZnO nanowire
arrays may be destroyed. More important, if the nanowires are embedded in the channels of
the AAO template, the nanowires could not be integrated with other circuitry as the aluminum
oxide is an insulator. Wong et al. [73] reported that ZnO nanorods can be grown on
polycrystalline zinc foil by electrodeposition in an aqueous zinc chloride/calcium chloride
solution at 80
o
C. It was illustrated that the growth of ZnO nanorods on zinc foil by solution
electrochemistry was strongly influenced by electrolyte solution concentration as well as by
the substrate electrode. Intrinsic ultraviolet (UV) emission of ZnO was observed from the
annealed ZnO nanorods. More recently, Pauport et al. [74] grew arrays of vertically oriented
epitaxial nanorods of ZnO on GaN at low temperature (80
o
C) from an electrolytic aqueous
bath using electrochemical reactions. The preparation is a template-free and does not use any
foreign species. At room-temperature, UV simulated emissions were also measured at 382 nm
with an excitation threshold at 4.4 MW/cm
2
. Due to the big lattice mismatch between the ZnO
and silicon substrate (electrode), it is difficult to epitaxially grow ZnO nanowire arrays
directly on silicon substrate, which is extremely important for their device applications.
Usually, only polycrystalline ZnO films or nanoparticles can be grown on silicon substrate by
ECD methods [75]. So preparation of ZnO 1D nanostructure arrays on widely used silicon
substrate by a soft and template-free method at a low cost is very appealing for their potential
applications in nanodevices. The next parts will discuses the progress in this area.
ZnO Nanowire Arrays 249
2.2.3. Template-Free Electrochemical Deposition
a. Substrate-Induced Growth of ZnO Nanowire Arrays [76]
Experiment A 50nm-thick gold layer was firstly deposited on Si(100) substrate with low
resistivity (<10 cm). Galvanostatic electrochemical deposition was then employed on the
gold coated Si substrates (Au/Si) at a current density of 0.9 mA/cm
2
. Zinc sheets (99.99%
purity) acted as the anode electrode. The electrolyte solution was Zn(NO
3
)
2
aqueous solution
(0.05 M). The pH value of the solution was about 6. The deposition temperature was fixed at
70
o
C by a temperature-controllable water bath and the deposition time was 2 hours.
Figure 6. (a) SEM image (tilted view) of well-aligned ZnO nanorod arrays grown on Au/Si substrates;
(b) XRD spectrum of ZnO nanorods array on Au/Si substrate and (inset) -rocking-curves of
ZnO(0002) peak. [After ref. 76, Cao, et al. Nanotechnology, 16, 2567 (2005)].
Characterizations Fig.6 (a) is the general morphology of the as-synthesized samples on
Au/Si substrate. A layer of well-aligned nanorod arrays with high density has grown on the
substrate surface erectly. Typically, the nanorods electrodeposited in 0.05 M Zn(NO
3
)
2
Bingqiang Cao and Weiping Cai 250
electrolyte under a current of 0.9 mA for two hours show a mean length of two micrometers
with tip of tens of nanometers in diameter. From the XRD pattern of the as-prepared sample
shown in Fig.6 (a), only four peaks are observed, which can be assigned to: ZnO(002)/(004),
Au(111) and Si(400). The absence of any other peaks confirms the well alignment of these
nanorods with c-axis orientation. Meanwhile, the XRD -rocking curves of the ZnO (0002)-
peak shows a full width at half maximum (FWHM) value of 7.5
o
, which is comparable to that
of the ZnO nanowire arrays grown on silicon substrates (3
o
~10
o
)

or on ZnO films (~6.5
o
) by
vapor phase methods [77-78]. It indicates the alignment of the nanowires is normal to the
surface of the Au/Si substrates.

Figure 7. (a) TEM image of a single ZnO nanorod; (b) corresponding HRTEM image and its selected
area electron diffraction pattern (inset), showing clearly the (0001) growth direction. [After ref. 76,
Cao, et al. Nanotechnology, 16, 2567 (2005)].
TEM images (Fig.7) indicate that the ZnO nanorod is of single-crystal structure without
visible defects. It is also clearly shown that the (0001) crystal planes are perpendicular to the
axis of the nanorod and <0001> is the preferred growth direction. The corresponding selected
area electron diffraction pattern (SAED) pattern further proves the single-crystal nature of the
nanorods and their <0001>-growth direction. The EDS result of a single ZnO nanorod,
illustrated in Fig.8, indicates that the atomic ratio of zinc to oxygen is about 1.05, which is
near the stoichiometric composition of pure ZnO. The carbon and copper signal are from
carbon-coated copper TEM grid.
Growth Mechanism This template-free ECD growth strategy of ZnO nanowire arrays
makes use of the surface properties of the substrate. Working electrodes have an important
influence on the initial ZnO nucleation process in the ECD method. It is shown in the SEM
image (Fig 9a) of the Au/Si electrode that the gold film is composed of smooth and
featureless grains (nanoparticle film) with about 100 nm in size. XRD measurement (Fig.9b)
has proved that such gold nanoparticle film has a strong preferential orientation of Au(111)
planes parallel to the Si substrate. Obviously, during the initial period of the ECD process,
ZnO will nucleate on the flat gold nanoparticles on the cathode. Since the interface energy is
directly related to the lattice mismatch of interfaces, to lower the interface energy, there will
exist an orientation relationship between the ZnO nuclei and Au film to reduce the lattice
ZnO Nanowire Arrays 251
mismatch, which can be deduced to be (1x1)ZnO(0001)[11-20]//(1x1)Au(111)[-110]. The
lattice mismatch between ZnO(0001) and gold(111) planes is 12.7%. So the ZnO nuclei on
the substrate should be {0001}-oriented. In addition, as mentioned above, fast crystal growth
along the <0001>-direction for ZnO is energetically favorable due to its higher surface energy
of the polar {0001}-plane. For thermodynamic stability of growth habit, the growth rate along
<0001> direction is faster than other directions, which leads to the formation of ZnO
nanowires perpendicular to the substrate. So the ECD growth of the nanowire arrays can be
described in two steps: (I) formation of {0001}-oriented ZnO nuclei on the {111}-oriented
Au film due to the smaller lattice mismatch between them, (II) and then the oriented ZnO
nuclei serve as seeds and grow preferentially along c-axis due to the high surface free energy
of the {0001} plane. Thus, the growth of ZnO nanorod arrays on Au/Si substrate through this
template-free ECD method is a typical self-assembly process.
Figure 8. EDX spectrum of a single ZnO nanorod on a TEM copper grid and its elements analysis
(inset) [After ref. 76, Cao, et al. Nanotechnology, 16, 2567 (2005)].
Figure 9. (a) SEM image of the surface of Au(111)/Si substrate; (b) XRD spectrum of the Au/Si
substrate and (inset) -rocking-curves of Au(111) peak. [After ref. 76, Cao, et al. Nanotechnology, 16,
2567 (2005)].
Bingqiang Cao and Weiping Cai 252
b. Seed Layer-Induced Growth of ZnO Nanowire Arrays [79]
Experiment A 50nm-thick layer of ZnO film (seed layer) was deposited on silicon (100)
substrates (resistivity < 10 cm), by radio frequency sputtering methods. Then, galvanostatic
cathodic deposition was employed on the ZnO film coated silicon substrates at a current range
from 0.8 to 1.25 mA. The deposition area on cathode is all the same in these experiments.
Zinc sheets (99.99% purity) act as the anode electrode and the electrolyte solution was zinc
nitrate aqueous solution (0.05 M). The pH value of the solution was about 6. The deposition
temperature was fixed at 70
o
C with a water bath and the deposition time was 3 hours.
Figure 10. XRD spectra comparison of the samples electrodeposited under different currents: (a) 0.8
mA, (b) 1.0 mA, and (c) 1.25 mA. [After ref. 79, Cao, et al. J. Phys. Chem. C, 111, 2470 (2007)].
Characterizations All XRD spectra (Fig.10) of the samples electrodeposited under
different ECD currents show strong (002) peaks in addition to very weak (101) peaks
corresponding to the ZnO wurtzite structure. It indicates that these ZnO samples are all of
highly c-axis orientation. Macroscopically, all the whole cathodic substrates were covered
with a layer of white and homogeneous ZnO film or particle film in squared centimeter order.
But their microstructures show a notable evolution with the increasing deposition currents.
Fig. 11a shows the SEM image of ZnO electrodeposited under current of 0.8 mA. The film
shows flat and compact surface morphology and seems to be of many hexagonal nanosheets
from the top view. They are the (001) planes of wurtzite ZnO crystal. So such film has a c-
orientation, consisting with its XRD result in Fig. 10a. When the ECD current increases to 1.0
mA, large-area well-aligned ZnO nanowire arrays in high density are acquired, as shown in
Fig. 11b. These ZnO nanowires are all straight, smooth and relatively vertical to the substrate
with uniform diameters of about 100 nm. Their lengths could be easily controlled by the
growth time. The XRD spectrum (Fig. 10b) also indicates that all the ZnO nanowires grow
along the c-axis. When the current further increases to 1.25 mA, the electrodeposited film
ZnO Nanowire Arrays 253
seems to be composed of white ZnO particles watched with the naked eyes. But SEM images
of Fig. 12(a, b) show that such ZnO particles are somewhat like connective microcalabashes,
and their shells are made up of densely arrayed ZnO nanowires with sharp ends. These
hierarchical ZnO nanostructured arrays are growing nearly vertical to the substrate. One
broken microcalabash shown in Fig. 12c indicates that there are ZnO nanoparticles filled
inside. The TEM images and SAED pattern shown in Fig. 12d and e prove that such single-
crystal ZnO nanowire also grows along the c-axis.

Figure 11. SEM images of ZnO samples electrodeposited under current of 0.8 mA (a) and 1.0 mA (b).
[After ref. 79, Cao, et al. J. Phys. Chem. C, 111, 2470 (2007)].
Growth Mechanism To elucidate the growth mechanism of different ZnO nanostructures
in this electrochemical route, the properties of the ZnO seed-layer were firstly checked. It is
shown in the AFM image of Fig. 13a that the film is composed of smooth and featureless
grains about 20 nm in size. The XRD measurement shown in Fig. 13b indicates that the ZnO
seed-layer has a strong c-axis orientation. Since preferential growth along the c-axis (<0001>-
direction) is energetically favorable for ZnO, the seed-layer will have an important influence
on the initial ECD nucleation process. The ZnO seed-layer on the cathode has a c-orientation,
where the ZnO(001) planes are parallel to substrate. So, when the thermodynamically favored
(0001)-oriented ZnO nuclei deposit on the seed-layer, they will continue fast growth along c-
axis easily due to the exact lattice match. As a result, (0001)-oriented ZnO films or nanowire
arrays are formed, as shown in Fig. 11a and b. The reason for these two different
morphologies is that different deposition current will cause different growth velocity ratio
along c-axis to a-axis [80]. Obviously, under higher deposition current, the crystal growth
velocity along c-axis will be much faster than those of other directions and, therefore, the
growth ratio along c-axis to a-axis will be larger. So deposition at low current results in
compact (0001)-oriented ZnO film and, when the deposition current is higher, the samples are
well-aligned nanowires. If the current is further increased, the crystal growth velocity is faster
with a result that the lengths of nanowires are not quite uniform, and some nanowires are
obviously longer. When the newly formed ZnO clusters grow on the protruded parts by
secondary nucleation, it will lead to the accumulation of ZnO nuclei and then nanoparticles,
Bingqiang Cao and Weiping Cai 254
which serves as the cores of microcalabashes, as shown in Fig. 12c. Such ZnO nanoparticles
continually grow densely fast along the c-axis and then lead to the formation of prickly ZnO
microspheres (Fig.12 a and b), which are composed of nanorods. If such process is repeated,
microcalabashes are finally formed by this self-assembly process.
Figure 12. SEM images of ZnO microcalabashes (a, 30
o
tiled-view) and a single ZnO microcalabash
composed of densely-arrayed ZnO nanowires electrodeposited under current of 1.25 mA (b), and a split
microcalabash (c). TEM image of a single ZnO nanowire and inset is the corresponding selected-area
electron diffraction pattern (d), and its lattice fringe image (e). [After ref. 79, Cao, et al. J. Phys. Chem.
C, 111, 2470 (2007)].
Figure 13. AFM image (a) and XRD spectrum (b) of the ZnO seed layers on silicon substrate with an
obvious (001) orientation and mean roughness about 3nm. [After ref. 79, Cao, et al. J. Phys. Chem. C,
111, 2470 (2007)].
ZnO Nanowire Arrays 255
3 Physical Properties of ZnO Nanowires
3.1. Raman Scattering Property
3.1.1. Vibration Properties of ZnO
Due to its sensitivity to the crystallization, structural disorder and defects in
nanostructures, Raman scattering has been widely applied to investigate the crystal quality
and vibration properties of the ZnO nanostructures. Wurtzite ZnO crystal has two formula
unites per primitive cell and belongs to
4
6v
C space group. The optical phonons of ZnO with
wurtzite structure at the -point of the Brillouin zone belong to the following irreducible
representation [81]
= 1A
1
+ 2B
1
+ 1E
1
+ 2E
2
,
where, the branches with E
1
and E
2
symmetry are two-fold degenerated. Both A
1
and E
1
modes are polar, and split into transverse optical (TO) and longitudinal optical (LO) phonons
with different frequencies, due to the macroscopic electric fields associated with the LO
phonons. The short-range inter-atomic forces cause anisotropy, and, therefore, A
1
and E
1
modes possess different frequencies. As the electrostatic forces dominate the anisotropy in the
short-range forces in ZnO, the TO-LO splitting is larger than the A
1
-E
1
splitting. For the
lattice vibrations with A
1
and E
1
symmetry, the atoms move parallel and perpendicular to the
c-axis, respectively, as indicated in Fig. 14. Both A
1
and E
1
modes are Raman and infrared
active. The two non-polar E
2
modes, E
2
(high) and E
2
(low), are Raman active only. The B
1
-
modes are both infrared and Raman inactive (silent modes). For crystals with wurtzite crystal
structure, pure longitudinal or pure transverse phonons of well-defined symmetry can be
observed only if the phonon propagation is along or perpendicular to the c-axis. Group theory
in combination with polarization and propagation considerations can identify the symmetry of
the Raman active optical modes by applying different scattering configurations. Table 4
compares the theoretical optical phonons of wurtzite ZnO with the experimental data.
Figure 14. Scheme of optical phonon modes of wurtzite ZnO at the -point of the Brillouin zone. Black
dots: zinc atoms; black circle: oxygen atoms. Vertical direction: c-axis.
Bingqiang Cao and Weiping Cai 256
Table 4. Comparison of the experimental data of the optical phonon modes of ZnO with
theory predictions (after ref. [82])
Modes Raman(exp.) Infrared(exp.) Theory
A
1
(TO)
378
380
380
382
386
E
1
(TO)
407, 409
410, 413
409.1, 408.2
412
316
407
A
1
(LO)
574, 576
579
574.5
577.1
548
E
1
(LO)
583, 587
588, 593
588.3
592.1
628
E
2
(Low)
98, 99
101, 102
--
126
98
E
2
(high)
437, 438
444
--
335
433
3.1.2. Raman Spectrum of ZnO Nanowire Arrays
Figure 15. Raman spectrum of the ZnO nanowire arrays grown on gold coated silicon substrate. [After
ref. 76, Cao, et al. Nanotechnology, 16, 2567 (2005)].
Fig. 15 shows the Raman spectrum of the ZnO nanowire arrays grown on Au/Si substrate
by ECD method. The excitation light is Ar
+
laser of 514.5 nm. In the Raman experiment, the
incident laser light was parallel to the ZnO nanorods and the Raman signal was recorded in
the backscattering geometry. According to the Raman selection rules [83], LO and E
2
modes
are allowed while the TO modes of A
1
(379 cm
-1
) and E
1
(407 cm
-1
) are forbidden. From Fig.
ZnO Nanowire Arrays 257
15, the strong and characteristic E
2
(high) mode at 437cm
-1
is clearly observed, in addition to a
weak second order
2
E
2
mode at 332 cm
-1
. The wide peak at around 573cm
-1
is too weak to
identify its physical origin but it is in the Raman shift region of ZnO LO modes. The peak at
520 cm
-1
is the Raman signal from the silicon substrate because of the penetration of the
excitation laser light through the nanowire arrays. The peak position of the E
2
mode was red
shifted about 3 cm
-1
compared with that of bulk ZnO [84]. This redshift is usually attributed
to the optical phonon confinement effect in nanostructures that can cause uncertainty in the
phonon wave vectors, a downshift of the Raman peaks. [85]
Figure 16. (a) Resonant Raman scattering spectrum of the ZnO nanowire arrays excited with He-Cd
laser of 325 nm; (b) 1LO and 2LO resonant scattering modes and their Lorenz fitting results. [After ref.
76, Cao, et al. Nanotechnology, 16, 2567 (2005)].
Bingqiang Cao and Weiping Cai 258
As we know, ZnO has a direct band gap of 3.37eV and large polaron coupling
coefficient. Therefore, if we use the exciting photon energy in the proximity of the electronic
interband transition energy, the polar LO modes will be dominant since the resonance
enhancement of LO phonons is much stronger than that of the TO modes and other nonpolar
phonons, such as, E
2.
That is, multiphonon resonant Raman scattering (MRRS) process will
happen [86]. Fig.16a is the corresponding Raman spectrum of the ZnO nanorod array, excited
with 325 nm He-Cd laser. Three major peaks, centered at 571, 1142, and 1723cm
-1
respectively, are observed, which superimpose upon the PL background, in addition to the
almost imperceptible E
2
and
2
E
2
modes. These sharp lines are the multiples of the frequency
of 571cm
-1
and can be attributed to the Raman 1LO mode and its overtones. Due to the
anisotropic short-range force in the uniaxial ZnO lattice, the 1LO mode usually consists of the
contributions from both A
1
(LO) and E
1
(LO) (9 cm
-1
in frequency interval between them).
However, Lorentzian curve fitting has revealed that 1LO and 2LO peaks in Fig.16a consist
mostly of the A
1
(LO) mode and the contribution from E
1
(LO) is neglectable, as illustrated in
Fig.16b. Since the E
1
(LO) mode is ascribed to the defects in ZnO, such as, oxygen vacancies
or zinc interstitials

[87], absence of E
1
(LO) mode indicates the good crystal quality of the
nanorods. Moreover, the linewidths of the 1LO and 2LO modes are 21 and 35cm
-1
,
respectively, which are much broader than the results predicted by the formula:
1 1
9 ) (

= jcm jLO , where
1
is the FWHM of the jth order LO mode [88], and the
resonant Raman peaks also show obvious asymmetry. These facts are further evidence of the
optical phonon confinement effect of nanostructures.
3.2. Photoluminesce of ZnO Nanowires
3.2.1. General Remarks
Compared with its competitors, such as GaN and ZnSe, ZnO has higher exciton bound
energy of 60 meV. The stable excitons could lead to more efficient UV light-emitting even
laser actions. This is the most important physical properties of ZnO as optoelectronic
materials, which could be developed for light-emitting devices (LED) and laser diodes.
Besides its novel UV emission properties, visible luminescence in range of 400-700 nm has
also been widely studied because of its potential applications in new low-voltage field
emissive display [89]. So the optical properties from the UV to the visible region are all the
basal physical properties of ZnO and, therefore, extremely important for its applications.
Although luminescence properties have been the subject of ZnO studies for several decades,
the emission centers and mechanisms are still controversial due to their complexity and
sensitivity to the surface states, mirror changes of electronic configurations and preparation
methods [90-98]. For instance, many controversial viewpoints have been proposed on the
origin of the ordinary green emission around 520 nm [93-96]. As for the violet (around 410
nm) and red emission (around 600 nm) bands, there are only few discussions without more
proofs [97]. So the full understandings of the different luminescence mechanisms are still a
challenging and significant subject in the ZnO optical studies. In this part, intrinsic exciton
UV emission and defect-related visible emissions of ZnO nanowires are discussed with
emphasis on their luminescence processes.
ZnO Nanowire Arrays 259
3.2.2. Temperature-Dependent Photoluminescence Behavior of ZnO Nanowires
Fig. 17 is the PL spectra of ZnO nanowire arrays grown on silicon substrate with gold
buffer layer by ECD method, as previously described. These PL spectra were measured over a
temperature range from 10 to 300 K under excitation with 267 nm Ti: sapphire laser. There
are two distinct peaks situated at green (2.2 eV) and UV (3.3 eV) regions, respectively, and
one inconspicuous band superimposed between them for all spectra. With the temperature
increasing, the UV peak shows obvious redshift. But the green peak blue shifts and its relative
Figure 17. PL spectra of the as-prepared ZnO nanowires. (a), PL spectra at different temperatures. All
spectra are normalized by the UV peak intensity and shifted vertically for clarity. (b), Typical Gaussian-
fitting analysis of the PL spectrum at 50 K. Three emission bands are named Green, Violet, and UV
emission bands, respectively. [After ref. 98, Cao, et al. Appl. Phys. Lett, 88, 161101 (2006)].
Bingqiang Cao and Weiping Cai 260
intensity to UV peak decreases. Further analyses have revealed that all spectra can be well
fitted by three Gaussian peaks. The inconspicuous band between the green and the UV peaks
is mainly contributed from a violet (3.1 eV) emission. Fig. 17b gives a typical Gaussian
analysis result for the full PL spectrum at 50 K, where a violet emission band is clearly
illustrated. The Gaussian-fitted violet emission bands from 10 K to 300 K are shown in
Fig.18. The peak position shows a different style from the other two peaks. As the
temperature increases from 10 K to 70 K, the violet peak red shifts by 35 meV, which is much
larger than the bandgap shrinkage value (4 meV) over this temperature range predicted by
Varshni formula (more discussion later). When the temperature increases from 70 K to 150 K,
however, the peak

blue shifts by about 160 meV without considering the bandgap shrinkage
of 11 meV in this temperature range. Further increasing to room-temperature (RT) induces
the peak to

redshift again by 31 meV that is similar to the bandgap shrinkage in this
temperature range. In a word, the violet emission shows an abnormal S-shaped (or red-blue-
red) shift behavior with increasing temperature. Fig. 19 compares the temperature-dependent
behavior of these three emission peaks observed from the ZnO nanowires.
Figure 18. Gaussian-fitting violet emission bands at different temperatures, the curves from top to
bottom correspond to the temperatures shown in the left, respectively. [After ref. 98, Cao, et al. Appl.
Phys. Lett, 88, 161101 (2006)].
3.2.3. Physical Origin of Different ZnO Emission Bands
For the UV emission of ZnO crystal, it is usually attributed to the near bandgap
recombination of electrons and holes in form of excitons. Generally, due to the temperature-
induced lattice dilatation and electron-lattice interaction, the near bandgap emission peak
energy follows the Varshni formula [99]:
) /( ) 0 ( ) (
2
+ = T T E T E
g g
ZnO Nanowire Arrays 261
where E
g
(t) is the band gap at an absolute temperature (T), and , are the material-related
Varshni thermal coefficients. The solid line in the lower frame of Fig. 19 denotes the fitting
results for the UV emission from 10 K to 300 K. The obtained fitting parameters of E
0
,

and
are 3.379 eV, 7.5x10
-4
eV/K and 1050 K, respectively, which are comparable to the values
reported for ZnO films [100]. So the well-fitting of redshift with increasing temperature for
the UV emission proves its exciton origin.
The visible (green and violet) bands show anomalous temperature-dependent behaviors,
which differ remarkably from the monotonous bandgap shrinkage with increasing
temperature. Therefore, they must be associated with the defect-related levels in the ZnO
nanorods. To investigate their physical origins, X-ray photoelectron spectrum (XPS) and
electron paramagnetic resonance (EPR) were applied to detect the defect states existing in the
ZnO nanowires. In the full XPS spectrum of the ZnO nanowires (Fig. 20a, with sensing depth
of 2 nm), there is no any impurity detected besides the Zn, O, adsorbed carbon and gold (from
the Au/Si substrate) signals. Fig. 20b presents the high-resolution XPS peak of O
1s
centered at
531.25 eV with a large FWHM of 2.1 eV, which can be well fitted with three Lorentzian
peaks. The three binding energy components, centered at 531.89 eV, 531.13 eV and 530.40
eV, are usually attributed to the absorbed oxygen on the surface of the ZnO nanorods, O
2-
ions in the oxygen-deficient regions within the matrix of ZnO, and O
2-
ions on the wurtzite
structure of the hexagonal Zn
2 +
ion lattice, respectively [101]. It is also to be mentioned that
the intensity of the component at 531.13eV is higher than the other two components,
indicating the relatively higher concentration of oxygen-deficient states in the nanorod
surface layer.
Figure 19. The temperature-dependent peak position for the three typical emission bands. Dash-line: aid
to eyes; Solid line: fitting result by Varshni formula. [After ref. 98, Cao, et al. Appl. Phys. Lett, 88,
161101 (2006)].
Bingqiang Cao and Weiping Cai 262
Figure 20. (a) Full XPS spectrum of the ZnO nanowire array; (b) High-resolution spectrum of the O
1s
peak and its Lorentzian fitting results.
Fig. 21 is the EPR spectrum of the as-prepared ZnO nanowires, which shows a clear g-
factor of 1.96. Although this EPR signal was formerly attributed to the singly ionized oxygen
vacancy
+
o
V [93], now it has been unambiguously proved that this signal is typically
associated with shallow donors [102-106] and its position appears to be independent on the
shallow donor identity, such as, intrinsic Zn
i

[102-103] or doped copper [105], nitrogen
donors [106].
ZnO Nanowire Arrays 263
Figure 21. EPR spectrum of the as-prepared ZnO nanorod array showing a clear g-factor of 1.95.
As the XPS data proves that there is no any other impurity detected, therefore, the EPR
signal of g~1.96 in the ZnO nanowires corresponds to the Zn
i
shallow donors. It has a 0.2 eV
energy gap below the conduction band [107]. Moreover, the O
1s
peak analysis in the high-
resolution XPS spectrum shown in Fig. 20b proves the relatively higher concentration of
oxygen-deficient states in the nanowire surface layer. The oxygen vacancy is a deep level
situating at 0.9 eV higher than the valance band [108].
Similarly, temperature-dependent S-shaped shift behavior has also been observed in
nitride semiconductors, which are known to be closely related to the carrier localization
caused by alloy composition or inhomogeneities [109-111]. Accordingly, based on these two
existing defect levels in the ZnO nanorods, it is proposed that the violet emission (3.03 eV at
10 K) comes from the electron-hole recombination between the electrons localized at the Zn
i
-
shallow donor levels and holes in the valence band as shown in Fig.22(a, b). Its emission
energy is well consistent with the theoretical value between these two levels. As the
temperature increases from 10 K to 70 K, a redshift appears because the excitons gain thermal
energy sufficiently to overcome small energy barriers and are trapped in adjacent lower levels
of the localized states from where the recombination takes place (T
2
process in Fig.22 (b)).
Obviously, this redshift also includes the contribution from the temperature-induced bandgap
shrinkage of 4 meV. The following blueshift of 160 meV from 70 K to 150 K is caused by the
thermal population of electrons localized at higher energy states and transitions from these
higher levels to the valance band (T
3
process in Fig.22 (b)). In this temperature range the
influence of bandgap shrinkage is totally counteracted by the localization effect. At
temperatures over 150 K, the shift of the emission band is mainly determined by the behavior
of the bandgap shrinkage, and the shift energy is consistent with the prediction value by the
Varshni relation. Therefore, the S-shaped shift of the violet emission is the result of
competition between the temperature-induced localization effect and bandgap shrinkage.
Bingqiang Cao and Weiping Cai 264
Figure 22. (a) Schematic illustration of the ZnO band structure and the proposed UV, violet, and green
emission processes, NR: nonradiative transition; (b): model of the localized electrons at Zn
i
defect
levels and their transition process with increasing temperature. (c): model of the green emission with
increasing temperature. [After ref. 98, Cao, et al. Appl. Phys. Lett, 88, 161101 (2006)].
As for green emission, theoretical studies have identified the electron-hole radiative
recombination at the V
o
center as the source of the green luminescence

[108]. However, the
transition process is still not clear yet. Since it blueshift monotonously and its intensity
decreased with increasing temperature, it is proposed that the green emission at near room
temperature is composed of two transitions: from the conduction band to V
o
levels and from
Zn
i
levels to V
o
levels as shown in Fig.22 (a, c). In fact, the existences of these two types of
transitions have been confirmed by optically detected EPR (ODERP) experiments,
respectively

[104,112].

With temperature decreasing, more electrons in conduction band
firstly relax to lower Zn
i
levels nonradiatively, and then recombine with holes at V
o
levels,
which results in the green emission shift to lower energy with narrower FWHM, changing
from 600 meV at 50 K to 440 meV at 300 K. Accordingly, the green and violet emission
intensities, compared with that of UV emission, are increased as more electrons at Zn
i
levels
recombine with holes at oxygen vacancy and in valance band.
3.3. Field Emission of ZnO Nanowire Arrays
3.3.1. Field Emission Theory
Field emission source are widely used in flat-panel displays. The principle of field
emission is based on the application of a high electric field to extract electrons from a metal
or semiconductor surface [113]. A high electric field near the emitter can be sufficient to
ZnO Nanowire Arrays 265
lower the surface barrier, so that the barrier height is sufficiently reduced to increase emission
substantially. When the electric field is around several voltages per nanometer, the width of
the barrier is of order 1 nm, and electrons can escape from the emitter surface by tunnelling,
as schematically shown in Fig. 23. This process is field emission (FE). The electrical field of
FE plays a similar role to the temperature in thermionic emission, where electrons are emitted
from a heated filament. Compared with thermionic emission, field emission has the
advantages of less thermal shift, low energy spread, and low operating voltage. FE can be
observed even at room temperature, so it is also called as cold FE. Traditional field emission
devices require complicated micro-fabrication processes, e.g. electron beam lithography
[114]. An ideal field emitter should be highly conductive, very sharp at the tip end, robust,
and easy to fabricate. ZnO has a high melting point, low emission barrier, and high saturation
velocity. Furthermore, as a widely studied transparent conductive oxide, ZnO can be made
both highly conductive and optically transparent from the visible to near-UV range through
proper doping. These properties make ZnO nanowires a promising candidate for field
emission displays [115].
Figure 23. Scheme of the electron emission process from a metal or semiconductor emitter under an
electrical field (Fowler-Nordheim process).
Fowler-Nordheim (F-N) tunneling [116] has been studied extensively in Metal-Oxide-
Semiconductor structures, where it has been shown to be the dominant current mechanism of
FE, especially for thick oxides. The basic idea is that quantum mechanical tunneling from the
adjacent conductor into the insulator limits the current through the structure. Once the carriers
have tunneled into the insulator they are free to move within the valence or conduction band
of the insulator. According to F-N theory, the relationship between current density (J) and
applied electric field (E) can be expressed as follows:

=
E
B E
A J

2 / 3 2 2
exp ,
Bingqiang Cao and Weiping Cai 266
where A=1.54x10
-10
(AV
-2
eV), B=6.83x10
9
(Vm
-1
eV
-3/2
), and is the work function of the
emitter. is the field enhancement factor defined as: d V E E
local
/ = = , where E
local
is
the local electric field nearby the emitter tip. can be expressed ideally as =h/r, where h is
the height of the emitter (for example, nanowire) and r is the radius of curvature of the tip
apex. It can be easily deduced that the physical geometry of one-dimensional semiconductor
nanowire provides a field enhancement. Therefore, electrons can be extracted more easily
from nanowires and they are expected to be good emitter. According to F-N equation, the plot
of ) / (
2
E J Ln Vs
1
E (F-N plot) should be a straight line and is a good check on the field
emission mechanism. Experimentally, FE properties are measured in a vacuum chamber at
room temperature under a two-parallel-plate configuration, as schematically shown in Fig. 24.
The distance between the emitter and the current detector need to be precisely controlled.
Besides this, the emission area also needs to be calculated accurately.
Figure 24. Illustration of the FE measurement from a single nanowire emitter.
3.3.2. Field Emission of ZnO Nanowire Arrays
Fig. 25a shows the current density versus applied voltage (J-V) curves for the ZnO
nanowire array shown in Fig. 6 measured at various distances (d). The turn-on field, defined
as the applied field to draw an emission current of 10 A/cm
2
, is 22.1, 19.3 and 18.9 V/m,
corresponding to the d values of 100, 150 and 200 m, respectively. They are lower than the
turn-on value (18 V/m for 0.01A/cm
2
) of ZnO nanoneedles grown on gallium-doped ZnO
film by vapor phase method [117] and comparable to that of the silicon nanocone arrays
prepared by ion sputtering [118]. The current density as high as 1 mA/cm
2
corresponds to the
applied voltage of 4.3 kV (Fig. 25a) when d=150 m, which is comparable to those of other
wide-band-gap semiconductor, such as GaN nanowire

[119] or AlN

nanocone [120] arrays
grown on silicon substrates.
ZnO Nanowire Arrays 267
Figure 25. (a) Field emission curves of the ZnO nanowire array measured at the different distances
between the anode and cathode; (b) F-N plots corresponding to (a)
Corresponding F-N plots transformed from data of Fig. 25a for different d values are
shown in Fig. 25b. All the F-N plots show nearly straight-lines with slightly different slopes,
indicating the field emission process from the ZnO nanowire array is an F-N quantum
tunnelling process. The observed kinks on the F-N plots, which are located in the field region
of turn-on voltage, can attributed to the current-induced changes in the structures of the field
emitters

[121] or absorbates-induced emission saturation [122]. The slopes obtained from the
F-N plots can be used to estimate the values, as shown in Fig. 25b. They are comparable to
the value of multi-wall carbon nanotubes

[123] (830 at d=125m). Such well-aligned ZnO
nanowire array, with low preparation cost and wafer scale, could promise the industrial
application of flat display in a near future.
Bingqiang Cao and Weiping Cai 268
3.3.3. Field Emission Comparisons of ZnO Film and Nanowire Arrays
Figure 26. Field emission comparison of ZnO film and nanowire arrays measured at the same
conditions: (a) J-E curves and (b) corresponding F-N plots.
The successful synthesis of ZnO films and nanostructures with different morphologies by
ECD method paves the way to study its FE property contrastively. Fig. 26 shows the emission
current density versus applied electrical field (J-E) curves for ZnO film, nanowire array and
hierarchical nanowire array (H-array) corresponding to Fig. 11~12. All the ZnO film, ordered
nanowire array, and H-array show steady FE properties at various measuring distances (d)
between the electrodes. For simple comparison, Fig. 26 (a) shows the J-E curves measured at
the same conditions (d=200m). The turn-on fields, defined as the applied field to draw an
emission current of 10 A/cm
2
, are 16.9, 15.5, and 9.5 V/m, for ZnO film, dense nanowire
array, and H-array, respectively.
From the data in Fig. 26(a), according to the F-N theory, corresponding F-N plots of
) / (
2
E J Ln Vs
1
E for different ZnO are shown in Fig. 26(b). All the F-N plots are nearly
ZnO Nanowire Arrays 269
straight-lines with different slopes, indicating the field emission process from the ZnO film
and nanowire arrays is consist with F-N mechanism. There is a kink on the F-N plot of ZnO
film, which is located in the region of turn-on field, maybe caused by the absorbates-induced
emission saturation of the film surface. On the other hand, the obvious nonlinearity is also
observed from the F-N plots, indicating that local electric field enhancement factor ( ) is not
exclusively determined by the emitter radius. The values obtained from the slopes of the F-
N plots have been shown in Fig. 26(b). In the normal electron emission region, the FE
properties of ZnO nanowire arrays, such as turn-on electric field and factor, are both better
than that of ZnO film due to their high aspect ratio and small curvature radius, which are all
efficient for FE as emitters. But the value of the ordered ZnO nanowire array with high
density is much smaller than that of the hierarchical ZnO nanowire array, which is caused by
the local electric field screening effect around the tips of nanowires [124]. This result
indicates that, for practical field emission display application, the planar density of
semiconductor nanowire array needs to be optimized to get efficient emission current.
4. Conclusion
In this chapter, a review on growth and physical properties of ZnO nanowire arrays are
presented. Among various growth techniques for ZnO nanowires, all kinds of vapor phase
methods based on VSL or VS mechanism, depending on the presence or absence of a metal
catalyst, are all widely adopted probably due to the simplicity of the growth. In general, vapor
phase method is proved to be a high-temperature synthesis process with low productivity. On
the contrary, many solution methods, which are typical low temperature synthesis process
with high productivity, have been proved well suitable for growth of ZnO nanowires. Among
them, template-assisted growth is the simplest in principle but may have difficulties in
producing high quality single-crystal ZnO nanowire arrays. To overcome this point, a new
template-free strategy is developed to grow ZnO nanowire arrays. The growth mechanism can
be attributed to formation of {0001}-oriented ZnO nuclei on the designed substrates and then
faster growth along <0001> direction in terms of minimum interface and surface energy,
which is a template-free self-assembly process.
As for physical properties of ZnO nanowire arrays, Raman, photoluminescence and field
emission are studied with the samples gown by this template-free growth strategy. Raman
studies have confirmed that the ZnO nanowires are of good crystal quality. Resonant Raman
scattering spectrum were also observed and applied to study the phonon interaction of ZnO
nanowires. Detailed photoluminescence spectra of ZnO over the temperatures from 10 to 300
K show three typical emission bands. They are ultraviolet, violet, and green emission,
respectively. With increasing temperature, these bands show different temperature
dependences: a normal redshift for the ultraviolet emission, S-shaped shift for the violet
emission and blue shift for the green one. The origins of these three bands and their
temperature dependent shifts are explained based on defect levels (zinc interstitial and oxygen
vacancy levels) and electron localization effect at the defect levels in addition to bandgap
shrinkage. ZnO nanowire arrays with optimized planar density also exhibit good field
emission properties due to their physical geometry. Such wafer-scale ZnO nanowire arrays
Bingqiang Cao and Weiping Cai 270
with good field emission performance and low preparation cost could promise the industrial
application of flat display in a near future.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp.275-292 2010 Nova Science Publishers, Inc.
Chapter 7
SPATIALLY RESOLVED CONTROL OF ELECTRICAL
RESISTIVITY IN ORGANIC MATERIALS
DEVELOPMENT OF A NEW FABRICATION METHOD
OF JUNCTION STRUCTURES
Toshio Naito
Division of Chemistry, Graduate School of Science,
Hokkaido University, Hokkaido, Japan
Abstract
Organic materials (OMs) are diverse and are interesting in terms of application in electronic
devices. In particular, organic charge transfer salts (OCTSs), which are typically composed of
positive and negative ionic (and often radical) organic molecules, attract continued attention.
Without carrier doping, they generally have high conductivity, magnetism, and well-defined
unique nanostructures in their crystalline form. In order to apply the OCTSs to electronic
devices, they should be made junction structures. Although there are established ways and
advanced methods for doping and fabrication of junction structures in the current industrial
techniques for the silicon devices, few of them are applicable to the OMs due to totally
different chemical and physical properties between inorganic and organic materials. In this
comment, we would like to discuss a new method for simultaneous realization of doping and
junction structures beginning with the single crystals of the OCTSs. The method utilizes a
photo-induced chemical reaction, and produces a stable solid state composed of well-defined
different parts of different conducting/magnetic properties. With reference to our recent and
previous work as well as related studies of other groups, discussion will briefly cover
experimental methods, preparation of materials, examination of irradiation conditions and
resultant solids characterization, outline of mechanism of this photochemical modification,
and remaining problems to be explained or overcome.
Toshio Naito 276
Introduction
Why Organic Materials for Electronic Devices?
Molecular or organic materials (OMs)
*1
now attract the growing interest of a wide range
of researchers for application in electronic devices such as transistors and displays [1,2].
Their advantages over other materials are practically unlimited choice of compounds,
accumulated knowledge of material design along with simulation/calculation of the properties
using computers, and possible low cost due to industrial large-scale production. Ambient
conditions in temperature and pressure is required or adequate for dealing with them, which
makes many of the facilities and the procedures for them simple and inexpensive. In addition
to experimental techniques such as lithography, one can use wet chemistry, i.e., a variety of
procedures of moving, removing, purifying, mixing, and forming desired/undesired organic
substances in solution. The products equipped with organic devices can be small or large,
depending on their purposes, but anyway they are expected to be light, thin, flexible, and can
be suitable for portable equipment [35]. Low cost may provide disposable electronic
products in the future; in such cases organic devices will not seriously suffer from fragility.
Organic electroluminescence (EL) displays, for example, have recently been in practical use
in cellular phones. It is also advantageous in usage of the OMs that nanowires and other
functional nanostructures are often easily obtained as bulk products owing to their
controllable self-assembly properties and well-established synthetic chemistry. Since
nanowires, nanotubes, and nanoparticles are considered to be key materials for future
electronic and bio-devices such as sensors, the OMs will keep attracting strong attention for
the next decade or more.
Beginning with Thin Films
A substantial body of research on development of organic devices utilizes various OMs
as thin films on appropriate substrates [35]. This trend is partly because they are
comparatively easily made thin films of desired shapes and dimensions, while it is generally
extremely difficult to make their single crystals, like silicon and gallium arsenide, with
sufficiently large dimensions for industrial use. Additionally, the chemical, thermal, and
mechanical properties of the OMs are quite different from those of silicon and other typical
inorganic semiconductors; the OMs do not stand severe conditions such as elevated
temperatures and ion beam bombardment required in the current device fabrication processes
for the inorganic semiconductors. As a result most organic devices are commonly studied and
fabricated on the basis of their unique processes (sublimation and/or various methods of wet
chemistry) partly in combination with the current silicon technology (lithography and so on).
For example, different kinds of organic and inorganic materials are layered on a plastic
substrate using ink jet, vacuum sublimation and other techniques [35], functioning as a field-
effect transistor (FET). Each different kind of material plays its own role such as an insulator,
a dielectric, an electrode, and so on. Such an assembled structure with interfaces between
Spatially Resolved Control of Electrical Resistivity in Organic Materials 277
materials with qualitatively different electrical properties is called a junction structure and is
necessary for any kind of device function. The current device fabrication technology has been
established mainly upon doping methods to control the electrical properties of the materials in
addition to the lithography techniques to make elaborate junction structures by combining
different materials.
Different Strategies Required
Besides the differences in chemical, thermal, and mechanical properties, it is the high
anisotropy (low dimensionality) mentioned in detail below that we must keep in mind as an
intrinsic difference between inorganic semiconductors and OMs. This means that electrical
conduction is seriously disturbed in a disordered/incoherent arrangement of
molecules/domains/grains such as amorphous, thin films, powders and so on. In particular,
electrical properties generally depend more on the grain boundaries than on the intrinsic
electrical properties inside each grain in highly conductive materials. In other words, in a
given OM, the electrical conduction is higher and better-defined in a single crystalline state
than any other solid state. The ill-defined electrical conduction pathways in a disordered
molecular assembly result not only in extrinsically higher resistivity but also in ambiguous
electrical behavior. For example, one might observe a much smaller current ratio between on
and off states with higher leak current in an FET than it should have. Two sheets of thin films
of the same material never exhibit identical electrical behavior, because their mesoscopic
structures, i.e., the sizes and the distribution of grains in the films, differ from each other.
Therefore utilization of single crystals may improve or modify the performance of many
kinds of organic electronic devices based on thin films. Now we have a problem; how can we
fabricate devices from single crystals instead of thin films? The OMs in crystalline forms
have more difficulties in processing than inorganic materials and thin films of the OMs.
Examples include small dimensions ( 1 mm), and low plasticity (every crystal has its own
shape and is fragile). In particular, the crystalline organic charge transfer salts (OCTSs)
mentioned below additionally suffer from low solubility (typically almost insoluble) and low
vapor pressure (practically non-volatile). These properties lead to the following problems
mainly on doping methods when we apply the known strategies to them.
1) Few of the standard doping methods of the current silicon technology can be applied.
2) The only known doping method applicable to the OMs is simple mixing of foreign
chemical species in the synthesis, yet it is very difficult to control precisely the dopant
content, homogeneity, and the part to be doped using the chemical method.
3) Inclusion of dopants might seriously lower the crystal quality and/or might cause
unexpected changes of the crystal structures, both of which certainly deteriorate the
resultant device performance.
4) One can not use the device fabrication methods suitable for organic thin films based on
the wet chemistry or sublimation.

*1
Molecular materials may include metal complex molecules and clusters as well as organic molecules. In this
chapter the two terms, the molecular materials and the organic materials, are used in an identical context and
not distinguished unless such usage is misleading.
Toshio Naito 278
In this chapter we will discuss the problems of the crystalline OCTSs in the fabrication
process of electronic devices, and will propose a new strategy. It involves spatially resolved
control of electrical resistivity of molecular crystals using photochemical solid state reactions,
which practically transforms the single crystals to junction structures.
Discussions
-Conjugated Planar Radical Ion Molecules
The OMs can be divided into groups in terms of their component molecules: neutral or
ionized molecules, those with or without unpaired electrons, -conjugated planar molecules
or not, and so on. Hereafter we will focus our attention on the OMs including -conjugated
planar radical ion molecules. Such materials are generally called charge transfer salts and
often have high conductivity, magnetism, and well-defined nanostructures, especially in their
crystalline form. Compared with the inorganic semiconductors and the OMs of neutral
molecules, the OCTSs have unique advantages for electronic devices as follows.
a) multi-component: different chemical species can simultaneously play different roles in
a single material, which may enable multi- or advanced functions of resultant devices.
b) anisotropy: different (usually incompatible) electrical properties appear in different
directions. This and the next features (b and c) can be favorable for many kinds of
organic devices, because the electric current is expected to flow through some
particular parts in given directions and should not flow otherwise.
c) nanostructure: in a given crystal structure, the electrical conduction pathways can be
clearly defined within an atomic scale.
d) low concentration of the carriers: many OCTSs have relatively high conductivity in
spite of lower concentration of carriers than naturally occurring metals (about one-
order lower number density per unit volume). This and the next (d and e) features
enable effective control of carriers or conductivities by applying electric field and
thermodynamic methods.
e) high sensitivity to perturbations: their electrical behavior markedly varies under
external fields and different thermodynamic conditions.
f) correlated electrons: many of them have strongly correlated electron systems, which
often lead to superconductivity, ferromagnetism, and other unusual as well as useful
physical phenomena.
Here we should take a look at an example of the OCTSs; M(R
1
,R
2
-DCNQI)
2
(R
1
,R
2
-
DCNQI = 2-R
1
-5-R
2
-N,N-dicyanoquinonediimine, R
1
,R
2
= halogen atoms and organic
substituent groups, abbreviated as DCNQI below; M = cations of lithium, silver, copper and
so on) [6-8]. Figures 1 and 2 show the molecular structure of DCNQI and the crystal structure
of M(DCNQI)
2
, respectively. In the crystal the planar DCNQI molecules exist as radical
anion species, and stack to form a one-dimensional (1D) columnar structure. Such structure
can stabilize the unpaired electrons, which are originally delocalized within each DCNQI
molecule, in the most effective way by fully delocalizing them within each DCNQI column.
Except for the case of Cu(DCNQI)
2
, the unpaired electrons cannot travel between columns
Spatially Resolved Control of Electrical Resistivity in Organic Materials 279
through the cations. As a result this material exhibits metallic conductivity only in the
stacking (// c axis) direction, and behaves as a dielectric (or an insulator) in other directions
(thus called 1D conductor). Such a structure can be regarded as a single crystal of nanowires
composed of the DCNQI molecules. In this case, the cations do not play a role in the
electrical conduction except for insulation of the neighboring columns. However, in the case
of M = Ag it was thought, by analogy with photography, that the conduction (unpaired)
electrons might be reduced in number by photo-induced charge- (electron-) transfer from the
DCNQI
0.5-
radical anions to the Ag
+
cations. This phenomenon may enable direct control of
the electrical resistivity. Further detail is discussed below.
N
N
C
N
C
N
R
1
R
2
Figure 1. Molecular structure of R
1
, R
2
-DCNQI (R
1
, R
2
= halogen atoms and organic substituent
groups).
Figure 2. Continued on next page.
Toshio Naito 280

~ 0.5 nm
Figure 2. Crystal structure of Ag(DBr-DCNQI)
2
, where DBr-DCNQI = 2,5-dibromo-N,N-
dicyanoquinonediimine. Views down along the c axis (upper), and perpendicular to the c axis (lower).
Thin lines indicate the unit cell. Colored spheres indicate silver (pink), nitrogen (light blue), carbon
(grey), hydrogen (white), and bromine (red) atoms, respectively. White vertical arrows in the lower
figure indicate the conduction pathways through the DBr-DCNQI columns (// c axis) of ca. 0.5-nm
thick. Other related salts designated as M(R
1
, R
2
-DCNQI)
2
(M = metal and organic cations) take
isostructures with the structure shown herein.
Basic Problems to be Solved
For making an electronic device from a single crystal of a given OM, two basic problems
are to be solved.
1) How can we obtain a suitable single crystal with a desired crystal structure and a
desired electrical property?
2) How can we make a junction structure from the single crystal?
The first problem appears to require a fine and accurate control of the crystal structure as
well as precise prediction of the electrical property of the resultant material, either of which is
impossible at present. Fortunately, instead of developing a novel material with perfectly
desired crystal and electronic structures, one can select a known material with an appropriate
crystal structure [9] only if one can control its electrical property.
The second problem can be solved in some ways. The straightforward way is to carry out
the similar procedures with those for the organic thin film devices. For example, combined
Spatially Resolved Control of Electrical Resistivity in Organic Materials 281
with other materials, single crystals of OMs can be actually made FETs [10,11]. Here, we
would like to discuss a different strategy, which can simultaneously solve both problems [12].
Using photochemical reactions, it is thought that a part of a single crystal could be modified
in the electrical properties, remaining the rest of the crystal intact (Figure 3). In other words,
an organic single crystal itself can be made a junction structure after irradiation on a part of
the crystal. This method, tentatively named optical doping, can be performed under mild
conditions and suitable for the OMs.
Figure 3. Schematic presentation of optical doping on the single crystal of Ag(DM)
2
. Arrows with
broken lines in the lower figure indicate the conduction pathways through each nanowire.
Toshio Naito 282
Photochemical Control of ResistivityInitial Idea
By way of illustration, details are explained with reference to Ag(DM)
2
(DM = DMe-
DCNQI = 2,5-dimethyl-N,N-dicyanoquinonediimine). In order to realize the idea above, the
crystal must contain the following two kinds of chemical species. The first species (Ag
+
) are
inert without irradiation, but are reductive or oxidative under irradiation. The second species
(DM
n-
; 0 n 2) are multistep redox systems like transition metal atoms, where some
different oxidation states are (meta-)stable to occur. When the material composed of the two
species is exposed to light of appropriate wavelengths, a photo-induced electron transfer
(redox reaction) is expected to occur between Ag
+
and DM
0.5-
, and the numbers of valence
electrons of both species should change. In Ag(DM)
2
the electrical conduction is dominated
by the unpaired electrons on the DM radical anions, and the Ag
+
ions may become strongly
oxidative only when they are irradiated with ultraviolet (UV) and/or visible (Vis) light. What
is more, the coordination bonds between Ag
+
and DM
0.5-
prove that there is interaction
between them. Therefore UV-Vis irradiation is expected to change (reduce) the number of
unpaired electrons on the DM columns, and thus should change (increase) the resistivity only
at the irradiated part of the sample. Because the resistivity of Ag(DM)
2
is metallic, i.e. low (~
0.01 cm above 100 K) before irradiation, it may be changed to a wide range of values by
this method. Based on this idea, we tried to arrange for single crystals of this kind of salts to
be continuously irradiated with UV-Vis light.
Main Experimental Results
The crystalline and powder samples of Ag(DM)
2
were synthesized following the reported
procedures [6-8]. The detail of irradiation conditions, measurement and analysis equipments
are described in previous reports [12-14]. Various irradiation conditions (temperatures and
atmospheres during irradiation, duration, wavelengths and intensity of light) were examined
[15]. The results clearly depended on the intensity and the sample temperature, however, did
not depend on the wavelengths or on the atmospheres. All the samples in this study were
stable under room and spectroscopic lights of various wavelengths with a standard intensity.
They were also stable in air and in water. The pristine Ag(DM)
2
was thermodynamically and
chemically stable below 155C, at which temperature it irreversibly turned into amorphous
solid retaining the original chemical formula. Whether there were thermal and/or irradiation
damages/decompositions on/in the samples were examined using matrix-assisted laser
desorption ionization (MALDI) mass, infrared (IR), UV-Vis, solid state NMR, Auger
electron, and X-ray photoelectron spectra (XPS), X-ray absorption fine structure (XAFS),
elemental analysis, differential scanning calorimetry (DSC), thermogravimetry differential
thermal analysis (TG-DTA), scanning electron and atomic force microscopes (SEM, AFM).
No damage/decomposition was detected in the samples of the data below. The resistivity of
the single crystals was measured with a standard 4-probe method along the stacking (c) axis.
All the spectra were measured on the powder samples; the single crystals of Ag(DM)
2
were
finely ground in an agate mortar and irradiated in a similar manner with that the single
crystals were irradiated.
Figure 4 shows the irradiation effect of the resistivity of the single crystal of Ag(DM)
2
using UV light of 250-450 nm (filtered from 200 W Hg/Xe lamp equipped with a multimode
Spatially Resolved Control of Electrical Resistivity in Organic Materials 283
quartz optical fiber (length = 1 m, core diameter = 5 mm)) [14]. The resistivity measurement
and irradiation were simultaneously carried out in air. The temperature was measured with a
silicon diode thermometer (LakeShore DT-470-SD fixed with Apiezon N), which was also
put in the UV light immediately beside the sample on a brass plate and thermally in contact
with it. The resistivity increased in accordance with irradiation time. Sufficiently long interval
(75 min) of the irradiation let the sample cool down, which enabled quantitative estimation of
the effect of heating involved with the UV irradiation. After ca. 10000 s (~ 3 h) the sample
temperature became nearly constant (~ 45C). Accordingly, nearly linear increase in
resistivity after ~ 10000 s can be attributed to an irreversible photochemical reaction. Similar
experiments were carried out in liquid nitrogen using a different light source (200-1100 nm, 5
W tungsten-halogen and 30 W D
2
lamps) and a quartz optical fiber (length = 1 m, core
diameter = 800 m) (Figure 5) [12]. It should be noted here that only a part of the sample (a
single crystal) was irradiated in order to examine whether the electrical properties can be
modified only at the part of the crystal. The temperature dependence of resistivity before
irradiation (the pristine sample) exhibited metallic behavior from room temperature (RT)
down to~ 100 K, where a metal-to-insulator (MI) transition occurred and resistivity rapidly
increased below this temperature.
*2
After irradiation the resistivity clearly increased; the
longer the irradiation became, the more the resistivity increased [12,16]. The observed
temperature dependence of the resistivity can be explained as a sum of the two different types
of behavior: one is semiconducting behavior, of which resistivity increases with decreasing
temperature, and the other is metallic behavior, of which resistivity decreases with decreasing
temperature. The behavior around RT and MI transition was nearly retained after irradiation,
which means that a part of the sample retains its original electrical behavior after irradiation.
This is consistent with the fact that the sample was only partially irradiated.
In order to confirm that the silver ions are reduced after irradiation and also to confirm
that the non-irradiated part of the sample retains its original chemical state, only the center of
the pressed powder pellet (10 mm) of Ag(DM)
2
was irradiated for four days through the
abovementioned (800 m) optical fiber with putting the end of the fiber directly upon the
sample and then examined with XPS by scanning along a diameter of the pellet and
measuring the spectra at every 100 m [12]. The result showed that the formal charges
(oxidation states) of C, N, and Ag atoms in this material changed after irradiation only at the
irradiated part of the sample with a clear borderline, while the rest of the pellet retained its
original chemical state. On the surface of Ag(DM)
2
in the irradiated part all the silver ions
were reduced to be metallic silver, while the carbon and the nitrogen atoms in DM were
oxidized [17].
*3
This method has a spatial resolution. Simply by covering half of the single
crystal with Al foil during irradiation, a sharp borderline between the irradiated and the non-
irradiated parts was observed in Ag(DM)
2
as well as in Ag(DI-DCNQI)
2
(DI-DCNQI = 2,5-
diiodo-N,N-dicyanoquinonediimine) (Figure 6). Identical spectra (XPS) were obtained after

*2
Due to fluctuation and metal instability characteristic to the low-dimensional conductors, an MI transition was
observed at ~ 100 K with fluctuation (gradual increase in resistivity with decreasing temperature) below ~ 180
K.
*3
In this case the silver ions in the pristine sample were fully reduced to be bulk silver and the irradiated part
(surface) of Ag(DM)
2
was decomposed. This turned out to be due to the elevated temperature ( 155C) of the
sample during irradiation. After the examination of the photochemical products under various irradiation
conditions, it proved that one could control the resistivity without decomposition by retaining the sample
temperature around RT.
Toshio Naito 284
half a year using the same pellet kept at RT in air, which means that the change is irreversible
and the resultant state is stable without particular treatment. The formal charge (n) of DM
n-
was found to change from n = 0.5 to n ~ 0.35-0.40 progressively with irradiation on the basis
of the Raman spectra [12].
Figure 4. Change in the resistivity of Ag(DM)
2
during UV irradiation. (a) Overview, and (b) Close view
of the initial stage [encircled part of (a)]. The irradiation commenced at ca. 700 s after the resistivity
measurement started. Before the irradiation (< 700 s) the resistivity was constant within experimental
error. When the UV light was turned on, the resistivity suddenly increased (
heat
). This could be
attributed to heating effect involved with the irradiation. Reproduced and modified from Figure 2 in ref
[14] with copyright permission.
Spatially Resolved Control of Electrical Resistivity in Organic Materials 285
Figure 5. UV-VIS illumination effects on the electrical behavior of the single crystal of Ag(DM)
2
. a)
Temperature-dependence of the resistivity of Ag(DM)
2
. b) Top: Schematic description of the resistivity
measurement by a standard 4-probe method after illumination. The curves with arrows indicate possible
different current routes. Bottom: Conceptual section views of the partially illuminated single crystal
taking domain structures with different electrical properties at different temperatures. Reproduced and
modified from Figure 1 in ref [12] with copyright permission.
Toshio Naito 286
Figure 6. (Upper) Scanning electron micrograph (SEM) of single crystals of Ag(DM)
2
after partial
irradiation with UV-Vis light using Al foil as a mask. Because of the clear difference in electrical
resistivity of the two parts, one can distinguish them owing to the difference in charge-up effects under
electron beams. (Lower) Optical micrograph of Ag(DI-DCNQI)
2
(DI-DCNQI = 2,5-diiodo-N,N-
dicyanoquinonediimine) fixed on the conducting carbon tape after partial irradiation with UV-Vis light
using Al foil as a mask. The irradiated part turned bluish hue, while the masked part retained its original
brownish reflection. Because of the clear difference in electronic structures of the two parts, one can
distinguish them owing to the difference in reflectance spectra. (Inset of lower figure) Atomic force
micrograph (AFM) of the area (4040 nm
2
; around the yellow square) on the borderline of the
irradiated and non-irradiated parts. The AFM shows as fairly smooth surface as the crystalline solid
should have, and in fact roughness of the surface on the borderline is less than 1 nm, which suggests
that the irradiation does not cause mechanical/thermal damage on the surface of the single crystal.
Now that this photochemical modification of resistivity is found to serve as a chemical
fabrication method of junction structures, we should discuss whether a prototype of some
device can be made. After irradiating on a half of the single crystal of Ag(DM)
2
(long needles
with typical dimensions of 1-10 mm in length and 0.01-0.1 mm thick), the current (I)-voltage
(V) property curves were measured at RT across the borderline of the irradiated and the non-
irradiated parts in the longitudinal direction of the needle-shape crystal, which is parallel with
the conducting direction (// c axis). The result (Figure 7) indicated rectifying behavior, a
characteristic property of a diode, which is the simplest device with a single junction
interface. The similar measurements at lower temperatures ( 100 K) resulted in poor
Spatially Resolved Control of Electrical Resistivity in Organic Materials 287
asymmetry of the I-V curves with higher resistivity, which is consistent with the fact that the
pristine Ag(DM)
2
becomes an insulator at T 100 K.
Figure 7. Current-Voltage property curve of the single crystal of Ag(DM)
2
after UV-Vis illumination
upon only half of it for ~21 days; observed (red) and theoretical fit (blue). The theoretical fit was based
on the following formula; } 1 ) {exp( =
kT
eV
I I
S

, where I, I
s
, , e, V, k and T denote observed
current (mA), saturation current (mA), reducing factor, elementary electric charge (C), applied voltage
(mV), Boltzmann constant (JK
-1
) and temperature (K). The parameters which give the best fit are I
S
=
0.166, = 0.016, when T = 290.47. Reproduced and modified from Figure 4 in ref. [12] with copyright
permission.
Mechanism
We will discuss here an outline of the mechanism of the above photochemical
modification. Here, for simplicity, we should call the semiconducting photochemical product
, and the starting material [18]. produces when it is irradiated with UV and/or Vis
light of an arbitrary wavelength, intensity and atmosphere as long as the sample temperature
is retained well below 155C during the irradiation. By varying duration of irradiation on ,
the resistivity of can be continuously controllable. It should be noted here that indicates
any solid derived from by irradiation around RT for various duration. Thus may be an
inhomogeneous mixture and may exhibit different physical properties from another
produced under different irradiation conditions. Accordingly we had carefully checked
reproducibility and consistency of the data from different samples/measurements. has an
identical appearance with , dark blue or black fine needles (Figure 8). The measurements of
TG-DTA, DSC, IR and MALDI mass spectra, elemental analysis, and X-ray powder
diffraction (XRD) consistently indicated that and share the chemical formula of
Ag(DM)
2
. High resolution solid state
13
C-NMR of by a cross polarization magic angle
spinning (CPMAS) method indicated that the molecular electronic state of DM in
progressively changed with irradiation [14]. It is consistent with the fact that the electrical
conduction of Ag(DM)
2
is dependent on the DM molecules, and the way the NMR spectra
changed depending on the irradiation time qualitatively agreed with the way the electrical
resistivity and the Raman spectra did. Similarly the magnetic susceptibility measurements of
with different irradiation times indicated that more and more part of the sample became
Toshio Naito 288
semiconducting (Curie-like behavior) progressively with irradiation (Figure 9). Between
and what makes their electrical behavior differ from each other? The answer was given by a
series of XRD patterns of with different irradiation times (Figure 10). Within the first ~ 20
h of irradiation, the crystal structure of gradually changed so that the diffraction peaks did
not change in their positions (2) but did change in their relative intensities. However, beyond
~ 60 h of irradiation, a crystalline state with a different structure suddenly appeared and
rapidly increased in intensity with rapid decrease of the original powder pattern.
Taking the data above into consideration, we can put forward a hypothesis on the
mechanism of transforming metallic into semiconducting by UV-Vis irradiation. It
appears to be more complicated than we had anticipated.
(Step 1) Immediately after irradiation, Ag and DM are excited to be nearly neutral
species by transferring electrons between them.
(Step 2) During relaxation from the abovementioned excited states, a part of Ag and DM
species remain as lattice defects, which is consistent with the increase in resistivity and
paramagnetic susceptibility, particularly evident at early stages of irradiation.
(Step 3) Increase and accumulation of such lattice defects make the crystal structure of
unstable, and finally a structural transition occurs. This interpretation is corroborated by the
powder XRD data.
(Step 4) The newly appeared solid state exhibits semiconducting behavior. When the
structural transition finishes, the irradiation effect on the resistivity is expected to saturate.
This is consistent with the observed electrical behavior and the electronic states of DM
determined by various spectroscopic methods [14,15,17].
Figure 8. Micrographs of -Ag(DM)
2
and -Ag(DM)
2
.
Spatially Resolved Control of Electrical Resistivity in Organic Materials 289
Figure 9. Temperature- and irradiation-time-dependence of paramagnetic susceptibility of - (0 h) and
-Ag(DM)
2
(12 and 40 h). Measured on the powder (polycrystalline) sample after irradiation (250-450
nm) with the Hg/Xe lamp. The jump and peak behavior around 50 K in the data of 40 h is due to
impurity (residual oxygen on the surface of the sample).
Figure 10. Continued on next page.
Toshio Naito 290
Figure 10. (a) Change in the powder XRD patterns of Ag(DM)
2
during UV irradiation from 0-40 h. (b)
Close-up view of high 2-angles in (a). (c) (from top to bottom) Ag plate (99.95%), 60, 50, 12 and 0 h
with background [Scotch tape (broad peaks at 2 = 10-20 deg) and base Cu plates (*)]. Black arrows in
(b) indicate the diffraction peaks which changed intensity during irradiation. Black and red arrows in
(c) indicate the diffraction peaks which progressively weakened (black) or emerged (red) during the
irradiation. Reproduced from Figure 3 in ref. [14] with copyright permission.
Remaining Problems
By examination of the electronic and structural features of Ag and DM, the change in the
electrical property was connected with the changes in the chemical states of the DM
molecules and the crystal structure of Ag(DM)
2
. Yet the details are still to be examined to
obtain experimental evidence so that the mechanism can be established. Open questions
include the following.
1) How is the actual structure of ?
2) What kind of relaxation stabilizes the lattice defects produced by irradiation in the
early stages of the crystal structure of until the structural transition occurs?
3) Why is so stable?
4) How is the interface between and in a single crystal?
Spatially Resolved Control of Electrical Resistivity in Organic Materials 291
Clearer understanding of the mechanism will contribute to enhance/improve the
performance of devices fabricated by this method.
An important and interesting problem lies in the mechanism of the function of devices
based on the low-dimensional, strongly correlated, conducting OCTSs with marked
fluctuation. Some organic superconductors exhibit an unusual electronic state at higher
temperatures (RT-ca.40 K), where there is no distinction between metals and insulators
because it corresponds to a supercritical liquid of a strongly correlated metal and a Mott
insulator [19]. If one makes a junction structure with these kinds of materials in crystalline
forms, how will the resultant devices behave? Will the junctions belong to known categories
such as pn-junction and Schottky junction, or totally unknown categories? Because of the
anisotropy, their performance must depend on the orientation of the single crystal relative to
the direction of junction layers and the voltage applied, but how? Theoretically or
experimentally, there is no prediction at present. Recently a series of intriguing experimental
results have appeared one after another [20-24], which may indicate a bright prospect of the
devices based on the crystalline OCTSs.
Conclusion
It has become possible to modify the conducting properties of a part of an OM by
controlled irradiation. The OMs are now widely recognized as important candidates for
advanced electronic materials, and many applications could be realized if an effective,
controllable, and versatile way of doping is available. The new method discussed here is
simple, requiring only irradiation as long as the material contains a photosensitive
oxidizing/reducing chemical species in addition to a multistep redox active species such as -
donor/acceptor molecules. The latter condition is usually satisfied by most conducting
OCTSs, while the former can be easily met considering the many choices of the OMs. The
photochemical process discussed here is obviously irreversible, and the resultant state
survived at least for several months after completion of irradiation. The irradiation can be
ceased or resumed at any time, and the resistivity can be continuously controlled simply by
(total) duration of the irradiation. Thus, by combining this method with current advanced
technology of controlling light beams for the manufacture of integrated circuitry, a new path
towards manufacturing various or novel kinds of organic electronic devices will be opened.
Acknowledgment
This work is carried out mainly in collaboration with Professors T. Inabe and K. Asakura,
a post-doctor and students of their laboratories (Dr. H. Niimi, Mr. H. Sugawara, Mr. A.
Kakizaki and Mr. T. Miyamoto) at Hokkaido University.
References
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 293-308 2010 Nova Science Publishers, Inc.
Chapter 8
FABRICATION OF ELECTRICAL CONTACTS
ON INDIVIDUAL METAL OXIDE NANOWIRES
AND NOVEL DEVICE ARCHITECTURES
Francisco Hernandez-Ramirez
1

a,b,c
, Juan Daniel Prades
a
,
Roman Jimenez-Diaz
b
, Olga Casals
b
, Albert Cirera
b
,
Albert Romano-Rodriguez
b
, Joan Ramon Morante
a,b
,
Sven Barth
d
and Sanjay Mathur
d,e
a
M-2E / XaRMAE, Catalonia Institute for Energy Research (IREC), Barcelona,
E-08019 Spain
b
Departament dElectrnica, Universitat de Barcelona, C/Mart i Franqus 1,
Barcelona, E-08028, Spain
c
Electronic Nanosystems S.L. (e-nanos), Barcelona E-08028, Spain
d
Nanocrystalline Materials and Thin Film Systems, Leibniz Institute of New Materials,
Saarbruecken, D-66123, Germany
e
Institute of Inorganic Chemistry, University of Cologne, Cologne, D-50923, Germany
Abstract
Metal oxide nanowires exhibit novel properties due to their high surface-to-volume ratio and
high surface stability. For this reason, they are considered excellent candidates to be
incorporated into a new generation of devices with improved performance. Nevertheless,
reaching complete control of their physical, chemical and electrical properties is needed
before they can be widely used in our everyday life. This objective can be only fulfilled if
reproducible electrical measurements on individual nanomaterials are performed. However,
the fabrication of electrical nanocontacts in a fast and well-controlled process is still an
unsolved issue. In this chapter, the main nanofabrication techniques that are commonly used
to electrically access individual metal oxide nanowires, and to study their intrinsic properties
are presented. Advantages and limitations of these methodologies are discussed in detail. By
integrating bottom-up and top-down techniques, the first functional prototypes based on

1
E-mail address: fhernandezra@gmail.com
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 294
individual nanowires have already been implemented, paving the way to the future
developments of nanoscale electronics, optoelectronics and chemical sensing devices.
1. Introduction
Since the 1950s, the miniaturization of the electronic components in integrated circuits
(IC) has become the pillar of the huge growth and success of high-tech industries. During the
last decades of the 20
th
century, the most popular electronic systems have penetrated into
every aspect of modern life, and considerable business opportunities have arisen around them:
the market of consumer electronics in the European Union is estimated to be approximately
one billion euro per year [1,2]. The beginning of the 21st century has represented a new
revolution of this miniaturization process and, according to some authors, this has been driven
by recent advances in nanoscience and nanotechnology, which are defined by a unit of length,
the nanometer (1 nm = 10
-9
m) [3].
Nanoscience is a young field of research that involves several disciplines of traditional
science and engineering, and it is attracting increasing public and private interest. The main
goal of nanoscience is to build innovative materials and devices with new physical, chemical
and electrical properties derived from the phenomena characteristic of such tiny scales [4-7].
Although the synthesis and characterization of nanomaterials has progressed in the last years,
this work is still far from being finished, since there are a large number of technological
issues associated with handling and manipulation of these small structures; which remains an
enduring task.
In first approximation, nanowires have their electrons confined in two of their spatial
dimensions, while they are free to move along the third one. As a result of this geometry, new
electrical transport properties with potential applications in multiple fields have been
observed in these materials [7-9]. Metal oxide (MO
X
) nanowires are among the most
promising 1D systems due to their low cost and economic relevance [10]. The majority of
works devoted to the electronic applications of individual metal oxide nanowires have
focused on zinc oxide (ZnO) [13-19], which is a large bandgap material (Eg 3.4 eV) with
promising properties in visible-blind UV optoelectronics, such as photodetectors,
photodiodes, and energy harvesting applications. Furthermore, metal oxide nanowires such as
SnO
2
[11,12,20-23] have also been studied, mainly motivated by their application in gas
sensing [24].
In this chapter, the fabrication of devices based on individual metal oxide nanowires and
their applications are briefly reviewed. The first part deals with the challenges of fabricating
good and small electrical nanocontacts to individual nanowires. This issue is crucial to
develop reproducible and reliable devices with superior performance. The second part is a
short overview of the most significant examples of the use of MOX-nanowire systems as the
key elements of a new generation of functional devices, such as UV photodetectors and gas
sensors. Although most of these prototypes still do not fulfill the requirements for becoming
commercial products, they are significant demonstrations that the here-presented technologies
could become competitive alternatives in the near future. Finally, some important conclusions
are summarized and the main research guidelines that should be followed before obtaining
new and better devices are identified.
Fabrication of Electrical Contacts on Individual Metal Oxide Nanowires 295
2. Fabrication of Electrical Nanocontacts to MO
X
Nanowires
The electrical characterization of nanowires is a maturing subject. Although the first
works were based on the study of bundles of nanowires located between two microelectrodes
[25,26], the lack of reproducibility of this type of measurements forced the repetition of the
experiments in systems much easier to model. In other words, the scientific community
realized that good control over the intrinsic properties of nanowires could only be achieved if
the first experiments were performed with individual nanowires. Nevertheless, the fabrication
of electrical contacts to one nanowire is not a trivial process, and even nowadays it remains
one of the most challenging issues [27].
Here, a short review of the different approaches developed in the last decade to overcome
the bottleneck of nanofabrication is presented. Although this book chapter focuses on MOX
nanowires, most of the techniques presented here are similar to those employed with other 1D
nanomaterials [1,28-31].
2.1. First Approaches
The first attempts to electrically access individual 1D nanomaterials made use of very
simple techniques that did not require any sophisticated equipment to develop single-
nanowire devices.
The nanowires were randomly deposited onto prefabricated microelectrodes using a
suspension of inorganic material and organic solvents [32]. This method was not
reproducible, but some of the attempts were always positioned touching at least two
microelectrodes, and thus, enabling their electrical characterization in a fast way. Thanks to
these first prototypes, it was possible to demonstrate the feasibility of performing basic
studies on individual metal oxide nanostructures. However, the poor quality of the electrical
contacts formed between the nanowire and the pre-patterned microelectrodes, and the
limitation of extending this technique to large-scale processes emphasized the development of
new nanofabrication alternatives. To date, this methodology has been replaced by more
versatile approaches, such as e-beam and FIB lithography.
2.2. E-Beam, UV and Shadow Mask Nanolithography Techniques
The need for well-controlled and reproducible electrical nanocontacts motivated
researchers to develop alternatives to the simple fabrication method described in the previous
section. On one hand, the most promising technology was e-beam lithography, which is
considered a powerful technique for operating at the nanometer scale [1]. On the other hand,
the suitability of using traditional techniques like UV- or resist free lithography as feasible
alternatives to obtain measurable prototypes was demonstrated as well [33,34].
E-beam lithography is a nanofabrication technique with a lateral precision below 100 nm
[1,35,36] and thus, metal depositions with well-defined shapes in the nanometer range can be
obtained with commercial equipment, enabling the formation of high-quality electrical
contacts with MO
X
nanowires by a well-established process. Nevertheless, e-beam
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 296
lithography requires several time-consuming steps before reaching the final device and, as a
consequence, it is only appropriate for prototyping purposes.
The typical protocol necessary to contact a (MO
X
)

nanowire with e-beam equipment [37]
is summarized in figure 1. First, some nanowires are dispersed onto a silicon substrate with
predefined alignment marks to locate the position of the nanowires. Afterwards, an electron-
beam resist is spin coated onto the substrate and the e-beam lithography (sensibilization of
some regions of the resist by impinging on them a controlled electron beam) is performed to
define two or more electrodes touching the nanowire. Finally, a metallization followed by a
liftoff process is done, resulting in a contacted nanowire ready to be measured [38].
Figure 1. e-beam lithography methodology to electrically contact a single nanowire. (a & b) The
nanowire is dispersed onto a silicon substrate. (c) A resist is spin coated onto the substrate. (d) e-beam
irradiation is performed. (e) Metallization and lift-off process of the metal contacts (f) Final device
ready to be measured.
Figure 2. Shadow mask lithography methodology to electrically contact a single nanowire. (a & b) The
nanowire is dispersed onto a silicon substrate. (c) Metallization is performed using a mask to protect the
nanowire (f) Final device ready to be measured.
Fabrication of Electrical Contacts on Individual Metal Oxide Nanowires 297
It is noteworthy that most of the works devoted to the electrical studies on individual
MO
X
nanowires exploit the high degree of freedom provided by e-beam lithography to define
the final position and shape of the nanoelectrodes. However, its suitability to contact (MO
X
)
nanowires has been questioned by some authors [39], who argue that coating the nanowires
with a polymeric resist may irreversibly modify any of their intrinsic properties, changing the
performances of the final devices. Thus, e-beam and by extension other techniques such as
UV photolithography techniques, all of them based on the use of resists, have been gradually
replaced by less aggressive alternatives like shadow mask nanolithography [39-42]. In this
resist-free approach, the evaporation of metal micropads is directly performed onto the
nanowire. The exact position of this deposit is determined by a shadow mask (figure 2)
containing the appropriate pattern. This technology, which can be neither extended to large-
scale processes, has allowed reaching some of the most significant results in the
characterization of individual MO
X
nanowires in spite of being less flexible and precise than
e-beam and UV lithography.
2.3. Focused Ion Beam (FIB) Nanolithography Techniques
Focused Ion Beam (FIB) is a technique developed in the 1970s for the patterning and
deposition of different materials with nano-scale resolution. Their usual applications are
focused on circuit edit, mask repair, material characterization and fabrication of micro-nano
systems [43-48].
Its basic principle is scanning the sample surface with a focused ion beam (generally Ga
+
ions accelerated at tens of keV) that sputters the exposed area. On introducing a metalorganic
precursor in the beam path, accelerated electrons decompose this compound, and a significant
part of this material is deposited onto the sample surface [49-52]. Thus, metallic and isolating
patterns are easily obtained without the need of masks. That is the main reason why FIB has
emerged as a competitive alternative to e-beam and other techniques [1].
First attempts of contacting individual nanomaterials with FIB soon demonstrated that it
was possible to fabricate nanodevices in a fast and simple way. Nevertheless, the use of this
technique was restrained during years because of the damage and the structural modification
of these nanomaterials originated by ion bombardment. Later on, technical improvements on
FIB equipments allowed fabricating nanocontacts by using low ion currents in the proximity
of the nanomaterials to reduce undesired modifications. Although ion exposure was not
completely eliminated, these innovative works inspired subsequent studies on the use of FIB
nanolithography [53-59]. In them, well-established strategies such as nanowire dispersion on
organic solvents and the use of pre-patterned microelectrodes were combined with FIB metal
depositions, improving the overall quality of the electrical contacts between the nanowire and
microelectrodes [60-62].
The development of the so-called Dual Beam FIB systems, which comprise a
conventional FIB microscope (ion beam) and a Scanning Electron Microscope (electron
beam) in a single instrument [63], facilitated the possibility of performing both ion- and
electron-assisted depositions without masks, renovating the interest on this technique. In this
configuration, electrons can be used for imaging the sample and then, depositing conductive
materials with well-defined shapes.
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 298
Figure 3. Sketch: (a) Microelectrodes distribution onto a silicon wafer; (b) detail of the four
microprobes; (c) nanowire placed near the microelectrodes using the manipulator inside of the focused
ion beam, FIB; (d) electron beam FIB deposited Pt stripes; (e) ion beam FIB deposited Pt stripes.
Reprinted with permission from Ref.[115] F. Hernandez-Ramirez, et al., Sensors Actuators: B 121, 3,
2007. Copyright Elsevier (2007).
Thanks to the fact that the interaction between electrons and the sample is less destructive
than using ions, the structural modification and contamination introduced during the
nanofabrication process is significantly reduced if first, electron-assisted depositions are
performed onto and in the proximity of the nanowire to be contacted, and then, the rest of the
metal strips are fabricated using ion-assisted lithography without imaging the nanowire
[27,64] (figure 3). The process described here, whose suitability to contact individual
nanomaterials was previously proved with carbon nanotubes (CNTs) [65], has been
successfully used in different works devoted to the fabrication of individual metal oxide
nanowire-based devices [38,66,67]. Although this nanolithography methodology is neither
useful for large scale-processes, it is currently one of the most versatile alternatives to contact
and perform fundamental studies on individual nanowires.
Fabrication of Electrical Contacts on Individual Metal Oxide Nanowires 299
2.4. Self-assembly Approaches
Despite the advances in nanolithography techniques, which enable the fabrication of
electrical contacts on individual nanowires, they are merely suitable for prototyping and
academic purposes. To extend the use of nanowires to low cost and large scale fabrication
processes, self-assembling techniques must be taken into account. In this direction, the first
steps had already been made to self-align one-dimensional (MOX) nanostructures by means
of dielectrophoretic techniques [68-71].
Dielectrophoresis is an attractive alternative for the positioning and alignment of
nanowires thanks to its low-cost, simplicity and flexibility [68,72]. This method is based on
the well-known forces that appear when dielectrically polarized materials are in a medium in
which a non uniform electric field is applied [73,74]. It has been demonstrated for different
nanomaterials such as single- [75-77] and multi-walled carbon nanotubes [77,78], polymeric
[79], metal [80,81] and semiconductor nanowires [69,82], and of course MO
X
nanowires [68-
71].
Dielectrophoresis can be applied to the fabrication of a new generation of nanodevices
and it can be easily combined with other techniques like e-beam or conventional
photolithography. If the appropriate design of electrodes is used, nanowires are not only
aligned but also positioned at any desired position, and thus, the time necessary to fabricate a
device is significantly reduced. This advantage can be applied to the fabrication of the
simplest electronic elements, such as rectifying junctions [82] and transistors [76], paving the
way for the development of novel electronic devices exclusively based on nanostructured
semiconductors materials.
Nevertheless, before reaching this high control of self-assembly techniques, first of all the
performances of hybrid designs which combine conventional components integrated in silicon
and nanowire devices must be investigated in order to achieve novel microsystems with
enhanced capacities [83].
3. Applications and Functional Devices
The development of nanofabrication techniques has been motivated by two main aims:
(1) developing research prototypes to perform basic studies devoted to demonstrate novel
properties of MO
X
nanowires and, (2) evaluating their potential applications. Nowadays, it is
already possible tackling the second one in order to achieve functional nanodevices better
than their macro and micro counterparts.
In this direction, many research efforts have been recently undertaken to obtain the first
low-cost and portable prototypes based on nanowires with high response and accuracy. Since
the sole apparition of these devices justifies all the efforts invested in this field, we shortly
review some of the first nano-class functional devices appeared in the last years. The
application of nanowires in a new generation of electronic devices requires a cost-effective
solution to interface the contacted nanowire with a processing decision-maker unit.
Here, we first review the recent advances in low-cost multipurpose platforms to monitor
the electrical properties of individual nanowires followed by the description of sensing
applications. Among the large family of MO
X
nanowires synthesized to date, ZnO and SnO
2
nanowires are considered excellent candidates to demonstrate the feasibility of monitoring
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 300
their electrical response to different external stimuli (e.g., gas sensing) [10]. In particular, the
possibility of developing UV photodetectors based on ZnO nanowires is presented. The high
crystalline quality of the nanowires, which are almost defect-free 1D nanocrystals, enables to
reach superior optoelectronic performances when compared to their bulk or thin film
counterparts. Furthermore, the use of individual SnO
2
nanowires as conductometric gas
sensors, whose detection principle is the change of their electrical resistance after the
exposure to gases, is also reviewed.
3.1. Low-Cost Multipurpose Platforms
Most of the studies with nanowires make use of expensive and large lab instruments, and
thus, the effective transfer of this technology to our everyday life remains as an unfeasible
goal. For this reason, there is an increasing interest in demonstrating that low-cost portable
devices with integrated nanowires can be developed to operate as functional elements [84,85].
Recently, the feasibility of monitoring the electrical properties of individual nanowires
with portable cost-effective and consumer-class electronics (figure 4) was demonstrated [85].
This low-cost instrument, compared to lab equipments, was able to detect and quantify the
response of individual nanowires to UV light pulses and various gas species with long-term
stability due to the low current injected by the platform to the nanowire, which prevented any
undesired damage of the nanocontacts due to Joule self-heating [85].
Besides the electronic instrumentation, there are other important issues concerning the
appropriate operating conditions of the nanowires for certain applications. For instance, it is
well-known that metal oxide materials need to be heated at a specific temperature to
maximize their response to a specific target [86]. Therefore, the use of a heater becomes a
fundamental tool to modulate the final performance of these materials. For this reason, both
bottom-up and top-down fabrication techniques have been successfully integrated in a single
process; nanowires are electrically contacted to a micro-hotplate with an integrated heater
[85] (figure 4). This set up allows modulating the effective temperature of the wire as
function of the power dissipated at the heater in a fast and completely reproducible manner. It
is noteworthy that this solution combined with a good electronic interface, which integrates
the thermal control of the nanowire, is extremely useful in manifold sensing applications [85].
Other architectures are also being explored to solve one of the major issues of sensors:
the lack of selectivity to interfering stimuli. Typical examples are photodetectors sensible to a
wide range of light wavelengths or gas sensors responsive to parasitic species, like moisture.
For this reason, brand-new studies are attempting to develop electronic systems based on
arrays of different individual MO
X
nanowires [87]. According to this approach, their
responses are monitored in parallel, and the specific sensing characteristics of each one are
determined and electronically recorded following one of the strategies previously described.
Later, the data are processed by pattern recognition software to determine the composition of
the external stimuli [88]. Although these studies are currently ongoing, they are the most
promising solution to overcome the lack of selectivity, which is characteristic of metal oxide
nanowires.
Fabrication of Electrical Contacts on Individual Metal Oxide Nanowires 301
Figure 4. Low-cost electronic interface and detail of a micromembrane with an integrated microheater.
Additional magnification (inset) is necessary to see the nanowire.
3.2. Photodetectors
MO
X
nanowires are gaining a great interest as photodetectors due to their potential
applications in optoelectronics [89-91]. Among all MO
X
nanomaterials, the response of ZnO
and SnO
2
nanowires has been widely studied [92-94].
The energy of the absorbed light is used to promote an electron from the valence band to
the conduction band of the material (for example in a MO
X
semiconductor) leaving behind a
hole in a process known as photogeneration of charge pairs [95-97]. Consequently, the
conductance of the material increases after exposure to light and, in a first approach, the
minimum detectable wavelength corresponds to the band gap energy of the material. Since
this phenomenon is essentially a bulk process, the main advantage of using nanosized
materials is that the entire bulk contributes to the final response because of their high surface-
to-volume ratio [98].
Besides these simple photoconductors, there are a large number of other macro and micro
devices based on the photogeneration of charge pairs that are conventionally used in real
applications [95-97,99]. Most of them are based on the charge separation of the
photogenerated pairs (electron and hole) by a built-in electric field. In these cases the junction
of different materials (metal-semiconductor, heterojunction and homojunction of
semiconductors) is used to generate this internal field. Figure 5 illustrates some these devices
architectures. Recently, many of these configurations have been successfully reproduced
using nanowires (diodes in individual nanowires [100,101], core-shell nanowires [102,103],
nanowire-wafer unions [104]), paving the way to further improvements in photodetection
applications using nanowires as the basic component.
Finally, it must be mentioned that similar nanostructures and devices can be also used in
solar energy harvesting applications, in which the same principle of separation of
photogenerated pairs is used to provide useful power (voltage and current) to an external
electrical load [95,105,106]. Particularly, the integration of nanosized materials in cost-
effective dye-sensitized solar cells is necessary to efficiently collect the charge generated by
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 302
light in the organic dye layer [107-109]. Another promising achievement is the integration of
a fully functional solar cell in a single nanowire [100,101,110].
Figure 5. Schematic structure of different photodetectors based on semiconductors such as MO
X
.
3.3. Gas Nanosensors
The response of MO
X
s to gases is mainly due to a transfer of electrical charge between
gas molecules and atoms located at their surfaces. In rough approximation, oxidizing species
lead to a rise of the resistance in MO
X
s, whereas reducing molecules cause a drop of this
parameter. Additionally, these reactions are highly influenced by oxygen vacancies inside the
bulk of these materials [111] which are created during their synthesis, and other experimental
parameters such environmental moisture [112] or temperature. The general theory, which
explains the sensing capabilities of this type of sensors, has been reviewed in many literature
reports [86,113].
Once the first individual MO
X
nanowires were electrically contacted using any of the
techniques presented in this chapter, researchers focused on monitoring the changes of the
nanowires resistance as a function of the surrounding atmosphere. It was soon demonstrated
that the observed resistivity change in the presence of different gas species was in good
agreement with the general theory for metal oxide sensors [114]. Moreover, low gas
concentrations could be easily detected [115].
According to these preliminary results, the main advantage of using individual nanowire-
based gas nanosensors in comparison to traditional MO
X
microsensors is the excellent
recovery of their initial resistance baseline when the target gas is removed from the chamber,
due to the fact that nanowires are single crystalline materials with well-defined and stable
surfaces, in which adsorption and desorption of molecules may occur in a fast and reversible
way. On the contrary, MO
X
microsensors are composed of a thick layer of nanoparticles
agglomerated onto a substrate, whereby uncontrolled gas diffusion occurs through them, and
long-term drift processes are experimentally observed [116]. It is noteworthy that the
recovery of the initial resistance baseline of an individual nanowire-based gas sensor can be
Fabrication of Electrical Contacts on Individual Metal Oxide Nanowires 303
enhanced, illuminating the system with UV light pulses in order to clean their surface thanks
to a gas photodesorption induced process [117].
The main disadvantage of MO
X
nanowires in performing gas measurements is the lack of
selectivity to different gas species. This issue is common to other MO
X
-based sensors, and it
is worsened because of the extremely high sensitivity of MO
X
s to environmental moisture,
which dramatically changes both the nanowire resistance baseline and the cross-sensitivity to
other gases, such as CO [38]. For this reason, many research efforts are being devoted to
developing new devices able to overcome this intrinsic limitation [87,88]. Some of these
challenging difficulties are currently being tackled with the use of doped [118] or
functionalized [119] nanowires.
4. Conclusion
Determining and modeling the novel properties of individual MO
X
nanowires requires
working with only a single nanomaterial in order to reduce the parameters that have an
influence on their experimental responses. For this reason, particular attention has been paid
to the techniques necessary to fabricate electrical contacts with a precision of only a few
nanometers. Traditional processes in the field of microelectronics, such as e-beam, UV- and
shadow mask lithography have demonstrated a high rate of success in developing prototypes
based on individual MO
X
nanowires. Nevertheless, all of these techniques have intrinsic
disadvantages which in some cases even restrain their use. FIB nanolithography has recently
emerged as a competitive alternative to electrically contact individual nanomaterials in a fast
and reproducible way, becoming one of the best solutions for the development of research
prototypes. Although the mastering of all of these technologies is crucial to obtain future
breakthroughs in nanotechnology studies, they are not suitable for large-scale processes; thus,
novel self-alignment techniques are currently being evaluated.
On the other hand, it has been demonstrated that MO
X
nanowires are excellent candidates
for integration into functional devices, like UV photodetectors and gas sensors. Although
significant progress in this field has been achieved during the last years, the transfer of this
technology to real devices is still scarce due to the high costs and other technological issues.
All of the methodologies presented here to interface with nanomaterials should pave the way
for obtaining new and enhanced technological applications in the near future.
Acknowledgments
We cannot conclude this chapter without thanking the outstanding researchers who have
actively participated in this piece of work. A considerable part of this scientific research
consisted of collaborations with them. For this reason, my thanks go to all of these people we
have worked with, such as our present and past colleagues at the University of Barcelona and
the friends of the Leibniz Institute of New Materials. We would also like to thank Dr. C. de
Mairena for the critical comments to the earlier versions of the manuscript.
Francisco Hernandez-Ramirez, Juan Daniel Prades, Roman Jimenez-Diaz et al. 304
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 309-330 2010 Nova Science Publishers, Inc.
Chapter 9
FUNCTIONALIZATION OF NANOPARTICLES,
NANOTUBES AND NANOWIRES BY SURFACE-
INITIATED ATOM TRANSFER RADICAL
POLYMERIZATION
Jinying Yuan
*
, Mi Zhou and Yingwu Yin
Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of
Education, Department of Chemistry, Tsinghua University, Beijing 100084, Peoples
Republic of China
Abstract
The inorganic-polymer hybrid nanomaterials have many excellent properties. So they are
becoming increasingly important for various applications ranging from biomaterials to
semiconductors in many fields and arouse much interest of scientists all over the world. This
chapter highlights the development of surface-initiated living radical polymerizations from the
inorganic materials, including nanoparticles and one-dimensional (1D) nanostructures, by
surface-initiated atom transfer radical polymerization (SI-ATRP). The emphasis is put upon
the new developments of SI-ATRP taken to prepare hybrid nanomaterials in the recent years.
Keywords: inorganic nanomaterials; surface initiated polymerization; atom transfer radical
polymerization (ATRP); surface-initiated atom transfer radical polymerization (SI-
ATRP)
Organic/inorganic composite materials have both the strongpoints of organic polymers
and inorganic materials, and could be expansively applied in mechanism, optics, electronics,
separation, catalysis, and biology in the future, and now have become a new hotspot in
material science. In recent years, considerable interest exists in inorganic-organic hybrid
compounds due to their excellent properties combining inorganic and organic materials.

*
E-mail address: yuanjy@mail.tsinghua.edu.cn
Jinying Yuan, Mi Zhou and Yingwu Yin 310
Among them, functionalization or modification of gold, silicon dioxide, titanium oxide, ferric
oxide nanoparticles and carbon, silicon dioxide nanotubes, zinc oxide nanowires, lanthanum
hydroxide nanowires etc., has attracted special attention for their applications in medicine or
electronics. It is necessary to find a convenient method for modifying inorganic
nanomaterials. Up to now, synthetic polymers or biomacromolecules have been grafted or
assembled onto the surface of the nanostructures via covalent bonding, electrovalent bonds or
chemisorption. However, it is difficult to control the thickness of the functionalization layer.
To combat this, the living polymerization technologies, such as atom transfer radical
polymerization (ATRP)[1-3] can meet the challenge. Recently, living radical polymerization
techniques were applied to surface-initiating graft polymerization. Many researchers
successfully prepared a core-shell hybrid nanostructure though the covalent bonds of carbon-
carbon bond or silicon-carbon bond. Using this new method of functionalization on the
surface of inorganic nanomaterials, the solubility in organic solvent has increased, and it
affords a new application of the inorganic nanomaterials in the multiplex materials. This
offers potential applications in optoelectronic, nanoscale devices, materials science and
biotechnology.
In this chapter, the progress of functionalization of nanoparticles, nanotubes and
nanowires by surface-initiated atom transfer radical polymerization (SI-ATRP) was reviewed.
1. Functionalization of Nanoparticles by ATRP
Considerable attention has been focused on the surface functionalization of inorganic
nanoparticles by a polymeric shell with well-defined architecture due to the improvement of
the properties of the nanoparticles, such as the dispersion and stability in various solvent.
More important, the nanoparticles functionalized by polymer could combine the advantages
of inorganic nanoparticles and polymer materials. Progress in polymerization has made it
possible to produce polymer chains or brushes on a surface with controlled length and
structure. Polymers of various architectures (block, comb, graft, hyperbranched, star, etc.)
have been synthesized by living radical polymerizations. Successful examples of living
radical polymerization include nitroxide-mediated radical polymerization, ATRP, reversible
addition-fragmentation chain transfer polymerization, and so on. ATRP does not require
stringent experimental conditions, as in the case of cationic and anionic polymerization.
Growing polymer brushes on the surface of substrates by ATRP is a mature technology
and a hot point. We consider it is mature, because ATRP was discovered by Matyjazewski in
1995, and the conditions of ATRP, including initiators, catalyst ect., have already been
studied systemically. Another key is the chemistry of surface of substrates had been
researched deeply and how to connect the polymer chains and the substrates is clearly. It is a
hot field, because ATRP is a controlled and living radical polymerization. It has at least
three strongpoints: (1) many kinds of monomers can be polymerized by ATRP, including
acrylate, styrene etc. This affords the possibilities of the functions of the polymers. (2) the
polymers that synthesized by ATRP have narrow polydispersity. This is an aim of almost all
the scientists of polymer field. (3) ATRP is a living polymerization, so block copolymers
are synthesized easily by ATRP. This affords the possibilities that many functions are
presented at one substrate.
Functionalization of Nanoparticles, Nanotubes and Nanowires 311
Among the numerous inorganicorganic hybrid materials, silicapolymer hybrid
materials are the most commonly reported in the literature. This may be attributed to their
wide use and the ease of particle synthesis. Silica nanoparticles have been used as fillers in
the manufacture of paints, rubber products, and plastic binders. Silica particles coated with
organic modifiers are used in applications that include stationary chromatography phases,
heterogeneous supported catalysts, and in the automotive, electronics, appliance, consumer
goods, aerospace, and sensor industries. In general, two approaches, grafting from and
grafting to can be utilized to prepare silica or other inorganic nanoparticles covalently
protected with polymers. The grafting-from approach allows polymers to be built up at the
surface of the silica naonoparticles using surface-initiated polymerization. End-functionalized
monolayers, regarded as macroinitiators, may be used to initiate living/controlled
polymerization, such as ATRP, directly on the surface of silica.
Hult et al[4] synthesized organic-inorganic hybrid materials consisting of nanosized silica
particles with surface grafted PS or PS-b-PMMA using ATRP. The surface of the nanosized
silica particles was first functionalized by the reaction of silanol groups with 3-Aminopropyl-
trimethoxysilane (APTMS) (Fig. 1). These hybrid materials were used in the fabrication of
highly-ordered isoporous membranes. Optical characterization revealed that the membranes
consisted of hexagonally ordered pores of uniform size. The combination of an open pore
structure and high surface area makes isoporous membranes into materials of high interest in
fields as biotechnology and photonics.
OH
OH
OH
Si MeO
OMe
OMe
NH
2
THF
O
O
O
Si NH
2
O
O
O
Si N
H
Br
O
Br
O
Br
Figure 1. Surface Functionalization of Silica Particles[4]. Copyright Copyright Wiley-VCH (2005).
Fukuda et al[5] polymerized an oxetane group-carrying methacrylate, 3-ethyl-3-
(methacryloyloxy)methyloxetane (EMO), via copper-mediated ATRP initiated from the
surface of monodisperse silica particles (SiPs). The polymerization proceeded in a living
manner producing SiPs grafted with well-defined poly(EMO) (PEMO) of target molecular
weight up to about 400K with a graft density as high as 0.36 chains/nm
2
. The surface-initiated
ATRP of methyl methacrylate (MMA) with PEMO-grafted SiPs as macroinitiator afforded
SiPs grafted with block copolymer of the type PEMO-b-PMMA ((PEMO-b-PMMA)-SiPs).
The PEMO layer of (PEMO-b-PMMA)-SiPs, located between the PMMA shell and the SiP
core, was cross-linked by cationic ring-opening reaction of the oxetane groups of the EMO
moieties. The removal of the SiP core of the cross-linked (PEMO-b-PMMA)-SiPs by HF
etching gave polymeric hollow spheres having sizeuniformity and good dispersibility in
organic solvents.
Jinying Yuan, Mi Zhou and Yingwu Yin 312
SiO
2
-g-PDMAEMA was synthesized successfully by our group[6], with APTMS and 2-
Bromo-propionyl bromide linked in sequence, and ATRP of (2-Dimethylamino)ethyl
methacrylate) (DMAEMA) initiated at surface to get the organic/inorganic hybrid
nanoparticle SiO
2
-g-PDMAEMA (Fig.2). Core/shell structure was obtained, and the hybrid
nanoparticle showed better dispersion in THF than primary silica nanoparticle. Under the
same temperature, the average hydrodynamic diameter of the PDMAEMA-grafted particles in
acidic environment was much larger than that in basic environment. As temperature increased
from 20
o
C to 50
o
C, R
h
became obviously larger, indicating LCST between 20
o
C and 50
o
C,
which led to the aggregation behavior of particles. These results indicate that the particles
with PDMAEMA brushes are double-responsive, which provides potential applications in
biomedicine and biotechnology.
SiO2
Si
O
O
O
H
2
N
O
Br
Br
O
O
N
O
Si
O
O
NH
2
O
Si
O
O
N
H
O
Br
O
Si
O
O
NH
O
Br
O
O
n
N
Figure 2. Synthesis of SiO
2
-g-PDMAEMA nanoparticles[6]. Copyright Elsevier (2008).
Fe
3
O
4
magnetic nanoparticles have been used in various fields such as sealing, oscillation
damping, information storage and electronic devices. One of the rapidly developing applications
of Fe
3
O
4
magnetic nanoparticles in recent years is in biomedical areas, including rapid biologic
separation and drug delivery. Surface functionality of Fe
3
O
4
magnetic nanoparticles with
polymeric shell is of current research interest owing to the flexibility in the controls of the
chemical structures, compositions, and function of the polymers. Magnetite nanoparticles
coated with polymers in the aqueous phase have the advantages of high stability, easy
engineering of the surface properties and functional groups on the nanoparticle surface and have
gained an increasing interest in a lot of fields such as hyperthermia, magnetic resonance
imaging, DNA seperation, enzyme purification, and targeted drug delivery.
Functionalization of Nanoparticles, Nanotubes and Nanowires 313
Fukuda et al[7] reported the synthesis of magnetite nanoparticles coated with a well-
defined graft polymer. The magnetite nanoparticles with an initiator group for ATRP, 2-(4-
chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were
prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of
methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles
in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride (Fig.3).
Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer
consumption and a proportional relationship between molecular weight of the graft polymer
and monomer conversion, thus providing well-defined, low polydispersity graft polymers
with an approximate graft density of 0.7 chains/nm
2
. The molecular weight and polydispersity
of the graft polymer were nearly equal to those of the free polymer produced in the solution,
meaning that the free polymer is a good measure of the characteristics of the graft polymer.
The graft polymer possessed exceptionally high stability and remarkably improved
dispersibility of the magnetite nanoparticles in organic solvent.
Fe
3
O
4
Immobilization
of CTCS
Si
SO
2
Cl
ATRP of MMA
O
O
O
Immobilized-CTCS
PMMA
Figure 3. Surface Functionalization of Magnetite Nanoparticles [7]. Copyright Elsevier (2004).
Schmidt et al[8] reported the preparation of Fe
3
O
4
/poly(-caprolactone) (Fe
3
O
4
/PCL)
core-shell particles. Schmidt et al[9] also described the synthesis of nanoscopic magnetite-
cored polymeric brushes by surface-initiated ATRP and the properties of novel
thermoreversible magnetic fluids based thereon. They presented the first results on the
synthesis and characterization of novel thermoreversible magnetic fluids based on magnetite
(Fe
3
O
4
) coated with a covalently anchored, polymeric shell of poly(2-methoxyethyl
methacrylate) (PMEMA). The presented combination of thermoresponsive polymers with the
properties of magnetic fluids, together with tailorable hydrodynamic diameter and critical
temperature, contributes to the development of easily recoverable polymer-supported
magnetic separation kits and catalytic systems.
Li et al[10] reported the synthesis of magnetic magnetite nanoparticles coated with
amphiphilic block copolymers of poly(ethylmethacrylate)-block-poly(2-hydroxyethyl
methacrylate) for use as new potential carriers for hydrophobic drug delivery (Fig.4). The
results show that a new core-shell-corona structural material is obtained with a very narrow
molecular weight distribution of the hydrophobic segment. UV-Vis results show that 37% of
progesterone is released from the nanoparticles after 22 h, much slower than free release
(99% after 14 h), which demonstrates that the presence of the hydrophobic segment can
effectively control the release of hydrophobic drugs.
Jinying Yuan, Mi Zhou and Yingwu Yin 314
Fe
3
O
4
ATRP
of EMA
HO
O
Br
HO
O
Br
HO
O
O
O
m
ATRP
of HEMA
HO
O
O
O
m
Br
O
HO
O
n
Figure 4. Synthesis of an amphiphilic block polymer on magnetite nanoparticles [10]. Copyright Wiley-
VCH (2006).
Our group studied a facile synthesis of magnetite nanoparticles coated with
homopolymers DMAEMA as noble potential carriers for targeted drug delivery. Different
from Lis work, there is no block copolymers linked to magnetite nanoparticles so that the
synthesis steps are fewer. Also, the preparation of special initiators is not required. These
Fe
3
O
4
/PDMAEMA nanoparticles with core-shell structure are able to load drugs into the
shell, and the release rate of drugs is approximately steady-going and can be effectively
controlled by altering the pH value. Furthermore, the hybrid nanoparticles are stable to
dilution because of the inherent strong interaction between the interface of the magnetite
nanoparticles and the carboxyl groups of the initiators, and still have superparamagnetism
which is important for drug delivery.
Metal nanoparticles have attracted continuous interest owing to their unusual properties
and potential uses in electronics, optics, magnetics, catalysts, and sensors. As a well-known
noble metal, gold is widely investigated due to its specific impact in the fields of
biotechnology and bioscience.
Choi et al[11] investigated the formation of thermoresponsive gold nanoparticle/poly(N-
isopropylacrylamide) (AuNP/PNIPAAm) core/shell hybrid structures by surface-initiated
ATRP in aqueous media and the effect of cross-linking on the thermoresponsiveness of the
AuNP/PNIPAAm hybrids (Fig.5). The disulfide containing an ATRP initiator was attached
onto AuNPs and the monomer, N-isopropylacrylamide (NIPAAm), was polymerized from the
surface of AuNPs in the absence or presence of a cross-linker, ethylene diacrylate, in aqueous
media at room temperature. They expect that these hybrids could be useful as a stimuli-
responsive optical device, such as surface plasmon resonance-based sensing materials,
because of the combination of optical properties of AuNPs and control over the interparticle
distance using thermoresponsiveness of PNIPAAm.
Initiator
ATRP of
NIPAAm
Initiator
S(CH
2
)
11
OOCC(CH
3
)
2
Br
2
Figure 5. Surface Functionalization of gold nanoparticles[11]. Copyright Wiley-VCH (2005).
Functionalization of Nanoparticles, Nanotubes and Nanowires 315
Li et al[12] fabricated novel nanocomposites of gold nanoparticle and poly(4-
vinylpyridine) (Au@PVP) through surface-initiated atom-transfer radical polymerization (SI-
ATRP) at ambient conditions. The citratestabilized gold nanoparticles were first modified by
a disulfide initiator for ATRP initiation, and the following polymerization of 4-vinylpyridine
(4VP) occurred on the surface of gold particles. The assembled Au@PVP nanocomposites are
pH-responsive because of the pyridyl groups, which are facially protonated and positively
charged. At low pH (<3.2), the polymer chains attached on gold nanoparticles are expanded
by electrostatic forces, and the polymer layer is loosely swelled; hence, the Au@PVP
composite particle displays a comatulid-like nanostructure in 3-D AFM images. However, at
a relatively high pH (>3.2), the polymer chains shrink and wrap around the gold particle
surface, which results in the aggregation of gold nanoparticles with a thin shrunken polymer
layer under TEM observation. Such assembled Au@PVP nanocomposites as a smart
supporter can entrap transition metal ions by their efficient coordinating segments, and
subsequently, the metal ions can be reduced in situ to construct novel bimetallic
nanocomposites, which are regarded as intelligent catalysts with environmental stimuli
activity.
2. Functionalization of One-Dimensional Nanostructures by
ATRP
Ever since the discovery of carbon nanotubes (CNTs) by Iijima[13], there has been great
interest in the synthesis and characterization of other one-dimensional (1D)
nanostructures[14-29]. Nanowires, nanotubes, nanorods nanobelts and 1D array constitute an
important class of 1D nanostructures, which provide many new and promising fields
including nanofabrication [23,30-32], nanodevices [33-38], nanobiology [39], nanocatalysis
[40], etc.
Six families of inorganic 1D nanostructures which are more than one hundred have been
synthesized up to now. The current list is as follows[14]: (1) carbon nanotubes; (2) transition
metal oxide and chalcogenide 1D nanostructures; (3) transition metal halogenous 1D
nanostructures; (4) mixed-phase and metal-doped 1D nanostructures; (5) boron- and silicon-
based 1D nanostructures; and (6) metal 1D nanostructures.
But the surface energy of the 1D nanostructures is too high to disperse the nanostructures
in organic solvents, and make them difficult to explore and understand the chemistry of the
nanostructures at the molecule level. For conquering this problem, two methods are used by
the scientists. The first string is developing the method for growing inorganic 1D
nanostructures; the second string is debasing the surface energy of the nanostructures by
modifying them.
Carbon nanotube is the first kind of 1D nanostructures which are discovered, and the
properties of CNTs are studied deeper than other 1D nanostructures[41-45]. So the problem
how to disperse the CNTs in organic solvent was studied at first. In 1998, the paper from
Haddens group that was published in science[46] reported a method that the long-chain
molecule octadecylamine was added to the open ends of shortened SWNTs via formation of
the amide functionality, and the modified CNTs could be disperse in CS
2
easily. This is an
exciting work that is considered as a milestone of the field of modifying 1D nanostructures,
Jinying Yuan, Mi Zhou and Yingwu Yin 316
because they had demonstrated a methodology for preparing solutions of naked carbon
metals and semiconductors in organic solutions, and explored the chemistry of single-walled
CNTs primarily.
Almost at the same time, Professor Tang group reported other method to prepare soluble
poly(phenylacetylene)-wrapped CNTs by in situ polymerization[47]. This is the first paper
that was reported how to make the soluble polymer-CNTs complex consciously, and greatly
influences the field of making polymer-CNTs complex.
But these two papers still leave challenges. For Haddens work, although the CNTs can
be diepersed in organic solvent, the solubility is low. And for Tangs work, the solubility is
increased, but it is still a black box that nobody knows why the polymer can wrap CNTs,
and how strong the force between the chain of the polymer and the nanotubes is.
How to open the black box? This problem has puzzled the scientists until 2003. From
the end of 2003 to the beginning of 2004, at least three groups reported the same model of
reaction almost at the same time: to make the polymer-CNTs complex by atom transfer
radical polymerization (ATRP) on the surface of the CNTs[49-51].
Figure 6. Grafting PnBMA from the surface of CNTs using ATRP[49]. Copyright American Chemical
Society (2004).
All of the three groups chose the same kind of initiator, alkyl bromides, and the same
kind of monomer, acrylate (Fig.6-8). But the details of the functionalization were a litter
different. Fords group and Yans group chose the similar method to make the initiators: first,
carboxyl-contained CNTs were prepared by oxidation of the crude nanotubes; second, the
initiators were prepared by two esterifiable steps. The difference between their methods was
the order of the two esterifiable steps. Adronovs group chose a different procedure to prepare
the initiator involving first 1,3-dipolar cycloaddition to introduce phenol unctionalities,
followed by an esterification with 2-bromoisobutyryl bromide.
Functionalization of Nanoparticles, Nanotubes and Nanowires 317
Figure 7. Synthesis of an ATRP macroinitiator using a 1,3 dipolar cycloaddition[50]. Copyright
American Chemical Society (2003).
The second difference among the three groups works is the aim. We consider that Fords
work leans to increase the solubility and stability of CNTs in organic solvent; Adronovs
work prefers to change the structures of polymer on the surface by easy reaction to control the
solubility of nanotubes in organic solvent or water; and Yans work selects to synthesize
block copolymer on the surface to prove the chemistry excellence of ATRP.
Figure 8. Grafting PMMA from the surface of CNTs using ATRP[51]. Copyright American Chemical
Society (2004).
However, the three groups works opened the black box which puzzled the scientists
who researched in the polymer-nanotube field. The polymer chains are grown from the
initiators on the surface, and the key became how to connect the initiator molecules onto the
nanotubes. But this key has been solved already. These important works hearten the field of
CNTs-polymer complex. The following scientists, Warren T. Ford from Oklahoma State
University, Alex Adronov from McMaster University and Deyue Yan from Shanghai Jiao
Tong University, are the precursors. There is another interesting thing that the first authors of
the three paper are all from China.
Jinying Yuan, Mi Zhou and Yingwu Yin 318
Nowadays, different structures of carbon -polymer complex have been prepared by
ATRP[48]: CNTs-poly(n-butylmethacrylate) (CNTs-PnBMA)[49], CNTs-poly (methyl
methacrylate) (CNTs-PMMA)[50-52], CNTs-poly(methyl methacrylate) -b-polystryene
(CNTs-PMMA-b-PS)[52], CNTs-polystryene (CNTs-PS)[52-46], CNTs-polystryene-b-
poly(methyl methacrylate) (CNTs-PS-b-PMAA)[52], CNTs-poly(tert-butyl acrylate) (CNTs-
PtBA)[50], CNTs-poly(acrylic acid) (CNTs-PAA)[50,68], CNTs- polystyrene/ poly(N-
isopropylacrylamide) (CNTs-PS/ PNIPAAm)[54], CNTs-poly(methyl methacrylate)-b-
poly(hydroxyethyl methacrylate) (CNTs-PMMA-b-PHEMA)[50], CNTs-polystryene- b-
poly(tert-butyl acrylate) (CNTs-PS-b-PtBA)[53,55], CNTs-polystryene- b- poly(acrylic acid)
(CNTs-PS-b-PAA)[53,55], CNTs-poly(N-isopropylacrylamide) (CNTs-PNIPAAm)[57,58],
CNTs-poly(sodium 4-styrenesulfonate) (CNTs-PSS) [59,60], CNTs-poly(2,2-
diethylaminoethyl methacrylate) (CNTs-PDEAEMA) [61,62], CNTs-poly(2,2-
dimethylaminoethyl methacrylate) (CNTs-PDMAEMA) [63], CNTs-poly(glycerol
monomethacrylate) (CNTs-PGMA) [64], CNTs-poly (3-(trimethoxysilyl) propyl
methacrylate) (CNTs-TMSPMA) [65], CNTs- polystyrene-b-polyacrylonitrile (CNTs-PS-b-
PAN)[66], CNTs-poly(Methacryloyloxyethyl phosphorylcholine) (CNTs-PMPC)[67], CNTs-
poly(lactobionamidoethyl methacrylate) (CNTs-PLAMA)[67], CNTs-poly(3-O-methacryloyl-
1,2:5,6-di-O-isopropylidene-D-glucofuranose) (CNTs-PMIG) [68], and so on.
Among them, Yans systemic and in-depth works are deserved to emphasize especially.
They not only prepared many structures of the CNTs-polymer complexes by ATRP, but also
found another field called functionalization and re-functionalization of CNTs. The work
published at first was to prepare CNTs-PNIPAAm [67]. The resulting hybrid molecular
nanotubes showed temperature switching assembly and disassembly behaviors in water,
because of the hydrophilic and hydrophobic transformation of the bonded PNIAAm chains at
30-35
o
C .
Figure 9. SEM and TEM images of PNIPAAm-modified ACNTs. SEM images viewed from the a) top
and b) side. c) The magnified image of (b). d) TEM image of a single CNT taken from the ACNT film
with PNIPAAm modification.[68] Copyright Wiley-VCH (2004)
Functionalization of Nanoparticles, Nanotubes and Nanowires 319
Jiang&Li and their co-workers successfully grafted PNIPAAm onto aligned carbon
nanotubes by ATRP combined the technology of aligned carbon nanotubes and temperature
responsiveness of PNIPAAm chains (Fig.9)[68]. A water droplet exhibits different spreading
behaviors on the film surface that had been modified, which shows different wettability under
low and high temperatures. The good reproducibility of this effect shows a high degree of
control over the responsive wettability of the ACNT film.
Gao and his co-worker synthesized CNTs-PMIG[68], R.Narain group prepared CNTs-
PMPC, CNTs-PLAMA[67]. Both the two works, the resulting hybrids can be found many
applications in biomedical fields, because the polymers that be used to coat CNTs are
biocompatible. Zhangs group prepared a steady core-shell nanostructures due to the
hydrolysis and polycondensation of PTMSPMA[65].
Figure 10. The layer-by-layer self-assembly procedure on CNTs surface.[59] Copyright Elsevier
(2005).
Jinying Yuan, Mi Zhou and Yingwu Yin 320
Then Yans group prepared polyelectrolyte-CNTs by ATRP and layer-by layer self-
assembly (Fig.10)[59]. It is an interesting work. The polyanion coated carbon nanotubes was
prepared by ATRP and used as the substrates for layer-by-layer (LBL) deposition of
PDMAEMA or hyperbranched poly(sulfone amine) (HPSA) and then deposition of
poly(sodium 4-styrenesulfonate) (PSS). The cycle was repeated and the core-shell
heterostructures had been accomplished to produce. Almost at the same time, Ford and his co-
workers did the similar work[60].
Another important function that had been exploited is some kinds of polymer that contain
a large number of hydroxyl groups or carboxyl groups coated carbon nanotubes could
sequester metal ions and produce metal nanoparticles. Gao and his co-worker prepared CNTs-
PGMA[64]. And the hydroxyl groups of the polyGMA chains grafted onto the MWNTs are
still highly active and can be further reacted with succinic anhydride to be converted into
carboxylic acid groups. The complex was successfully loaded with Ag
+
, Co
2+
,Ni
2+
, Au
3+
, Y
3+
,
and La
3+
ions (Fig.11-13). In the case of Ag
+
ions, the loading capacity of the complex is
higher than that of pristine or oxidized CNTs by 1-2 orders of magnitude that had been
reported. Farther, Ag
+
ions were reduced to zerovalent Ag nanobead-like structures by the
residual hydroxyl groups on the esterified polyGMA chains. These nanobeads with a diameter
of 3-10 nm on the surface of the nanotubes were tightly enwrapped by the polymer chains,
forming stable necklace-like structures.
Figure 11. Functionalization of CNTs with PGMA by ATRP, Esterification of the Hydroxyl Groups of
CNTs-PGMA, and Metal Sequestration/Reduction by the Grafted Polyacid Chains.[64] Copyright
American Chemical Society (2005).
Functionalization of Nanoparticles, Nanotubes and Nanowires 321
Figure 12. Transmission electron microscopy (TEM) images of CNTs-PGMA/metal (ion)
nanocomposites: (a, b) CNTs-PGMA/Ag with a silver concentration of ca. 0.46 g per gram of CNTs-
PGMA, (c) CNTs-PGMA/Ag with a silver concentration of ca. 0.15 g per gram of CNTs-PGMA, (d)
CNTs-PGMA/Ag hybrid nanowire, (e) CNTs-PAA/Ag nanowire section, and (f) CNTs-PGMA/La
3+
nanocomposites.[64] Copyright American Chemical Society (2005).
Figure 13. High-resolution transmission electron microscopy (HRTEM) images of CNTs-PGMA/Ag (a,
b).[64] Copyright American Chemical Society (2005).
Further research extended the concept of sequestering metal nanoparticles within the polymer
chain. Gao and his co-worker prepared CNTs-PDMAEMA and CNTs- PDEAEMA[61-63].
And the resulting composites were treated with methyl iodide, quaternizing the amino groups
and forming a cationic polyelectrolyte modifying CNTs. Due to high density of ammonium
groups on the surface of nanotubes, higher amounts of CdTe or Fe
3
O
4
can be adsorbed. The
optical properties of quantum dots and the magnetic properties of the Fe
3
O
4
nanoparticles in
the tri-composes hybrids were maintain. The author also showed the sheep blood cells that
Jinying Yuan, Mi Zhou and Yingwu Yin 322
could be attached with magnetic nanotubes in a buffer solution can be selectively rotated or
conveyed in a magnetic field (Fig.14, Fig.15), because the magnetic nanotubes can be easily
manipulated in the magnetic field.
Figure 14. The procedure to synthesize the magnetic CNTs hybrids.[62] Copyright American Chemical
Society (2006).
Figure 15. Continued on next page.
Functionalization of Nanoparticles, Nanotubes and Nanowires 323
Figure 15. Representative TEM images of the magnetic nanotube sample with 6.3 wt % of iron (a, b)
and the sample with 22.5 wt % of iron (c-e). HRTEM image of an iron oxide nanoparticle attached on
tube surface, showing the lattice of iron oxide crystal (f). STEM images of the magnetic nanotube
samples with 6.3 (g) and 22.5 (h) wt % of iron. The scale bars in a, b, c, d, e, and f correspond to 100,
20, 100, 50, 20, and 2 nm, respectively.[62] Copyright American Chemical Society (2006).
Figure 16. Electrophilic addition on SWNTs to produce an ATRP macroinitiator.[69] Copyright
Springer(2005).
Another developmental direction of polymer-CNTs complex by ATRP is to prepare new
initiators on the surface. Many methods have been reported. Direct electrophilic addition of
chloroform to SWNT sidewalls, followed by hydrolysis in methanolic KOH to produce
hydroxylated SWNTs was reported by Paiks group[69]. The ATRP initiators which could be
used for polymerization of stryene were prepared by esterification of the hydroxylated
SWNTs with 2-chloropropionyl chloride (Fig.16).
Terrones and co-workers also utilized a free radical process for the surface-
functionalization of nanotubes[70]. This was accomplished by thermolysis of benzoyl
peroxide at 105
o
C to produce phenyl radicals, which efficiently coupled to the surface of N-
doped MWNTs (Fig.17). Subsequently, the covalently grafted aromatic rings on the surface
of the tubes, were brominated by Br
2
/FeBr
3
. The doped tubes did not require any acid
treatment to protect the structure of CNTs farthest.
Jinying Yuan, Mi Zhou and Yingwu Yin 324
Figure 17. The functionalization process of CNTs by radical reaction.[70] Copyright Elsevier (2006).
Because the research of the chemistry of CNTs and the experience that ATRP growing
chain ends have shown reactivity toward C
60
via radical addition reactions. Liu and his co-
worker found that the ATRP active species could transfer to CNT surfaces (Fig.18)[64], after
an addition reaction. With the interesting result, linear PS and V-shaped PS-b-PNIPAAm
polymer chains were successfully incorporated on CNT through the grafting-from and
sequential grafting-on and grafting from method, respectively. With the functionalization,
CNTs-PS/PNIPAAm showed amphiphilic behavior.
Figure 18. Incorporation of Amphiphilic V-Shaped Poly(styrene)-b-poly(N-isopropylacrylamide) (PS-
PNIPAAm). Polymers onto Carbon Nanotube Surface through Sequential Grafting-To and Grafting-
From Techniques.[64] Copyright American Chemical Society (2007).
Hong and Pan reported a method to grow hyperbranched macromolecules on the surface
of CNTs by a self-condensing vinyl polymerization (SCVP) strategy via ATRP[71]. It is a
good attempt for development more kinds of polymer structure, and it is good for research the
chemistry of the CNTs.
Functionalization of Nanoparticles, Nanotubes and Nanowires 325
Figure 19. Grafting PMMA from the surface of Si/SiO
2
core/shell nanowires using ATRP.[72]
Copyright American Chemical Society (2005).
Figure 20. (a) SEM image of the pyrolysis product from a surface-initiated polymerization of PMMA
on ZnO. (b) TEM micrograph of the sample in a. (c) TEM micrograph of the pyrolysis product from a
sample of dipcoated PAN on ZnO.[73] Copyright American Chemical Society (2006).
Just like the discovery of 1D nanostructures, the scientists dissatisfy to modify carbon
nanotubes only. Because of the particularity of carbon element, the methods used to carbon
nanotubes are not suitable to other 1D nanostructures. But the key idea for polymer-1D
nanostructures, how to prepare the initiators on the surface, was inherited. According to the
Jinying Yuan, Mi Zhou and Yingwu Yin 326
experience to prepare polymer-inorganic nanoparticles hybrids, Arnold and his co-workers
from University of California[72,73], Berkeley and our group from Tsinghua University[74]
reported the methods to synthesize functional polymer from inorganic 1D nanostructures
successively.
Arnold and his co-workers took the lead in demonstrating a simple method to produce
coaxial poly(methyl methacrylate) silica / silicon oxide/ poly(methyl methacrylate) core-shell
nanostructures, then the Si cores were etched using XeF
2
giving polymer nanotubes supported
on silicon oxide (Fig.19)[72]. The polymer layer makes the outer surface of these tubes
hydrophobic, while the SiO
2
on the inner surface is hydrophilic.
Later, they reported ATRP on ZnO nanowires[73]. By controlling catalyst and reaction
conditions, polymerizations of methyl methacrylate, phenyl methacrylate, ethylene glycol
dimethacrylate, and styrene on ZnO were all successfully performed (Fig.20). And these
hybrid organic-inorganic materials were used as precursors for graphitic carbon tubes.
OH
n
NH
2
Si
MeO
MeO
MeO
toluene,reflux,36h
* O Si NH
2
O
O
n
* O Si
O
O
n
Br
O
Br
Et
3
N,CH
2
Cl
2
,24h
N
H
Br
O
Styrene,CuBr,PMDETA
100
o
C, 24h
* O Si
O
O
n
N
H
H
2
C
O
H
C Br
m
La(OH)
3
Figure 21. Grafting PS from the surface of lanthanum hydroxide nanowires using ATRP. [74]
Copyright IOP(2007).
As a consequence of their unique electronic structures and the numerous transition modes
involving the 4f shell of their ions, lanthanide compounds usually have outstanding optical,
electrical, and magnetic properties, and have been widely used as high-quality phosphors[75],
up-conversion materials[76], catalysts[77], and time-resolved fluorescence (TRF) labels for
Functionalization of Nanoparticles, Nanotubes and Nanowires 327
biological detection[78]. Our group demonstrated a method for preparation of polystyrene
shells based on surface of lanthanum hydroxide nanowires (Fig.21, Fig.22)[74].
Figure 22. (a) TEM image of La(OH)
3
nanowires (bar = 200 nm), (b) Electron diffraction pattern of a
single La(OH)
3
nanowire, (c) HRTEM image of a single La(OH)
3
nanowire, (d) TEM image of Sample
1 (bar = 20 nm), (e) HRTEM image of Sample 1 (bar = 10 nm), (f) HRTEM image of Sample 2 (bar =
10nm), (g) HRTEM image of Sample 3 (bar = 10 nm).[74] Copyright IOP(2007).
The key step of the synthetic process is the initiator of the polymerization for the process,
using the hydrolyzation of the silane that the amino substituted, the amidogen was inducted
on the surface of the nanowires; using 2-bromo-propionyl bromide or 2-bromo-2-
Jinying Yuan, Mi Zhou and Yingwu Yin 328
methylpropionyl bromide to react with the amidogen on the surface. The only difference is
the order.
Recently, Zhaos group reported hyperbranched polymers were grafted onto halloysite
nanotubes by SCVP via ATRP[79]. The initiator was prepared by adsorption of 2-
bromoisobutyric acid on the surface of the nanotubes, and then, polymers were synthesized
with the same method that Hong and Pan had used[71].
In conclusion, inorganic nanomaterials have caused for widespread concern. However,
they could not be dispersed well in water or organic solvents, due to their particularly surface
areas. Thus the application of inorganic nanomaterials is limited. Meanwhile, polymers have
excellent properties that inorganic compounds are difficult to replace, such as processability
and biocompatibility. The inorganic-organic hybrid nanomaterials emerge. The controlled
polymerization, especially the surface-initiated atom transfer radical polymerization, was
used to improve the inorganic nanomaterials. Using this new avenue of functionalization on
the surface of inorganic nanomaterials, the solubility in organic solvent increased affording
new applications in the multiplex materials. A variety of new types of nanomaterials,
combined the properties of inorganic compounds and polymer, were prepared. These new
inorganic-organic hybrid nanomaterials are expected to use as sensors, biological probes, and
so on.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 331-370 2010 Nova Science Publishers, Inc.
Chapter 10
SYNTHESIS AND APPLICATIONS OF NANO-SIZED
FERROELECTRICS VIA MECHANOCHEMICAL
ACTIVATION
L.B. Kong
a
, Z. Xu
b
and T.S. Zhang
c
a
Temasek Laboratories, National University of Singapore,
10 Kent Ridge Crescent, Singapore 119260
b
Electronic Materials Research Laboratory, Xian Jiaotong University,
Xian 430069, P. R. China
c
Institute of Materials Research and Engineering, 3 Research Link,
Singapore 117602
Abstract
Ferroelectric materials have been found to be promising candidates in applications of a wide
range of electronic devices, such as high-dielectric constant capacitors, piezoelectric sonar or
ultrasonic transducers, pyroelectric security sensors, medical diagnostic transducers, electro-
optical light valves, and ultrasonic motors, and so on. Ferroelectric materials were
conventionally fabricated via solid-state reactions at relatively and sometimes extremely high
temperatures for calcining and sintering. Due to the presence of volatile components, such as
lead (Pb), bismuth (Bi) or lithium (Li), in most ferroelectric compounds, high temperatures
processing would brought out the problems of losing of the elements, which often resulted in
the deteriorations in microstructures and thus electrical performances of the ferroelectric
materials. To reduce the fabrication temperatures of ferroelectric ceramics, it is necessary to
use ultrafine powders. High-energy mechanochemical technique, as an alternative method, has
been used to synthesize nanosized ferroelectric powders directly from their oxide and other
precursors. This chapter serves as an overview of progress in the synthesis of various
ferroelectric materials by using various mechanochemical milling facilities. In addition,
applications of nanosized ferroelectric powders in materials preparation and device fabrication
will be also be included.
Keywords: Mechanochemical synthesis, mechanochemical activation, oxide, materials, nano-
sized powders, ferroelectrics
L.B. Kong, Z. Xu and T.S. Zhang 332
1. Introduction
Ferroelectric materials possess spontaneous polarizations that are reversible under an
external applied electric field [1-3]. The distinct dielectric, piezoelectric, pyroelectric and
insulating properties of ferroelectric materials have made them useful for a wide range of
applications, such as sensors, actuators and transducers. As a result, ferroelectrics have been
one of the most intensively studied topics in scientific researches.
Properties and performances of materials are determined by both their intrinsic and
extrinsic characteristics [3, 4]. Intrinsic properties include types of elements and the
combinations of them, while extrinsic ones are closely related to the processing parameters.
Parameter-related properties include microstructures, grain size and size distribution, density
and porousity, and so on. One of the most important processing parameters is synthesis
technique. It has been shown that synthesis method of ferroelectric powders has played a
significant role in determining the microstructural, electrical and optical properties of the final
ferroelectric ceramics. Ferroelectric powders were conventionally prepared via solid-state
reaction process, starting from constituent oxides, hydroxides or carbonates. Solid-state
reaction process usually requires relatively high temperature, which results in powders with
large grains or particles. Due to the rough grains or particles, these powders can only be fully
sintered at even higher temperatures to achieve ferroelectric ceramics with desired
performances. Many ferroelectric materials contain lead (Pb) component that has a high
volatility and is likely to be lost during the high temperature process, which in turn leads to
worsened properties. To reduce the sintering temperature, it is necessary to use powders of
with fine grain size and narrow size distribution. During the last decades, a lot of attempts
have been made to synthesize submicron or even nanosized ferroelectric powders. Various
wet-chemistry methods, including chemical coprecipitation, sol-gel process, hydrothermal
synthesis, microemulsion, combustion, thermal pyrolysis spray, molten salt, etc. have been
developed for this purpose. Besides the significant achievements of these chemical methods,
they also have various unavoidable disadvantages. For example, sol-gel process uses metal
alkoxides as the starting materials, which are very expensive and extremely sensitive to the
environmental conditions such as moisture, light and heat. Moisture sensitivity makes it
necessary to conduct the experiment in dry boxes or clean rooms. Co-precipitation processes
involve repeated washing in order to eliminate the anions coming from the precursor salts
used, making the process complicated and very time consuming. Furthermore, it is difficult to
produce large batches by using most of the chemical solution processing routes. Therefore,
exploring alternative methods for the preparation of ferroelectric ceramics is still of
technological as well as scientific significances.
Mechanochemical synthesis, which is also known as mechanical alloying, high-energy
mechanical milling, high-energy milling, high-energy activation and many others (they are
not differentiated in the present review unless otherwise stated), was initially invented to
prepare oxide-dispersed metallic alloys for structural applications and subsequently applied to
extensions of metallic solid solubility, synthesis of intermetallics, disordering of
intermetallics, solid-state amorphization, nanostructured materials, and mechanochemical
synthesis of nanosized oxides or metal powders [5, 6]. Up to now, this technique has been
used to synthesize various ferroelectrics [7]. The mechanical technique is superior to both the
conventional solid-state reaction and the wet-chemistry-based processing routes for several
Synthesis and Applications of Nano-sizedFerroelectrics... 333
reasons [7, 11, 23]. First of all, it uses cost-effective and widely available oxides as the
starting materials and skips the intermediate temperature calcination step, leading to a simpler
process. Secondly, it takes place at room temperature in well-sealed containers, thus
effectively alleviating the loss of the volatile components, such as lead, bismuth and lithium.
This is of particular interest to the synthesis of ferroelectric materials, since most ferroelectric
ceramics contain lead (Pb), bismuth (Bi) or lithium (Li). Furthermore, due to their nanometer
scale size and very high homogeneity, the mechanochemically derived ceramic powders
demonstrate much better sinterability than those synthesized by the conventional solid-state
reaction and wet-chemical processes. Also, the high-energy milling can greatly improve the
reactivity of precursors by reducing the phase formation temperatures of some ferroelectric
materials that cannot be directly synthesized, such as BaTiO
3
[76-81] and many Arivillius
family ferroelectrics [86-88, 91-102]. A thorough review on the progress in synthesis of
nanosized ferroelectric powders and ceramics has been published recently [7]. This chapter
aims to provide a briefly overview on the progress in synthesis and moreover to introduce
several applications of the nanosized ferroelectric powders produced by the mechanochemical
activation techniques [120-133].
2. Experimental Procedure
2.1. High-Energy Mechanical Milling
Excellent reviews on the application of high-energy ball milling process to various
metallic materials can be found in the open literatures [5, 6], where detailed experimental
procedures have been discussed. Here, only a brief introduction is given to each type of the
milling techniques. There are various types of high-energy milling machines that have been
used and reported in the literature [5]. Different types of mills have different efficiencies and
capabilities. The productivity of high-energy mills can be from several grams to as much as
thousands of kilograms. High-energy mills that have been widely used for research purpose
are vibrational shake mills (SPEX), planetary mills and attritor mills. Other equipments, for
example, multi-ring-type mill (Model MICROS: MIC-0, Nara Machinery, Tokyo, Japan), are
also used in mechanochemical synthesis of some of the ferroelectric powders. Either stainless
steel or tungsten carbide milling media were used in the experiments of high-energy milling.
2.1.1. Vibrational Shake Mills
SPEX vibrational shake mill is one of the most widely used equipments in the research
community of mechanochemical synthesis. The common variety of SPEX shaker mill has one
vial, containing the sample and grinding balls, secured by a clamp and swung energetically
back and forth several thousand times a minute. The back-and-forth shaking motion is
combined with lateral movements at the ends of the vial, so that the vial appears to be
following a figure 8 or infinity sign as it moves. With each swing of the vial, the balls
impact against the sample and the end of the vial, both milling and mixing the sample. Due to
the amplitude (~5 cm) and speed (~1200 rpm) of the clamp motion, the ball velocities are
very high (on the order of 5 m/s) and consequently the force caused by the balls impact is
very large, hence, it is a high-energy mill. The only shortcoming of this type of mill is its
L.B. Kong, Z. Xu and T.S. Zhang 334
relatively small throughput, but this problem has been addressed by designing two-vial
equipment [5]. Another type of shake mill is Fritsch Pulverizette 0 (provided by Fritsch
GmbH in Germany). Both types of equipments, SPEX 8000 [9, 20, 37-42, 46-54] and Fritsch
Pulverizette 0 [57], have been employed to synthesize ferroelectric nanosized powders.
2.1.2. Planetary Ball Mills
Planetary ball mills have better capability than the SPEX mill. Vials are arranged on a
rotating support disk and a special drive mechanism causes them to rotate around their own
axes. The centrifugal force produced by the vials rotating around their own axes and that
produced by the rotating support disk both act on the vial contents, which include the
materials to grind and the grinding balls. Since the vials and the supporting disk rotate in
opposite directions, the centrifugal forces acted alternatively in the same and opposite
directions. This causes the grinding balls to run down the inside wall of the vial (the friction
effect) followed by the material being ground and grinding balls lifting off and traveling
freely through the inner chamber of the vial and colliding against the opposing inside wall
(the impact effect). A planetary mill, combined with high-density milling media such as
stainless steel and tungsten carbide, also can provide high-energy ball milling. The most
popular planetary mills that are reported in the literature are supplied by Fritsch and Retsch in
Germany. Various ferroelectric powders have been synthesized using planetary mills [11, 12,
24-26, 30-36, 43, 56].
2.1.3. Attritor Mills
Although attritor mill has been rarely reported to be used as a tool to synthesize
ferroelectric powders, it is of significance to give a brief description. A conventional
planetary ball mill consists of a rotating horizontal drum half-filled with small steel balls. As
the drum rotates the balls drop on the powders that are being ground; the rate of grinding
increases with the speed of rotation. When speeds are too high, however, the centrifugal force
acting on the flying balls exceeds the force of gravity, and the balls are pinned to the wall of
the drum. As a result, the grinding action stops. An attritor consists of a vertical drum with a
series of impellers inside it. Set progressively at right angles to each other, the impellers
energize the ball charge, causing powder size reduction because of impact between balls,
between balls and container wall, and between balls, agitator shaft, and impellers. Some size
reduction appears to take place by interparticle collisions and by ball sliding. A powerful
motor rotates the impellers, which in turn agitate the balls in the drum.
The most important advantage of attritor mills is their capability of processing large
quantities of powders (from about 0.5 to 40 kg). The operation of an attritor is different from
vibration and planetary mills. Powders to be milled are placed in a stationary tank together
with the grinding media. During milling process, the mixture is agitated by a shaft with arms,
rotating at a speed of about 250 rpm. This causes the media to exert both shearing and impact
forces on the material [5].
Synthesis and Applications of Nano-sizedFerroelectrics... 335
2.1.4. Process Parameters
Mechanical milling process involves a number of variables that can be adjusted to
achieve different performances [5]. The important parameters include type of mill, materials
used for the milling vial and balls, milling speed, milling time, ball-to-powder weight ratio,
milling environment, process control agent (PCA) used, temperature controlling and
application of electrical or magnetic field during milling. Typically, for a SPEX shaker mill, 5
g of starting mixture is milled, using a stainless-steel cylindrical vial of 40 mm in diameter
and 40 mm in length, with a milling ball of 12.7 mm in diameter. The milling speed is ~900
rpm. Milling time is dependent on the formation abilities of the designed compounds. The
planetary mill can mill 20 g of powder at a time. A tungsten carbide vial of 250 ml and
tungsten carbide balls with various diameters are used as the milling media. Typical ball-to-
powder weight ratio is 10-50:1. Milling speed is 200-400 rpm in most cases. The milling
temperature is not controlled intentionally. However, the milling really causes temperature to
rise during the milling process. Till now, it remains impossible to monitor the temperature of
high-energy milling. However, the raised temperatures should be much lower than the
calcination temperatures used in the conventional solid-state reaction process. Unless
otherwise specified, milling is generally carried out in air.
3. Direct Phase Formation of Ferroelectrics
3.1. Normal Ferroelectrics and Antiferroelectrics
3.1.1. Lead Titanate and Lead Lanthanum Titanate
Lead titanate (PbTiO
3
or PT) ceramics is a typical ferroelectric material, with a phase
transition temperature (Curie temperature or T
C
) of ~490C. The unique properties of PT
ceramics, such as high transition temperature, low ratio for the planar-to-thickness coupling
factor, low aging rate of the dielectric constant and low dielectric constant, make them useful
to a variety of applications. For example, PT ceramics are very good candidates as stable
pyroelectric and piezoelectric devices for high temperature or high frequency applications. It
is well known that PT ceramics cannot be prepared via the conventional ceramic process
without the addition of other elements. This is because the anisotropic thermal expansion
caused by the phase transition from cubic paraelectric to tetragonal ferroelectric (with a
relatively large c/a ratio of ~1.065) during cooling from a high sintering temperature induces
large internal stresses, which destroys the ceramics by creating numerous microcracks.
Modification with other dopants allows for the fabrication of dense PT ceramics using
conventional ceramic process, but it tends to worsen their electrical properties. Therefore,
there is very rare report on preparation of undoped, dense PT ceramics.
Spontaneous cracking in polycrystalline ceramics results from internal stress among the
grains, which is caused by incompatible strains from thermal expansion anisotropy during the
phase transformation. The area in which microcracking is likely to initiate is defined by a
certain grain size limit. The stress per unit grain boundary area is proportional to the grain
volume. PT has been reported to crack spontaneously when the average grain size is larger
than ~3 m and to completely disintegrate into powders when the grains are larger than 10
L.B. Kong, Z. Xu and T.S. Zhang 336
m. Therefore, crack-free PT ceramics can only be prepared as the grain seizes of the sintered
samples are well controlled below 3 m.
Figure 1. XRD patterns of the mixture of PbO and TiO
2
powders milled for different times, using a
SPEX shaker-mill operated at ~900 rpm (open circle: PbO, filled rhombus: TiO
2
, filled circle: PT)
(Reproduced with permission from [9] Xue et al, Mater Lett 1999; 39: 364, Copyright Elsevier 1999)
Crack-free PT ceramics has been successfully prepared via a sol-gel process. By carefully
controlling the calcination temperature of the derived gels and the sintering parameters of the
sol-gel derived powders, the grain sizes of the PT powders and thus the sintered PT ceramics
could be less than 0.2 and 1.8 m, respectively. Since the anisotropic stress due to the phase
transition was totally buffered by the grain boundaries, crack-free PT ceramics could be
achieved, which are consistent with the prediction mentioned above. Preparation of crack-free
PT ceramics has also been realized by other methods, such as seeding-assisted sol-gel process
and refined ceramic process. Additionally, dense PT ceramics with submicrometer grains can
be obtained by spark plasma sintering (SPS). The SPS process is able to sinter a compact
powder at relatively low temperature in a very short time (a few minutes), which is very
Synthesis and Applications of Nano-sizedFerroelectrics... 337
effective in suppressing exaggerated PT grain growth. However, it is found that special
caution must be given to control the grain size of the PT powders when sol-gel processes are
used. The SPS process uses expensive facilities with relatively low productivity.
Comparatively, mechanochemical process is able to synthesize nanosized PT powders
directly from oxide precursors.
Figure 2. TEM image of the PT powders synthesized via a mechanochemical process with SPEX shaker
mill. (Reproduced with permission from [38] Wang et al, Solid State Ionics 1999; 124: 271, Copyright
Elsevier 2001).
20 30 40 50 60 70
1.40
1.20
1.00
0.85
0.75
2 Theta
I
n
d
e
n
s
i
t
y

(
a
.

u
.
)
Figure 3. XRD patterns of the PT powders derived from mixtures with different Pb/Ti molar ratios.
(After [7] Kong et al, Prog Mater Sci 2008; 53: 207, Copyright Elsevier 2008).
Synthesis of PT powders via mechanochemical milling has been reported by several
research groups, with different types of milling equipments [7-17]. Wang et al [9, 10] used
SPEX vibrating mill to synthesize PT powders from oxides (PbO and TiO
2
) and amorphous
Pb-Ti-O precursor derived from a coprecipitation process. Kong and co-workers [11, 12] used
Fritsch Pulverisette 5 planetary high-energy ball mill for the preparation of PT powders from
different TiO
2
precursors. Fig. 1 shows the XRD patterns of the mixture of PbO and TiO
2
powders milled for different durations, showing representatively the evolution of PT phase
formation as a result of the high-energy milling [9]. Typical TEM image of the 20-h-milled
L.B. Kong, Z. Xu and T.S. Zhang 338
sample is shown in Fig. 2 [38]. It is found that PT powders have a particle size of 20-30 nm.
Experimental results indicated that the phase formation of PT is also affected by the
properties of starting materials, especially during the early stage of phase evolution. There is
also a fairly significant effect of PbO/TiO
2
ratio on the phase formation of PT via the high-
energy mechanical milling. Fig. 3 shows the XRD patterns of the mixtures with PbO/TiO
2
(anatase) ratios from 1.4 to 0.75 [7, 17]. It is found that single phase PT can be formed from
the mixtures with different PbO/TiO
2
ratios. However, the tetragonality (c/a ratio) of the PT
phases obviously decreases from ~1.03 for PbO/TiO
2
=1.4 to ~1.01 for PbO/TiO
2
=1.00. The
samples from the mixtures with PbO/TiO
2
ratio less than 1 are of cubic structure. It is
important to note that the PT powders have almost the same grain size, although they have
different tetragonalities. It means that high-energy ball milling technique is able to synthesize
PT compound with compositions far away from the 1:1 stoichiometric state. Such a wide
range of nonstoichiometry has not been reported for PT powders prepared by the
conventional solid-state reaction method and wet-chemistry processing routes. This result is
expected to be applicable to other lead containing ferroelectric compounds.
More significantly, crack-free PT ceramics can be obtained from the synthesized PT
powders [11, 12]. The reason is that the average grain size of the PT ceramics is about 1 m
and decreases gradually with increasing milling time, which is much less than the critical size
of 3 m, below which crack-free PT ceramics will be produced. The formation of crack-free
PT ceramics can be attributed to the fact that PT powders synthesized via the high-energy
mechanical milling process are of nanometer scale grains. Such powders possess very high
sinterability, and hence, can be sintered at relatively low temperature. The low sintering
temperature effectively suppressed the grain growth of the PT ceramics.
Figure 4. DTA curves of the PT ceramics derived from the nanosized powders. (Reproduced with
permission from [12], Kong et al, Ferroelectrics 1999; 230: 281, Copyright Taylor & Francis 1999).
It is worth mentioning that the crack-free PT ceramics is not due to the contamination of
tungsten carbide that comes from the vials and balls during the high-energy milling process,
which has been conformed by TEM element analysis. The results indicated that the content of
any impurities in the as milled powders in the sample milled for 80 h was less than 1 at%
[17], which is similar to that reported by Jiang et al [19], who examined the tungsten
Synthesis and Applications of Nano-sizedFerroelectrics... 339
contamination in ZrO
2
powder milled for as long as 120 h with a tungsten carbide milling
media and found that the tungsten content is less than 1 at%. Additionally, no second phases
could be detected by the XRD measurement of the PT ceramics. This, together with the non-
contamination statement, has also been supported by the differential thermal analysis (DTA)
results of the PT ceramic pieces. As shown in Fig. 4, the DTA curve of the PT ceramics
produced from the 20-h-milled powder clearly shows an endothermic peak at 491C during
heating up and an exothermic peak at 471C during cooling down, respectively. The
endothermic peak at 491C is the Curie temperature T
C
of PT, corresponding to the phase
transformation from tetragonal ferroelectric state to cubic pyroelectric state. The exothermic
peak at 471C is 20C below the endothermic peak, due to the hysteresis of the phase
transition of PT. Almost similar DTA curves were observed for the samples made from
powders milled for longer durations. If there were impurities that have been incorporated into
the PT ceramics, their Curie temperatures would have been changed.
In summary, high-energy mechanical milling has been shown to be a unique method in
the preparation of PT powders and crack-free PT ceramics. As compared to most chemical
processing routes such as sol-gel and hydrothermal method, high-energy mechanical milling
technique is much simpler and more cost-effective.
3.1.2. Lead Zirconate Titanate
Figure 5. XRD patterns of the mixtures of PbO and TiO
2
powders milled for different time durations.
(Reproduced with permission from [23] Kong et al, J Mater Res 2001; 16 (6): 1636, Copyright
Materials Research Society 2001).
Lead zirconate titanate [Pb(Zr
x
Ti
1-x
)O
3
or PZT] ceramics, solid solutions of PT and PZ,
are important to a variety of applications such as transducers, sonars, micropositioners, rotary
actuators and pyroelectric sensors, etc, due to its outstanding ferroelectric, piezoelectric,
pyroelectric, and opto-electronic properties, and have been extensively and intensively
studied for several decades [1-4]. Although PZT ceramics of different compositions have
L.B. Kong, Z. Xu and T.S. Zhang 340
various functions, one of the important features of this solid solution system is the existence
of almost temperature-independent phase boundary around x=0.52-0.53, which separates a
rhombohedral Zr-rich phase from a tetragonal Ti-rich phase. The dielectric constant,
piezoelectric constant and electromechanical coupling coefficient all exhibit a pronounced
maximum value for the composition corresponding to this phase boundary, which is generally
referred to as the morphotropic phase boundary (MPB) in the literature [1, 2]. This is mainly
attributed to the existence of a mixture of phases at the boundary and the presence of a larger
number of reorientable polarization directions existing in the MPB mixed-phase region [1, 7].
It is found that the microstructural and electrical characteristics of PZT ceramics made
from the powders milled for different durations are significantly different. Using SPEX
shaker mill, 10-h-milling leads to the formation of perovskite PZT with small amount of the
unreacted oxides, while single phase PZT is obtained after milling for 25 h. The Milling also
enhanced the reactivity of the precursors. For example, perovskite phase formation of the
mixture milled for 10 h can be fully realized at 700C, while 800C is required by the
unmilled sample. At the same time, there are intermediate phases, such as PT, appearing in
the unmilled mixture calcined at relatively lower temperatures (600C-700C). These
observations indicate that PZT phase formation was greatly enhanced as a result of the high-
energy mechanical activation. The enhanced PZT phase formation can be readily attributed to
the refinement of the oxide precursors as a result of the high-energy milling. Furthermore,
PZT ceramics demonstrated better properties than those derived from the unmilled precursors.
400 600 800 1000
-1.6
-0.8
0.0
0.8
Temperature (
o
C)
-10
-5
0
5
S
i
n
t
e
r
i
n
g

r
a
t
e

(
%
/


o
C
)
L
i
n
e
a
r

s
h
r
i
n
k
a
g
e

(
%
)
4 h
8 h
15 h
24 h
Figure 6. Thermal mechanical properties of the PZT powders. (Reproduced with permission from [23]
Kong et al, J Mater Res 2001; 16 (6): 1636, Copyright Materials Research Society 2001).
Similar results have been reported for PZT ceramics prepared by using a planetary mill.
Combining with thermal mechanical analysis, it is found that the reaction temperature to form
Synthesis and Applications of Nano-sizedFerroelectrics... 341
a perovskite structure can be greatly reduced as a result of high-energy milling. As shown in
Fig. 6, the volumetric expansion temperatures, which is attributed to the formation of PZT
from the constituent oxides, are gradually decreased from 771C to 763C and to 752C for
the powders milled for 4, 8 and 15 h, respectively [23]. The PZT ceramics prepared in this
way have properties comparable with those fabricated via the conventional ceramic process.
The high-energy milling technique has also been applied to PZT ferroelectric materials doped
with various components [28]. Also, rapid formation of PZT is possible by simply increasing
the milling intensity, i. e. high milling speed and large ball-to-powder weight ratio. In this
way, PZT phase can be obtained by milling for just 1 h.
3.1.3. Lead Lanthanum Zirconate Titanate
Figure 7. XRD patterns of the mixtures for PLZT8/65/35 milled for different time durations: (a) 4 h, (b)
15 h and (c) 36 h. (Reproduced with permission from [31] Kong et al, Mater Lett 2002; 52: 378,
Copyright Elsevier 2002)
Lead lanthanum zirconate titanate (PLZT) ceramics, with variable dopant concentrations
of lanthanum and different Zr/Ti ratios, exhibit a variety of ferroic phases such as
ferroelectric (FE), antiferroelectric (AFE) and paraelectric (PE) phases. As a result, PLZT
ceramics are widely investigated during the last decades. The general formula of PLZT is
(Pb
1-y
La
y
)(Zr
1-x
Ti
x
)
1-y/4
O
3
, usually being shorted as PLZT100y/1-x/x. A typical room-
temperature phase diagram of PLZT solid solution is quite complicated, where various phases
exist with different compositions. The phases of great importance include antiferroelectric
orthorhombic (AFE
O
), ferroelectric rhombohedral (FE
Rh
), ferroelectric tetragonal (FE
Tet
),
relaxor ferroelectric (RFE) and paraelectric cubic (PE
Cubic
). Several PLZT ceramics, including
PLZT8/65/36, PLZT7/60/40, PLZT2/95/5 and PLZT15/65/35, have been synthesized by the
high-energy milling technique, showing the feasibility of the technique in synthesizing
multicomponent materials [30-34]. Compared to PZT, the phase formation of PLZT is more
difficult, which is because the presence of La element. As shown in Fig. 7, single phase
L.B. Kong, Z. Xu and T.S. Zhang 342
formation of perovskite structure requires a time duration of 36 h. However, similar to PZT,
PLZT ceramics with desired electrical properties can be well achieved from the incompletely
reacted mixtures. For example, transparent PLZT8/65/35 ceramics can be obtained from the
mixtures milled for 4, 15 and 36 h [31]. It is also found that excessive PbO that must be used
in conventional solid-state reaction process is not a crucial requirement when PLZT ceramics
are prepared from mixtures treated by a high-energy ball milling process. This conclusion
should also be applicable to other PbO-containing materials.
3.1.4. Antiferroelectrics
In antiferroelectrics, neighbour spontaneous polarization dipoles are anti-parallel to each
other. The phase transformation of antiferroelectric ceramic from antiferroelectric (AFE) to
ferroelectric (FE) phase can be induced by a sufficiently high electric field, which is usually
accompanied by a large volumetric change since the unit cell of FE phase is larger than that
of AFE phase. As a result, a very large longitudinal strain is associated with the AFE to FE
phase transformation, as compared with the strains achieved by ferroelectric materials. This
characteristic of antiferroelectric ceramics makes them good candidates for high displacement
electromehanical actuator applications. In addition, the transformation of antiferroelectrics
from AFE to FE phase leads to a significant energy storage, which can be used in energy
storage applications. Antiferroelectric ceramics are also studied because of their unique
pyroelectric, electrooptical and many other useful properties. It is difficult to synthesize
antiferroelectrics, especially for those with multicomponent compositions, using chemical
processing methods, such as coprecipitation and sol-gel process. Antiferroelectric materials
synthesized via high-energy mechanical milling process include lead zirconate (PbZrO
3
or
PZ) [35], lead lanthanum zirconate titanate (PLZT2/95/5) [30], and La-/Nb-doped lead
zirconate titanate stannate [Pb(Zr,Ti,Sn)O
3
or PSZT] [36]. This success is especially is of
special significance when more components are needed to modify the properties of the
materials.
3.2. B-site Perovskite Relaxor Ferroelectrics and Their Derivatives
Another important group of ferroelectric materials are lead-containing relaxor
ferroelectrics also with the perovskite structure [1]. They have a general formula of
Pb(B'B'')O
3
, where B is a low-valence cation, such as Mg
2+
, Zn
2+
, Fe
3+
or Sc
3+
, and B is a
high-valence cation, such as Nb
5+
, Ta
5+
or W
6+
[1]. Relaxors are characterized by their high
dielectric constant, broad and frequency-dispersive temperature dependence of dielectric
constant. These properties can be ascribed to the so-called local compositional heterogeneity
caused by the lack of ordering among the cations within the B-site sublattice. Their high
dielectric constant, together with excellent electrostrictive response, makes relaxor
ferroelectrics very useful for a wide range of applications, such as high dielectric constant
capacitors, various sensors, transducers and actuators. The main problem for the synthesis of
relaxors is the presence of pyrochlore, which seriously degrades the performance of relaxor
ferroelectrics. To address this problem, two-step processing routes (e. g. columbite or
Wolframite) are used to synthesize single phase or pyrochlore-free perovskite relaxors, via
the conventional solid-state reaction process. Many chemistry-based methods, such as co-
Synthesis and Applications of Nano-sizedFerroelectrics... 343
precipitation, sol-gel, gel combustion and molten salt, have also been developed to produce
phase-pure ultra-fine powders of relaxor ferroelectrics. Comparatively, high-energy
mechanochemical activation has been shown to be an alternative and effective process to
prepare a wide range of phase-pure relaxor ferroelectric materials. Typical relaxor
ferroelectrics include lead magnesium niobate [Pb(Mg
1/3
Nb
2/3
)O
3
or PMN], lead zinc niobate
[Pb(Zn
1/3
Nb
2/3
)O
3
, or PZN], lead iron niobate [Pb(Fe
1/2
Nb
1/2
)O
3
or PFN] and lead scandium
tantalate [Pb(Sc
1/2
Ta
1/2
)O
3
or PST] (PMN), etc. Base on these basic relaxors, modifications by
addition of other components such as PT, PZT, BT (BaTiO
3
) and ST (SrTiO
3
) or combination
with each other have led to tremendous new types of materials with binary or ternary
compositions.
3.2.1. Monophase
Pyrochlore-free nano-sized PMN powders have been directly synthesized from the
mixture of PbO, MgO and Nb
2
O
5
powders, using SPEX shaker-mill (stainless steel) [37-42]
and planetary high-energy ball mill (tungsten carbide) [43-46]. Nanosized PMN powders can
be produced either from oxide precursors or coprecipitation-derived amorphous precursors.
The formation mechanism of phase-pure PMN via the high-energy ball milling process is
different from that via the solid-state reaction of oxides. The reaction is very complex in the
solid-state process, where perovskite phase of PMN is not directly formed from the oxides.
PbO and Nb
2
O
5
firstly react at about 500C resulting in a cubic pyrochlore (Pb
3
Nb
4
O
13
). The
cubic pyrochlore compound further reacts with PbO leading to a rhombohedral pyrochlore
(Pb
2
Nb
2
O
7
) at about 600C. Pb
2
Nb
2
O
7
then reacts with MgO to form perovskite PMN, with
the appearance of Pb
3
Nb
4
O
13
at higher temperature of 800C. Although the amount of
Pb
3
Nb
4
O
13
phase can be reduced by adding excessive amount of PbO and MgO, it is very
difficult to obtain single phase PMN by the conventional solid-state process. However, this
problem is readily addressed by using the high-energy ball milling technique. The high-
energy ball milling technique provides the milled system with energies high enough to trigger
the reaction directly, avoiding the formation of pyrochlore phases, which are usually formed
at high temperatures. Therefore, the mechanism that governs the formation of PMN via the
mechanochemical activation is different from that of the solid-state reaction.
Slightly different from the observations reported earlier, a recent study indicated that the
reaction sequences of the formation of PMN from oxide precursors are relatively complicated
[45]. Under the milling conditions used, it was found that pyrochlore-type compounds were
also formed together with perovskite PMN. However, after milling for 60 h, almost single
phase perovskite was obtained, with a very small amount of pyrochlore phase (~1 wt%). The
formation of PMN was found to experience the following reactions. During the initial stage of
milling, PbO massicot was transformed into PbO litharge and traces of hydrocerussite
PbCO
3
PbO(H
2
O)
2
were detected by XRD, while orthorhombic Nb
2
O
5
and cubic MgO were
kept unchanged in terms of phase structure. The presence of the complex compound could be
due to the absorption of CO
2
during the milling. At the same time, a particle size reduction
and the formation of an amorphous phase, as a result of the high-energy milling, were
observed in the mixtures. The degree of amorphization of PbO and Nb
2
O
5
was found to be
more significant than that of MgO, which means that the latter is harder than the former in
this case. The amount of amorphous phase decreased with increasing milling time from 57 to
L.B. Kong, Z. Xu and T.S. Zhang 344
42 wt% as the milling time increased from 8 to 48 h. Interestingly, the composition of the
amorphous phase changed with milling time. With increasing milling time, the relative
amount of PbO decreased until the milling was carried out up to 48 h, while the relative
amount of Nb
2
O
5
increased up to 32 h and after further milling up to 60 h it remained
constant. The relative amount of MgO decreased from 8 to 32 h of milling and after that its
relative amount increased. After milling for 8 h, pyrochlore phase was predominant. Only a
small amount of Pb(Mg
1/3
Nb
2/3
)O
3
were detected by the quantitative XRD analysis. The
quantity of Pb(Mg
1/3
Nb
2/3
)O
3
increased almost linearly with increasing milling time, which
was accompanied by the consumption of MgO. The amount of MgO decreased slowly with
increasing milling time. A small amount of MgO was still present in the powder after milling
for 60 h. The reduction in the relative amount of PbO and Nb
2
O
5
was due to the formation of
the lead-niobium pyrochlore phase and the presence of them in the amorphous phase. As the
lattice parameter of the pyrochlore decreased with milling time, it was highly suggested that
an isostructural PMN pyrochlore was formed, which reacted with PbO and MgO into
perovskite. The maximum concentration of pyrochlore was reached after milling for 16 h.
The formation of perovskite was significantly accelerated by the high-energy milling process.
Perovskite phase was also promoted by thermal annealing from the mixtures milled for short
times [45]. This difference is understandable, since the outcome of a high-energy milling
could be determined by a number of factors.
It is of particular interest to produce single-phase PZN powder via a mechanical milling
process because no one has succeeded in trying to synthesize phase-pure PZN powder by
either the conventional solid-state reaction process or chemistry-based routes. So far, molten
salt flux is the only technique to grow phase-pure PZN in the form of single crystal. This is
because that the conventional solid-state reaction process and most chemistry routes require
calcination temperatures of 600-900C. In this temperature range, PZN is unstable. The fact
that PZN crystal can be grown in PbO flux at high temperature is due to the unequilibrium
state.
Phase formation of PZN was reported by Shinohara et al [66], where the authors used a
soft-mechanochemical route to prepare PMN-PZN ceramics. Although they noted the
formation of perovskite PZN by the mechanical milling, they didnt pay much attention to the
observation and made no attempt to synthesize phase-pure PZN powder. The synthesis of
perovskite PZN via mechanochemical process was formally reported by Wang et al [47, 48].
They found that nanocrystalline PZN powders could be synthesized either from oxide mixture
of PbO, ZnO and Nb
2
O
5
or a mixture of PbO and ZnNb
2
O
6
. The phase evolution of PZN is
similar to that of PT, PZT and PMN, as discussed above. The formation of single phase PZN
indicates again the difference in formation mechanism between mechanochemical synthesis
and conventional solid state reaction process. However, due to its poor thermal stability, PZN
powders cannot be used to prepare phase-pure PZN ceramics.
Lead iron niobate [Pb(Fe
1/2
Nb
1/2
)O
3
, or PFN) and lead iron tungstate [Pb(Fe
2/3
W
1/3
)O
3
or
PFW] are important relaxor ferroelectric materials. Due to their high dielectric constants,
broad ferroelectric-paraelectric phase transition, and especially relatively low sintering
temperature, PFN and PFW have been acknowledged to be promising candidates for
application of multilayer ceramic capacitors (MLCs). The low sintering temperature of PFN
and PFW makes it possible to use low melting temperature inexpensive inner electrodes,
leading to a significant reduction in the cost of MLCs products. Also, these iron containing
ferroelectric materials are of particular interests due to their possible magnetic properties. For
Synthesis and Applications of Nano-sizedFerroelectrics... 345
example, PFN has a diffuse ferroelectric phase transition at ~380 K and an antiferromagnetic
phase transition at ~145 K. PFW ceramic sample demonstrates a Curie temperature (T
C
) of
~175 K and antiferromagnetic-to-paramagnetic at ~340 K. These multiferroic magnetoelectric
materials simultaneously show electric and magnetic polarizations. The coupling between
ferroelectric and magnetic activity offers the possibility to manipulate the magnetic properties
through electric field and vice versa, making these materials potential for a wide range of
applications in spintronics, multiple state memory elements or memory devices, which use
electric and/or magnetic field for read/write operations.
The synthesis of iron containing relaxor ferroelectric phases, via high-energy mechanical
milling process, has been demonstrated by Wang et al [49-52] and other authors [64, 65].
Unlike PMN and PZN, the formation of PFN and PFW follows a relatively complicated
reaction sequence. It has been shown that single phase PFN powder can be formed from oxide
mixture via a mechanical activation. But PFN ceramics derived from this PFN powder
demonstrated poor microstructural and electrical properties. High performance PFN ceramics
can only be obtained from the columbite precursor of PbO and FeNbO
4
. PFW cannot be
directly synthesized from oxide mixture of PbO, Fe
2
O
3
and WO
3
by using a
mechanochemical activation [49]. Instead, nanocrystalline lead tungstate (PbWO
4
) and
pyrochlore (Pb
2
FeWO
6.5
) are formed in the oxide mixture as a result of the mechanical
activation. However, the subsequent thermal treatment showed that the reactivity of the
milled oxide mixture is enhanced for the formation of PFW perovskite phase. This is not
surprising because the precursor have been significantly refined as a result of the high-energy
milling. Although the reduction in calcination temperature leading to the formation of
perovskite PFW phase is not very significant, the milled powders result in PFW ceramics
with much better electrical properties as compared to those from the unmilled samples. PFW
ceramics, with high density, uniform microstructure and better dielectric properties, are
obtained from the milled powders, while the ceramics derived from the unmilled mixture
have high porosity, rough microstructure and poor electrical properties. This observation is
similar to that observed in PFN.
Single phase PFW can also be formed from oxide mixture of PbO, Fe
2
O
3
and WO
3
with
0.4 mol PFW powder as seeding, via a high-energy mechanical activation [49]. This seeding
level is much higher than those for solution processing, which is because the diffusion rate of
species in a liquid solution or in a solid state at high temperature is much higher than that in
the case of the high-energy milling, since the milling was carried out at relatively low
temperatures. Another way to synthesize PFW is to use pre-formed constituents, such as
Fe
2
WO
6
, PbWO
4
and Pb
2
FeWO
6.5
[52].
Lead scandium tantalate [Pb(Sc
1/2
Ta
1/2
)O
3
or PST] is a typical candidate for investigating
the relationship between structural ordering and electrical characteristic of relaxor [53].
Ordered PST behaves as a normal ferroelectric material, whereas disordered PST is a relaxor
having properties such as frequency dependent dielectric constant and broad phase transition
temperature range. The degree of the B-site ordering in PST can be controlled by thermal
annealing, which has been acknowledged to be a very useful way to tailor the electrical
properties of PST. The definition and characterization of B-site ordering and disordering will
be discussed later.
Single phase PST of perovskite structure has been synthesized from oxide mixture via a
mechanical milling [53]. 20-h-milling leads to the formation of single phase PST. However,
although the PST phases derived from the mechanical activation and the solid-state reaction
L.B. Kong, Z. Xu and T.S. Zhang 346
both possess the perovskite structure, they have different ordering characteristics. As shown
in Fig. 8, the superlattice reflection (111), an indication of ordering characteristic, is observed
in the sample derived from the Wolframite precursor via the conventional solid-state reaction
process, while no such peak is detected in the mechanochemically synthesized phase. The
former has an ordering parameter of 0.729, in contrast to a totally immeasurable order
parameter of the later. Due to the high sinterability, the mechanical activated derived PST
sample has a relative density of 97.1%, as compared to 92.6% of the ceramics made from the
Wolframite precursor. After sintering at 1200C for 2 h, their ordering factors increase to
0.764 and 0.23, respectively. The difference in the disordering characteristics between the
PST ceramics is also confirmed by the difference in their dielectric properties [53]. The
1200C-sintered PST ceramic sample derived from the 20-h-activated oxide mixture
demonstrates a typical relaxation behavior. A maximum dielectric constant of ~14000 was
measured at 0.1 kHz, with a dielectric loss tangent of 0.032, which are better than the
dielectric properties of its Wolframite counterpart. The most significant aspect of these
observations is that the disordering character in the mechanical activated PST can be retained
after sintering at high temperatures. Therefore, the mechanochemical technique offers us an
effective and simple way to prepare disordered PST ceramics, without any special treatments
used in the conventional solid-state reaction process.
Figure 8. XRD patterns of the PST phases derived from 20-h-milled oxide mixture and from
Wolframite precursor. (Reproduced with permission from [53] Lim et al, Mater Chem Phys 2002; 75:
157, Copyright Elsevier 2002)
Synthesis and Applications of Nano-sizedFerroelectrics... 347
3.2.2. Binary-Phase
Numerous binary systems have been created through the combination of relaxors with
ABO
3
compounds, such as BT, ST and PT. Combination of relaxor and relaxor is also an
effective way to produce materials with desired electrical properties. Representative binary
phases, such as PMN-PT [54-58, 63], PZN-BT [59-62] and PMN-PFN [67], will be discussed
to show the feasibility of high-energy mechanical activation in synthesizing ferroelectric
materials. Three subsections, i. e. PMN family, PZN family and relaxor-relaxor combination,
will be discussed.
(1-x)PMN-xPT binary phases with different compositions demonstrate various dielectric,
ferroelectric and piezoelectric properties. 0.9PMN-0.1PT is a pronounced candidate to replace
BT (BaTiO
3
) in MLCs (multilayer ceramic capacitors) because it has lower sintering
temperature as well as higher dielectric constant than BT. It is also one of the best candidate
materials for devices of actuators because of its large electrostrictive and piezoelectric
coefficients. (1-x)PMN-xPT system has also a morphotropic phase boundary (MBP), similar
to that in PZT family [1]. The piezoelectric properties of the (1-x)PMN-xPT system, however,
are much higher that of PZT system. 0.65PMN-0.35PT has been shown to exhibit the highest
piezoelectric properties among various ferroelectric materials, thus making it important for
applications of many actuators and sensors.
The first example to synthesize 0.9PMN-0.1PT using mechanochemical process was
reported by Baek et al [55], with a primary object to improve the performance of the
ferroelectric ceramics. More recently, it has been reported that single phase nanocrystalline
0.9PMN-0.1PT powders can be directly synthesized from oxide precursors via high-energy
mechanical milling process [54-58]. The phase evolution of PMN-PT follows a similar
pattern of PMN, as discussed above. The presence of pyrochlore phase is not observed. As
summarized in Table 6, the 0.9PMN-0.1PT ceramics, derived from the high-energy
mechanically synthesized nano-sized powders, demonstrated very promising dielectric and
ferroelectric properties. Compositions with high contents of PT have also been reported to be
synthesized using high-energy milling technique. Similar to PZT, the synthesis of PMN-PT
powders can be readily speeded up by increasing the milling rates.
As discussed above, although single phase PZN powder has been synthesized from oxide
precursor via mechanical activations, it is impossible to have phase pure PZN ceramics from
the synthesized powder since it is not stable at high temperatures. However, it has been
reported that perovskite structure of PZN can be stabilized by the addition of BaTiO
3
(BT),
SrTiO
3
(ST) and PbTiO
3
(PT) to form binary solid-state solutions of PZN-BT, PZN-ST or
PZN-PT, via the conventional ceramic process or single-crystal growth. PZN based binary
materials have many outstanding properties. For example, 0.91PZN-0.09PT, which is near the
morphotropic phase boundary (MPB) at room temperature shows a surprisingly large
dielectric and piezoelectric constant and higher electromechanical coupling coefficient than
the PZT family of ferroelectrics. Among various additives, BT is the most effective additive
to suppress the formation of pyrochlore phase in PZN binary ceramic materials. (1-x)PZN-
xBT with x=0.05-0.30 have been synthesized via high-energy mechanical milling process
[54-58].
The results indicated that the mechanochemical technique is advantageous over some of
the chemical processing routes for the preparation of PZN based ceramics. For example,
special carefulness must be taken to obtain high percentage of perovskite 0.75PZN-0.25BT.
L.B. Kong, Z. Xu and T.S. Zhang 348
Although high chemical homogeneity was achieved in the synthesis method, the maximum
weight percentage of perovskite was 96%, which was only achieved under proper thermal
treatment (14 min calcination at 800C after at fast firing rate of 50C/min). Comparatively,
the mechanochemical process is much simple and effective. There is also report about the
synthesis of other PZN based binary compositions, such as 0.92Pb(Zn
1/3
Nb
2/3
)O
3
-0.08PbTiO
3
(0.92PZN-0.08PT).
Relaxor-relaxor combination has shown many particular interests. For example, PMN has
a Curie temperature T
C
of ~50C, where as PZNs T
C
is ~140C. It is, therefore, possible to
make a relaxor with T
C
close to room temperature by combining PMN and PZN. This kind of
material is expected to have very high room temperature dielectric constant, which is
important for the fabrication of small dimension ceramic capacitors with high values of
capacitance. Although normal ferroelectrics such PT, BT or PZT can be used to modify the
properties of relaxors, they alter the relaxor characteristics at the same time. For example,
with increasing concentration of BT, PZN-BT will become normal ferroelectric gradually. As
discussed above, single phase PFW cannot be directly synthesized from oxide mixture via a
mechanochemical process, but the mechanically activated mixture can be used to fabricate
PFW ceramics because single phase is formed at high temperature. In contrast, PZN has been
successfully derived from the oxide mixture. However, PZN is not stable at high temperature.
It is expected that an appropriate combination of PFW and PZN might lead to a relaxor that
can be obtained from oxide mixture via a mechanochemical activation and is also stable at
high temperatures. so that PZN-PFW ceramics Successful applications of mechanochemical
synthesis to these kinds of relaxor binary systems will be presented as following.
A soft-mechanochemical processing was used to treat precursors of PbO, Mg(OH)
2
,
Nb
2
O
5
and 2ZnCO
3
3Zn(OH)
2
H
2
O, in order to synthesize PMN-PZN ceramics [66]. It was
found that perovskite phase was formed even after milling for only 30 min and became major
phase after 3 h of milling. About 80% perovskite phase was achieved for (1-x)PMN-xPZN
with x0.9 and ~60% for pure PZN. The thermal stability of the as-milled PMN-PZN powder
is greatly dependent on the content of PZN. With increasing PZN, the thermal stability of the
PMN-PZN decreases. Phase-pure PMN-PZN ceramics can only be obtained as the
concentration of x<0.7. Another example is (1-x)PFW-xPZN.
3.2.3. Ternary-Phase
The electrical properties of relaxor ferroelectrics can be significantly modified using
multi-component compositions. Representative ternary systems prepared by the high-energy
mechanochemical process are 0.54PZN-0.36PMN-0.1PT and 0.48PFN-0.36PFW-0.16PZN,
reported by Wangs group [68-71]. The results suggested that it is not necessary to use the
columbite precursor to synthesize PZN-PMN-PT powder via a high-energy mechanochemical
milling process and the PFN-PFW-PZN ceramics derived from the 20-h-milled mixture, had
better dielectric properties, as compared to that from its unmilled counterpart (<500).
3.2.4. Order-Disordering Transition Induced by Mechanical Activation
A schematic diagram, showing an ordered and a disordered crystal structure of
A(B'
1/2
B''
1/2
)O
3
, is demonstrated in Fig. 9 [7]. In the ordered structure (Fig. 9 (a)), sublattice
B' or B'' can be readily identified, while in the disordered one (Fig. 9 (b)), no sublattice can be
Synthesis and Applications of Nano-sizedFerroelectrics... 349
established, because B' and B'' ions are distributed randomly. The degree of ordering
(disordering) is dependent mainly on the difference in size of the two B-site ions and the
difference in their valence states. A large difference in size and valence state is favorable to
B-site ordering. Depending on their scales of dimension, B-site ordering can be classified into
three groups: (i) random cation distribution for coherence length below 2 nm, (ii) short
coherence long-range ordering for nanoscale of 2-50 nm and (iii) long coherence ordering of
above 100 nm. It has been found that an order-disorder transition can be triggered by high-
energy activations in the conventionally synthesized ordered powders of monophase PST [72]
and binary system 0.4Pb(Mg
1/3
Nb
2/3
)O
3
-0.6Pb(Mg
1/2
W
1/2
)O
3
(0.4PMN-0.6PMW) [73, 74].
Due to the fact that the grain sizes of the PST ceramics were far beyond nanometer scale, the
disordering and dielectric behaviors has been considered to be associated with the pre-
sintering mechanical activation in the sintered PST ceramics, and not related to particle size.
This finding offers us an opportunity to tailoring the disordering of PST and PMN-PMW and
other relaxor ferroelectric ceramics through proper combinations of mechanical activation and
subsequent sintering.
Figure 9. Schematic diagram of crystal structure for A(B
1/2
B
1/2
)O
3
: (a) ordered and (b) disordered (B:
larger open circle and B: smaller filled circle). (Reproduced with permission from [7] Kong et al, Prog
Mater Sci 2008; 53: 207, Copyright Elsevier 2008)
3.3. BaTiO
3
and CaTiO
3
Barium titanate (BaTiO
3
or BT) is the first ferroelectric ceramics [1, 75-83], which is a
good candidate for a variety of applications, such as piezoelectric actuators, multiplayer
ceramic capacitors (MLC) and positive temperature coefficient resistors (PTCR), due to its
excellent dielectric, ferroelectric and piezoelectric properties [1].
BaTiO
3
powders were conventionally synthesized by solid-state reaction between BaCO
3
and TiO
2
at temperatures higher than 1200C [1]. The high calcination temperature required
by solid-state reaction process leads to many disadvantages of the BaTiO
3
powders, such as
large particle size, wide size distribution and high degree of particle agglomeration. In this
regard, it is desired to lower preparing temperature in order to get BaTiO
3
powder with fine
and homogenous structures. Various chemistry based methods have been developed to
L.B. Kong, Z. Xu and T.S. Zhang 350
prepare BaTiO
3
at low temperatures. Examples include chemical co-precipitation, sol-gel
process, hydrothermal, molten salt, microemulsion and auto-combustion.
It was reported by Kong et al [77] that single phase BT cannot be synthesized directly
from BaCO
3
and TiO
2
mixture by high-energy activation, but it brought out a significant
reduction in phase formation temperature of BT from the mixture. As shown in Fig. 10, well
developed single phase BT is observed in the sample after calcining at 800C for 2 h. This
temperature is much lower than that required by a standard solid-state reaction process.
A later finding showed that single phase BT can be synthesized from oxide mixture of
BaO and TiO
2
via a mechanical milling only under nitrogen environment or vacuum. The
phase evolution of perovskite BT is similar to those of PT, PZT and PMN and the BT powder
obtained is of nanometer size and narrow size distribution. High-energy mechanical milling
can also reduce the phase formation temperature of BT by altering the reaction process.
Recently, however, there was a report showing that perovskite BT can be directly synthesized
from BaO and TiO
2
via mechanical milling in air. There are also reports of synthesis of
nanosized Ba
1-x
Sr
x
TiO
3
(BST) with a whole composition, using mechanochemical technique
[83, 123]. CaTiO
3
, with a similar structure to BaTiO
3
, have also been synthesized via the
high-energy technique [84, 85].
Figure 10. XRD patterns of the mixtures of BaCO
3
and TiO
2
powders milled for 10 h calcined at
different temperatures: (a) 600C, (b) 700C, (c) 800C and (d) 900C for 2 h. (Reproduced with
permission from [77] Kong et al, J Alloy Comp 2002; 337: 226, Copyright Elsevier 2002)
3.4. Aurivillius Ferroelectrics
Aurivillius type structure compounds have a general formula [Bi
2
O
2
][A
n-1
B
n
O
3n+1
], which
are built up by n pseudo-perovskite [A
n-1
B
n
O
3n+1
]
2-
layers alternating with [Bi
2
O
2
]
2+
layers.
These materials have received great interest due to their high Curie temperatures and
excellent piezoelectric properties. Various ferroelectric materials of Aurivillius family have
Synthesis and Applications of Nano-sizedFerroelectrics... 351
been synthesized via high-energy mechanical milling process. Some of them can be produced
directly from oxide mixtures, while others are crystallized from amorphous of oxide
precursors created by high-energy activations.
3.4.1. Bi
4
Ti
3
O
12
[86-89]
Bismuth titanate (Bi
4
Ti
3
O
12
, BiT) is the most famous Aurivillius type ferroelectric
material with n=3. It is a good candidate for high-temperature piezoelectric applications,
memory storage, and optical displays because of its high Curie temperature (675C) and good
electro-optical switching behavior. Nano-sized BiT powders have been synthesized from
oxide mixture via a high-energy planetary ball milling process. BiT ceramics with good
dielectric and pyroelectric properties are obtained from the nano-sized BiT powders.
Although BiT nanosized powders have been successfully synthesized via high-energy
mechanochemcal activations, no attempt has been made to examine and explain the structural
change in detail. The structural variation of the system 2Bi
2
O
3
3TiO
2
, as a result of high-
energy milling, was carefully studied by Zdujic et al in a recent article [89]. To have a better
understanding of the effect of high-energy milling on the structural evolution, the authors also
milled BiT powders synthesized via a reactive sintering method separately. Both the oxide
mixture (Bi
2
O
3
and TiO
2
) and the BiT powder were milled using a Fritsch Pulverisette 5 type
planetary ball mill. Stainless steel vials of 500 ml and hardened-steel balls of 13.4 mm in
diameter were used as milling media. The ball-to-powder weight ratio was 20:1.
Two sets of milling experiments were used to check the effect of milling power on phase
evolution of BiT. In the first set, the powders were milled up to 15 h initially at an angular
velocity of the basic disc of 180 rpm and vials of 225 rpm. After that, the angular velocities of
both basic disc and vials were increased to 317 rpm and 396 rpm, respectively. The samples
were milled for extra time durations of 1, 3 and 5 h, after which additional 10 h milling was
applied at basic disc and vial velocities of 180 rpm and 225 rpm (the initial speed). The
second milling set conducted at the maximum speed (317 and 396 rpm) for 20 h, followed by
an additional 10-h-milling at low speed (180 and 225 rpm).
It was found that the formation of BiT phase in the 2Bi
2
O
3
TiO
2
mixture took place
through the crystallization of an intermediate phase Bi
2
(CO
3
)O
2
, which was not observed by
other researchers [86-88]. The formation of this intermediate compound was found after
milling for 1 h. Further milling resulted in the formation of amorphous BiT phase. The
mechanochemical reaction between 2Bi
2
O
3
and TiO
2
was triggered due to the creation of
highly reactive fresh surfaces of particles and interfaces between the reactants. An additional
high intensity milling induced a partial crystallization of the amorphous BiT phase. Prolonged
milling for another 10 h at low speed led to amorphization of the crystalline BiT. The
structural evolution of BiT powder as a result of the high-energy milling was similar, with
only slight differences in degree and time of amorphization and crystallization transition. In
this study, the kinetics of the reaction and phase transition have been systematically
investigated.
3.4.2. Other Aurivillius Type Ferroelectrics
Besides Bi
4
Ti
3
O
12
, many other ferroelectric materials belonging to the Aurivillius family
have also been produced using high-energy milling techniques. They include bismuth
L.B. Kong, Z. Xu and T.S. Zhang 352
vanadate (Bi
2
VO
5.5
or BiV) [90-94], bismuth molybdate tungstate (Bi
2
Mo
1-x
W
x
O
6
or BiMW)
[95], calcium and strontium bismuth titanate (CaBi
4
Ti
4
O
15
and SrBi
4
Ti
4
O
15
or CBiT and
SBiT) [96-98], bismuth titanate niobate (Bi
3
TiNbO
9
or BiTN) [99-101] and (1-x)Bi
2
SrNb
2
O
9
-
xBi
3
TiNbO
9
[(1-x)SBN-xBTN] [102-105]. Some compositions were made into ceramic
samples and characterization results indicated that the ceramics made from the nanosized
powders exhibited good dielectric and piezoelectric properties.
3.5. LiNbO
3
and NaNbO
3
Lithium niobate (LiNbO
3
or LN) is a ferroelectric material with a variety of attractive
properties, such as high pyroelectric, piezoelectric electro-optical and photo-elastic
coefficients, large acoustic-optic figure-of-merit, and significant photorefractive effects.
Conventional synthesis of LN requires high temperatures. Similar to lead containing
ferroelectric materials, the high temperature required causes loss of Li element. The loss of
stoichiometry by Li
2
O evaporation, together with the formation of Nb-rich grain boundaries is
seriously harmful to the planar coupling coefficient (K
p
) and piezoelectric coefficient (d
33
) of
LN ceramics. Although ultrafine LN powders can be produced by wet-chemical routes, such
as sol-gel, coprecipitation and Pechinis method, problems are similar to those encountered by
lead containing ferroelectrics. Therefore, high-energy milling is an alternative way to
synthesize LN powder. The work reported by de Figueiredo et al [106] is probably the only
example. The starting materials used were Nb
2
O
5
and Li
2
CO
3
and milling duration varied
from 2 to 42 h. A planetary mill (Fritsch Pulverisette 5) and stainless steel milling media were
used [106]. Sodium niobate (NaNbO
3
or NN) is another example of niobate ferroelectric
materials synthesized via mechanochemical milling, reported by Castro et al [107-110].
Unlike LN, NN crystalline phase cannot be directly synthesized from the mixture of Na
2
CO
3
and Nb
2
O
5
, using a vibrating mill (Fritsch Pulverisette 0). A post thermal anneal, at a
temperature though much lower than that required by the conventional ceramics process, is
necessary to facilitate the phase of NN. NN ceramics prepared from the powder possessed
better piezoelectric properties.
4. Mechanisms
Phase formations by thermal activation in the conventional solid-state reaction and wet
chemistry-based process are through various interfacial reactions or diffusions at boundaries
between/among the precursor components, where one or more intermediate phases were
usually formed preferentially prior to the formation of desired compounds. In contrast, the
direct production of nano-sized ferroelectric phases activated by various high-energy
mechanochemical milling involves nucleation and subsequent growth of the ferroelectric
crystallites, without the occurrence of interfacial reactions and diffusions.
However, reactions to form ferroelectric phases, caused by high-energy
mechanochemical activation, could a complicated process, which is significantly different
from the solid-state reactions at high temperatures or those in solutions with a molecular
dispersion. It has been accepted that the phase formation of ferroelectric materials via high-
energy milling experiences two stages. Firstly, the grain/particle sizes of the precursors are
Synthesis and Applications of Nano-sizedFerroelectrics... 353
greatly refined. The fragmentation results in high defect densities, shorter diffusion distances,
and more intimate contacts of precursors. At the same time, large amounts of fresh/cleansed
surfaces/interfaces are created. All these factors will increase the reactivity of the precursors.
After a certain period of activation, depending on the materials involved and facilities used,
spontaneous reactions towards desired ferroelectric phases start to occur at some spots where
the reactants are sufficiently reactive enough or where localized temperature is high enough
to trigger the reactions. The phases formed serve as nucleation and cites of grain growth.
Amorphization is occasionally also observed in the synthesized powders, depending on
milling conditions and/or materials characteristics [39, 41, 62, 89, 123]. Also, the very high
localized-pressure created by the strong collision during the milling process could be an
additional factor to facilitate the reactions [62, 112].
It is reported that, when a planetary mill is used to synthesize lead containing
ferroelectric compounds, the final products are usually hard agglomerates, instead of loose
powders [11, 22-26, 30-36, 119]. The hard layers are strongly stuck at the bottom of tungsten
carbide vials. However, the agglomerates can be easily pulverized into powders. It has been
found, from the surface SEM images, of the pieces of PbZr
0.7
Ti
0.3
O
3
(PZT) agglomerates
derived from oxide mixture of PbO, ZrO
2
and TiO
2
, after milling for 20 hours, that there are
areas with two types of morphologies, dense and porous [26]. The dense area consists of rod-
like particles with a length of 0.2-0.5 m and a thickness of less than 100 nm. The appearance
of such hard layers means that sintering of the formed PZT powder occurred during the
milling process. This is a strong support to the suggestion of high localized-temperature
caused by the high-energy ball milling [9]. In this case, PZT phase is first formed incidentally
at the bottom of the WC vial where the flying balls could collide at all time. After a certain
number of nanosized PZT crystallites were formed, they would act as nuclei from which grain
growth takes place. High local temperature and high pressure produced by the collision could
cause the growth and densification of the PZT grains.
Figure 11. Schematic drawing of free energy for Pb(Zn
1/3
Nb
2/3
)O
3
(PZN). (Reproduced with permission
from [114] Wakiya et al, Mater Res Bull 1995; 30: 1121, Copyright Elsevier 1995)
The formation of PZN nanosized powder from oxide constituents, via high-energy
activation, is a miracle, since there is never such report via solid-state reaction or chemical
synthesis methods. It is well known that single phase PZN crystals can only be formed in
excess PbO at high temperature [114], which has been successfully explained by the
Ostwards step rule, as shown schematically in Fig. 11 [114]. The PZN single crystal is
precipitated from supercooled melt under unequilibrium state. The variation in free energy in
L.B. Kong, Z. Xu and T.S. Zhang 354
the molten system follows the thick line from high temperature. At a certain temperature, the
supercooled melt becomes supersaturated so that crystallization will take place in the
supercooled melt. According to the Ostwalds step rule, the phase precipitated from the
supercooled melt is that with smaller free energy difference from the supercooled melt.
Therefore, PZN perovskite, rather than pyrochlore, is precipitated from the molten state, as
indicated by the arrow in the figure. Since the free energy of perovskite PZN is higher than
that of pyrochlore, the precipitated PZN is in a metastable state. As a result, the PZN crystals
grown from excess PbO flux will be decompose to pyrochlore phase, a state of lower free
energy. However, Fig. 11 also indicates, the free energy-temperature curves of perovskite and
pyrochlore cross each other at a point. Below this point, perovskite has a lower free energy
than pyrochlore. According to Jang et al [113], this temperature is ~600C. Therefore, the
synthesis of PZN via the high-energy mechanochemical process takes place at a temperature
at least not high than 600C. Otherwise, PZN cannot be obtained via a high-energy milling.
This result also suggests that the localized temperature during the high-energy ball milling
should not be too high (>800C). Of course, this suggestion is not applicable to the cases of
milling induced combustion [111].
In summary, most of the lead-containing ferroelectric powders can be directly
synthesized from their oxide precursors as a result of high-energy mechanochemical process.
Because the high-energy milling effectively suppresses the grain growth of the synthesized
phases at the same time, ferroelectric powders produced in this way possess nanosized
crystalline grains, thus having very high sinterabilities. Ferroelectric ceramics derived from
the nanosized powders have demonstrated promising electrical, dielectric, ferroelectric,
piezoelectric and pyroelectric properties.
Some ferroelectric compounds cannot be directly obtained via a high-energy milling
process, but their phase formation temperatures of these compounds can be significantly
reduced as compared to that required by conventional solid-state reactions from unmilled
precursors. This can be called activation-assisted phase formation. This assisting effect of a
high-energy milling is readily attributed to the refinement of the precursors by the mechanical
activation. The refinement not only means the reduction in grain or particle size, but also
means the creation of defects, dislocations, lattice distortions and microstrains in the
precursor lattice. An extreme case of the refinement is amorphization of the precursors.
Amorphous metallic alloys or metallic glasses are solid alloys, with a liquid-like or non-
crystalline atomic structures, have been extensively investigated [115-118]. Three critical
requirements for the production of metallic glasses, via rapid solidification method, are (i)
multiconmponent systems with three or more constituent elements, (ii) significantly different
atomic size ratios typically with difference exceeding ~13% and (iii) negative heats of mixing
among constituents. Recently, mechanochemical activation is found to be very effect way to
produce amorphous metallic alloys. Metallic alloys can be even made in the systems with a
positive heat of mixing. Mechanical alloying can produce amorphous alloys with wider
composition ranges than those made by rapid solidification process. The mechanochemical
activation has also been applied to amorphization of semiconductors, such as Se [116], Si
[117] and SiC [118], oxides, such as mullite and zeolite. High-energy milling can induce not
only accumulation of vast lattice and point defects but also chemical disordering of lattice. If
the rate of dynamic recovery is less than the rate of defect production, the accumulation of the
topological and chemical disorders will lead to a collapse of crystalline structure.
Synthesis and Applications of Nano-sizedFerroelectrics... 355
5. Applications of Nanosized Ferroelectrics
5.1. Powder Refining
Besides the direct synthesis and assisted synthesis of ferroelectric powders, high-energy
milling has also been used to treat commercial and lab-synthesized ferroelectric materials,
such as PZT [119, 120], BT [121] and BST [122]. It is found that high-energy milling is an
effective way to modify the morphology, reduce the grain/particle sizes and thus enhance the
densification behavior of ferroelectric powders.
For example, a commercial PZT powders, consisting of large particles (tens of micron)
with grains of about 1 m, can be refined to less than 100 nm, after milling for 10 h, using a
planetary high-energy mill [119]. The milled PZT powders can be sintered at a temperature of
100C-200C lower than that required by the unmilled powders. The enhanced sinterability of
commercial PZT powders is of interest to thick film and multilayer PZT devices. Thick films
are usually fabricated by screen-printing technique with PZT paste consists of PZT powders,
sintering aids and organic binders. The sintering aids, which are glasses with low melting
temperature, are used to lower the sintering temperature of thick films by forming liquid
phase during sintering process. These glasses consisting of non-ferroelectric phases, however,
are harmful to the performance of the final devices. As a result, PZT powders that can be
sintered at low temperature (<1000C) without any glasses additives will be attractive to thick
films PZT based devices. Such powders are also important to multilayer PZT devices for at
least two reasons. First consideration is cost reduction. Multilayer PZT devices are fabricated
in such a way that the PZT layers and electrode layers are alternatively stacked via tape
casting and screen-printing and then co-fired (sintered) at high temperatures. If the sintering
temperature is too high (>1000C), only expensive metal like Pt, Au, Pd and Ag can be used
as electrode layers, leading to higher cost devices. The reduction of device cost needs to use
cheaper metals like Ni, Cr, and Cu as electrode materials. In this case, the sintering
temperature of ferroelectric materials must be sufficiently low. Additionally, with the
development of modern microelectronics, multilayer structured ferroelectric devices have to
be able to work at low-driving voltage, to meet the requirement of miniaturization and
hybridization. The pre-requisition is to reduce the thickness of the PZT active layer from
hundreds (currently) to tens of micrometers. As the thickness of ferroelectric layer is reduced
to 20 m or less, the grain size of ferroelectric materials should not be larger than 1 m.
Otherwise, the electrode will be very easily shorting through the ferroelectric layers and
hence the yield of the device will drop. Therefore, low temperature sintering is also desired to
prevent grain growth.
5.2. Thick Films
There has been report that nanosized ferroelectric powders can be used to fabricate thick
films using screen-printing technique [123]. Nanosized 0.65Pb(Mg
1/3
Nb
2/3
)O
3
-0.35PbTiO
3
powders were synthesized from oxide constituents, using a planetary high-energy mill [45].
Analysis of sintering behavior indicated that the nanosized PMN-PT powder started to shrink
at 800C. Due to the presence of ~30 wt% amorphous phase, the synthesized powders were
L.B. Kong, Z. Xu and T.S. Zhang 356
annealed at 700C to promote a full crystallization before being used to prepare thick films.
The presence of the amorphous phase is probably because the milling speed used to
synthesize the PMN-PT powder is too high (300 rpm). The contents of amorphous phase in
the ferroelectric powders, reported by other researchers, are much lower [54, 56].
Figure 12. Schematic drawing of free energy for Pb(Zn
1/3
Nb
2/3
)O
3
(PZN). (Reproduced with permission
from [123] Kosec et al, J Eur Ceram Soc 2007; 27: 3775, Copyright Elsevier 2007).
Figure 13. Dielectric properties of the PMN-PT thick films annealed at different temperatures. Inset (a)
shows the real part of permittivity of the film annealed at 850C. Inset (b) shows the imaginary
permittivity of the thick films annealed at different temperatures. (Reproduced with permission from
[123] Kosec et al, J Eur Ceram Soc 2007; 27: 3775, Copyright Elsevier 2007).
PMN-PT thick films were fabricated on Al
2
O
3
substrate using the screen-printing
technique with paste made from the nanosized powders. Fig. 12 shows the SEM images of the
Synthesis and Applications of Nano-sizedFerroelectrics... 357
thick films annealed at 850C, 900C and 950C, respectively. It is found that thickness
decreases with increasing annealing temperature, due to the densification of the films. At the
same time, significant grain growth can be observed. Almost fully dense thick film with a
thickness of about 35 m is obtained after annealing at 950C for 2 h. Fig. 13 shows the
dielectric constant of the thick films annealed at different temperatures. Room temperature
dielectric constant of the film is 4100, while the peak value of dielectric constant at T
C
is as
high as 41000. The 950C-annealed sample has a remanent polarization of 26 C/cm
2
, a
coercive field of 5.7 kV/cm, a piezoelectric constant of 170 pC/N. All these properties of the
PMN-PT thick film are comparable with those of bulk ceramics, making it to be potential
candidates for applications of micro-piezoelectric devices.
5.3. Nanocomposites
A very interesting approach, called nanocomposite processing route, was proposed to
incorporated high-energy ball milling technique with sol-gel process to deposit thick films,
which cannot be realized using the typical sol-gel with solution precursors [124-128]. This
approach has combined advantages of high-energy milling and the sol-gel process.
Figure 14. Flow chart of the processing sequence to prepare uniformly dispersed suspensions or
slurries. (Reproduced with permission from [124] Wang et al, Mater Chem Phys, 2002; 75: 71,
Copyright Elsevier 2002).
L.B. Kong, Z. Xu and T.S. Zhang 358
Fig. 14 shows the processing sequence of the nanocomposite technique [125]. In this
processing, commercial PZT powder was milled using a high-energy mill to produce
nanosized PZT powder, which similar to that reported in Ref [119]. The nanosized PZT
powder was then milled for one more time with appropriate dispersants, which are used to
modify its surface characteristics. The modified PZT nanosized powder can be readily mixed
with sol-gel solutions without the presence of agglomerations or precipitations. This kind of
mixture can be used as same as the typical sol-gel solutions to deposit thick films on various
substrates. The slurries may also directly used to other processing, such as tape casing, screen
printing and molding [125]. The outstanding features of this technique are summarized in Fig.
15 [125]. Due to these basic characteristics, the technique can be used for various purposes.
For example, if a sol-gel solution has the same composition as the nanosized powder, the
resulting production will have single phase, while if different compositions of solution and
powder are used, multiphase composites will be produced.
Figure 15. Features of the nanocomposite processing technique. (Reproduced with permission from
[125] Zhu et al, Jpn J Appl Phys 2002; 41: 6969, Copyright The Physical Society of Japan 2002).
PZT ceramics have been reported to be prepared from the nanocomposite precursor at
much lower temperature than that required by the conventional ceramic process [125]. Fig. 16
shows representative SEM images of PZT ceramics derived from nanocomposite precursors.
Together with measured density results, it is found that fully dense PZT ceramics can be
achieved after sintering at a temperature of as low as 800C. Another interesting feature is
that no obvious grain growth is observed in the samples sintered at temperatures from 850C
to 1000C, which means that the grain growth was stopped at ~850C. The absence of grain
growth at high temperatures has been attributed to the uniform size distribution and non-
Synthesis and Applications of Nano-sizedFerroelectrics... 359
agglomeration of the nanocomposite precursors. This feature is particularly of interest if this
kind of precursor is used to fabricate multilayer structured devices in which small thickness of
single layer is required.
Figure 16. SEM images of the PZT ceramics derived from nanocomposite precursors sintered at
different temperatures: (a) 750C, (b) 800C, (c) 850C and (d) 950C for 2 h. (Reproduced with
permission from [125] Zhu et al, Jpn J Appl Phys 2002; 41: 6969, Copyright The Physical Society of
Japan 2002).
Figure 17. SEM images of thick film prepared from nanocomposite precursor: (a) and (b) cross-section
and (c) surface. (Reproduced with permission from [126], Wang et al, Mater Sci Eng B 2003; 99: 56,
Copyright Elsevier 2003).
Another significant progress is to use nanocomposite precursor to prepare thick films for
piezoelectric transducers [129-132]. Thick films with thickness of up to 25 m have been
readily prepared via multilayer deposition with one layer being ~2 m, which is nearly 50-
100 times the typical sol-gel solution process. An example is shown in Fig. 17 [126]. The film
is very uniform in thickness, with a dense microstructure and narrow distribution of grain
sizes (~100 nm). A well-developed P-E hysteresis loop is observed for the thick films, as
shown in Fig. 18 [126]. Compared with the thick films prepared using a precursor made of
L.B. Kong, Z. Xu and T.S. Zhang 360
microsized PZT powder, the nanocomposite film has a higher dielectric constant and a lower
loss tangent, which has been attributed to the factor that the latter has a dense microstructure
than the former. Such kind of composite thick films have been successfully combined with
silicon technology to fabricate MEMS piezoelectric devices. An example is shown in Fig. 19.
Figure 18. Representative P-E hysteresis loop of a 10-m PZT thick film. (Reproduced with permission
from [126], Wang et al, Mater Sci Eng B 2003; 99: 56, Copyright Elsevier 2003).
Figure 19. Continued on next page.
Synthesis and Applications of Nano-sizedFerroelectrics... 361
Figure 19. Structure of a membrane-type p-MUT fabricated on a silicon wafer: (a) schematic view, (b)
top profile image of a fabricated element, and (c) detailed cross section image of the membrane.
(Reproduced with permission from [130], Wang et al, Sens Actuat A 2006; 130-131: 485, Copyright
Elsevier 2006).
5.4. Nano-microcomposites
Similar approach has been also applied to barium strontium titanate (Ba
0.6
Sr
0.4
TiO
3
, or
BST) [133]. BST thick films and dense ceramics were obtained from a sol-gel solution mixed
with a combination of microsized and nanosized BST powders. Therefore, there is a slight
difference between the two kinds of composites. The use of microsized powder is to
compensate the shortage of nanosized components. A great reduction in annealing/sintering
temperature has been achieved in such a process. Microsized BST powders were prepared via
the conventional ceramic process, while nanosized powders (20-60 nm) were made from the
microsized ones using a high-energy ball milling with tungsten carbide media. BST sol-gel
solutions were prepared separately. Mixtures of the solutions and the microsized and
nanosized powders were made by a normal milling. The mixture can be directly used to
deposit thick films via spin-coating. By a simple calination at relatively low temperatures, the
powders can be used to prepare films via screen-printing and bulk materials through the
ceramic processing.
It has been reported that the films derived from microsized powder has a large number of
cracks, which is attributed to the presence of interstices among the BST particles [133]. With
the use of nanosized BST powder, dense and homogeneous films are obtained. Using
different electrodes (Ag or Pd-Ag), the annealing temperatures for the BST thick films can be
varied from 750C to 1200C. Generally, the electrical properties of BST films will increase
with increasing annealing temperature. Therefore, a tradeoff should be considered between
performance and cost. Nevertheless, this technique provides us with flexibilities in
fabrications of BST thick films. The electrical properties can be further improved by using
screen-printing method to prepare the BST films. At the same time, BST ceramics have been
obtained from the precursors at relatively lower temperatures than that required by the
conventional ceramic processing.
L.B. Kong, Z. Xu and T.S. Zhang 362
6. Summaries
High-energy mechanochemical activation has been shown to be a versatile and reliable
technique to synthesize various ferroelectric ceramic powders, especially those containing
lead (Pb). Direct production of ferroelectric materials via the high-energy mechanochemical
technique leads to nanosized powders, because the activation not only is able to trigger
chemical reactions but also suppresses the grain growth. Various ferroelectric and
antiferroelectric ceramics derived from the synthesized nanosized powders have relatively
lower sintering temperatures and possess better or similar dielectric, ferroelectric, pyroelectric
and piezoelectric properties. Ferroelectric ceramics, with promising microstructural and
electrical properties, can be fabricated not only from the synthesized powders, but also from
partially reacted or even unreacted mixtures activated by a high-energy ball milling.
The activation of high-energy milling to synthesize relaxor ferroelectrics reveals some
interesting aspects. For example, polycrystalline lead zinc niobate (PbZn
1/3
Zn
2/3
O
3
or PZN), a
low-temperature stable and high-temperature unstable phase, can never be synthesized via the
conventional solid-state reaction process. However, by using a high-energy shaker mill, single
phase PZN has been directly obtained from the oxide mixture, although PZN ceramics cannot
be prepared from the synthesized powder. According to the phase diagram of PZT, it is
confirmed that that the mechanochemical process is a low-temperature process. It is also
found that single phase lead iron niobate (PbFe
1/2
Nb
1/2
O
3
or PFN) can be formed from oxide
mixture via a mechanical activation, but high performance PFN ceramics can only be derived
from the columbite precursor of PbO and FeNbO
4
. Single phase lead iron tungstate
(PbFe
1/2
W
1/2
O
3
or PFW) can be synthesized neither from the oxide mixture of PbO, Fe
2
O
3
and WO
3
, nor from the mixture of PbO and Fe
2
WO
6
. It is only possible to produce PFW from
the combination of Pb
3
Fe
2
O
6
and WO
3
. PFW is also available when 0.4-mol-PFW was used
as seeds. Mechanochemical activation can be used to control the order-disorder status in some
relaxors.
Multilayer structured bismuth-containing ferroelectrics, belonging to the Arivillius
family, have been either directly synthesized from oxide/carbonate precursors via high-energy
milling techniques, or derived from amorphized precursor produced by post thermal
annealing at relatively low temperatures, compared to their counterparts prepared via the
conventional ceramic process.
The mechanism that governs the phase formation of ferroelectric materials via high-
energy mechanical milling process deserves further studies to clarify. The refinement of the
precursor constituents, the creation of defects and imperfections, localized temperatures or
pressures are all contributors the increase in reactivity of the starting materials. Significant
progress has been made in the synthesis of ferroelectric materials using the high-energy
mechanochemical process. Future studies should be focused on (i) systematically
investigating the effect of various processing parameters on the ferroelectric phase formation,
microstructure of the synthesized powders, as well as the microstructural and electrical
properties of the final ceramic products, (ii) developing mechanisms/models to account for
the phase evolution of ferroelectric compounds as a result of high-energy mechnaochemical
milling.
Examples have demonstrated that nanosized ferroelectric powders, produced by high-
energy mechanochemical synthesis or activation, can find interesting applications in
Synthesis and Applications of Nano-sizedFerroelectrics... 363
fabrications of thick films, nanocomposites and bulk ceramics. The hybrid nanocomposite
processing technique has well combined the advantages of both nanosized materials and sol-
gel process. Further works are necessary to explore more applications the materials
synthesized via the new technique.
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[133] Zhang H, Yao X, Zhang L. Microstructure and dielectric properties of barium
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 371-407 2010 Nova Science Publishers, Inc.
Chapter 11
PREPARATION AND CHARACTERIZATION
OF MONOATOMIC CARBON CHAINS: UNRAVELING,
FIELD ION MICROSCOPY, AND FIELD EMISSION
Igor M. Mikhailovskij
National Scientific Center Kharkov Institute of Physics and Technology,
Academicheskaja, 1, 61108 Kharkov, Ukraine
Abstract
Linear forms of carbon are important in a wide variety of application, ranging from highly
conducting interconnects to field emission materials. By methods of field ion microscopy
(FIM) and mass-spectrometry, it was revealed the presence of linear carbon chains at the
surface of carbon fibers after high-voltage treatment. We present in this chapter a brief review
of these research emphasizing recent developments. The carbon chains attached to the
specimen tips can be produced in situ in a field ion microscope using low-temperature pulsed
evaporation by electric fields of the order of 10
11
V/m. Atomic C-chains are produced during
the high-field unraveling of nanofibers. The experimental procedures used in FIM carbon
chains studies are reviewed and the results in relation to the atomistics of unraveling processes
are discussed. Molecular dynamics simulations and high resolution FIM experiments are
performed to assess the evaporation of atomic chains under high-field conditions. Carbon
exhibits a very rich dynamics of bond-breaking that allows transformation from graphenes to
atomic chains. High-field experiments, theories leading to carbon chain formation, and
methods to extract quantitative information on a variety of chain-surface interactions are
described in detail. Isolated atomic carbon chains can be obtained at different temperatures,
pulling speeds and forces. Current versus voltage field electron characteristics of monoatomic
carbon wires were investigated. These results lend strong support to the conjecture of Smalley
that linear carbon chains may provide the ultimate atomic-scale field emitters.
1. Introduction
The continuing miniaturization of nanoelectronics raises the prospect of nanometre-scale
devices with mechanical and electrical properties that are qualitatively different from those at
larger dimensions. At the moment one of the major challenges of the research on molecular
Igor M. Mikhailovskij 372
electronics is in connecting those nanodevices. Monoatomic chains and nanowires are viewed
as having great potential as interconnects in molecular electronics applications. The
fabrication of nanodevices using one-dimensional nanomaterials involves a new level of
complexity that must be accompanied by an atomic-level understanding of involved
processes. To develop realistic models of chain formation, it is necessary to determine
quantitatively the topological and energetic peculiarities of chains. Most early studies have
focused on metallic elements due to their capability to form nanowires by mechanical
stretching. Interest in this field has been risen by electron microscopy observation of
monoatomic gold chains with atomic resolution and by confirmation of the correlation
between quantum conductance and their atomic structure [1].
Triggered by these studies on gold, theoretical investigations have been expanded to
atomic chains of other elements, including nonmetals. Linear atomic chains of nonmetals are
of great interest as either free-standing objects, or components of nanoelectronic device.
Analysis of electronic structures of atomic chains reveals fundamentally and technologically
interesting phenomena, such as structural instabilities [2]. Their topology and electronic
structure may be controlled by charge doping gendered by the presence of an electrical
current or the chemical enviroment [3,4]. Carbon atomic chains

of various sizes have been
registered in stellar atmospheres, in comet tails, and in the interstellar space. The carbon chain
species, which had been discovered in the Universe, might be related to the carbon dust
blown out from the shell of carbon-rich red giant stars [5,6].
As far as terrestrial studies of carbon chains, the major motives are due to the unusual
electrical, optical and mechanical properties that result from the small sizes of these one-
dimensional materials. The understanding and functionalization of carbon atomic chains has
become a topic of great interest to the nanomaterials science and technology communities.
Monoatomic wires can sustain very large current densities, proving that the electron transport
is ballistic, and that most of the power is dissipated in the supporting electrodes far away from
the contact. This makes the atomic chains suitable for investigation as conductors in
molecular electronic circuits and it is crucial for the design and fabrication of the
nanodevices. The experimental studies and technological applications require advanced
techniques of production of carbon atomic chains. Those include chemical synthesis [7],
electric arc discharge between graphite electrodes submerged in a chemically inert liquid [8],
electric-field-induced unfolding [9], and by mechanical pulling [10-12] of carbon nanotubes.
In their paper, Rinzler et al. [9] showed that field electron emission from individual
carbon nanotubes (CNTs) has been enhanced when the nanotube apexes are opened by laser
evaporation. After considering several alternative explanations, authors concluded that the
sharp emitting element is a linear chain of 10 to 100 carbon atoms pulled out from the open
CNT by the high electric field in a manner that resembles unraveling the sleeve of a sweater.
In these experiments, carbon chains were pulled out with no net decrease in effective bond
order. Free-standing linear carbon chains pulled out from the open CNT are held taut under
the action of the high electric field. The carbon chain at the point of attachment to the CNT is
bonded to the delocalized -orbitals of the CNT outer shell, this carbon system is both
mechanically and electrically well coupled. Free-standing multi-wall nanotubes have been
demonstrated to emit field electron current of up to several microamperes. Based on obtained
results, Rinzler et al. conjecture that such a large current originate from atomically sharp
structures and these structures may provide the ultimate atomic-scale field emitters. There
was no information available about the detailed disintegration mechanism or about the
Preparation and Characterization of Monoatomic Carbon Chains 373
threshold field strength needed for a CNT to unfold. The viability of the exotic unraveling
mechanism was verified by Yacobson et al. [10] in molecular-dynamics simulations of CNT
deformation, although used many-body interatomic potentials may not be fully reliable for
one-dimensional structures. The plausibility of occasional formation of carbon atomic chains
during plastic deformation of CNTs was revealed in these computer experiments. Despite its
probabilistic character of formation, once a carbon chain is pulled it remains very stable.
Various theoretical approaches used to the unraveling model were discussed, proceeding from
simple pair-potential calculations to sophisticated, first-principles calculations. It was shown
that that CNTs undergo a process of necking and some of the tubes deform into a single chain
configuration, spanning the nanotube fragments before fracture [11,12].
Yuzvinsky at al., [13] have demonstrated a method to controllably shrink CNTs to any
diameter. The method uses high-energy electrons from a transmission electron microscope to
knock carbon atoms out of the nanotube while monitoring the changing CNT geometry in real
time. The high temperatures attained through resistive heating assist a self-healing annealing
and electromigration, resulting in a smaller CNT with perfect atomic structure. As the
diameter of a multiwalled CNT decreases below 1 nm, the inner wall breaks and endcaps
form on both ends of the CNT connected by a very thin bridge. The conductance of the
nanotube device is determined mostly by the size of its narrowest cross-section and that,
during the modification of CNT, all important structural and topographic transformations are
localized to the neck region. The thinnest section of the nanobridge cannot be imaged in high-
resolution TEM but it is likely that the bridge had a carbon-chain-like structure. This
conclusion was confirmed by a subtle conductance measurement. Authors found that the total
conductance of the CNT device with a narrow neck is linearly proportional to its cross
sectional area. During the last stage of the shrinking process, conductance stays in a limited
range of values corresponding to one atom in cross-section. In this regime, the CNT device
exhibits negative differential resistance at both negative and positive bias of a fraction of a
volt. Theoretical investigations showed that such a behavior of the bridged nanotube junction
at the end of the shrinking process is typical of the monoatomic chain regime [14].
The possibility of creating carbon chains in high electric fields was confirmed by the
theoretical investigation using ab initio density functional formalism [15,16]. Linear carbon
chains with more than ten atoms are thermodynamically less favorable than ring isomers,
except for a C
6
chain, which has degenerate linear and ring isomers in zero electric field.
However, the linear chains are stabilized by the application of an external electric field
relative to rings due to the preferential field-induced polarization for the linear chains [17].
Due to the polarization effect, the high external electric field can assist the extension of an
atomic wire unraveled from the open edge of a graphene layer.
Even though the unraveling mechanism is very appealing and promising, it has not been
conformed by independent atomic-scale experiments till recently. Combined field ion and
electron microscopy and mass-spectrometry have just now revealed the presence of linear
carbon chains at the carbon surface treated by electric fields of the order of 10
11
V/m [18,19].
The linear chains attached to the of sharpened carbon fibers consisting of more than ten atoms
can be produced in situ in a field emission microscope during low-temperature field
evaporation. The key findings of these works are the mechanical stability of the chains
emanating from graphite in ultra-high electric fields and that linear carbon chains may
provide the ultimate atomic-scale field emitters. This chapter ties together several aspects of
Igor M. Mikhailovskij 374
recent research on carbon atomic chains and techniques used, focusing on a high-field
technology, high-resolution microscopy, field emission, and molecular dynamics simulation.
2. Techniques and Instrumentations
Although recent advances in experimental and theoretical methods yield detailed
information on structure of nanomaterials, an essential part of our current atomic-scale
understanding of atomic processes at surfaces of nanomaterials in a high electric field has
come from investigations with the field ion microscope (FIM), an instrument invited in the
early 1950s. The unique attributes of this technique allow one to view an individual atom and
track its motion as it moves across a well-defined specimen surface. A comprehensive review
of the technique of field ion microscopy is beyond the scope of this book. For more
information on the basic principles of field ion microscopy, the reader is referred to several
review articles and books [20-22]. Only a brief overview of field ion microscopy is given here
to provide a basis for the succeeding discussion of atomic chain studies.
The FIM presents images of the protruding atoms at the apex of a sharp needle,
chemically or electrochemically polished to a sharp point. The needle-shaped specimen is
attached to a cryostat and a high voltage supply. FIM specimens are similar to the tips in
scanning tunneling microscopy [20]. However, instead of using the tip to scan the specimen
surface, the tip itself is studied in the FIM. An image of the atoms at the tip apex is obtained
in the FIM after being evacuated to ultra-high vacuum by applying a high positive voltage in
the presence of an image gas such as neon or helium. These gases were chosen because of
their lack of chemical reactivity and their ability to be purified. A high voltage applied to the
sharply pointed sample produces an extremely high and inhomogeneous electric field, of the
order of several volts per . The voltage required is proportional to the end radius the tip and
is typically 2-30 kV. Image gas atoms are polarized by the inhomogeneous electric field and
draw towards the apex of the specimen. Gas atoms will hop around the specimen apex until
they either escape to the free space or are field ionized a few above the surface and
accelerates them toward an imaging detector in the radial direction of the tip hemisphere.
Image contrast results from the field strength being higher at the position of protruding
surface atoms. The magnification of the field ion microscope is dependent on the tip-to-
detector distance and typically is of the order of a million times. The resolution is a function
of several factors including the sample temperature. At cryogenic temperatures (77 K or
below) the resolution may approach of 2 and it is sufficient to identify individual atoms.
The precision with which the relative positions of individual atoms can be measured is better
then the nominal resolution and approaches 0.3 . A better resolution (~0.1 ) may be
achieved normal to the specimen surface using the indirect magnification phenomenon [20].
If the field strength is raised to a sufficiently high value, the most prominent surface atoms
are themselves ionized and removed by the electric field. As a result, the clean uniform
hemispherical end-form is produced. Such a cleaning process is unique to field ion
microscopy and is known as field evaporation. In the region of the low-index planes, field
evaporation removes atoms from the edge of the plane inwards, one atomic layer at the time.
For stable operation of the FIM, it is necessary that the field strength required for evaporation
of the specimen should exceed that required for field ionization.
Preparation and Characterization of Monoatomic Carbon Chains 375
Specimen tips having an initial radius of curvature at the tip in the range 20-50 nm were
prepared from carbon polyacrylonitrile-based fibers by the electrochemical etching in a 3N
KOH solution. Carbon fibers, which have a cross-sectional size of 7-10 m and an average
strength of 3-5 GPa, are composed of nanofibrils, the average size of which varies between 50
and 200 nm. In addition to optical control the specimens during the course of electrochemical
polishing, the tip topographies were examined using the transmission electron microscope
(TEM) employing a goniometric tilt device and high-resolution scanning electron microscope
SEM Germini 1540 (FIB) with the resolution of 0.5 and 0.7 nm, accordingly.
Experiments were made in a field ion microscope (FIM) in which the samples were
cooled to 4.2, 21 and 77 K [23,24]. The microscope was evacuated by cryogenic pumps to a
residual gas pressure of about 10
-7
Pa. Field ion and electron images were normally obtained
in a voltage range 1-22 kV. Field ion images were formed by using helium gas under a
pressure of 10
-4
10
-3
Pa. After sample mounting in the microscope, the surface was polished
by low temperature field evaporation [21] until the formation of an atomically smooth
hemispherical tip with a radius of curvature in the interval 3070 nm. Field evaporation
spectra of needle-shaped samples were determined by using the mass-spectroscopic add-on
device. Evaporation of ions subjected to mass-analysis was implemented by a high-voltage
pulse generator with the front steepness of 20 ns and pulse duration of 10 ns at a level of 0.8
the amplitude. The voltage pulse amplitude was varied from 0.5 to 7 kV. A total voltage of 1-
22 kV was applied between the specimen tip and the entrance aperture of a straight drift tube
1.50 m long. The signals generated by individual ions or ionized clusters of atoms after the
flight through the drift tube were detected by the chevron channel plate multiplier, and fed to
the input of the timer. Field evaporation occurred under the action of the total voltage (a
constant voltage required for the formation of the field ion image and a pulse voltage).
Field-evaporation spectra in AP FIM are usually analyzed from the number of individual
ion signals detected for different ion species. Since the time digitizer used with the chevron
channel plate cannot discriminate signals according to the output pulse height, the ions with
the same mass-to-charge ratio, which arrive simultaneously at the detector, are counted as
only one signal. This problem is generally alleviated by operating the atom-probe at a very
low counting rate. In this regime, the probability of pulse overlap becomes small, and the ion
spectra derived should be accurate. But a preliminary study of the field evaporation of carbon
specimens showed that this process is very irregular at low temperatures. A miss-counting of
the simultaneously arriving ion signals cannot be eliminated even if the average evaporation
rate of the carbon specimens is reduced below 0.01 atom/pulse. Usual time measuring devices
were not convenient in this case, and the flight times of the ions were measured with an
oscilloscope. A high voltage pulse removed the surface atoms in a form of singly or multiply-
charged ion clusters and activated a time sweep oscillator. The signal voltage increased
proportionally to the number of the ions or ionized clusters with the same mass-to-charge
ratio, therefore the field evaporation spectra could be derived from the signal intensities
measured for various ion species.
The field F
0
at the apex of a field ion specimen is reduced from the equivalent value at
the surface of a free conducting sphere by the presence of the shank and can be expressed as
0
0
0
r k
V
F
f
= (1)
Igor M. Mikhailovskij 376
where V
0
is the applied potential, r
0
is the apex radius and k
f
(the geometric field factor) is a
numerical constant which depends on the taper angle of specimen, but has an approximate
value of 5. A usual for this method accuracy is 15%. More precise electric field calibration
is based on the comparison with the best image field and voltage in the FIM operated with
helium, hydrogen or nitrogen. The best image conditions are correspondent to the sharpest ion
patterns with the best spatial resolution and contrast. The best image fields for He, H
2
and N
2
within 5% accuracy are 4.410
10
, 2.210
10
and 1.710
10
V/m, respectively [21]. Some control
measurements of the field strength was made by the conventional method based on the
validity of the Fowler-Nordheim (FN) equation for field electron emission with a usual for
this method accuracy of 15%.
Field ion microscopic images of carbon samples were analyzed by using the geometrical
method of computer simulation of the images [20,21]. In the approximation of the model of
thin envelope, it was assumed that the contribution to the formation of the ion-microscopic
image comes from atoms located in a surface layer of a certain finite thickness.
3. Cluster Formation during Field Evaporation
The potential technological benefits to be gained from a fundamental understanding of
cluster formation have stimulated considerable research in recent years, both experimental
and theoretical. There are plenty of subjects of scientific interest, such as binding energies of
atoms in clusters, critical and magic numbers, ionization energies, topology of clusters,
electronic energy levels, ets. It is usually guessed that carbon chains are produced during the
vapor cooling process [25, 26]. The evaporation of individual atoms and their aggregation
into clusters during low-temperature field evaporation are among the most fundamental
atomic interactions. Several aspects in carbon cluster science can be investigated using low-
temperature pulsed-voltage field evaporation. In pulse field evaporation of carbon, clusters
produced are ever charged and are accelerated at once in a high electric field and so after the
cluster formation it no longer have any chance to interact with other clusters and atoms.
Therefore, the abundance of cluster mass represents how carbon clusters are formed at the
surface, the binding mechanism of clusters, and the absolute stability of the carbon species.
During field evaporation of metals, ions formed are almost always monoatomic ions
[21,22]. Carbon cluster ions were found in low-temperature [27] and pulsed-laser-stimulated
[28] field evaporation. Mass spectra of graphite tips were obtained with a pulsed-laser time-
of-flight atom probe with subnanosecond time resolution. When laser pulses were focused to
the tip apex, a temperature rise of about 1000 K could be achieved. It was found that under an
electric field strength of 20 - 30 V/nm and a temperature above 1000 K, carbon atoms were
field evaporated generally as C
++
and C
+
ions but with about 10 20 % of cluster ions of
various sizes and charge states. Cluster ions up to about 11 atoms were detected. The number
of cluster ions decreases exponentially with increasing of cluster size. Clusters with an even
number of atoms are less abundant than clusters with an odd number of atoms. Authors [28]
established the existence of very large high-energy tails extending to about 350 V and it was
supposed that some of carbon clusters were ejected out the specimen surface with a large
initial kinetic energy. This result was explained by a strong photoexcitation effect in pulsed-
laser stimulated field evaporation. Up to now there is neither a detailed explanation nor a
comprehensive experimental study of this phenomenon. Analysis of the energy distribution in
Preparation and Characterization of Monoatomic Carbon Chains 377
the time-of-flight spectra of low-temperature field evaporation of graphite [27] revealed that
the registered charged clusters were not occurred right at the surface but were produced by
dissociation within the acceleration region into several particles. The dissociation products are
separately accelerated, until they reach the field-free region. As a result C
n
clusters exhibit
broadened energy distribution with both low and high energy tails. A mathematical treatment
of obtained results showed that the carbon clusters were dissociated at a distance of 30 to 300
nm away from the specimen apex, which is reached within a travel time from 0.6 to 6 ps.
The process of low-temperature field evaporation at the pulse voltage loading occurs
sporadically with an anomaly large instant intensity of evaporation corresponding to
explosive rate of about 1

10 m/s. Under an averaged electric field of about (7-8) 10
9
V/nm
carbon atoms are field evaporated mostly as C
n
+
clusters with n = 2-6. A typical scan
illustrating the cluster-wise field evaporation of the needle-shaped carbon nanofiber is shown
in Figure 1. This time-of-flight mass spectrum is obtained at a low level of the signal voltage
amplification, which precludes from the possibility to detect single ions. The height of steps
at the oscillogram is proportional to the number of the clusters with the same mass-to-charge
ratio. Taking into account this fact we showed that the maximum of carbon atoms registered
by the detector is about of 10
3
atoms/pulse at the average evaporation rate of the carbon
specimens of about 1 atom/pulse. Consequently, these results confirm our preliminary
conclusion about significant irregularity of the field evaporation process for carbon specimens
at low temperatures. This process was controlled by using the TEM with the resolution of
0.5 nm. It was shown that explosive field evaporation is accompanied by significant blunting
and smoothing of the needle-shaped carbon specimens (Figure 2).
Figure 1. Field evaporation mass spectrum of carbon nanofibers at 77 K.
In the mass-spectroscopic mode, it was possible to determine the abundance of carbon
clusters produced by field evaporation of graphite specimens at 77 K. Each set of mass-
spectroscopic data contained about 10
4
ions which were collected from a probe hole of the
area covering about ten atomic diameters at the specimen surface. Singly charged carbon
clusters of up to 7 atoms are observed under pulse field evaporation of graphite fibers at
cryogenic temperature (table 1). The number of clusters with odd carbon atoms is
significantly larger than that with an even number of atoms. The intensity of C
3
+
peak in the
mass spectra was prominently strong, indicating either a preferred formation or a high
stability of the chains C
3
+
. An anomaly abundance of the clusters C
3
may be explained also by
field-induced fragmentation of larger molecules. Really, for clusters with six or more atoms
the dominant fragmentation channel is the loss of C
3
to give C
n-3
clusters [29].
Igor M. Mikhailovskij 378
Table 1. Relative abundance of field evaporated carbon ions
Ion C C
2
C
3
C
4
C
5
C
6
C
7
Scaled abundance 0.84 0.24 1.00 0.09 0.58 0.06 0.08
An observed abrupt disappearance of the FIM image spots is readily understood as field
evaporation of C
3
+
and other small charged radicals from the end part of the chain until this
chain is so small that the electric field enhancement factor is no longer sufficient to produce
field ionization of helium atoms.
Experimental results and theoretical calculations ranging from sophisticated, first-
principles approaches are now able to provide insight concerning the underlying physics
involved in cluster nucleation and stability. The numbers of atoms in clusters produced by
pulse field evaporation are much smaller as they are formed by vaporizing with a laser or an
ion beam a graphite target [30]. The magic carbon cluster ions produced by desorption under
a high electric field were also observed in field evaporation spectra of single-walled and
multi-walled nanotubes in experiments of Hata et al. [31].
The spectral width is not due to a degradation of time-of-flight spectrum caused by
neither in the initial kinetic energy of clusters nor by the space charge screening. The space-
charge effect is also negligible because the ion current density of our measurement amounts
to less then 1% of the saturation limit caused by the space charge [32]. Since the wide spectral
width is not caused by extrinsic effects, it has to come from disintegration of evaporated
carbon clusters within the period of acceleration in the AP FIM.
4. Field Ion Microscopy of Carbon Chains
As was shown in [18,19], graphite specimens are mechanically stable in the field-ion
microscope and can withstand the evaporation field and imaging field strength of helium,
which is about 4.510
9
V/nm. Field evaporation in the field ion microscope was accompanied
by a dramatic blunting of the needle-shaped carbon specimens. SEM and TEM observations
showed that the specimens having initial radii of curvature r
0
in the range 20-50 nm were
blunted up to r
0
= 200-1000 nm in these conditions. Figures 2(a) and (b) show the electron
shadowgraph and top-view SEM image of the carbon specimen formed by field evaporation
(a) (b)
Figure 2. Electron microscope shadowgraph (a) and top-view SEM (b) images of a typical carbon tip
after low-temperature field evaporation. (Reprinted with permission from [18]. 2007, Institute of
Physics.)
Preparation and Characterization of Monoatomic Carbon Chains 379
Figure 3. FIM image of a carbon tip after low-temperature field evaporation at 6.60 kV.
during a steep (~ 1 V/s) increase of voltage V up to 6.60 kV. Examination of such
micrographs shows that the apex part of specimens is more or less spherical without sharp
edges and nanoprotrusions which would give rise to field enhancement and would show up
by locally intensified field emission.
Figure 3 shows the FIM image of the specimen formed by low-temperature field
evaporation at 6.60 kV in ions of helium. As one can see in Figure 3 unlike metallic tips in
high electric fields, hemispherical surface formed by field evaporation is microscopically
rough. Its FIM image is the carbon characterized by an irregular distribution of image points.
This type of FIM contrast is correspondent to the random character of the low-temperature
field evaporation of carbon materials. During a field increase, the brightness of the image
spots enhances. The FIM images reveal the process of long-range jumps of image spots at
some stage in the voltage increase [19]. The main attribute of the FIM for the investigation of
an atomic topography is its ability to reveal the location of atomic protrusions on a surface
formed by field evaporation. Such protrusions are characterized by an enhancement in the
local electric field. Due to the nature of the image formation process, these local field
enhancements produce high-contrast image spots on a uniformly dark background. The
observation of long jumps of bright FIM image spots during a high-field treatment points out
that in this case a local field enhancement at bright image spots is not due to a sharp
microprotrusion on the graphite tips.
FIM images of carbon samples were analyzed by using Moores geometrical model of
mathematical simulation [20,21]. Most features of FIM image contrast can be usually
understood on the basis of this consideration. The main attribute of the FIM for the structure
investigations is its ability to reveal the location of the isolated atom on a perfectly defined
single-crystal terrace. Individual atoms typically protrude from the surface by a sufficient
amount to cause an enhancement in the local electric field. Due to the nature of the image
formation process, these local field enhancements produce high-contrast image spots on a
uniformly dark background. In the approximation of the thin shell model, it was assumed
that the atoms which give contribution to image spots are located in a surface layer of a
certain finite thickness
M
, typically 20-40 pm. The atoms lying at a greater depth will not
field ionize enough gas atoms to form FIM image spots. It is important that the overall shape
of the tip surface is usually assumed to be spherical and atomically smooth. In a spherical
model, the shell has a constant, single value for the radius of curvature. The FIM image can
Igor M. Mikhailovskij 380
be simulated by projecting the atoms in a thin shell onto a plane located at a specified
distance from the specimen apex.
A comparison of field ion micrographs of pure metals with shell model simulations
usually illustrates a good matching in spite of fact that the model does not account for
possible effects due to chemical bonds. However, in case of graphite the situation is entirely
different. The process of regular field evaporation of graphite tip is illustrated in Figure 4
which shows computer simulated FIM images. The image plane is parallel to graphite layers.
Parameters of the model in units of the interatomic separation a: the radius of curvature r
0
=
500 a, the thickness of the imaged shell
M
=0.04 a, the radius of the FIM image of 200 a.
The decrease in diameter of the central atomic plane from Figure 4(a) to 4(b) indicates that
atoms are removed from the surface during field evaporation.
(a) (b)
Figure 4. Computer simulated FIM images of the atomically smooth graphite specimen formed by low-
temperature field evaporation: (a) immediately after removal of the previous atomic layer and (b) after
formation of an atomic island at the center of the specimen (courtesy of V.A. Ksenofontov).
When metal tips are viewed in real time, a continuous series of collapsing rings are
observed. Each time a ring collapses, one atomic layer is removed, leaving behind a surface
smooth on an atomic scale. From comparison of real FIM images of carbon tips (Figure 3)
with that obtained by computer simulations (Figure 4) it is clearly evident that FIM images
are characterized by an irregularly distribution of image spots. It points out that low-
temperature field evaporation can not produce an atomically smooth surface of carbon tips.
The mesoscopic field F at the apex of a field emission specimen is determined by Eqn.
(1). For the specimen shown in figures 2 and 3 V = 6.60 kV and r
0
= 297 nm, the averaged
field is 4.4410
9
V/m. This value is orders of magnitude lower than theoretical ones for low-
temperature field evaporation (10.310
10
V/m) and the best image field for field ion
microscopy (4.4010
10
V/m) [21]. However, it was revealed that this mesoscopic field
required for low-temperature field evaporation of the carbon specimen exceeded that required
to produce the helium field ion image (Figure 3). Taking into account ultra-high vacuum
conditions and preliminarily cleaning the surface of the tips by field desorption and
evaporation, we are confident that the localized emitting structures are not produced by
Preparation and Characterization of Monoatomic Carbon Chains 381
chemisorption. One can arrive at a conclusion that there are the protrusions of a
subnanometric thickness on the surface of the carbon tips invisible in the electron microscope.
These ultrathin protrusions (nanowires) can provide areas for which the local field strength is
much greater than that calculated for perfectly smooth needle-shaped specimens. The field-
enhancement factor is about 10 or more. An analogous result was obtained by Rinzler et al.
[9] in laser-beam studies on field emission from carbon nanotubes. Their results have been
interpreted in terms of nanometric all-carbon atomic wires on an open-ended nanotube. The
carbon atomic wires connected to the edges of graphene sheets are likely to experience very
high electric field due to their high aspect ratio.
5. The Field Enhancement Factor for Linear Atomic Chains
5.1. The Linear Chain on the Tip
Careful examination in TEM did not reveal protrusions, which could be characterized by
such a high field-enhancement factor (Figure 2). We suggested above that the field
enhancement is caused by invisible in the scanning electron microscope objects with
dimensions below the resolution limit of used TEM. The most available candidate for such a
high field-enhancement factor is the normal to surface atomic C-chains with a high aspect ratio.
We used the analytical model to calculate the field-enhancement factor for the single carbon
chain on the needle-shaped electrode, described. It is supposed that the chain located normally
on the parabolic electrode, having a cylindrical shape of height L and closed with a
hemispherical cap with the radius . The bond length structures of C-wires are essentially
cumulenic with only a small dimerization with bond lengths between 1.27 and 1.29 [33]. So
for appraisal the use of a constant interatomic distance d = 1.28 is satisfactorily accurate. The
length of carbon chains C
n
can be estimated as ( ) 1 10 28 . 1
10
=

n L . The carbon atomic
chain can be considered as a conducting cylinder with the radius = 1.2 [34].
5.1.1. The Model for the Electric Field
Field-induced charges are exiting near the end of the atomic carbon chain. Therefore, the
hemisphere cap and the cylinder under the cap can be replaced by two charges and dipoles
taking into account the image forces at the conductor surface [35]. The contribution of the
needle-shaped carbon specimen can be estimated using a model of the field ion emitter
approximation by equipotential surfaces for a point charge situated at the end of a uniformly
charged filament [36]. The potential around the hemispherical end of the chain on the surface
of a needle-shaped specimen with the radius of the apex equal to r
0
can be expressed at an
arbitrary point (x,y) as
( )
( ) [ ] ( ) ( )
( )
( ) [ ]

+ +
+

+
+

+
+ +
=
2 / 3
2 2
2
2 / 3
2 2
2
2 / 1
2 2
2 / 1
2 2
0
2
2
2
1
2
1
2
,
L y x
L y
y x
y
L
y x
L
L
L y x
L
F y x


( ) [ ]
C
r
L r y x
Ln r F +

+ + +
+
0
2 / 1
2
0
2
0 0
, (2)
Igor M. Mikhailovskij 382
Where F
0
is the external field at the needle-shaped specimen, C is the constant potential
and the carbon chain is oriented along the x-axis. The surface of the chain and carbon tip
constitute an equipotential surface (x,y)= 0. Figure 5 shows the calculated potential
distribution in the vicinity of nanowire on the parabolic specimen formed by field evaporation
at +15.0 kV.
-15 -10 -5 0 5 10 15
-5
0
5
10
15


z
,

C
x, C
14
17
20
23
4
0
8
11
Figure 5. Equipotential lines for a terminating C-wire on the paraboloidal electrode. The atomic wire is
at 0 V.
The equipotential lines are bent around the carbon nanowire producing, as expected, an
enhancement of the applied electric field. Figure 6 gives our calculated field-enhancement
factor as a function of aspect ratio L/. We have performed such calculations for several
radii r
0
of the paraboloidal electrode and obtained nearly the same results. The only quantity
that matter in this problem is the ratio L/.
10 20 30 40
0
10
20
30
40
50

L/
Figure 6. Field-enhancement factor for atomic chain on the tip as a function of aspect ratio L/.
Preparation and Characterization of Monoatomic Carbon Chains 383
In fact at r
0
>> we obtained by fitting within an error of 2 % the following empirical
formula for the field-enhancement factor at the end of carbon chain on the needle-shaped
electrode:
/ 4 . 3 L + . (3)
By using this formula, we showed that observed values of a local field strength can be
obtained at the open end of C
n
-chains with n = 10-12.
5.1.2. The Local Magnification of FIM Images
The number of atoms in the linear chain can be obtained by an independent comparison
of experimental and theoretical values of local magnifications [21] for field-ion images.
Determination of the ion and electron trajectories is an essential aspect when interpreting
results from experiments with the field ion microscopy and field electron emitters. When a
nanoprotrusion is on the top of a conventional needle-shaped FIM specimen, the half-width
angle of the divergent beam is reduced by factor of ten. This effect is a result of a self-
focusing process caused by the changed configuration of the electric field in the close vicinity
of the sample. Conducting line chains distort and compress the equipotentials in their vicinity.
This gives rise to local field enhancement and increased magnification. The resultant
magnification will exceed that of the supporting tip but will not correspond to the radius of
the chain because of a strong compression factor.
The behaviour of ion trajectories in the FIM has been treated analytically, for a general
field which is symmetric about the main x-axis of the microscope [21]. The ion paths are not
only independent of the mass and charge of the ion, but also of applied voltage, being wholly
a function of the field distribution, which is controlled by specimen and counter electrode
geometry. The locations of the image spots corresponding to individual surface atoms are
identical for hydrogen, helium or any other image gas. The image of a given specimen is also
completely unaffected by raising or lowering the applied voltage, provided that the geometry
of the specimen end-form remains unchanged. The calculations show that the effect of the
specimen shank is to introduce some degree of curvature into the trajectories, compressing
them towards the axis of the microscope. The comparison of the electric lines and the ion
trajectories in a region close to the specimen apex showed that the ion trajectories do not bend
as sharply as the electric field lines since the ions acquire kinetic energy near the specimen
surface. Field evaporated ions are formed right at the surface and imaging gas atoms are
ionized at the critical distance away from the surface. Therefore, the trajectory of the field
ionized gas atoms is not the same as that of field evaporated carbon ions. In the idealized case
where the specimen and screen of the FIM consisted of two concentric spheres, the
trajectories of ions would be straight lines normal to the specimen surface and the
magnification of the image M would be given simply by the ratio of the specimen-to-screen
distance R to the apex radius of the specimen r
0
.
Most of the difficulties in determining a local magnification arise from the necessity of an
adequate model for the electric field in the vicinity of the wire and for the overall shape of the
needle-shaped tip, which, in general, does not coincide with analytical model. Since the
image size should be independent of length for a long wire this effect must arise from the
Igor M. Mikhailovskij 384
influence of the needle-shaped substrate on the potential distribution near the tip of wire. It
can be seen that an image compression must result from the finite length of the atomic wire.
This problem was solved by analytical methods with minor simplifications only for the
particular case of a hemisphere on the emitting tip [21,37]. It was shown that resolution and
magnification for small protrusions on the surface of tip are much greater then that calculated
for a perfectly smooth tip. An approximate solution was developed by Rose [37] for the
special case of a small hemispherical protrusion of radius r
p
, at the apex of a paraboloidal
specimen of end-radius r
0
. The overall magnification of the protrusion M', is given by
M
r
r
M
p
0
1 . 1 ' , (4)
where M is the conventional magnification of the image (without microprotrusion). One
consequence of this local magnification effect is that the apparent size of, for example, a
precipitate particle in an FIM image may differ from its true size.
We calculated the magnification for ions, originating from a point at the end of a
nanowire (figure 5), based on numerical calculations of the equation of motion in an electric
field determined by Eqn. (2) from a starting position, where the ion is assumed to be at rest.
For the case of the single carbon chain on the needle-shaped electrode (figure 5), we obtained
the semiempirical expression for the local magnification M :

H
r
L
M
0
6 . 1 , (5)
where r
0
is the radius of the paraboloidal tip, H is the interelectrode distance. One
consequence of this local magnification effect is that the apparent size of a nanosized object
in an FIM image may differ from its true size. This expression was used for an independent
determination of the average wire length and was shown again that in our experiments n was
of order of 10.
5.2. Multistage Nanostructures
In the special case (often realized) of multistage emitters [38], the field enhancement
factor can be defined as
= F/F
M ,
(6)
where F is a local field and F
M
is the macroscopic field defined as F
M
= V/D. Here D is the
interelectrode distance in geometrical configuration resembling a parallel-plate capacitor. In
our experiments a voltage corresponding to the threshold of low temperature field evaporation
ranged from 2.5 to 22 kV was applied on the electrodes with D of about 5 mm. As was shown
above, low temperature field evaporation of carbon takes place at electric field strength F of
about 70-80 V/nm. Consequently, one can obtain the calculated value of the field-
Preparation and Characterization of Monoatomic Carbon Chains 385
enhancement factor in the range of 1.5910
4
< < 1.3310
5
. The extremely large field-
enhancement factors have been reported previously from field electron emission
measurements made over large areas and individual tips [38-40] Huang et al. [38] showed
that a giant field-enhancement factor (up to 1.8810
4
) is a result of a multistage structure of
the nanoemitters.

Their structure is characterized by an order of magnitude smaller features
(nanotubes or nanowires), growing at the tips of larger features. A multistage structure, with
each stage much smaller than the previous one is characterized by the total field-enhancement
factor at the tip of the smallest feature given by

=
=
m
i
i tot
1

, (7)
where m is the total number of stages, i is the stage index. The experimental value of the total
field-enhancement factor for one of typical specimens formed by evaporation at electric field
F
ev
= 754 V/nm can be found from
V
D F
ev
tot
= . (8)
By using the value of D equal to 50.5 mm, we obtain the experimental value

tot
= 6.4710
4
.
The value of
1
is correspondent to the mesoscopic field-enhancement factor at the apex
of carbon needle-shaped emitters. The electric field and potential distribution between such a
tip and a counter-electrode can be considered in terms of the hyperboloidal model [21]. In this
approximation, the tip and counter-electrode are represented by two confocal hyperboloids of
revolution. A local field F at the tip surface is a logarithmic function of the radius of
curvature and D. Taking r
0
to be the radius of curvature at the specimen apex, simple
transforms of the equation for F yielded the following expression for the mesoscopic field-
enhancement factor in the hyperboloidal approximation:

=
0
0
1
4
2
r
D
Ln r
D
. (9)
Thus, from equation (9) for the specimen under consideration, the mesoscopic field-
enhancement factor is equal to 3.5410
3
and
1
<<
tot
. Such a discrepancy shows that the
carbon specimen formed by field evaporation has a multistage structure and a local electric
field is determined to a considerable degree by smaller topographic features.
A certain contribution to
tot
is introduced by an additional enhancement of the local field
in the vicinity of the nanoscale undulations. But it is intuitively clear that observed
nanoprotrusions with low aspect ratios can not responsible for a high discrepancy of the
experimental and theoretical field-enhancement factors. To our knowledge the field-
enhancement factors were calculated only for protrusions with high ratios of the total
Igor M. Mikhailovskij 386
protrusion length to the radius ( = L/ 1). In this range of the ratio two analytical models
give satisfactory results: the hemisphere on the plane model and the hemisphere on a post
model [35 and references therein].
In terms of the hemisphere on the plane model the potential at the sphere surface is given
by a superposition of the field of a dipole of strength
M
F p
3
0
4 = located at the centre of
a hemisphere of radius and a planar charge sheet of density
0
F
M
where
0
is the electric
constant:

Cos rF
r
p
M
o
+ =
2
4
cos
. (10)
There (r, ) denote the spherical coordinates with the origin in the sphere center. The
total potential at any point on the hemisphere surface is zero: the emitter plane and the
hemisphere boss surface constitute an equipotential with = 0. Figure 7 shows the calculated
potential distribution in the vicinity of the hemisphere on a plane. The equipotential lines are
bent around the hemisphere producing an enhancement of the applied electric field. This data
can be used for a determination of the field-enhancement factor for smooth protrusions with
< 1. To pursue this object, we calculated a family of equipotentials such that one coincides
with the protrusion surface and one with the counter-electrode. Such a representation for
rather short nanoprotrusions was given in Cartesian coordinates (x, y).
-6 -4 -2 0 2 4 6
-1
0
1
2
3
4

y
x
0
1
3
5
Figure 7. Equipotential lines generated by the hemisphere on a plane. The numbers near the
equipotentials denote the potential in volts.
It was found that the geometry of a typical nanoprotrusion could be fitted accurately by
one equipotential surface from the set surrounding a charged body which consisted of an
isolated hemisphere on the plane. Figure 8 illustrates this possibility for an approximation of
one of rather short nanoprotrusions on the specimen with = 0.24. The surface of the
nanoprotrusion coincides with an equipotential surface of value (x, y) = 4 V.
Preparation and Characterization of Monoatomic Carbon Chains 387
a
b
5 nm
Figure 8. Electron microscope image (a) of the nanoprotrusion on the carbon tip formed by field
evaporation and its electrostatic approximation (b). For the matching equipotential (x, y) = 4 V.
(Reprinted with permission from [19]. 2007, Institute of Physics.)
Figure 9 (curve 1) gives the nanoscopic field-enhancement factor
2
obtained from
equation (10) as a function of aspect ratio for < 1. For < 1, the values of were
determined at the apex of the matching equipotentials. The field enhancement was obtained
from equation (10) using the gradient of at the apex equipotentials. It demonstrates the well-
known exact result that the local field enhancement factor at the hemisphere apex ( 0) is
3. In the range 0.01 1 the factor is represented, to within 4 %, by
2
2
49 . 0 30 . 2 19 . 1 + = . (11)
In the vicinity of = 1 our results are very close to that for > 1 (curve 2 in figure 9)
represented by the approximation [35]
( )
90 . 0
15 . 2 2 . 1 + =
P
, (12)
obtained for the hemisphere on a post model.
0 1 2 3
1
2
3
4
5

L/
1
2
Figure 9. The field enhancement factor as function of the aspect ratio < 1 (curve 1). The dotted line 2
corresponds to equation (12) for > 1.
Igor M. Mikhailovskij 388
For the average value of the aspect ratio = 0.30 for nanoprotrusions on the specimen
under consideration the equation (11) gives the field-enhancement factor
2
of 1.84 and
1

2
= 6.5110
3
. The magnitude
1

2
is much smaller than the experimental total field-
enhancement factor (
tot
= 6.4710
4
). To interpret this result, we can conclude that the carbon
emitters with nanoprotrusions formed by field evaporation are not atomically smooth
electrodes but have invisible in TEM atomic-scale features possessing high aspect ratios. An
atomic-scale
3
is equal to
tot
/
1

2
. The specimen shown in Figure 2 has the atomic-scale
field-enhancement factor
3
= 9.94. This value is corresponding to atomic-scale protrusions at
the apex of nanoprotrusions. For flat parts of the needle shaped carbon specimen
2
1 and
therefore,
3
= 15.3. The most available candidate for such a high field-enhancement factor
3
is the normal to surface atomic carbon wires with a rather high aspect ratio.
To determine the length of C-nanowire on the needle-shaped electrode we used the model
[34], in which the nanowire stands normally on, having the length L and radius = 1.2 .
Taking into account that << r
0
the mesoscopic electrode (hyperboloid) can be replaced by
plane. In this case the equation (7) is valid and gives the aspect ratios of 8.34 and 14.79 and
the lengths of the nanowires of L = 11.9 and 18.4 for
3
= 9.94 and 15.3, accordingly. The
numbers of carbon atoms in a linear chain estimated as n L/d + 1 were equal to 10 and 15
for these two field-enhancement factors on the surface of a typical carbon tip, where
d = 1.28 (5.1).
The size of clusters (n = 2-7) produced by pulse field evaporation is smaller then those
above calculated for linear chains on the needle-shaped electrode. As was shown [27] that
small carbon clusters could be the result of the decomposition of field evaporated heavier
cluster ions within the period of acceleration in the spectrometer. The spectral width and the
low energy tails of mass marks are correspondent to the flight time of the primary clusters
before dissociation of the order of 10
-12
s. Due to the low-energy tail of the C
5
+

mass mark and
the very small voltage signal of the C
6
+
cluster, it is difficult to determine the abundance of
the C
6
isomer.
6. Atomic Resolution of One-Dimensional Nanomaterials
The imaging process in field ion and electron microscopes has continuously been a topic
of debate [20,21]. However, there are not convincing arguments which explain the shape of
the image and other intrinsic peculiarities of the formation of field ion and electron images of
1D nanomaterials. In a general case, the image magnification is given by
0
r f
R
M
k
= , (13)
where f
k
is an image compression factor which takes into account the fact that field ions do
not follow exactly the radial direction of the nearly hemispherical tip surface because of the
tip shank and other supporting leads. For simple field emitter geometries, f
k
can be calculated
by determining the ion trajectories. It can always be found from field ion images where
angular separations among different crystallographic poles are well known. In normal tip
geometry the magnification is reduced by an image compression factor f
k
equal to 1.5-1.8
Preparation and Characterization of Monoatomic Carbon Chains 389
[21]. The image compression factor f
c
for ions, starting from the end of the linear chain
(Figure 5), was determined by numerical calculations of the equation of motion in an electric
field described by Eqn. (2). Figure 10 shows the dependence of the image compression factor
on the number atoms in carbon chains on the needle-shaped electrodes of the radius 100 (1),
200 (2), and 500 (3) nm.
1 10 100
0
5
10
15
20
25
30

f
c
n
1
2
3
Figure 10. The FIM image compression factor for the case of the single carbon chain on the needle-
shaped electrodes of the radius 100 (1), 200 (2), and 500 (3) nm.
The FIM image resolution is primarily determined by the ion beam broadens on its way
to the screen by the slightly compressed radial projection. Besides the broadening due to the
radial projection of the ions, the tangential component of the momentum of the particle will
further broaden the spot size. De Castilho and Kingham [41] expressed the resolution of the
FIM image in terms of the following expression:
( )
2 / 1
2
2
2 / 1
2 / 1
2
0
16
2
2

+ + =
T
c
f
f c
eV
f
k
meV
k h f

, (14)
where e is the elementary charge, h is Plancks constant, m is the mass of the image gas ion,

T
is the transverse thermal energy associated with the imaging gas atom when it is ionized
and the
0
is the diameter of the ionization zone above a given atom. The value of
0
2
in this
equation relates to the ionization area and depends on the field strength as well as some other
parameters. Lacking detailed calculations, one may assume that
0
is of the order of the radius
of the image gas atom (0.12 nm). The second term is correspondent to the broadening of the
ion image to the uncertainty principle. The third term takes into account the spreading of the
ion beam due to the thermal energy of the image ions.
Atoms of the imaging gas, striking the surface of the nanotube or atomic chain, have a
high kinetic energy
T
of about 0.1 eV, acquired when the polarized atoms are drawn into the
region of high nonuniform electric field. This energy is partially diminished in the collision of
the gas atom with the surface of the cooled sample. Upon repeated collisions the gas atoms
lose kinetic energy, leading to thermal accommodation down to the temperature of the
Igor M. Mikhailovskij 390
sample. In a theoretical determination of the resolution of the FIM it is assumed that the
atoms of the imaging gas have accommodated to the sample temperature and, accordingly,
the accommodation factor is equal to unity [20]. Figure 11 shows a calculated dependence of
the FIM image resolution on radius for helium atoms accommodated to various
temperatures.
0 10 20 30 40 50
0.12
0.16
0.20
0.24
0.28
0.32

(
n
m
)
77K
4.2K

(nm)

Figure 11. Theoretical FIM image resolution for helium atoms accommodated to cryogenic
temperatures. (Reprinted with permission from [42]. 2007, American Institute of Physics.)
The magnitude of in Eqn. (14) is correspondent to the radius of the closed carbon
nanotubes or the effective radius of the end of the carbon chain. The compression factor for
CNT is assumed to be ~10. As follows from the data in Fig. 11, at nanotube radii of ~1 nm
the resolution of the microscopic is equal to the theoretical limit (0.13 nm). It is certainly so
for the case of carbon atomic chains characterized by = 0.12 nm. As a result, the end atom
of a carbon chain is perfectly resolved in the field ion microscope (Figure 3).
Due to an enhanced FIM resolution of 1D structures, a direct imaging of the atomic
structure of the cap of closed carbon nanotubes was achieved for the first time by the methods
of high-resolution field ion microscopy with sample cooling to liquid helium temperature
[42]. We used in the study the products of gas-phase catalytic pyrolysis of hydrocarbons in
the form of graphitized fibers containing carbon nanotubes. A fiber is a graphitized carcass
containing a large number of ropes of cylindrical and conical multiwall carbon nanotubes
which are oriented approximately along the axis of the fiber and do not contain catalytic
particles.
The surface of the samples was subjected to controlled field evaporation to clean it of
adsorbed gases, remove the microscopic asperities formed during the electrochemical etching,
and form an apex of hemispherical shape. As was shown above in section 3, unlike metallic
samples in strong electric fields, carbon materials evaporate not atom-by-atom but in the form
of atomic clusters. Because of this, the hemispherical surface formed by field evaporation is
microscopically rough. FIM images of needle-like carbon specimens formed by field
evaporation are usually characterized by an irregular distribution of image spots as that in
case of the graphite specimens (Figures 3 and 12(a)). This type of FIM contrast is
correspondent to the random character of the low-temperature cluster field evaporation and
Preparation and Characterization of Monoatomic Carbon Chains 391
surface defects, such as process-induced microroughness, of a nanostructured carbon
material. In the process of field evaporation the interior region of the needle-shaped samples
was exposed, irregularly revealing nanotubes characterized by another form of ion images.
The brightness of the nanotube cap with a diameter of about 0.90 nm is significantly greater
than the brightness of the image of the graphite matrix. On the surface of the cap one observes
several regularly spaced dark and bright spots. Analogous contrast was observed previously
on field ion microscope images of the cap fragments of multiwall carbon nanotubes of
relatively large diameters [43,44].
(a) (b) (c)
Figure 12. Field ion microscope images of a graphite fiber (a) and carbon nanotube of diameter 0.90
(b). Diagram (c) illustrates the predominance of hexagonal rings in the structure of the cap of the
carbon nanotube. (Reprinted with permission from [42]. 2007, American Institute of Physics.)
The value of f
k
was determined empirically as the coefficient of angular image
compression, equal to the ratio of the angle of field ion emission to the angle between lines
drawn from the tip to diametrically opposed peripheral parts of the FIM image of the
nanotubes. Measurements showed that for the tip-nanotube configurations used in the present
study the local compression factor was about 13, and the field factor was equal to 300. The
full resolution of the structure of the fullerene caps of the carbon nanotubes achieved in these
experiments is apparently due to deep cooling of the samples. On cooling to 4.2 K a
monolayer of helium atoms can form on the surface of the tip, which is found in a high
electric field [20], and this improves substantially the conditions of accommodation of the
polarized helium atoms.
7. Field Emission Characteristics
The development of field electron sources based on the phenomenon of emission in high
electric field is a promising direction of application of new nanostructural carbon-based
materials. Advanced field electron sources often are regarded as the most important short-
term application of carbon nanotubes and nanowires. Multi-emitter carbon cathodes are
characterized by high local electric field enhancement factors and, accordingly, relatively low
values of working voltages. The same advantages can be used for the development of new
field-emission sources of inert gas ions [45,46] for various fields of physical metallurgy,
Igor M. Mikhailovskij 392
accelerator technology, supersonic molecular flux detectors, etc. Difficulties encountered in
the creation of highly effective ion sources are mostly related to the high field strengths
necessary for the field ion emission and to the irregular character of the process of emitter
surface shaping by means of field evaporation. The phenomenon of cluster evaporation of
carbon materials in an electric field with a strength exceeding 510
10
V/m (see section 3)
substantially limits the use of high-field surface finishing nanotechnology.
7.1. Field ion emission
We demonstrated the possibility to create a wide-area field-emission source of inert gas
ions with based on a nanostructural carbon, which can operate at a relatively low applied
voltage [36]. The proposed field ion emitter represented a tungsten point with a ball of
aluminum-filled epoxy resin composite formed on the point tip. The surface of the ball with a
diameter of about 10 m was covered with a disperse layer of the catalytic carbon vapor
deposition products obtained by gas-phase pyrolysis of hydrocarbons. An FIM and TEM
analysis of the deposited carbon material showed the presence of multi-wall nanotubes in the
graphite matrix. The ion source was tested in a FIM with a sample holder cooled by liquid
helium. The residual gas pressure in the working chamber was 10
-8
Pa, and the partial
pressure of helium could be varied from 10
-3
to 10
-2
Pa. The field strength at the spherical
surface of the emitter, which is necessary for the field ionization, was created by applying a
positive potential variable within 110 kV. The distance D from the ion source apex to the
counter-electrode was 310 mm.
(a) (b) (c)
Figure 13. FIM images of the surface of a multi-emitter field ion source obtained by a high-field
shaping at a voltage of (a) 5.80 (b) 6.45, and (c) 5.82 kV.
As shown in Figure 13(a), at first the main contribution to the ion current was due to
separate microprotrusions present on the hemispherical surface. The surface density of
emitting centers was in the range (520)10
9
m
-2
. In order to increase the homogeneity of ion
emission, the applied voltage V was increased at a rate of about 100 V/min. The field
evaporation led to the removal of sharpest and highest microprotrusions, which were
characterized by the maximum local electric field enhancement factors. As can be seen from
the series of FIM images in Figure 13 (a-c), the surface density of emitting centers was
gradually increased by almost two orders of magnitude to reach a level of 210
12
m
-2
. It is
difficult to determine atomic structures of nanoprotrusions. Upon completion of the high-field
surface shaping process, the ion beams emitted from the neighboring centers exhibited
Preparation and Characterization of Monoatomic Carbon Chains 393
overlap, thus creating a nearly homogeneous FIM pattern. The electric field strength at the
emitting element of the field ion source can be expressed as D V F / = , where and
are the meso- and nanoscale electric field enhancement factors, accordingly. The value is
determined by the configuration of the field ion source and is less dependent on the pulling
electrode shape. The value of can be estimated using a model of the field ion source
approximation by equipotential surfaces for a point charge situated at the end of a uniformly
charged filament. These equipotential surfaces are characterized by a dimensionless form
factor that varies from 0 (for a parabolic source) to infinity (for a spherical source). Within
the framework of this model, the mesoscale electric field amplification factor can be
expressed as
( )
0
0
0
1
ln
D
r D
r
D r

+
=


+





. (15)
There r
0
is the curvature radius of the field ion source apex. For the configurations of
field ion sources used in that study, the estimates of varied from 250 ( = 1) to 650
( = 10). The calculated values of the nanoscale electric field amplification factors fell within
70150. The total field amplification factor varied within (2.5-6.5)10
4
in the course of the ion
source surface shaping by field evaporation. These estimates are close to the maximum
electric field amplification factors reported for the apexes of carbon nanotubes [38].
Increasing the positive voltage on the carbon tip with the cap resulted in a growth of field ion
emission up to 2 nA (Figure 14). Such a behavior of field ion images is characteristic of very
small aggregates of atoms acting like a lengthy conducting protrusion on the tip surface.
3.8 3.9 4.0 4.1
-2.0
-1.5
-1.0
-0.5
0.0
0.5
L
g
I
i


LgV
Figure 14. Currentvoltage characteristics of the helium field ion source at 4.2 K.
Figure 14 shows an experimental currentvoltage characteristic of the helium ion source
plotted on the logarithmic scale. In the low-field region the ion current increases extremely
rapidly with voltage, amounting to 8-th power of the field. In this case the ion current is
Igor M. Mikhailovskij 394
measured in the units nA. The slope for relatively high-field strengths (above 4 10
10
V/m) is
correspondent to about the 3-d power of the field strengths. This character of the IV curves
of the multi-emitter field ion source shaped by field evaporation is close to that of the
characteristics of metal field emitters [20,21], but the slope of the low-voltage part is about
four times smaller than that typical of the metal emitters. In the region of low field strengths,
the total current is limited by the rate of ionization for helium atoms colliding with the emitter
surface. For field strengths above that of the best image, the field ionization rate is
sufficiently high to provide for the ionization of virtually all helium atoms trapped by the
polarization forces. A lower rate of current growth increase in this region is explained by a
small increase of the volume of the region of trapping related to the attraction of inert gas
atoms (polarized in the inhomogeneous electric field) to the region of maximum field strength
at the surface of a multi-emitter field ion source. A relatively low field sensitivity of the
ionization rate in the region of high fields indicates that the total ion current is only limited by
the supply of helium atoms from the gas phase. This is an additional evidence of a high
efficacy of the field strength leveling over microprotrusions in the course of the emitter
surface shaping by field evaporation [47].
7.2. Field Electron Emission
Rinzler et al. [9] for the first time conjectured that atomic carbon chains may provide the
vital point field electron cathodes. The delocalized, cylindrically symmetrical -bonding
along the linear carbon chain is responsible for nearly metallic screening of the electric field.
Ab initio calculations of carbon chains in an applied uniform electric field showed these
chains to screen the electric field as efficiently as metal rods of the same configurations [48]
and revealed that unlike bulk carbon, monoatomic C-chains are metallic independent of
doping [49]. The character of the bonds in the linear chain was found to be of cumulene-type,
i.e., with all nearly equivalent bond lengths. The electronic structure determines the physical
properties and the equilibrium geometry of nanoobjects. On the contrary, geometrical
structure determines the local electric field confining the electrons. This close
interdependence underlies the complex behavior of monoatomic chains in electric fields. The
high aspect ratio and small dimensions of the carbon chains are responsible for the field
concentration. The maximum induced field strength outside the end atom of the linear carbon
chain was more than 100 V/nm. Field electron emission properties of atomic carbon chains
were studied in detail using of sophisticated theoretical methods [33,34], and was shown that
a carbon chain is really a good candidate as a nanomaterial for fabricating field emitters.
To investigate the field emission characteristics of linear carbon nanowires, their current
versus voltage characteristics were measured. The question arises whether the Fowler-
Nordheim (F-N) theory of field emission [20] is still valid for carbon atomic wires, as it was
elaborated for a surface that appears flat for imaged electrons, which might not be the case
for nanowires on account of their ultrahigh curvature at the wire apex. Figure 15 shows a
typical result as a F-N plot for the multiwire field emitter formed by field evaporation of the
carbon tip. In this case the electron emission pattern was formed by about twenty
nanoprotrusions. The data follows a straight line in the F-N coordinates, which is an apparent
indication of a field electron process and a possibility to qualify linear carbon chains as
metallic atomic wires. As can be seen in figure 15, significant current instabilities took place
Preparation and Characterization of Monoatomic Carbon Chains 395
at 77 K and some long-term current drift occurred. The typical current fluctuation is of the
order of 1 A. The exact origin of the current fluctuations is not clear at the moment. These
instabilities of the field emission current may be due to the residual gas ion bombardment and
the process adsorption desorption [50].
0.17 0.18 0.19 0.20 0.21 0.22
-29.0
-28.5
-28.0
-27.5
-27.0
-26.5
l
n
(
I
/
V
2
)
10
3
/V (V
-1
)
Figure 15. Fowler-Nordheim plot of the multiwire field electron emitter at 77 K.
The field electron emission patterns usually consist of doublets and/or singlets. Figure 16
shows field electron images of the needle-shaped specimen formed by field evaporation at
+14.50 kV. The images obtained at negative voltages 1.21 (a) and 1.38 kV (b).

(a) (b)
Figure 16. Field electron images of the carbon tip after pulse field evaporation obtained at the bias
voltages 1.21 (a) and 1.38 kV (b).
In Figure 16 (a), the doublet consisted of two elliptical spots are clearly resolved. This
microphotograph was taken at current. An increase of voltage was accompanied by the
stepwise change from a doublet to a singlet shown in Figure 16(b). A further increasing the
negative voltage on the tip resulted in a growth of field electron emission from this image
spot up to about 1 A. Such a behavior of field electron images is characteristic of very small
aggregates of atoms acting like a lengthy conducting protrusion on the tip surface [50,51].
The images in figure 16 are selected out of about 10
3
microphotographs which revealed the
great variation in size, shape and intensity of the duplets and singlets. The variation in the
emission patterns can be ascribed to variation in the length of linear carbon chains connected
to the edges of graphite layers.
Igor M. Mikhailovskij 396
The measurements of the current-vs-voltage characteristics were performed also at 21K
in a vacuum system with the residual pas pressure of 510
-7
Pa. Figure 17 shows the typical
experimental current-vs-voltage plot (curve 1) for the multiwire field emitter formed by field
evaporation of the carbon tip. In these cases the electron emission pattern was formed by
about twenty nanoprotrusions. An observed in figure 17 suppression of current instabilities at
a deep chilling up to 21 K can be explained by decreasing the ion bombardment and the rate
of surface migration of adsorbed atoms.
Because of the lack of reliable experimental data for emission properties of the linear
carbon chains our results can only be compared to theoretically determined data. In
theoretical studying the field electron emission from linear carbon chains, it was found [34]
that these chains can be viewed as atomic-scale metallic wires with a diameter of 2.4 . In
keeping with Refs. [33,34], for one-dimensional systems like the linear atomic chains,
quantum size effects are of considerable significance, and the total field electron current is the
summed contribution of single-particle quantum levels. The equivalent to the Fowler-
Nordheim law for an atomic carbon chain is the modified equation with a prefactor linear in
the electric field
3/ 2
exp
HOMO
b E
I aF
F

=


(16)
where a and b are modified FN constants, E
HOMO
is the energy of the highest occupied
molecular orbits.
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
0
2
4
6
8
10
12

l
n
(
I
/
F
)
1/F (/V)
1
2
3
Figure 17. Modified Fowler-Nordheim plot for the multiwire field electron emitter at 21 K (1) and the
theoretical data [15] for C
10
(2) and C
11
(3) monoatomic carbon chains. (Reprinted with permission from
[19]. 2007, Institute of Physics.)
Figure 17 shows a modified F-N plot for the current-vs-voltage characteristic of the
multiwire carbon emitter formed by field evaporation at 21 K (1) and the theoretical data [34]
for two typical even and odd C
n
-chains with n = 10 (2) and 11 (3) at 0 K. In this case the
current and the field are measured in the units nA and V/, correspondingly. The data follow
Preparation and Characterization of Monoatomic Carbon Chains 397
the best fit straight lines in the modified FN coordinates and the plot slopes are 8.13 0.10,
6.68, and 8.63 V/ for the carbon emitter, C
10
and C
11
monoatomic carbon chains,
correspondingly. Taking into account that the validity of the FN theory has been established
experimentally to within about 15% [20], the plot slope for the carbon emitter under
consideration and that for theoretically studied C
11
-chains can be considered as equals. We
can conclude that even linear clusters with lower E
HOMO
are marginals in the morphology of
multiwire carbon emitters. These emitters formed by field evaporation at 21 K predominately
consist of odd carbon atomic chains. This conclusion is in accordance with the results of
comparative studies of thermodynamic stabilities of odd and even atomic carbon chains [33].
The length of the carbon nanowires in our cathodes could not be controlled. The natural
fluctuations in the length of self-assembled nanowires contributed to the non-uniformity of
field emission in the device. Despite the fact that uniformity and stability the field emission
from the carbon multiwire cathode is not yet sufficient these results lend strong support to the
conjecture of Rinzler et al. [9] that linear carbon chains may provide the ultimate atomic-scale
field emitters.
8. Atomic Simulation of Unraveling and Disintegration
8.1. High-Field Induced Unraveling of Graphene
It was shown in Ref. [9] that monoatomic chains can be formed by unraveling suggested
in field electron emission experiments with carbon nanotubes, where the electric force
unravels the multiwalled tube like the sweater. An analogical conclusion was made as a result
of computer experiments on mechanical pulling of carbon nanotubes [10]. It was revealed in
these molecular-dynamics simulations of CNT deformation that CNTs undergo a process of
necking up to formation of a single chain configuration, spanning the nanotube fragments. As
was revealed in [52], it is possible to use the electron bombardment in a TEM to elaborate a
CNT synthesis method from an amorphous carbon film. In earlier irradiation research [53]
was suggested that the end stage of radiation induced CNT reconstruction should involve the
creation of an atomic carbon chain. Atomic chain formation was verified for short lengths of
time (seconds) both experimentally and through computer simulations [11,54]. Authors [11]
find that there is a significant probability for formation of a stable bridge with the smallest
cross-section of one atom. It was concluded that all the evidence combines to show that a
freely suspended atomic chain was formed. Chain lifetimes of up to several minutes prior to
fracture were registered for the lowest current density conditions. In computer experiments
[11], it was observed the formation of a single or a double wire, or more complicated wire
structures, between the tube ends. Authors obtained linear carbon chains, which had a
remarkable length up to 14 atoms. The high rate plastic deformation resulted in numerous
collisions between the wires, and at last only one wire survived. An additional increase of the
distance between the tube fragments does not break this wire, which elongates by increasing
the number of atoms that burst forth out from both ends into the chain. Linear carbon chains
were also revealed in samples of double-wall CNTs annealed at temperatures between 1000
and 2000C [55]. From the comparison between the first-principles calculations and the
resonance Raman experimental results authors concluded that some unusual Raman features
are related to short C
5
and C
7
linear carbon chains, interconnecting the CNT surfaces.
Igor M. Mikhailovskij 398
Detailed calculations of the graphene unraveling were carried out to examine the
mechanism and trend for atomic chain formation in high electric fields [18,19]. The
numerical simulations were performed using the classical molecular dynamics (MD) method,
employing the short-range Tersoff-Brenner bond order potential, which reproduces lattice
constants, binding energies, and the mechanical properties of diamond, graphite, and carbon
nanotubes. The electric force producing an axial tension is localized at the top of the chain. In
our molecular dynamics modeling the electric force was 3.8-5.6 nN. Figure 18 shows a linear
carbon chain extending out from the graphene layer under the action of electric field at the
beginning (a) and after 3.210
-14
s (b), 6.410
-14
s (c) and 9.610
-14
s (d). The nanowire held
taut in this case by the electric force of 5.1 nN.
(a) (b)
(c) (d)
Figure 18. Forming of the carbon nanowire during the unraveling of a graphene sheet in a high electric
field. Labels (a)(d) denote the various unraveling stages.
At first, the dangling bond at the graphene edge orients along the electric force. After that
the weakest link has proved to be the nearest bond aligned along the applied electric force.
This bond stretches and finally breaks up first under a local force produced by a high electric
field (Figure 18(b)). After that the atomic wire turned longer and straightened under the
action of an electric field. The resulting effect is to increase the chain length by two atoms
without any change in bond order of the open edge of the graphene sheet. The atomic chain
extending out from the graphene edge held straight and taut by the electric field. Further
pulling of the atomic chain by the electric field repeats the described sequence of events,
Preparation and Characterization of Monoatomic Carbon Chains 399
unraveling the linear carbon. The second bond normal to surface the graphene sheet also
starts to stretch and breaks up (Figure 18(c)).
The orientation of electric force favors breaking the bonds normal to the open edge of the
graphene layer. It is also essentially that the failure force of the linear carbon chain is slightly
higher than those of the graphene bonds. Therefore, the disintegration process is successive
and clearly localized, with sudden complete drop in the local failure force due to the bond
breaking. The energy per bond in general depends in a complicated way on the geometry.
However, as was shown by Abel [56] and Tersoff [57], for covalently bonded systems the
most important variable appears to be the coordination number. The bond strength of carbon
atoms is a monotonically decreasing function of the number of nearest-neighbour atoms close
enough to form bonds. If the bond energy decreases rapidly with the coordination number,
then the linear atomic chains along with the diatomic molecule will be characterized by a high
value of the bond strength. This effect for carbon interatomic bonds quantitatively described
by the Brenner version [58] of the Abel-Tersoff bond-order formalism used in our simulation.
(a) (b)
Figure 19. Linear carbon chains on a graphene sheet without an electric field at step (a) and kink (b)
sites.
Figure 19 shows two carbon chains formed as a result of the high-field unraveling of the
graphene sheet at 0 K. Orientations of the chains without an electric field are determined by
the equilibrium angles between atomic bonds of the nearest neighbors indicating a high extent
of orientational correspondence of the liner chains and the perfectly defined graphene edges.
8.2. Dissociation and Explosive Heating of Carbon Atomic Chains
Snapshots of the dissociation dynamics of a single C-chain extending out from the
graphene sheet is in Figure 20. One can observe an eight atom chain that detached from the
graphene edge after the high-field unraveling (Figures 20(a) and (b)). Carbon species are
evaporated from a graphite surface initially as linear clusters which decompose mostly into
smaller atomic clusters (Figures 20(c) and (d)). The number of C
3

clusters in the field
evaporation spectra was prominently large, indicating their preferred formation during
fragmentation of the chains. These results of simulation confirm given above conclusion that
the carbon clusters experimentally registered in the field evaporation spectrum are not
occurred right at the specimen surface but are produced in a high vacuum by dissociation into
Igor M. Mikhailovskij 400
several particles (see section 3 and the review [59]). It is also become obvious that the
numbers of atoms in registered carbon clusters are much smaller as they are formed by the
graphite unraveling. The carbon clusters were dissociated at a distance of about 1 nm away
from the specimen apex, which is reached within a travel time of about 0.1 ps. The time of
cluster disintegration found in MD simulations is an order of magnitude less then that
obtained by analysis of the energy distribution in the time-of-flight spectra of low-
temperature field evaporation of graphite discussed in section 3. Such a discrepancy is away
from possible errors in measurements and needs a special consideration.
(a) (b)

(c) (d)
Figure 20. Snapshots of the dissociation dynamics of a single C-chain extending out from the graphene
sheet: (a) at the beginning; (b) after 3.210
-14
s, (c) after 6.410
-14
s, and (d) 7.110
-14
s.
Heating of linear carbon chains produced by unraveling of CNTs was observed in the
molecular dynamics experiments [11]. Remarkably, the kinetics of chain breaking varies with
strain rate and temperature. The drop in potential energy makes the temperature of the chain
rise very sharply. The excess kinetic energy in the region just unraveled then propagates to
the graphene, until the whole system again reaches the equilibrium state. The potential energy
rises steadily with the tensile deformation until the CNT breaks. The succeeding contraction
of the carbon-carbon atomic bonds leads to a sudden drop of potential energy and to a sharp
Preparation and Characterization of Monoatomic Carbon Chains 401
increase of the temperature to about 10000 K. Despite the very high temperature, the
formation of some short-lived wires was still possible to observe. The fact that the computer
simulations demonstrate CNT breaking modes with the presence of carbon atomic wires
emphasizes two aspects: that CNT breaking proceeds in a high-temperature region and that
the carbon structure is unable of evacuating the heat fast at high rates of local deformation.
We note that under the simulation conditions the unraveling graphite layers discussed in
section 8.1 is quasiadiabatic and does not occur at constant temperature [60]. At the beginning
of the experiment until the bond breaking starts, the graphene sheets are at about 0 K. Figure
21 shows that potential energy of the neighbor atom of the chain (curve 1) and the third
nearest atom (curve 2) in the graphene sheet rises gradually with the bond stretching until the
first bond breaks up. The time unit is 3.52610
-14
s and the time step is 7.05210
-16
s. The
consequent contraction of the atomic bonds causes an abrupt decrease of potential energy and
atomic oscillations with the period of 0.028 ps. The average amplitude of oscillations within
0.1 ps is correspondent to temperature of about 10000 K. It indicates that the graphene based
carbon structure is incapable of fast evacuating the heat. Therefore, the unraveling proceeds
in an ultrahigh-temperature surface region of carbon fibers. The possibility of explosive local
overheating above the critical point of carbon was demonstrated earlier in molecular dynamic
simulations of the CNT breaking [11]. One can conclude that ions are field evaporated from a
graphite surface initially in linear cluster forms, which decompose mostly into smaller atomic
clusters and individual ions because of the ultrahigh-temperature excitation during
unraveling.
0 20 40 60 80 100 120 140 160 180
-16
-14
-12
-10
-8
-6
-4

Q
,

e
V
t (time steps)
1
2
Figure 21. Potential energy per atom versus time for the MD simulation of the unraveled monoatomic
C-chain. Curve 1 is the neighbor atom of the chain, and 2 is the third nearest atom in the graphene
sheet.
8.3. Carbon Chains with Macro Length
Preparation of long atomic carbon wires is of immense importance for both technological
and scientific research. The results of mathematical simulations with the Brenner potential
Igor M. Mikhailovskij 402
showed that free atomic carbon wires with macro length could be obtained by pulling the
edge atoms of a graphene sheet with speeds lower than 30 m/s at about 300 K [61]. A
monoatomic wire was formed with the carbon atoms that burst forth out of the graphene sheet
in a process that resembles unraveling a knitted scarf. The computer experiments indicate that
the entire graphite atomic layer is unraveled at about 1000 K to form macroscopically long
monoatomic wires. On increasing pulling speed from 70 to 300 m/s the calculated atomic
block tended to form shorter chains. More sophisticated tight-binding MD calculations have
confirmed these classical simulations based on the bond-order potential. The bond breaking
process in graphite with release of atoms to joint the chain was described in details. In the
bond breaking process at constant temperature, failure of the chain itself is hardly probable
because the energy of the sp bond in a monoatomic wire is larger than that of the sp
2
in
graphene and the joining bond that connect the carbon chain and the graphene sheet.
Wang et al. [61] also performed mathematical simulations without the thermostat. In
these experiments, transverse vibrations of a monoatomic wire grow to be more and more
intensive during unraveling. This process is accompanied by rising temperature up to about
3000 K and by subsequent failure of the wire. The rupture in the constant pulling speed
regime is observed in the middle part of the wire but not at the junction of the wire and the
graphene sheet, in contrast to that in the constant force regime (Figure 20). The mechanical
loading regimes used in Ref. [61] and that described in section 8.1 are reciprocal. The
constant pulling rate can be experimentally realized with ideally stiff testing machines which
have two heads, one of which is driven to change the distance between them and thus to
impose a definite rate of elongation. A stiff system required little deflection for adjustment of
the load and can therefore follow the drop in load required for elongation in the unstable
region of unraveling. During the unraveling process, carbon atoms come off the graphene
sheet occasionally and join the linear chain. As was shown by Wang et al. the sheet shrinking
takes place after an avalanche event of atom bond breaking with a number of atoms joining
the carbon chain within a short time. The loading of linear atomic chains by the high electric
field in the FIM and our simulations (figures 19 and 21) is the other extreme. The high-field
loading discussed in section 8.1 is correspondent to the soft method based on dead-weight
loading through a lever. In this case the load cannot fall and remains above the load required
for plastic deformation or unraveling of specimens. Moreover mechanical testing in the FIM
alone is an ideally soft testing method ensured the absolutely constant pulling force regime. In
this regime the unraveling is accompanied by an ultrahigh-temperature surface heating of
carbon tips and atomic chains.
We can see that molecular dynamic simulations describe the main features of the high-
field chain formation. However, further investigation is required to determine how initial
atomic-sized faults, which could serve as nanowire nucleus at the graphene edges, emerge.
Local oxidation is one of the possible processes of graphite exfoliation to produce graphitic
nanoflakes. The details of how oxygen attacks carbon bonds to break up the atomic structure
of the graphite sheet were recently understood by Li et al. [62]. They connected oxidation
chemistry to the morphology of the graphene sheets and showed how the mechanical stress
generated by oxygen-containing groups led to unfolding of the graphite lattice. Epoxy and
hydroxyl groups make bridges across carbon atoms at the graphite layer. The oxygen acts
mechanistically like a minuscule wedge, pushing apart the bridges carbon atoms and
stretching the carbon-carbon bonds. As a result, epoxy and hydroxyl groups together induce
enough tension in underlying lattice to break the carbon links. These groups mainly attach at
Preparation and Characterization of Monoatomic Carbon Chains 403
defects or edge-atom sites in the graphite lattice, where the carbon atoms are not fully
bounded. The stress generated by epoxy bridges and structural relaxation around ridges can
lead to unraveling of the lattice near the edge sites and to the formation of nanowire nucleus
at the graphene edges.
8.4. Youngs Modulus and Tensile Strength of Atomic Chains
One can use the interatomic potential to find the ideal tensile strength and the value of
resistance to axial stretching, determining nanowire energetics at small strains. The second
derivative of energy with respect to axial strain divided by the cross section of a carbon chain
S corresponds to Youngs modulus Y. In the Brenner interatomic potential, the cutoff function
introduces an artificial increase in the restoring force. As was shown Belytschko et al [63],
the extremely large computed values of the CNT failure stress in early theoretical studies
were an anomaly due to the cutoff problem typical for Brenner-like potentials. Using the
modified Morse potential [63] that closely matches the Brenner potential in the 015 % strain
range, we calculated Youngs modulus of carbon atomic chains. The special treatment for
calculating the chain diameter or the load-bearing cross-sectional area must be carried out for
determining the breaking strength and Youngs modulus values. The result Y = 3.68 TPa was
obtained with the carbon chain diameter of 2.0 [64] equal to the cutoff distance in Tersoff-
Brenner bond order potential. The diameter of carbon atomic chains is not a well-defined
parameter but this value seems reasonable. In fact, according to recent first-principles
calculations of the electronic structure of molecular wires this value corresponds to the spatial
extent of the highest occupied -states [33]. We have also calculated the critical strain and
tensile stress of carbon nanowires.
The stress is defined by ( )
2
/ 4 d F
a
= , where F
a
is the axial force, d is the diameter
of carbon atomic chains. The strain is given by = (r r
*
)/r
*
, where r and r
*

are the current
and initial interatomic lengths per atom, respectively. The maximum force is 7.916 nN at a
strain of 0.19 and the ideal tensile strength is equal to 252.1 GPa. The ratio /E for
monoatomic carbon wires is of 0.069.
To our knowledge there are no experimental data on mechanical properties of linear
carbon chains. Real strengths of solids are orders of magnitude lower than theoretical ones. It
is usually observed that the strength of materials depends on size of the sample. The typical
strength for microfiber is 1-5 GPa, the strength of nanofibers can reach 12 GPa [65] and
graphite whiskers exhibit strength as high as 20 GPa. Carbon nanotubes have extremely high
tensile strength approaching 60 GPa and axial Youngs modulus of about 1 TPa [66,67]. This
behavior is due to the fact that the number density of defects is significantly reduced in
whiskers and nanosized objects. The experimentally measured strength of CNTs and the
theoretical results [63] are not in quantitative agreement but are of the same order of
magnitude. The nanotube fracture behavior depends on topological defects and vacancies
which are always present in the nanotubes used for mechanical testing. Vacancies and
vacancy-related defects have a strong effect on the tensile strength and critical strain of
CNTs. The tensile strength will significantly drop if single vacancy is present owing to the
quasione-dimensional structure of CNTthe strength of low-dimensional objects is governed
by the weakest part. Vacancies and other structure defects cannot be present in linear atomic
Igor M. Mikhailovskij 404
chains. Thereupon, we can expect that the real and ideal tensile strength of carbon chains
under consideration basically coincide. The values proved to be higher than most results of
similar simulations and tensile-loading experiments for carbon nanotubes. Studying the
mechanical properties of this unusual form of matter should enable rigorous tests of our
understanding of atomic interactions.
9. Conclusion
Linear carbon chains have drawn tremendous interest from fields ranging from
condensed-matter physics to astronomy because of their unique properties such as nanometric
dimensions, quantized conductance, high aspect ratio and modulus of elasticity, unusual
optical features and electromagnetic response. Monoatomic chains show transport properties
of fundamental and technological interest since they represent the ultimate size limit of
functional electronic devices. This interest is also stimulated to a large extent by a desire to
understand the atomic-scale mechanisms underlying the preparation of carbon chains.
Experiments with the FIM have revealed new mechanisms for low-temperature field
evaporation of graphite with important implications for device fabrication. This overview ties
together several aspects of recent research on carbon atomic chains and the techniques used,
focusing on a high-field technology, field-ion microscopy, field emission, and molecular
dynamics simulation. It was shown that carbon chains are perfectly resolved in the field ion
microscope. An analysis of the cluster images and determination of the field enhancement
factors strongly indicate that the field produced clusters are linear chains of one carbon atom
in diameter. The process of field evaporation of graphite at the pulse voltage loading is
sporadical with an anomaly large instant rate of evaporation corresponding to explosive
moving off about 10
11
atomic layers per second. MD simulations demonstrate that electric
field pulling a single carbon atom on the graphene edge does not preferentially breaks the
carbon-carbon chemical bond. Instead, it is found that this process leads to the formation of a
monoatomic carbon chain, followed by breaking a carbon-carbon bond at the graphene
surface with a high rupture force. A detailed experimental comparison with theory has not
been carried out, although such a comparison is critical for advancing our understanding of
these nanoobjects. FIM experiments and MD calculations indicate that carbon exhibit
pronounced many-body interactions with strong bonding in low coordinated systems. A
universal interpretation of the force-induced unbinding of graphite layers is established. At
the moment the stability of carbon chains is one of the main problems to deal with. We are
witnessing novel properties of linear carbon chains such as the explosive heating during the
high-field unraveling of graphene. Further theoretical and experimental research is still
required so that novel technologies will turn into a reality in the near future.
Acknowledgments
The author is grateful to A.S. Bakai and N. Wanderka for helpful comments. The author
would like to thank V.A. Ksenofontov, T.I. Mazilova, V.A. Sadanov, and O.A. Velicodnaja
for their help in preparation of this article, numerous fruitful discussions and collaboration in
some of the work reviewed here. The original research of the author discussed in this article
Preparation and Characterization of Monoatomic Carbon Chains 405
was supported, in part, by the NATO International Program No. SA (PST.CLG.976376) and
the Deutsche Forschungsgemeinschaft (grant 436 UKR 17/26/06).
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Reviewed by Professor A.S. Bakai, Institute of Theoretical Physics of National Scientific
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 409-433 2010 Nova Science Publishers, Inc.






Chapter 12



SEQUENTIAL NUCLEATION AND GROWTH
OF COMPLEX NANOSTRUCTURES
BY A TWO-STEP STRATEGY


Li Yang
1,*
, Paul W. May
1
and Lei Yin
2

1
School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS,
United Kingdom.
2
Department of Aerospace Engineering, University of Bristol, Queens Building,
University Walk, Bristol BS8 1TR, United Kingdom.
Abstract
Self-assembled nanostructures are new forms of materials which are interesting from a
fundamental scientific perspective, as well as having many potential technological
applications. It is believed that the ability of nanostructures to self-assemble with controlled
crystalline orientation, size, complexity and crystal morphology, provide potential
applications in data storage, functional devices, communications and technology. Recently, a
two-step strategy was successfully developed in our lab to produce two-dimensional or three-
dimensional carbon nitride well-defined hierarchical complex structures. This strategy is a
combination of a novel laser-induced deposition technique followed by self-assembly. In the
first step, a suspension of carbon nitride nanoparticles was prepared by liquid-phase pulsed
laser ablation (LP-PLA). In the second stage, this suspension was deposited onto a silicon
substrate to act as a seed layer. Via controlling the rate of evaporation of the liquid phase
part of the seed suspension, and the size and the quantity of nanocrystals within the droplet, it
was possible to create a range of nanoscale structures, including dense nanospheres, highly-
symmetric flowers, hollow core-shell and uniform grass-like structures. The growth of such
complex structures is governed by an evaporation-driven self-assembly process. As the
droplet dries, small building blocks, such as nanoparticles (NPs) or nanorods (NRs) nucleate
upon the existing crystals and template, sharing the same edges, to form a close-packed
arrangement. By varying the design of the building blocks, materials combination, interfacial
chemistry, and confining dimensions, it is expected to extend this synthetic approach to a
range of new structured materials with useful functional properties.
Li Yang, Paul W. May and Lei Yin 410
1. Introduction
Self-assembly is an incredibly powerful concept in modern molecular science. The
ability of carefully designed building blocks to spontaneously assemble into complex
nanostructures underpins developments in a wide range of technologies from materials
science through to molecular biology. Due to the multi-disciplinary nature of this new
subject, the definition of a self-assembling process may be different among researchers from
different fields. Generally speaking, self-assembly is a process in which components, either
separately or linked, spontaneously form ordered aggregates [1]. The interactions involved
usually are non-covalent, such as electrostatic interactions, hydrogen bonds, van der Waals
forces, coordination interactions and hydrophobic effects [2]. In self-assembled structures,
these intermolecular forces connect the molecular building blocks in a reversible, controllable
and specific way. Of particular value are the possibilities offered by self-assembly to generate
nanoscale complexity with relatively little synthetic input. Furthermore, the ability of
assembled superstructures to behave as more than the sum of their individual parts, and
exhibit completely new types of behaviour, is of special interest [3].
Due to the emergence of a new generation of high-technology materials, two-dimensional
(2D) and three-dimensional (3D) self-assembled, aligned nanomaterials have begun to be
widely investigated over the last decade [4,5]. It is believed that the ability of nanostructures
to self-assemble with controlled crystalline orientation, size, complexity and crystal
morphology provide potential applications in data storage, functional devices,
communications and technology. As a result, a rapidly growing field of science has emerged
to understand and control these self-organized architectures, involving the dedicated efforts of
chemists, physicists, material scientists and biologists. In general, physical methods
(including chemical vapour deposition [6], vapour phase transport [7], and pulsed laser
ablation in vacuum [8]) and chemical methods (including hydrothermal methods [9], soft-
template [10] and use of various surfactants [11,12]) have been developed to fabricate nano-
to microscale materials with a range of morphologies, such as compact hexagonal networks
[13], rings [14], dandelion-shaped hollow structures [15], strips [16], tubes [17], and flower-
like structures [18]. For example, ZnO forms micron- and submicron-scale dandelion-like
structures, which are comprised of single-crystalline building units (either nanorods (NRs) or
nanoparticles (NPs)) [19], and which can be constructed via a modified Kirkendall process in
solution, where the pre-formed oxide layer serves as a shell template for the initial nucleation
and growth. Also, uniform Sb
2
S
3
bundles coalesced from numerous NRs have been
synthesized on a large scale using a hydrothermal technique at a temperature of 180C for
20 h [20]. However, it is well known that these physical techniques require relatively high
temperature, vacuum conditions, and expensive equipment, or sometimes complicated
processes, which limit them to smaller scale fabrication. Also, conventional chemical
methods usually involve the use of catalysts, surfactants and possibly complex chemical
reactions, which often produce a significant amount of unwanted byproducts requiring further
purification. Therefore, a technique which combines the merits of both physical and chemical
methods, while giving high yield at low cost, would be desirable, if novel self-assembled
materials are to be produced on an industrial scale.
One such technique, liquid-phase pulsed laser ablation (LP-PLA), has only relatively
recently been applied to produce self-organized nanomaterials [21,22,23]. Details about the
Sequential Nucleation and Growth of Complex Nanostructures 411
technical aspects of LP-PLA can be seen in a recent review by Yang [24] who gives
comprehensive details of the nucleation thermodynamics, the phase transition, and the growth
kinetics of nanocrystals by laser ablation of liquids. Briefly, LP-PLA involves focusing a high
power laser beam onto the surface of a solid target, which is submerged beneath a liquid. The
interaction of the laser with the target causes the surface to vaporise in the form of an ablation
plume, which contains species such as atoms, ions, and clusters, travelling with high kinetic
energy. The species in the plume collide and react with molecules of the surrounding liquid,
producing new compounds containing atoms from both the original target and the liquid. Due
the intensity of the laser and the nanosecond timescales, the instantaneous temperatures and
pressures within the reaction volume can be extreme (many thousands of K at tens of GPa)
[25]. Such high temperature, high pressure, and high density conditions provide a brute
force method of synthesising novel materials that have hitherto been inaccessible using
milder, more conventional techniques.
Extensive progress has been made towards the production of many types of inorganic
nanoparticles, including metals, metal oxides, and other semiconductors [26]. However, to
date, research on the understanding of the self-assembly processes of Group IV-V
compounds, such as carbon nitride, is still in its infancy, and synthesis of complex
nanostructures has only just begun. Carbon nitride has been the subject of numerous
publications since the prediction by Liu and Cohen [27] in 1989 that crystalline C
3
N
4
should
have superhard properties. However, a successful synthesis of bulk amounts of this material
still remains a challenge. The synthesis difficulties are due to its low thermodynamic stability
and complex bonding environment. Recently Li and co-workers [28] demonstrated a range of
self-assembled carbon nitride morphologies (including nanotube bundles, aligned
nanoribbons and microspheres) could be prepared by a solvothermal technique. Also, our
recent findings [29,30] indicated that the instantaneous high temperature, high pressure and
high density conditions that arise when a high-intensity focused laser beam impinges upon a
graphite target confined by a thin layer of liquid ammonia can promote growth of crystalline
carbon nitride NPs. In this chapter, we will further demonstrate a successful synthesis of
carbon nitride hierarchical nanostructures via a two-step strategy, whereby the nanocrystals
self-assemble into complex 2D or 3D superstructures. Fabrication of these carbon nitride
structures from small building blocks via self-organization suggests that the chemical and
physical properties of these superstructures are intrinsic to the self-assembly induced by the
close vicinity of the NPs or NRs. Finally, a summary and expectation are discussed with
regard to the application of LP-PLA as a synthesis route for highly desirable complex
architectures.
2. Processing Hierarchically Structured Nanomaterials
Production of zero-dimensional (0D) NPs and one-dimensional (1D) nanocrystals by
laser ablation in liquid media has been extensively studied [31,32,33]. Since the 0D and 1D
nanocrystals can serve as building blocks in forming 2D or 3D complex architectures with
long-term periodic structures, it should be expected that the LP-PLA approach would have
great potential as a means to grow large arrays of hierarchical, complex, oriented and ordered
superstructures. Extending this concept, we performed a two-step synthesis to produce
oriented carbon nitride nanostructures based on previous results [Error! Bookmark not
Li Yang, Paul W. May and Lei Yin 412
defined.,Error! Bookmark not defined.]. In a typical synthesis process, the carbon nitride
seed solution was initially prepared by LP-PLA. Briefly, a solid graphite target (Testbourne
Ltd., 99.99%) was ablated at room temperature while submerged in a 5 ml solution of 25-35%
ammonia solution (Fisher Scientific, used as received without further purification) inside a
sealed stainless steel cell. In order to reduce the effect of target aging, the cell was rotated at
700 r.p.m. during ablation using a standard magnetic stirrer. A Q-switched Nd:YAG laser
(532 nm, pulse duration 15 ns, frequency 10 Hz) was directed by a prism and then focused
onto the graphite surface using a 25 mm-focal-length lens. The intense laser light passed
through a quartz window in the top of the cell, then through ~5 mm layer of the liquid
covering the graphite, to form a ~0.5 mm-diameter spot on the target surface. The ablation
was typically carried out at laser fluences of 25-125mJ / pulse for reaction times t = 0.5-24 h.
After ablation, a pale yellow colloidal suspension was obtained, which contained a mixture of
unreacted graphite and ablation product, both in the form of NPs. The suspension was stable,
with no precipitate being observed for months or even longer. The graphite sediments were
filtered and removed as much as possible by boiling with 70% perchloric acid, before further
characterization. For the second step, a few drops of this seed suspension was deposited onto
a 1 cm1 cm silicon p-(100) substrate and the liquid allowed to dry. Many more complex
nanostructures than the simple NPs and NRs can be produced in a controlled fashion by
simply altering the drying time and drying method of the suspension of ablated product. Four
different drying processes were used in the present study: (1) dry naturally in air; (2) dry in a
sealed tube; (3) dry rapidly in an oven or on a hotplate; (4) dry in a critical point dryer (CPD).
Those procedures allowed the time taken to evaporate the liquid to be controlled.
For materials analysis, a drop of the suspension was deposited onto a silicon p-type (100)
substrate or transmission electron microscopy (TEM) grid, and then allowed to dry. The
product was characterized using X-ray diffraction (XRD; Bruker-AXS D8 powder
diffractometer, Cu K radiation), field emission scanning electron microscopy (FE-SEM;
JEOL 6300 F), TEM (JEOL 1200 EX, 120 kV), high-resolution (HR) TEM (JEOL 3000F,
300 kV) and energy-dispersive X-ray analysis (EDX). X-ray photoelectron spectroscopy
(XPS; Thermo VG Scientific), laser Raman spectroscopy (Renishaw 2000, excitation
wavelength 325 nm) and Fourier-transform infrared spectroscopy (FTIR; using a KBr disc)
were performed to search for evidence of CN, C=C and CN bonds.
3. Sequential Nucleation and Growth of Complex Nanostructures
3.1 General Structure of the Nanocrystal Self-assembly
All reported samples in the present work were first examined with XRD, EDX, Raman
and XPS techniques to obtain their crystallographic structure and chemical composition.
Experimental details of the procedures can be seen in our previous reports [Error!
Bookmark not defined.,Error! Bookmark not defined.,Error! Bookmark not defined.].
Studies performed at various conditions showed that factors such as ablation time, laser
energy, ammonia concentration and the drying speed were important in order to obtain
organized assemblies of NPs. By depositing the carbon nitride seed solution onto a silicon
substrate and controlling the drying process under different conditions, four main classes of
structure were identified in the ablation product, categorised as Types I-IV based upon their
Sequential Nucleation and Growth of Complex Nanostructures 413
shape and size (Figure 1(a)). The first class of structure (Type I) had the shape of thin plates
with rounded edges. Since they were the components of the larger flower-like structures
(described later), they have been termed nano-petals. The quantity of these nano-petals and
their location with respect to the larger structures (see later) were dependent upon the
deposition and drying conditions. As shown in Figure 1(b-c), this indicated that these nano-
petals were 2D crystallites of carbon nitride which preferentially aligned themselves
perpendicularly to the surface of the Si substrate. The number and length of these nano-petals
increased with increasing laser ablation time from 0.5 to 2 h for the same laser fluence. X-ray
diffraction (XRD) analysis (spectrum not shown here) of these nano-petals showed that they
were crystalline, and all the diffraction peaks were consistent with (h00) preferential
orientation [Error! Bookmark not defined.]. The crystallographic information was indexed
to hexagonal -C
3
N
4
(P6
3
/m (176)) with lattice constants a
0
= 6.4017 and c
0
= 2.4041
[34]. Interestingly, it is also possible that these nano-petals began to aggregate and self-
assemble (Figure 1(d)). When the concentration


Figure 1. (a) Schematic illustration of the growth process leading to the observed four main classes of
hierarchical structures, labelled I to IV. (b)-(d) Scanning electron microscopy (SEM) images of carbon
nitride nano-petals following ablation times of: (b) 0.5 h, (c) 2 h, and (d) 3 h. (e-f) Overall flower-
like structure following 5 h laser irradiation (synthesis conditions: laser power 125 mJ, 35% ammonia
solution, drying in air). (g-h) 2D flattened flower, sample conditions identical to (e-f) except it was
dried on a hotplate at 200C (g) and an oven 80C (h). (Reproduced from [Error! Bookmark not
Li Yang, Paul W. May and Lei Yin 414
defined.] by the permission of Royal Society of Chemistry (RSC) and [Error! Bookmark not
defined.] by the permission of Nova publishers).
of nano-petals in the suspension increased, they tried to minimize their interfacial energy
upon subsequent drying of the liquid by preferential tilting with respect to each other. This
produced the second class of nanostructure (Type II), which has a grass-like shape and
exhibits several different morphologies (see later discussion). However, all are produced in
large quantities and cover the whole substrate.
By carefully controlling the drying process, flower-like spiked, crystalline
superstructures were formed (Figure 1(e-f)). This third class of structure (Type III), now fully
3-dimensional, with sizes 1-20 m, were created when many nano-petal structures coalesced
at a common centre with multi-fold symmetry. One possible explanation is that the presence
of the solid substrate physically hinders growth in that direction; so many branches are tilted
away from the substrate, towards the solution.
When the evaporation speed of the liquid was rapid (for example, drying in an oven or
hotplate), a fourth class of structure (Type IV) was observed (Figure 1(g-h)). Instead of 3D
flowers, the carbon nitride now formed 2D star-like or flattened flower-like structures. New
dendrites emanated from the core and acted as nucleation centres, eventually allowing the
structure to expand into 2D horizontal flowers (Figure 1(h)). It is suggested that the higher
water evaporation rate increased the interparticle capillary forces [35]. As the continuous flux
of particles filled up the spaces on the substrate, successive layers would be formed rather
than 3D complex shapes.
Although these four types of structures have different densities and morphologies, they
all exhibit high surface-to-volume ratios and so might have potential in semiconductor
devices, anticorrosion protective coatings and new applications.
By controlling the solution evaporation rate on a carbon-coated TEM copper grid (as our
substrate), different final complex architectures could be also achieved on various length
scales. If the droplet dried in air (less than 1 h), the structure had the shape of nearly
monodispersed spheres with rounded edges (Figure 2(a)). Those spheres have very high
density and are close-packed. When increasing the laser fluence and ablation time, the
nanostructure resembles flower-like spiked crystallites (Figure 2(b)) for the same drying
speed, where the NRs have coalesced at a common centre with multi-fold symmetry. It seems
that these flower-like structures are simply less dense versions of the spheres (Figure 2(c)),
with numerous voids between the NR framework comprising the flowers. Similar interior
space would be eventually generated within the solids, as the smaller NPs are undergoing
mass transport throughout the prolonging drying times (Figure 2(d)). The solid carbon nitride
flower (similar to that in Figure 2(b)) has become hollow (named hollow-flowers), which
divided the pristine solid sphere into two discrete regions and formed a core-shell structure. In
these structures, the NPs remain loosely attached to the outside, forming the interconnected
void space, although the interior vacant volume might vary in each individual hollow-flower
(for instance the interior void space size is in order: 1st >2nd >3rd >4th, as shown colour
contrast for two discrete regions of individual hollow-flower in Figure 2(d)). It is worth
pointing out that by simply altering the drying time and drying method of the suspension, the
final morphology can exhibit semi-hollow, core-shell, or even full-hollow structures. These
observations are similar to the report by Liu and Zeng [36], who demonstrated the fabrication
of ZnS nanomaterials with hollow interiors. Yang and Zeng also reported a simple approach
Sequential Nucleation and Growth of Complex Nanostructures 415
to prepare hollow TiO
2
nanospheres with highly organized crystallites in the shell structure
and surface regions [Error! Bookmark not defined.].
Compared to the flower-like structures, the hollow-flowers are less common. A longer
drying time in an above-ambient temperature aids the small crystallites to move freely in the
solution enabling oriented aggregation. The relative ratios the nanosphere, nanoflower and
hollow-flower structures are approximately 30%, 60%, and 10%, respectively (based on a
total of 800 TEM images), noting that the statistical ratios vary for different experimental
conditions. In general, a higher synthetic energy (i.e. high laser power, long ablation time,
high ammonia concentration and long drying time) leads to better crystallinity, but larger size
for the products.


Figure 2. (a) Nanospheres with rounded edges (synthesis conditions: laser power 50 mJ, ablation time
2 h, 35% ammonia solution, drying in air). (b-c) Nanoflowers with numerous protruding spiky surfaces
(synthesis conditions: laser power 100 mJ, ablation time 8 h, 35% ammonia solution, drying in air). (d)
Hollow-flowers with tunnels connecting from the centre to the outward shell (synthesis conditions:
laser power 100 mJ, ablation time 10 h, 35% ammonia solution, drying in a sealed tube). The numbers
denote the individual hollow-flower. (e) HR-TEM image of a single NR, the inset shows the atomic
arrangement and scale bar 1 nm. (f) The Fourier-Filtered Transform (FFT) pattern corresponding to the
Li Yang, Paul W. May and Lei Yin 416
region shown in (e). K, J, H, G, P and P' label the positions of the six domains (see text for details).
(Reproduced from [Error! Bookmark not defined.] by the permission of Institute of Physics (IOP)).
In principle, assembly is energetically favoured because the formation of larger crystals
can greatly reduce the interfacial energy of isolated NPs or NRs. Therefore, most of our final
products are either well-defined nanosphere structures or self-assembled flower-like
architectures if the TEM grid dried naturally in air. Only occasionally were monodispersed
NPs or isolated NRs seen by TEM. The mechanism for how these lower dimensional building
blocks construct to higher dimensional arrangements, rather than random clumps, is still
unclear. However, the above evidence indicates that oriented attachment [37] was observed
among the crystallites, in which a larger crystal structure is formed from smaller ones by
direct joining of suitable crystal planes. In particular, in the HRTEM image of Figure 2(e)
taken from a single NR, the periodic lattices show the atomic arrangement (Figure 2(e), inset)
with very few defects, and reflect the relationship between the orientation of the NPs and the
crystallography of the ordered NR array. The corresponding Fourier-Filtered Transform
(FFT) pattern illustrates that the nanocrystal consists of six domains with sixfold twins. The
split spots K and J, H and G in the FFT pattern is due to the small angle between the twin
boundaries. The reflections P and P' in Figure 2(f) are not split, and represent the coherent
positions of the twin boundaries.


Figure 3. FTIR spectra of three different carbon nitride structures: (a) nanosphere, (b) nanoflower, (c)
hollow-flower. (Reproduced from [Error! Bookmark not defined.] by the permission of Institute of
Physics (IOP)).
Information regarding the chemical bonding structure was obtained from Fourier
transform infrared spectroscopy (FTIR). Figure 3 shows the FTIR spectra of the above-
mentioned different morphology of carbon nitride crystals, which exhibits several peaks
related to the chemical bonding between carbon and nitrogen [38]. The region 1000-1500 cm
-
1
corresponds to C-N single bonding, while the regions 1500-1750 cm
-1
and 2150-2300 cm
-1

are related to C=N and CN bonding, respectively. Similar spectra were also obtained by
Sequential Nucleation and Growth of Complex Nanostructures 417
Zimmerman and co-workers [39]. In our case, for the nanosphere structures (Figure 3(a)) the
two peaks at 1040 cm
-1
and 1406 cm
-1
correspond to the C-N stretching mode. The absorption
band at 1639 cm
-1
is assigned to the stretching vibrational modes of C=N. Moreover, a small
peak at 2208 cm
-1
can probably be attributed to CN bonds, although it is much weaker
compared with the other stretching modes. A broad band centred at 3464 cm
-1
is due to NH
group vibrations [40]. The 558 cm
-1
peak can be assigned to the out-of-plane bending mode
for graphite-like sp
2
domains, which become IR active due to nitrogen incorporation into the
bonding network. The obvious differences between these samples are that the intensities of all
the features are weaker and broader for the nanoflower and hollow-flower shape
nanostructures. We attributed this to the voids in the nanoflowers and the internal nanospaces
existing in the hollow-flowers.
3.2. Control of the Quality of Self-assembly
3.2.1. Diffusion of the Building Blocks

Usually, ordered organization was obtained following evaporation of a drop of a
nanocrystal solution that had been deposited onto a TEM grid. Figure 4(a) shows a typical
symmetric carbon nitride flower together with its nano-petal building blocks (which look
like flattened rods in the TEM). Figure 4(b) shows that these nano-petals appear fused
together and interwoven to form a lattice-like framework of the flower-like superstructure.
The figure also shows the NPs that surround each nano-petal, and which fill in the holes
within the framework to produce a dense, solid structure. EDX analysis confirms that carbon
and nitrogen are present in all these structures, and micro-diffraction pattern (MDP, Figure
4(c)) was also consistent with crystalline hexagonal -phase carbon nitride oriented along the
[001] zone-axis. Several [001] patterns in Figure 4(c) can be identified at the same time,
indicating that the nano-petals consist of several domains, with different rotational
orientations contributing to the diffraction pattern. The HR-TEM image in Figure 4(d) shows
that the nano-petals at the very edge of the flower contain very few defects and are single
crystalline, as was anticipated from the MDP. Again, the lattice fringes (d
200
= 0.28 nm,
0 4 1
d = 0.15 nm) and their angles (106) are in good agreement with the calculated values for
hexagonal -C
3
N
4
[41].
The smaller NPs, which lie in and around the nano-petal-framework comprising the
flowers, appeared to be mobile with respect to this framework, and diffused outward from the
centre of the flower with longer drying times. The results of this diffusion can be seen in
Figure 4(e), where the solid carbon nitride flower (similar to that in Figure 4(a)) has become
hollow. The NPs have diffused from the centre but remain loosely attached to the outside,
making the outer shell of the flower appear fuzzy. The thickness of the fuzzy shell was
~ 140 nm and that of the hollow core was ~ 200 nm (shown as a lighter colour in the image).
When the suspension was placed onto a hot-plate at 200C for 0.5 h, the hollowing process
was accelerated to form a semi-core-shell structure. The radial distribution of the NRs formed
channels leading from the centre to the shell (Figure 4(f)). Another type of hollow structure
was observed when the core-shell structures were essentially separated by a hollow tunnel,
without linkage to the sphere (Figure 4(g)).
Li Yang, Paul W. May and Lei Yin 418

Figure 4. TEM image of the flower-like structures produced by LP-PLA of a graphite target in 35%
ammonia solution (laser fluence 125 mJ/pulse) for 5 h. (b) A higher magnification image of the framed
region in (a), showing a high density of NPs surrounding the nano-petal framework. (c) [001] zone-axis
MDP from the tips of the nano-petals in (b), which corresponds closely to the calculated interlayer d-
spacing of -C
3
N
4
. Arrows point to different sets of [001] reflections (see text). (d) HR-TEM image
recorded from the edge of the flower nanostructure that is oriented along [001]. (e) TEM image of a
hollow flower formed after 8 h LP-PLA and prolonged drying. (f) Semi core-shell structure. (g) core-
shell structure with a hollow tunnel. (Reproduced from [Error! Bookmark not defined.] by the
permission of Royal Society of Chemistry (RSC)).
3.2.2. Interconnection between the Big Structures

Self-assembly normally occurs when nanoscale objects interact with one another through
a balance of attractive and repulsive interactions. If the attractive force is dominant, the
components may interconnect and form larger aggregates. In contrast, the exterior appearance
of the interlinked nanostructures did not change appreciably when the interaction was weak. It
was found that the interconnections among the structures were different. Figure 5 shows two
examples of these cluster-like combinations, for nanospheres and nanoflowers. Figure 5(a)
shows a single, typical nanosphere with a dense surface, similar to those mentioned
previously in Figure 2(a). Figure 5(b-c) shows that two neighbouring spheres can be fused
together, or just joined loosely via their outside edges, with no change of internal structure.
However, for the nanoflowers, the situation was different. Figure 5(e) shows that when two
nanoflowers fuse, the inner spaces between the NRs were integrated throughout the entire
cluster structure. One important note is that the fusing together of pristine nanoflowers alters
the crystalline size slightly (~800 nm in diameter) but the morphology of nanoflower
remained (Figure 5(f)).
Sequential Nucleation and Growth of Complex Nanostructures 419

Figure 5. Examples of coalescence (eventually leading to clustering) of dense carbon nitride
nanospheres and porous nanoflowers. (a) A single nanosphere, (b) 2 nanospheres touching, (c) 2
nanospheres fused together. (d) A single nanoflower, (e) 2 nanoflowers partially fused together, (f) 2
nanoflowers completely fused.

Figure 6. (a-b) nanospheres (carbon nitride seed solution is identical to that used for Figure 2(a)). The
fused nanospheres are marked by arrows. (c-d) nanoflowers (carbon nitride seed solution is identical to
Figure 2(b-c)). The drying process was in air. The arrow in (d) shows possible fused nanoflowers. Note
that image (b) and (d) are recorded in higher magnification from (a) and (c), respectively.
Li Yang, Paul W. May and Lei Yin 420
If the TEM grid was replaced by a silicon substrate, and the previously prepared carbon
nitride seed suspension was applied and dried naturally in air, similar morphologies to those
shown in Figure 5 were obtained. However, the nanospheres were now formed with a more
uniform size distribution, as shown in Figure 6(a-b). Some nanospheres (size about 500 nm-
1 m) were attached with a boundary visible in between (highlighted by arrows for clarity).
The interaction between such interconnected nanospheres is weak since they could be broken
up with a few minutes of sonication. In contrast, the nanoflowers were dispersed individually
(Figure 6(c)) with a larger size distribution (~1-15 m). It is noted that the size of the
nanoflowers found by SEM on the Si substrate appeared much larger than those under TEM
observation (size about 500 nm-800 nm). This is probably due to some of the nanoflowers
fusing together completely to produce larger, interlinked nanoflowers (see Figure 6(d),
highlighted by the arrow). Such nanoflowers are stable and sustainable without any change
even after a few hours of sonication. The reason the nanoflowers fused more completely was
to do with the different interaction between the particles within the seed suspension and the
two types of substrate. The TEM grid was normally placed onto a filter paper and a drop of
carbon nitride aqueous suspension was pipetted onto the grid. Due to the presence of the filter
paper, water was quickly removed. For the SEM sample on a Si substrate, the droplet of
suspension took at least 2 h to dry in air. This allowed sufficient time for the nanoflowers to
aggregate. Further investigation needs to be carried out.


Figure 7. Fused-flower (carbon nitride seed solution is identical to that used in Figure 2(b-c)). Drying
process is in a sealed tube (~ 8 h evaporation). See text for discussion. Arrows in (c) and (d) are
marked for clarity.
Sequential Nucleation and Growth of Complex Nanostructures 421
Control experiments provide some evidence to support this proposed mechanism. Under
identical conditions, a droplet of carbon nitride suspension was deposited onto a Si substrate
and placed into a sealed tube. The drying process was now estimated to be around 8 h. As
expected, larger flowers constructed from hundreds of thin plates were formed (Figure 7(a)).
Careful observation found that these larger flowers were actually an aggregate of more than
one nanoflower. The boundary between the nanoflowers was perfectly fused and aligned. The
enlarged region in Figure 7(a) marked by black box shows that numerous nanoplates are
bunched up and cross-linked with recognizable boundaries or voids between the component
subunits (Figure 7(b)), which are still maintaining their close proximity. Such results can be
further seen in Figure 7(c-d). Occasionally, flowers were not fully developed, since the rate of
aggregation among the nanoflowers varies depending upon local conditions. But the arrows
marked in Figure 7(c-d) clearly indicate the fusion of the adjacent nanoplates. Given
sufficient time (e.g. by prolonging the drying time), the growth of the flower will fully
complete into three dimensions.


Figure 8. (a-b) 3D interconnected flowers. (c-d) 2D flattened flowers (synthesis conditions: 35%
ammonia solution, laser power 100 mJ, 3 h ablation and dried in a sealed tube, (c-d) seed solution was
diluted by using deionised water). Numbers in (a-d) denote the individual flower.
Li Yang, Paul W. May and Lei Yin 422
A few more examples of interconnection between larger complex structures are given in
Figure 8. As shown in Figure 8(a), the neighboring long-petalled crystals can further expand
themselves and eventually merge into an interconnected structure [42]. At least 10 petals are
needed to form the secondary flower-like architectures. Some of them sprouted out to three
dimensions but some were lying down along the substrate (see 3
rd
flower in Figure 8(b)).
However, when using diluted carbon nitride seed suspension, the morphology changes
(Figure 8(c-d)) in the mesoscopic structure may be correlated to interactions between
nanocrystals. The interconnection between those flowers was also observed, although the
forces seemed weaker (larger voids exist, see the numbered regions in Figure 8(c-d) for
demonstration) compared with those shown in Figure 7. The disappearance of the 3D
structural dimension and the occurrence of 2D flattened flowers which cover the substrate are
believed to be a result of a significant decrease in the interaction between the dispersed
nanocrystals in the droplets. In a slow evaporation, the attractive force between NPs is low
and they are likely to diffuse close to the substrate leading to formation of 2D flattened
structures.
3.3. Dynamic Study of Self-assembly Formation
3.3.1. Influence of the Drying Time

Morphology development of the high-order grass-like architectures at different growth
stages was monitored by SEM (Figure 9). The evaporation rate was controlled by either the
substrate temperature or the solvent saturation degree of the surrounding atmosphere. The
seed suspension used was spherical NPs with an average particle size of 15-20 nm under
TEM observation (see Figure 9(a) inset). When a droplet of this suspension was deposited
onto a silicon substrate and placed on a hot-plate, the solution dried quickly (about 30 min).
In this case, the NP morphology remained, and small islands of NP aggregates dispersed on
the surface sparsely (Figure 9(a)). In contrast, if the droplet on the Si substrate dried naturally
in air (~2 h), 1D NR nuclei started branching on the surface and gradually formed 2D roots
(~200 nm in size), see Figure 9(b). If instead, the droplet dried inside a sealed tube (~8 h), the
number of nanopetals increased and started interconnecting or aggregating (see the left side of
Figure 9(c)). The 2D primary nanopetals took about 12 h to coalesce into grass-like structures
(Figure 9(d)). Upon further increasing the drying time to 24 h, the NPs adjusted their position
and continued to assemble, stem-like, and eventually expanded into fully-developed 3D
architectures (Figure 9(e)). In the enlarged image of Figure 9(f), it can be seen that
nanopetals on each side stem were nearly parallel to one another. Moreover, NR bundles can
be clearly observed in each nanopetal (see the highlighted area in Figure 9(f)). It should be
noted that such heterogeneous nucleation and growth in solution were not observed by means
of TEM.
Similar experiments were also performed using the carbon nitride seed suspension
produced by 35% ammonia solution, laser power 50 mJ, 12 h ablation. This produced
nanoflowers which exhibited surfaces composed of NRs, where the NRs radiated outward
from the centre, as shown in Figure 10(a) inset. The starting seed morphology was more
complex than the NPs used in the previous time evolution study. Since it was observed that
nanoflowers exhibited a surface composed of NRs, we expect that a similar morphology
Sequential Nucleation and Growth of Complex Nanostructures 423

Figure 9. Time-dependent evolution of grass-like crystal morphology at different growth stages for (a)
30 min, (b) 2 h, (c) 8 h, (d) 12 h, and (e-f) 24 h, respectively. The box in (f) highlights the nanopetals
arrangement. (Synthesis conditions: 35% ammonia solution, laser power 75 mJ, 10 min ablation,
spherical NPs with an average particle size of 15-20 nm were used as seeds, as shown in Figure 9(a)
inset. See text for discussion).
should appear on the Si substrate. However, no regular shaped objects were detected by SEM
when the droplet was dried in air. Only some low contrast flower-shape patterns (Figure
10(a)) were seen which appeared uniformly dispersed. The enlarged image in Figure 10(b)
shows that such patterns are actually formed by a number of particles with preferential
arrangements, which were presumably the later nucleation sites for the growth of the flower.
With controlled drying time (~8 h) in a sealed tube, large numbers of flower-like structures
Li Yang, Paul W. May and Lei Yin 424
(Figure 10(c)) about 500 nm in size were distributed on the silicon surface. The enlarged
image Figure 10(d) from the area of Figure 10(c) shows these nano-objects possess external
bonding capacity or adhesiveness for self-assembly and self-alignment. For example, they
have extending arms (NRs or nanopetals) ideal for external connectivity (highlighted by
arrows in Figure 10(d)). Fully complex geometric flowers took more than one day to develop
(Figure 10(e)). Such structures comprise numerous 1D NRs or 2D nanopetals with their long-
axis pointing toward the centre of each flower. Those components were arranged side-by-side
and some were tightly bonded each other (highlighted by arrows in Figure 10(f)).


Figure 10. Time-dependent evolution of the flower-like crystal morphology at different growth stages
for (a-b) 2 h, (c-d) 8 h and (e-f) 24 h, respectively. Arrows in (d) and (f) highlight the bonding
components. Note that images (b), (d) and (f) are recorded at higher magnification than (a), (c) and (e),
respectively. (Synthesis conditions: 35% ammonia solution, laser power 50 mJ, 12 h ablation, a flower
exhibited a surface composed of NRs, where the NRs radiate outward from the centre as shown in
Figure 10(a) inset. See text for discussion).
Sequential Nucleation and Growth of Complex Nanostructures 425
From the above discussion, it seems that the morphology of the initial stage of complex
architectures (grass-like or flower like) was a small aggregate of compacted 15-20 nm-sized
dense particles, which were approximately spherical in shape. Although the nucleation and
growth of grass-like or flower-like carbon nitride superstructures might accompany NP fusion
and self-alignment to bigger building blocks (such as NRs or nanopetals), no direct evidence
was observed for this direct aggregation. Fusion and self-organization may also be associated
with thermal motion of the droplets, for example, the evaporation speed, which is determined
by the temperature and the flow rate of air above the surface. However, what is the driving
force that controls the final hierarchical complex? The mechanism is still not fully
understood. One possibility is that growth continues within the local fluid environment as
long as there is substantial mobility of the seed particles for further exchange. If the process is
sufficiently slow, this will continue until all the building blocks adjust to their desired (lowest
energy) position. Evidence for this is that the fully developed grass-like or flower-like
complexity was only observed on decreasing the evaporating rate, i.e. for drying times above
12 h in the later growth stage (Figure 9(e-f) and Figure 10(e-f)).
3.3.2. Influence of the Starting Seed Solution


Figure 11. TEM images obtained by LP-PLA in 25% ammonia solution: (a) isolated carbon nitride NRs
(50 mJ/ pulse, t = 1 h) (b) Branched NRs (50 mJ/ pulse, t = 3 h) (c) highly branched flowerlike
architectures (100 mJ/ pulse, t = 12 h). (d) Rod-like structures showing straight, long and sharp tips. (e)
Enlarged image of the region at the top of the NRs indicated by the open box in (d). (f) HRTEM image
of a single NR, the inset shows the atomic arrangement, scale bar 1 nm. (Reproduced from [Error!
Bookmark not defined.] with permission of Nova publishers).
Li Yang, Paul W. May and Lei Yin 426
When 35% ammonia was replaced by 25% ammonia solution, carbon nitride was still
formed; however, the morphology was different under TEM observation. For low laser power
(50 mJ) and short ablation time (1 h), the product contained mostly a sparse collection of
isolated NRs (Figure 11(a)). With longer ablation times (3 h), the NRs started to aggregate
into branched structures (Figure 11(b)), serving as the starting points (or nucleation seeds) for
the subsequent growth. With increasing laser power (100 mJ) and ablation time (12 h), the
concentration of NRs increased, and highly-branched flower-like architectures completely
composed of NRs can be observed (Figure 11(c)). The NRs at the edge of the flower
structures appeared to be protruding outward by ~10 nm. As shown in Figure 11(d-e), these
NRs are themselves composed of a large number of smaller NPs that have packed together in
an ordered arrangement to form the rod-like shapes. In particular, in the HRTEM image in
Figure 11(f) taken from a single NR, the periodic lattices clearly show the atomic
arrangement (Figure 11(f) inset) with no visible boundaries, and reflect the well-aligned the
orientation between the NPs and the ordered NR array.


Figure 12. SEM images of different rod-like patterns obtained by drying the carbon nitride colloidal
solution (a) in air (synthesis conditions: 25% ammonia solution, 50 mJ/ pulse, t = 1 h, TEM image
shows the isolated carbon nitride NRs (see Figure 11(a)). (b) in air and (c) in sealed tube (synthesis
conditions: 25% ammonia solution, 50 mJ/ pulse, t = 3 h, TEM image shows branched NRs (Figure
11(b)). Image (d) is recorded at a different magnification to (c).
Sequential Nucleation and Growth of Complex Nanostructures 427
The starting seed suspension can strongly influence the 2D and 3D arrangements of the
nanostructures. Using the carbon nitride seed suspension prepared from ablating 25%
ammonia solution, and varying the concentration and liquid evaporation rate, rod nanocrystal
formation was been observed with different morphologies (Figure 12). These include
irregular disordered rods (Figure 12(a)), rods with branches (Figure 12(b)), and celery-like
structure (Figure 12(c-d)). One thing these morphologies have in common is that they are all
originally made from rod-shaped seed particles.


Figure 13. SEM images of carbon nitride grass-like structures following ablation times (a) 0.5 h, (b-
d) 2 h (synthesis conditions: laser power 125 mJ, 35% ammonia solution, and drying process: (a-b)
drying in air and (c-d) drying in a sealed tube). Note that image (d) was recorded at high magnification
than (c). Arrows in (a) point out the vacancies and cracks within the film.
We found that the size of the NPs in the initial starting suspension is also very important
in determining the morphology of the carbon nitride hierarchical nanostructures. If the
starting seeds were short rods (Figure 13(a)), this favoured the sticking of the NRs onto the
substrate. The vacancies or cracks observed in Figure 13(a) were probably due to the fact that
not enough nanocrystals were deposited on the substrate. However, if the seed solution
contained sufficient number of nanocrystals with longer (about 500 nm) length, rod-rod
interaction dominated and they tended to form a denser and rougher grass-like surface (Figure
13(b)). The tips of those rods were very blurred, which implies that the solvent-substrate
Li Yang, Paul W. May and Lei Yin 428
interaction became unstable. With longer drying time, an identical seed suspension coated on
the substrate formed a homogenous grass-like film (Figure 13(c)) with plenty of radial NRs
(50-200 nm in width, 1-5 m in length). It seems that in a slow evaporation process,
increasing the size and the number of the NRs is beneficial to improve the crystallinity of the
individual NRs and the uniformity of the film (Figure 13(d)).


Figure 14. (a-b) TEM images of NR building blocks that form the grass-like structures shown in
Figure 13. (Synthesis conditions: laser power 125 mJ, 35% ammonia solution, 2 h ablation times, and
drying process: (a) drying in air and (b) drying in a sealed tube). (c-f) HRTEM images recorded from
the rods. (c) and (e) correspond to the region in (a), while (d) and (f) correspond to the region in (b).
Arrows in (a-d) point to the growth direction of the NRs. (g) Microdiffraction pattern of corresponding
(f) HRTEM image.
Sequential Nucleation and Growth of Complex Nanostructures 429
The crystallinity improvement related to the atomic and nanocrystal ordering was further
observed by TEM and HRTEM. Under identical synthesis conditions, but using different
drying methods, Figure 14(a) and (b) show apparent differences between those NRs subunits
corresponding to Figure 13(b) and (c), respectively. When the solution is immediately dried
in air (with the help of filter paper), the NRs were parallel-aligned and were 50-80 nm width
and had a short length. The outline of the NRs was very blurred (Figure 14(a)). However,
when drying was very slow, the NRs were very sharp, had longer length and larger width
(~80-200 nm). Some NRs were overlapped and tilted away, similar to those shown in Figure
13(c-d). These results support the previous SEM observations.
From the HRTEM images shown in Figure 14(c) and (d) (which correspond to the rod
area in Figure 14(a) and (b)), it was found that the crystallinity within the domain was
different. However, the growth direction for those rods perfectly matched the orientation that
appeared in the TEM images (highlighted by arrows in Figure 14(a) and (b)). The enlarged
images of Figure 14(e) and (f) show the individual atoms and their arrangements in this small
region. Figure 14(e) consists of two slightly distorted layers, which are superimposed with
respect to each other, and joined in the [101] direction. Consequently, the C
3
N
4
groups
deviate slightly from a planar arrangement. In contrast, Figure 14(f) is more close to the
idealized -C
3
N
4
structure. The atoms are linked with one edge parallel to, and one edge
perpendicular to, the (001) plane, with regular ordering [43]. The micro-diffraction pattern
(Figure 14(g)) from the self-aligned NPs (Figure 14(f)) shows the single-crystal type [001]
zone-axis pattern. Thus, the orientation order among the NPs in the assembly was further
confirmed.
4. General Discussion about Self-assembly Mechanism
Our results clearly indicate that the formation of 2D or 3D hierarchical complex
architectures is evaporation-driven self-assembly [44]. Evaporation-driven self-assembly is
one of the most promising techniques for practical use [45], because it is inexpensive, has a
high throughput, and it is a suitable technique for both low-dimensional assemblies and long-
range-ordered complex structures. Various factors in our system, such as the rate of
evaporation, the starting seed suspension, and the size and the quantity of nanocrystals within
the droplet, are very important to determine a well-defined self-assembly.
The formation of fully 3D carbon nitride structures was a slow process. During the
evaporation process, capillary forces arise. At the edge of the meniscus, the thickness of a
liquid film becomes small. The meniscus between particles has an unstable form in a thin
liquid film (Figure 15). There are strong attractive interactions among the colloidal particles
because of this instability. The attractive capillary force is called the lateral capillary force.
When the liquid evaporation rate is high, the liquid from the bulk suspension flows to the
edge of the meniscus, and other particles in the suspension are driven toward this nucleus by
the resulting convective transport (Figure 16). As in our system, the droplet was composed of
carbon nitride solid objects floating at the silicon substrate interface, which interact by lateral
capillary forces. Such forces might direct the patterning of the wettability of the surfaces via
self-assembly minimization of the interfacial free energy of the liquid-liquid interface [46].
Clearly, the morphology transformation process of NPs to hierarchical architectures requires a
significant degree of mobility in the local environment [47], which could explain why the
Li Yang, Paul W. May and Lei Yin 430
well-defined flower-like or grass-like structures are only formed during a slow drying
process. Similarly, the diffusion of the building blocks and the interconnection between the
larger structures are also related to such motion of the liquid flux. A high concentration of
starting seed suspension containing more components within the droplet may induce more
interaction between the nanocrystals and thereby increase the chance for the self-organization
of aggregates in the later stages.


Figure 15. Schematic diagram of the lateral capillary force caused by an unstable meniscus.
(Reproduced from [48] with permission of Wiley interscience).

Figure 16. Schematic diagram of evaporation-driven self-assembly.
In self-assembly, the molecular structure determines the structure of the assembly [49].
Therefore, it is believed that the self-assembly into functional structures can be fabricated
through design of the various components. Our results in section 3.3.2 have shown that the
different shape of the starting components leads to the formation of different structurally
defined aggregates. For example, the rod-like seeds generated rod-branches (Figure 12) or
grass-like structures (Figure 13) depending on the conditions, where the original shape of the
components remained intact. The more complicated the shape, the more difficult it is to
predict the final form of any aggregate. Further in-depth understanding of such phenomenon
is required in future research.
Sequential Nucleation and Growth of Complex Nanostructures 431
5. Conclusions
The formation and morphological evolution of 2D or 3D carbon nitride hierarchical
complex structures was studied in this chapter. A two-step strategy was developed to control
the final well-defined superstructures. In the first step, carbon nitride seed suspensions were
prepared by liquid-phase pulsed laser ablation. In the second stage the chosen seed suspension
was deposited onto a silicon substrate. Via controlling the rate of evaporation, the starting
seed suspension, and the size and the quantity of nanocrystals within the droplet, it was
possible to create dense nanospheres, highly-symmetric flowers, and uniform grass-like
structures, respectively.
Because of the mobility in the local environment, the smaller building blocks (NPs)
appeared to be mobile with respect to the larger structures (flowers), and diffused outward
from the centre with longer drying times. Such diffusion created different degrees of hollow
structure, including core-shell, semi-hollow, and hollow organization, which may find
applications in new technological areas. In addition, interconnection between the larger
structures was also observed for slow evaporation processes. For dense nanospheres, the
fusing of the pristine nanospheres was weak and they were easily separated. However, the
nanoflowers with many protruding NRs had sufficient capacity for the component NRs to
occupy the spaces within the nanoflowers and fuse the flowers together more strongly.
From studies of the dynamics of self-assembly formation, it seems that the morphology
of the initial stage of the complex architectures (grass-like or flower-like) was small
aggregates of compacted 15-20 nm-sized dense spherical particles. The self-organization in
the later stage may be associated with thermal motion of the droplets, for example, the
evaporation speed. Although the mechanism is still not fully understood yet, our experiments
which compared drying time and starting seed suspension indicated that self-assembly into
functional structures can be achieved through the design of the various components. A slow
drying process will favour an increase in the structural complexity.
The formation of 2D or 3D hierarchical complex architectures in this work seems to be
an evaporation-driven self-assembly process. The beauty of this approach is its simplicity and
efficiency. If combined readily with micrometre-scale film patterning strategies, such as
microcontact printing [50], direct writing, or lithography, it may provide a convenient
pathway to the formation of functional hierarchical devices. By varying the design of the
building blocks, materials combination, interfacial chemistry, and confining dimensions, we
should expect to discover new materials properties.
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 435-457 2010 Nova Science Publishers, Inc.
Chapter 13
PROGRESS OF SELF-STANDING DIAMOND FILM
FABRICATED BY DC ARC JET PLASMA CVD
G.C. Chen
1,*
, F.X. Lu
1
, B. Li
2
, C.M. Li
1
, W.Z. Tang
1
, J.H. Song
1
,
L.F. Hei
1
and Y.M. Tong
1
1
School of Materials Science and Engineering, University of Science and Technology
Beijing, 100083, Beijing, P. R. China
2
School of Metallurgy and Ecology, University of Science and Technology Beijing,
100083, Beijing, P. R. China
Abstract
Self-standing diamond films were fabricated by a 30 kW DC Arcjet CVD system. The novel
progresses, including layer-structured film (nano-/micro-crystalline layer) fabrication, high
orientated film deposition with high growth rate at very high ratio of CH
4
/H
2
, crack-free thick
and large area films growth, and single crystal fabrication, were reported.
Layer-structured self-standing films, 2- and 4-layered ones, were fabricated by
fluctuating the ratio of methane to hydrogen with deposition time. Results of scan electronic
microscopy (SEM) and Raman spectra showed that the layered films were constructed by the
micro-crystalline grains layer / nano-crystalline grains layer. The residual stress within the
films were balanced, and even diminished in the certain layer. The layer containing nano-
crystalline grains due to a plenty of secondary nucleation could weakly inherit the columnar
growth feature of the overlaid layer containing micro-crystalline grains. The grain size and
growth orientation of the layer containing micro-crystalline grains could be adjusted by
introduction a mid-layer containing nano-crystalline grains. Growth rate was over 10m/hr in
layered film fabrication.
The effect of very high concentration of CH
4
in H
2
, 10%CH
4
/H
2
25%, was studied on
the film morphology and orientation. Diamond films with morphology containing nice faceted
micro-sized grains were obtained with CH
4
/H
2
up to 17%. The film composition change was
found by Raman spectra. High (111)-oriented films were deposited under the condition of
CH
4
/H
2
=15% at the maximum growth rate about 50m/h. Deposition temperature could
influence both the morphology and orientation of the diamond films. The higher deposition
temperature, the higher CH
4
/H
2
could be allowed to deposit micro-sized grain-containing

*
E-mail address: guangchaochen@mater.ustb.edu.cn. (corresponding author)
G.C. Chen, F.X. Lu, B. Li et al. 436
films. However, high deposition temperature would spoil (111)-orientation. As a consequence,
(220) and (311) would be enhanced.
Crack patterns occurring in self-standing films were classified as network shape, river
shape and circle shape. The distribution and style of dominating crystalline surface was found
to influence the strength of self-standing film. The films with 60-120mm of diameter and
2mm of thickness were successfully deposited by controlling of dominating crystalline surface
in the films.
A new approach to single diamond crystal fabrication by arc jet was proposed and
discussed. This method was named as stable-tip method which was applied to overcome the
morphology instability. Single crystal, 110.6mm
3
in size, was successfully fabricated by
this method. The synchrotron radiation topography was adopted to characterize this single
crystal diamond.
Introduction
Self-standing diamond film, also as free-standing one [1], is the film that exists without
adhering to any substrates, and its thickness is usually 500-1000 micrometers. Sometimes,
self-standing diamond film (not discussed in this paper) also means that whose substrate is
got rid of by chemical solution, and the thickness even less than 15 micrometers. The
property of self-standing diamond film is very similar to that of nature diamond, and its area
has reached to 175mm in diameter [2]. Therefore, self-standing diamond film is very
promising material for application in window/dome of missile [3], thermal sink for electronic
power device [4], substrates of microelectrical engineering mechanical systems (MEMS) [5],
surface acoustic wave (SAW) devices [6] as well as cutting tool. In light of the film quality,
self-standing diamond film is classified as tool-grade, optical-grade and device-grade [7,8].
Tool-grade film is usually opaque due to relatively high concentration of non-diamond
composition. Optical-grade film is transparent with less or without non-diamond composition.
The device-grade one is applied into device fabrication.
No matter which grade film it is, mechanical strength of the film is expected as high as
the nature diamond. However, self-standing film has to face the fact that the fracture strength
is one-order-magnitude lower than that of nature single crystal. Gray and Windischmann [9]
regard that the high residual stress in the film results in the low strength. They give an
expression of the stress in the film:

f
=
th
+
in
where
th
is thermal stress, and
in
is instinct stress.
th
is due to the different expansion
property between diamond and the substrate.
in
is related to the structure of the film. For
self-standing diamond film, the first term in the right side of the expression is equal to zero
due to the release of thermal stress. The high stress in the film is, therefore, ascribed to the
instinct stress. This is not to say that there is no any effect of thermal stress on the film
strength. The fact is that the thermal stress has exerted on the film when the film peels off
from the substrate after the deposition finishes. As the stress is very high, micro- even macro-
cracks may occur. These micro- or macro-cracks result in low strength of the film.
Among various diamond synthesis techniques, DC Arc Jet Plasma enhanced CVD is
known as high growth rate diamond fabrication technique, and it is the first technique that
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 437
achieves at the fabrication of self-standing diamond film [10]. Kurihara et al first reported
diamond fabrication by this technique in 1988 [11], and then Ohtake and Yoshikawa achieved
at the highest growth rate, ~930m/hr, in 1990 [12].
The very high growth rate is commonly regarded due to high enthalpy arcjet flows in this
technique. Cappelli [10] regards that Arcjet is from the fact that the energy, via ohmic
heating in the electric arc discharge, is dissipated into a flowing, high-pressured gas, resulting
in the increase of the gas enthalpy and kinetic. The temperature in the core of the arc can
reach 40,000K, and high enough to form the plasma. The plasmas conductivity increases
with increasing temperature. The high gas temperature results in vigorous decomposition of
reactant gas and relatively high velocities (~1-10km/sec) in an arcjet flow. Therefore, more
efficient delivery of the atomic hydrogen to a substrate occurs because of productive atomic
hydrogen and reduced boundary layer thickness. He gives an expression for the fraction of the
plasma jet atomic hydrogen that is delivered to a substrate surface in terms of the expansion
pressure (in torr), p
e
, the plasma jet velocity (in cm/sec), u
0
, the substrate diameter (in cm), d
s
,
and the reaction probability of atomic hydrogen on the substrate, :
[H]
s
[H]
0

1
{1+1100
2
p
e
d
s
/u
0
}
(1)
Here, [H]
o
and [H]
s
are the mole fractions of atomic hydrogen in the incident plasma jet
and substrate respectively. It is apparent from this equation, that the maximum delivery of
atomic hydrogen to a substrate from an arcjet is favored by reduced pressure and increased jet
velocities.
The high growth rate, on the other hand, contributes some reverse effect on the film
quality. The most obvious phenomenon is morphology instability [13]. Palmer-Gordon
described the course of CVD by the expression as:
=

2
D
s

k
B
T

4

c
0
eq
D
0
(1+s)k
B
T

3
+
D
0
(n
0
-c
0
eq
)
(1+s)(L+s)
(2)
Where is the stability parameter, is the atomic volume in the bulk, is the
concentration of surface particles, is the surface tension, D
s
is the surface diffusion
coefficient, D
0
is the gas phase diffusion, c
0
eq
is the equilibrance concentration of the active
species in contract with a flat interface, s is the sticking parameter, L is the mean curvature of
the interface, is a constant, and T and k
B
are the absolute temperature and Boltzmanns
constant [14].
Palmer-Gordon model is based on the assumption that: there are three procedures for
deposit species arrive at the interface. It is either (a) incorporated into the surface; (b) it can
move over the surface by surface diffusion; or (c) it can be re-evaporated into the gas phase.
Therefore, the first term in right side of the equation is related to the surface diffusion, the
second is due to deposition or re-evaporation of surface particles, and the third term
represents the net flux of particles to the surface and is governed by the gas phase diffusion
coefficient. The first two terms in the equation work in such a manner as to stabilize and
smooth out the interface, whereas, the third term is destabilize and causes morphological
G.C. Chen, F.X. Lu, B. Li et al. 438
instability. However, this model neglects the effect of a temperature gradient in the gas and in
the growing film.
Mahalingam and Dandy [15] modify the Palmer-Gordon model. They assume that the
growth of diamond is due to both surface reaction and surface migration since re-evaporation
or desorption is expected to be negligible in the case of diamond deposition. They mentions
that diamond phase of carbon is very stable and gasification of diamond will occur very
slowly. The etching rates of diamond during diamond synthesis ambient are orders of
magnitude smaller than the deposition rates. Based on this consideration, the kinematic
equation for the growth rate of the deposited diamond film in the direction normal to the
surface (i.e., z-direction) is illustrated as:
V
z
=(-D
CH3
dC
s
CH3
dz
) + (
D
s

k
B
T
s
)
d
2
r
dz
2 (3)
where: V
z
is the linear growth velocity along z-direction; is the molar volume of diamond;
D
s
is the surface diffusivity of C atoms on diamond; is the interfacial energy of diamond per
unit area; is the molecular volume of diamond; is the number of atoms per unit area; k
B
is
the Boltzmann constant; and r is the total curvature at a point on the interface.
By this model, Mahalingam and Dandy analyze the effect of deposition temperature and
the species concentration. They point out that as the growth rate increases, the morphological
instabilities are enhanced in the growing film, and these instabilities are manifested as a
finger-like morphology. As the deposition is concerned, the increase of deposition time can
enhance the morphological instability.
Besides the morphology instability, the film quality also suffers from the rapid growth
rate in DC Arcjet method. The films usually contain relatively high compressive stress, and
much more cavities. General speaking, paralleled with low growth rate techniques, such as
microwave and hot filaments, the DC arc method possesses the fastest diamond nucleation
and crystal growth rates. The higher deposition rate tends to form smaller and poorly
developed crystals. These tiny imperfect crystals could trap more non-diamond carbons in
diamond crystals [16].
Cappelli, Goodwin and Harris created several methods to study the plasma property,
including electron temperature and electrode processes and arc jet enthalpy balance. The
detail can be seen in reference [17-20].
In summary, self-standing diamond film faces several problems, such as low strength,
morphological instability and much more defects. The high growth rate enhances these
problems by DC Arc jet method. How to increase the strength and whether the morphological
instability can be controlled, therefore, is the challenge for diamond fabrication by DC Arc jet
method. Here, we report our work in novel progresses of fabricating self-standing film.
Experiments
A 30 kW DC Arc Plasma Jet CVD system was applied to fabricate self-standing films
[21]. The fed gasses were Ar, H
2
, and CH
4
. The pressure of deposition chamber was usually
between 4-8kPa. The substrate was multi-crystalline molybdenum block with 50mm in
diameter and 30mm in height. In order to enhance the nucleation density, the molybdenum
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 439
substrate was cleaned in an ultrasonic bath with acetone and then rubbed with 20, 10, 5 and
0.5m diamond powder in turn, at last drying after rinsed by ethanol. Deposition temperature
was from 900 to 1100
0
C measured by IR pyrometer. During the experiments, we usually
changed the heat-conducting mediums between substrate and its holder, which allowed us to
control substrate temperature independently of deposition parameters.
As-deposited films were characterized by scanning electronic microscope (SEM, LEO
1450 or XL30 S-FEG), X-ray diffraction (XRD, D/MAX-RB) and Raman spectroscopy
(JYT64000).
The gas phase species in the reaction region were diagnosed by optical emission spectra
(OES) during diamond films growth. The emission light from the reaction region was
transferred to the entrance slit of a monochrometer (WDP500-2A) through the quartz window
and a lens system with an optical fiber. Scan rate was 200nm/min., and collection time was
1sec./step controlled by a computer. The detection position was focused 0.8mm above the
substrate. The typical optical emission spectrum from the CH
4
-H
2
-Ar mixture in the
deposition system is illustrated in Fig.1. The major optical emission lines from atomic H, CH
and C
2
are observed. No Ar related emission lines, like 714 nm, 750 nm, 763 nm, are found
due to the limit of narrow scanning band of the monochrometer (between 300 and 700 nm).
400 450 500 550 600 650
0
600
1200
1800
2400
3000
3600
4200
H
2
CH
H

C
2
H

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Wavelength (nm)
Figure 1. Typical optical emission spectrum from the CH
4
-H
2
-Ar mixture in the high power DC arc
plasma jet CVD system.
Results and Discussion
1. Fabrication of Nano-/Micro Multi-layered Self-standing Diamond Film
As stated above in part of introduction, low strength is regarded due to high residual
stress exerting on the film. Novel film structure fabrication may be useful to reduce or re-
distribute the stress so as to raise the film strength. Catledge et al proposed nano/micro
multiplayer diamond film in 2000 [22], and Takeuchi et al found that the fracture strength of
this multiplayer film rose up to 30% compared with the ordinary micro-crystalline diamond
film in 2001 [23]. Jiang et al [24] believed that the interface between nano/micro should
effectively prevent crack from propagation. That may be the reason why the fracture strength
became higher. Not only strength was expected to be raised, smooth surface was also
G.C. Chen, F.X. Lu, B. Li et al. 440
obtained by this multiplayer film based on the works of Jiang et al [24] and Xin et al [25]. It
shall be pointed out that these reported layered films are not self-standing ones, and all
fabricated by microwave or hot filaments CVD methods. For DC Arcjet method, the
deposition procedure is difficult to control. Meanwhile, the change of film structure may
result in the film peeling off during deposition. Thus, it is a challenge to fabricate nano/micro
multiplayer self-standing diamond film by DC Arc Plasma Jet CVD.
We tried deposition of self-standing films with this layered structure. During deposition,
the feed gasses flow rates were of H
2
6 slm, Ar 2 slm, and CH
4
60-900 sccm, respectively.
The deposition chamber pressure was maintained at 4kPa. The substrate temperature was kept
as 91010
0
C. By fluctuating the flow rate of CH
4
with deposition time, layered film structures
would be fabricated. The 2- and 4-layered film procedures were specified as following:
The 2-layered film was fabricated as that: 5% of CH
4
/H
2
was applied in the first
beginning 15 minutes to enhance diamond nucleation. Then, 1% was used to deposit micro-
crystalline diamond grains. 2 hrs later, 15% was used for 2 hrs to enhance the secondary
nucleation and expect to obtain the following deposition of nano-crystalline diamond grains.
The total deposition time was 4.25hrs.
The 4-layered film was fabricated as that: the first beginning 4.25 hrs deposition was as
the same as that of procedure 1. Then, 1% was used for a 2 hrs deposition. After then, the
ratio was increased to 15% for another 2 hrs deposition to deposit nano-crystalline grains. The
total deposition time was 8.25 hrs. The deposition procedures are marked in Fig. 2.
Figure 2. Ratio of CH
4
/H
2
during deposition process.
Figure 3 is the cross-section and growth surface SEM results of as-fabricated diamond
films. From Fig. 3a and 3c, the layered structures are clearly distinguished as 2-layered and 4-
layered films though the boundary between each layer is not very straight. The layer
fabricated under low ratio of CH
4
consists of micrometer-sized columnar crystals. However,
the layer fabricated under high ratio of CH
4
does not, and the columnar growth feature is
weakly inherited in these high ratio of CH
4
fabricating layers. The growth surfaces are
terminated by cauliflower-like morphology. Our former work showed that there were nano-
sized diamond crystalline grains in the film with cauliflower morphology [26]. Results in
Fig.3 and in reference [27] indicate that (1) the grain size in the layer with micrometer-sized
columnar crystals can be adjusted by introducing a different thickness mid-layer; (2) the layer
deposited by secondary nucleation under the condition of high CH
4
/H
2
ratio can inherit the
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 441
growth feature of the overlaid layer. The inherited growth feature becomes strong or weak
depending on the deposition time. This point can also be seen in other authors results [25].
Growth rate can be calculated by the thickness divided by deposition time. It is about
12mm/hr for 2-layered film and 9mm/hr for 4-layered film. This means that the growth rate
decreases with the increase of the layer number. It is also found that the deposition rate of
layer with columnar micro-sized crystal is smaller than that of the layer deposited under high
CH
4
/H
2
ratio condition. This phenomenon has also been mentioned by Sternschulte et al [28].
The reason is due to more amounts of nutritional radical for diamond growth. Although the
growth rate is different from each other, it is all about 10mm/hr. This value is much higher
than that in case of fabricating non-self-standing film by HFCVD and MWCVD. This shows
the attractive application of DC Arc Plasma Jet CVD in fabrication of layered structure
diamond film.

a b

c d
Figure 3. SEM results of as-grown layered films. a.cross-section of 2-layered film; b. growth surface of
2-layered film; c. cross-section of 4-layered film; d. growth surface of 4-layered film.
Raman spectra detection was done on both layered films nucleation surface and growth
surface. The results are shown in Fig.4. The peak ascribed to sp
3
band appears near 1332cm
-1
in both the nucleation surface and the growth surface. There are another two peaks of which
one appears at 1128.1cm
-1
, and the other one is the broadening peak between 1410 cm
-1
and
1620cm
-1
, in the growth surface. Nemanich et al believed that the peak at 1128.1cm
-1
was
ascribed to nano-sized diamond [29]. However, Ferrari et al regarded it due to the scattering
G.C. Chen, F.X. Lu, B. Li et al. 442
of TPA [30]. The broadening peak can be discomposed to two peaks of which one at 1548cm
-
1
ascribed to G-band of sp
2
[31], and the other one at 1470.9cm
-1
is believed to be relevant
with the nanometer diamond structure [32,33]. This means that the layer grown under high
ratio of CH
4
/H
2
condition consists of nano-crystalline diamond. These results are consistent
with the SEM results. The peak position of sp
3
is different from nucleation surface and
growth surface, which indicates that the stress style is different from each other. It is
compress stress in nucleation surface, and tensile stress in growth surface. Thus, there exists
an interlayer without stress in the film. Base on our work in reference [27], micro-crystalline
layer can be fabricated by introducing a interlayer with proper thickness.
a b
Figure 4. Raman results of layered films. a. 2-layered film; b. 4-layered film.
The growth surfaces and the nucleation surfaces of the films shown in Fig.3 were
surveyed by XRD. The results are shown in Fig.5. For 2-layered film and 4-layered film,
(111)-crystalline plan (at 2=43
0
) possess absolutely strong diffraction intensity while (220)-
crystalline plan (at 2=74
0
), (331) - crystalline plan at 2=93
0
and (400) - crystalline plan at
2=118
0
possess weak intensity in both the nucleation surface and the growth surface. Thus,
the growth orientation is <111> in both the nucleation surface and the growth surface. We
found the phenomena of transition of orientation by introducing a proper mid-layer between
two micro-crystalline layers [27].

a b
Figure 5. XRD results of as-grown films. a. 2-layered film; b. 4-layered film.
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 443
The fracture strength is measured by three-point-bend method [34]. The values of each
film are illustrated in Table 1. As reference value, the fracture strength of micro-layered film
is also measured under the condition of the thickness as same as the multiplayer film. One can
find that the value is 20% higher than that of mono-layer film.
Table 1. The fracture strength of layered film
Film structure
Thickness (m)
Fracture strength (MPa)
Mono-layered microcrystalline film
1705 33420
2-layered film
1703 39212
4-layered film
1744 40832
In summary, layered diamond films were fabricated by fluctuating the ratio of methane to
hydrogen in high power DC Arc Plasma Jet CVD. The film structure consists of the layers
containing nano- and micro-crystalline grains. The layer containing nano-crystalline grains
formed by a plenty of secondary nucleation can weakly inherit the columnar growth feature of
the overlaid layer containing micro-crystalline grains. The residual stress in film can be
balanced by this layered structure, and even can be diminished by a mid-layer containing
nano-crystalline grains with proper thickness. The grain size and growth orientation of the
layer containing micro-crystalline grains can be adjusted by introduction a mid-layer
containing nano-crystalline grains. The fracture strength is 20% higher than mono-layer
micro-diamond film. The growth rate was about 10mm/hr in layered film fabrication.
2. High Oriented Film Fabrication with Very High Ratio of CH
4
/H
2
Micro-crystalline diamond film is usually obtained by using mixture of hydrocarbon gas
(commonly methane) and hydrogen in which the concentration of methane in hydrogen,
CH
4
/H
2
, is always less than 2% [35] since Spitsyn [36] and Matsumoto [37] succeeded in
deposition of diamond under low pressure [38]. Nano-crystalline diamond grains will appear
by using methane rich fed gasses, or even without hydrogen [39]. The reason is well known
that atomic hydrogen plays an important role on suppressing the formation of unsaturated
carbon nuclei, and etching graphitic nuclei [38]. The more H fraction in reactive gas phase,
the easier faceted grains are obtained. DC Arc Plasma Jet is believed to possess higher
number density of atomic or ionic hydrogen compared to cool plasmas (such as microwave
plasma). Therefore, much higher concentration of methane can be used as 5-15% [40], and
very high growth rate (near to 1mm/h) has been achieved [12]. So far, however, the
morphology obtained at high concentration of methane (over 10%) is un-faceted. Therefore,
we report our experimental results of diamond deposition by DC Arc Plasma Jet CVD under
the condition of very high concentration of methane in hydrogen.
The high concentration of CH
4
/H
2
, up to 25%, was used to deposit diamond film. The as-
deposited films morphologies of growth surfaces are shown in Fig.6. The morphology with
nice faceted grains can be observed in the films deposited at the concentration of 10% and
15%, even 17%, seen in Fig. 6a, b and c. The size of grains in these four films is in the micron
order-of-magnitude. Cauliflower-like morphologies occur in the films deposited at the
concentration of 25%. In fact, a lot of secondary nucleation can be found in the film deposited
G.C. Chen, F.X. Lu, B. Li et al. 444
at CH
4
/H
2
=17% though nice faceted grains still remain. It seems that the morphology of the
film deposited at CH
4
/H
2
=17% is the middle-state between cauliflower-like morphology and
nice faceted grain-containing morphology. In other words, the secondary nucleation is the
important factor to result in the morphology changing from the nice faceted grain to
cauliflower.
a b
c d
Figure 6. SEM results of as-grown films under different ratio of CH
4
/H
2
. a. 10%; b. 15%; c. 17%; d.
25%.
This morphology change has also been proven by Raman Spectra survey (seen in Fig.7).
It can be seen that the composition in the film changes with the increase of CH
4
/H
2
. It is pure
diamond component first, and then nano-sized crystalline diamond existence, finally graphitic
composition occurring. Considering the SEM results in Fig.6, it can be deduced that
composition change is ascribed to the secondary nucleation, and results in the morphology
change.
Morphology change was also found when we varied the deposition temperature. Fig.8 is
the growth surface and cross-section SEM results of the films deposited at different
deposition temperature with CH
4
/H
2
=15%. Cauliflower-like morphology is obtained at 900
0
C
(seen in Fig.8a), which is similar to Fig.3b and 3d. Nice faceted micro-sized grains appear
when the deposition temperature higher than 900
0
C, seen in Fig.7b, c and d. There are co-
grown grains due to secondary nucleation on these faceted micro-sized grains, and the amount
of these co-grains increases with the increase of the deposition temperature. Growth rate of
each film in Fig.8 is calculated as about 40mm/h, 50mm/h, 30mm/h and 40mm/h according to
the film thickness and deposition time. It means that film with micro-sized grain can be
grown at the rate over 30mm/h, and the maximum is about 50mm/h.
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 445
a b
c d
Figure 7. Raman spectra results of the films shown in Fig.6. a. CH
4
/H
2
=10%; b. CH
4
/H
2
=15%; c.
CH
4
/H
2
=17%; d. CH
4
/H
2
=25%.

a b

c d
Figure 8. SEM results of as-grown films under different deposition temperature. a. 900
0
C; b. 970
0
C; c.
1000
0
C; d. 1050
0
C.
G.C. Chen, F.X. Lu, B. Li et al. 446
XRD was used to analyze the orientation in the films shown in Fig.8. The results are
illustrated in Fig.9.The intensity of (111) crystalline surface is the most strongest one, and the
ratio of intensity of (220) to that of (111), I
(220)
/I
(111)
, is less than 25% in all the films spectra.
This means that (111) crystalline surface is the dominant surface in the films growth surfaces
no matter whether the films morphology is cauliflower-like or faceted grain-containing. In
the film with the faceted grain-containing morphology, the intensity of (220) increases with
the deposition temperature increasing. The same case occurs for the intensity of (311). The
phenomenon of high intensity of (311) has been reported by Ohtake [12]. Generally speaking,
high (111)-oriented film can be obtained under the condition of CH
4
/H
2
=15%, and the highest
degree of orientation, I
(220)
/I
(111)
, can arrive at 16 occurring at 970
0
C of deposition
temperature. The degree of orientation becomes weak with the increase of deposition
temperature.
Figure 9. XRD results of as-grwon film in Fig. 8.a. 900
0
C; b. 970
0
C; c. 1000
0
C; d. 1050
0
C.
In summary, very high concentration of methane in hydrogen, from 10% to 25%, was
applied to deposit self-standing diamond films. The effect of concentration of methane in
hydrogen and deposition temperature on the films morphologies and orientations was
studied. Morphology containing nice faceted micro-sized grains were obtained with CH
4
/H
2
up to 17%, and high (111)-oriented films were deposited under the condition of CH
4
/H
2
=15%
at the maximum growth rate about 50mm/h. Columnar growth feature was weak in the film
with cauliflower-like morphology, and became weak with the increase of deposition
temperature in the films with faceted micro-sized grain-containing morphology. Micro-sized
grain-containing films are prone to be grown at high deposition temperature and high CH
4
/H
2
.
However, high deposition temperature would spoil (111)-orientation. As a consequence,
(220) and (311) would be enhanced. The change of morphology and orientation was ascribed
to the change of the composition in the film due to the occurrence of secondary nucleation.
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 447
3. Large Area Film with High Fracture Strength
Self-standing diamond film is currently fabricated on the substrates, such as Si, W, Mo,
WC-Co. These substrates possess the larger thermal expension coefficence than diamond (41-
44). Thus, the thermal stress is not able to eliminate at the time of plasma shut-off if these
substrates are still employed. Sussman (45), Field (46), Windischmann (9) and Lu (47) have
already noted that the film structure have a special effect on the fracture strength of self-
standing film. They all find that the fracture strength decreases with the increase of crystal
size. This indicates that the fine crystalline grain is pursued. Their results seem more useful
not for optical grade self-standing diamond films, but tool grade ones. Jeong (48) found that
the crack-free film can be obtained if the fracture strength is larger than the shear stress at the
film edge. Kamiya (49) found that the crack path is along and/or around the large crystal
grain boundary. These two results indicate that the crystalline structure design is necessary for
self-standing crack-free diamond film to obtain high fracture strength. In the passed two
decade, lots of works (13,35,50,51) were done on crystalline structure development. The
effect of growth parameters on crystalline structure have been studied well. However, there is
little work on the relationship between crystalline structure and strength.
Figure 10. Relationship between growth temperature and ratio of X-ray diffraction intensity.
Fig. 10 is the relationship between growth temperature and ratio of X-ray diffraction
intensity, I
(111)
/I
(220)
. The ratio decreases with the increase of growth temperature on both
nucleation side and growth side of the film body. It is larger than 4 below 900C, and less
than 4 over 900C on nucleation side. On growth side, the boundary of growth temperature
becomes 800C, i.e., the ratio is larger than 4 below 800C, and less than 4 over 800C. This
means that (111)- and (220)-crystalline surface alternately becomes dominant with the
increase of growth temperature, and transfer temperature is higher on nucleation side than that
on growth side. By reducing the size of X-ray beam to 400m4mm, the fractured sections
are also detected. The variety of ratio, I
(111)
/I
(220)
, is unlike on neither nucleation nor growth
side. It is less than 4 only in a very narrow temperature range that is around 900C. Beyond
this range, the ratio is much larger than 4. This means that (111)-crystalline surface keeps on
being dominant surface under most of employed growth temperature in fractured sections.
(220)-crystalline surface becomes dominant only in a very narrow temperature window. In
G.C. Chen, F.X. Lu, B. Li et al. 448
this research, (311)- and (400)-crystalline surface are not considered because the intensity of
these two surfaces are very small, and little variety occurs.
Three kinds of crack patterns are found in the film body. They are network-shape pattern,
river-shape pattern and circle-shape pattern, depending on the different growth temperature.
The typical patterns are shown in Fig. 11. The network-shape patterns usually occur at the
growth temperature below 800C. The cracks always pass through the whole film body in
thickness direction, and are exposed on both growth and nucleation side. The samples are,
therefore, very brittle, and their shapes are irregular. The circle-shape patterns take place at
the growth temperature over 900C. The curvature of the crack is, somehow, related to the
curvature of the substrate. The samples show a regular shape like ribbon with certain
curvature, and they are not easy broken. The river-shape patterns are never found below
800C, and tend to combine with circle-shape patterns over 900C. Unlike network-shape
patterns, the cracks dont always pass through the film body in thickness direction. They are
only exposed on growth or nucleation side sometimes. The condition is not clear for the
cracks to pass through the film body yet. The brittleness of samples is in the middle rank
comparing with the former two patterns. The fractured sections are detected by AFM. The
very smooth surface is found in the samples with network-shape patterns. The typical
roughness is about 30nm, seeing in Fig. 12a. The terraces are found in the samples with
circle-shape patterns, seen in Fig. 12b. The roughness is also small, but it is higher than the
former. Both smooth surface and terraces are found in the samples with river-shape patterns.
The roughness is the highest one among the patterns. The typical result in Fig. 12c shows
three adjacent broken grains and their boundaries.

a b c
Figure 11. Different crack pattern. a. network-shape pattern; b. river-shape pattern; c. circle-shape
pattern.
The full width at half maximum (FWHM) of sp
3
peak along the crack in river-shape
pattern was measured by micro-Raman. In this procedure, we made the laser beam very near
to the crack path in which the distance is less than 2m localized by optical microscope
attached to micro-Raman. The measured points are shown in Fig. 10. It is found that the
FWHM of Raman peak becomes the minimum value at the tip of the crack no matter on the
growth surface or the nucleation side. The values are almost same besides the crack path. The
results are showing in the Table 2.
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 449
a b
c d
e f
Figure 12. SEM and AFM results of different crack path. a. and b. network-shape pattern; c. and d.
river-shape pattern; e. and f. circle-shape pattern.
G.C. Chen, F.X. Lu, B. Li et al. 450
Table. 2 FWHM at different point along crack path
side of the crack path Tip of the crack
sample
A-point B-point C-point
nucleation side 9.31cm
-1
9.22 cm
-1
8.74 cm
-1
M2
growth side 9.02 cm
-1
8.90 cm
-1
6.77 cm
-1
nucleation side 7.25 cm
-1
7.25 cm
-1
5.89 cm
-1
H3
growth side 6.07 cm
-1
5.63 cm
-1
4.01 cm
-1
Base on these results, the effect of dominant surface on film are discussed.
Dominant surface vs. Crack patterns:
Corresponding to the XRD results, it is easy to find that the network-shape patterns occur
in the films with (111)-crystalline surface being dominant on all of the three detected
surfaces, i. e., growth side, nucleation side and fractured section. The circle-shape patterns
occur in the films with (220)-crystalline surface being dominant in all of the three detected
surface. The river-shape patterns occur in the films with (111)-crystalline surface being
dominant on one of the sides at least. AFM results indicate that the circle-shape patterns are
mainly due to intergranular fracture, and network-shape patterns are due to transgranular
fracture. The river-shape patterns seem due to the combination of inter- and trans- granular
fracture. Therefore, we can conclude that different fracture mechanism results in different
crack patterns, and different dominant crystalline surface is ready to excite different fracture.
Dominant surface vs. Fracture strength
We assume that the diamond film body is made of the pack of (111)- or (110)- crystalline
surface. In 3-point-bending test, the film body will sustain shear stress. Fracture will occur
when the shear stress is over fracture strength. It can be seen that the shear stress, , is 1/2P
(P: load) in both (111)-surface and (110)-surface. According to reference (52), the cleavage
energy is related to surface energy. It is known that the surface energy increase according to
the order as v(111)<v(110)<v(100) in diamond crystalline cell. Therefore, the film body made
of (110)-crystalline surface will possess higher fracture strength than that of (111). Reference
(7, 53) gives the evidence that the fracture strength decreases with I
(111)
/I
(220)
increasing. Base
on this discussion, the ideal crystalline structure in film body should be (100)-crystalline
surface being dominant along the force axis. Actually, we have successfully grown the crack
free self-standing diamond films with the largest diameter of 120 mm, and thickest thickness
of 2mm, seen in Fig. 13.
In summary, three kinds of crack patterns are found as network-shape pattern, circle-
shape pattern and river-shape pattern depending on growth temperature in self-standing
diamond film. They are resulted from transgranular fracture, intergranular fracture and
combination of trans- and inter-granular fracture, respectively. Corresponding to XRD results,
transgranular fracture is ready to occur in the films with (111)-crystalline surface being
dominant. Intergranular fracture occurs in the film with (220)-crystalline surface being
dominant. The uniform crystalline surface distribution benefits to reduce the intrinsic stress,
and (110)-surface is more capable to reduce the intrinsic stress than (111)-surface. The
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 451
analysis of stress state in film body suggests that the (111)-surface is easier cleaved than
(110)-surface under the same load. Crack propagation depends on the crystalline quality. It
will be blocked by the crystal with little point default. By controlling the crystalline structure
of the films, crack-free self-standing diamond films with 2mm in thickness and with 120mm
in diameter are successfully grown.
Figure 13. Crack-free diamond wafer with 2mm of thickness and 120mm or 60mm of diameter.
4. Fabrication of Single Crystal
CVD single crystal diamond was pursued almost since Spitsyn [36] and Matsumoto [37]
succeeded in deposition of diamond under low pressure [38]. Flame CVD first showed the
possibility of single crystal fabrication [54], and then microwave CVD fabricated the single
crystal diamond [55]. It is recently that carat-grade single crystal diamond was fabricated by
microwave CVD [56,57]. So far, however, no report on DC Arcjet is found.
As mentioned in part 1, morphology instability easily occurs in DC Arcjet method. This
may be one of the important reasons to keep this method from fabrication of single crystal
diamond. However, carat-grade single crystal diamond fabrication indicated that the very
high growth, ~100m/hr, is necessary by Microwave method. DC Arcjet, in other hand, is
well known for its very high growth rate. Therefore, DC Arcjet may be more feasible to
fabricate single crystal if morphology instability can be controlled.
From the analysis of D.S. Dandy [15], we can see that the morphology instability is due
to the change of radical concentrate and the change of growth tip curvature of crystal grain. If
these two changes can be eliminated, the morphology instability can be controlled. Therefore,
a method, named as stable-tip, is proposed to try to fabricate single crystal diamond in DC
Arcjet. This method is that the substrate holder is descent during growth so that the growth tip
of fabricated crystal is fixed to a position referenced to the sample holder.
By this method, we fabricated a 110.6mm
3
single crystal diamond. The optical
microscope result is shown in Fig. 14. To distinguish the substrate, synchrotron radiation
topography was applied to detect the CVD fabricated diamond and nature diamond. Fig. 15
shows the synchrotron radiation topography result. It can be seen that there are very clear
dislocation net in {111} surface in the substrate. However, the Laue spots becomes deformed,
and there are very high dense dislocation in {111} surface of the CVD fabricated diamond.
G.C. Chen, F.X. Lu, B. Li et al. 452

a b
Figure 14. Single crystal diamond grown by stable-tip method. a. lateral view; b. top view.
a b
c d
Figure 15. Synchrotron radiation topography results of nature diamond and grown diamond. a. nature
diamond single crystal (substrate); b. enlarged (111) surfaces Laue spot in a.; c. CVD diamond single
crystal; d. enlarged (111) surfaces Laue spot in c..
Progress of Self-standing Diamond Film Fabricated by DC Arc Jet Plasma CVD 453
Conclusion
30 kW DC Arcjet CVD system was used to fabricate self-standing diamond film. Layer-
structured, i.e., nano-/micro-layer, films were fabricated by fluctuating the ratio of methane to
hydrogen. The film structure transformation could be ascribed to the plenty of secondary
nucleation. The film with this layered structure possessed higher fracture strength than that
with microcrystalline mono-layer.
Very high concentration of methane in hydrogen, from 10% to 25%, was surveyed.
Morphology containing nice faceted micro-sized grains were obtained with CH
4
/H
2
up to
17%, and high (111)-oriented films were deposited under the condition of CH
4
/H
2
=15% at the
maximum growth rate about 50m/h.
The distribution and style of dominating crystalline surface could influence the strength
of self-standing film. The Large area film with 120mm of diameter and 2mm of thickness was
successfully deposited by controlling of dominating crystalline surface in the film..
Stable-tip method was used to overcome the morphology instability. Large single
crystal was successfully fabricated by this method. The sychrotron radiation was one of
effective testing technique to characteristic CVD single crystal diamond.
Acknowledgment
This work was supported by NSFC (No.50472095), Beijing Novel Project (No.
2003A13) and Beijing NSF(No.2062015).
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 459-477 2010 Nova Science Publishers, Inc.
Chapter 14
NANOSHELL ARRAYS: FABRICATION AND ENHANCED
PHOTOLUMINESCENCE
Zhipeng Huang and Jing Zhu
*
Beijing National Center of Electron Microscopy, Tsinghua University, Beijing, 100084
(P. R. China)
Laboratory of Advanced Materials, Department of Materials Science and Engineering,
Tsinghua University, Beijing, 100084 (P. R. China)
Abstract
Low emission efficiency of silicon (Si) based light emission devices (LED) still blocks
application of Si-LED. Therefore, studies focusing on improving light emission of Si-LED
still attract researches passion. Recently, we have developed a new method combining
nanosphere lithography and pulsed laser deposition to fabricate Si-based arrays
nanostructures, and have obtained remarkably enhanced photoluminescence (PL) from these
structures. The Si based nanostructures are hemisphere shell arrays (HSSAs) or nanoflower
arrays assembled by silicon-germanium (SiGe) alloy. These structures include non-close-
packed and close-packed ones, single layer and multilayer ones, as well as arrays on different
substrates.
We investigated the photoluminescence of these arrays structures, and found that all these
structures could enhance the photoluminescence intensities. Among them, the enhancement of
light emission from SiGe double layer HSSAs (DL-HSSAs), which is as high as 700 folds, is
the highest among those of all structures.
Employing transmission electron microscopy (TEM), scanning electron microscopy
(SEM), time-resolved PL, and electromagnetic simulation etc, we found the enhancement of
light emission in Si based nanostructures originated mainly from the increase of extraction
efficiency of photons from the nanostructures. The electromagnetic simulation of
enhancement matched well the experiment data. We also found that these enhancements are
related to degree of order of arrays. In highly order arrays, the enhancement is higher than that
in other arrays.

*
E-mail address: jzhu@mail.tsinghua.edu.cn
Zhipeng Huang and Jing Zhu 460
1. Introduction
In past decades, scaling-down has been a common scheme to improve performance of
integrated circuit. However, scaling-down scheme is facing varied problems, such as
interconnects latency, bandwidth limitation and crosstalk etc [1,2,3,4], which become more
prominent as the decrease of line-width in large-scale integrated circuit. These problems are
intrinsic features of circuit employing electron as carrier of information. Optic or
optoelectronic interconnection, in which photon is carrier of information, will help to
overcome these obstacles, and therefore attract researchers attention [5,6,7].
Among candidates, silicon-based optic interconnect is noteworthy because of its low cost
and compatibility with current complementary metal-oxide-semiconductor process [8,9,10].
Guide, modulation, and transmit device of photon are basic units for optoelectronic
interconnect. Silicon-based optic guide and modulation devices have been successfully
demonstrated [8]. However, silicon-based photon transmitter remains in development. The
challenge is to increase especially low intrinsic emission efficiency [11] related to indirect
band gap nature of silicon.
Many efforts have been attempted to increase emitting efficiency of silicon. The
approaches include the modification of electronic structure and optical structure. Fabricating
nano-crystal silicon [12,13,14,15], doping silicon with reactive center [16,17,18], tuning band
gap by formation of silicon germanium alloy [19,20], employing defects such as dislocation
[21,22] or point defects [23,24], increasing local electron density [25,26], and so on, are
common ways to modify electronic structure of silicon. The popular methods to modify
optical structure are fabricating surface pattern like inversed pyramid arrays [27] or SOI
photonic crystal structure [28,29,30].
Here we introduce a simple and low-cost method to fabricate silicon-based
nanostructures, and show the enhancement of room temperature photoluminescence of these
structures. We will firstly introduce the fabrication details, photoluminescence properties,
morphology and microstructure characterization, and electromagnetic simulation concerning
single- and double-layer Si/Ge hemisphere shell arrays (SL-/DL-HSSAs) on silicon substrate
[31], and then will introduce the fabrication and photoluminescence of multilayer Si/Ge
HSSAs (ML-HSSAs) on Si substrate as well as on SiO
2
nanosphere arrays on Si substrate.
2. Single- and Double-Layer Hemisphere Shell Arrays
2.1. Fabrication Procedures
A five-step procedure was employed to fabricate HSSAs, as shown in Figure 1 and
introduced in details below:
1) Single layer polymer nanosphere arrays on silicon substrate were used as template in
our experiment, as shown in Figure 1a. Arrays of polymer nanosphere, which was polystyrene
(PS) nanosphere with nominal diameter of 400 nm in our experiment, was formed by self-
assembly on Si substrate. Before self-assembly process, the substrate was washed in turn in
boiling Piranha solution and RCA solution, and then rinsed with copious amount deionized
water. These treatments of substrate produced a hydrophilic surface suitable for the self-
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 461
assembly of PS nanosphere. Drop-coating was employed for the self-assembly of PS
nanosphere. The substrate was horizontally placed, and a drop of PS nanosphere/water
solution was applied onto the substrate. With the control of PS nanosphere concentration and
dose of PS nanosphere solution, large-area single layer PS nanosphere arrays with highly
ordering on Si substrate were obtained. However, double layer or multilayer arrays were also
inevitable in this simple self-assembly method. The single layer, double layer or multilayer
region of arrays showed different colors, and could be distinguished by naked eye.
2) The close-packed PS nanosphere arrays fabricated in step 1 were transferred into non-
close-packed ones via reactive-ion-etching (RIE), as shown in Figure 1b. For RIE, the etching
gas was oxygen, the flow rate was 40 SCCM, the pressure was 5 Pa and the applied RF power
was 30 W. The interstice between PS nanospheres can be adjusted by varying the etching
duration of RIE. For the resulting introduced in this chapter, the duration of RIE was 105
seconds.
3) The non-closed-packed PS nanosphere arrays were used as template for the deposition
of Si/Ge alloy, as shown in Figure 1c. The Si/Ge alloy was deposited via pulsed-laser-
deposition (PLD) at room temperature. The temperature in PLD process was important,
because temperature higher than glass transition temperature (T
g
) of PS caused the melting of
polymer and thus the failure of template. T
g
of PS is about 110
o
C [32]. In the deposition, a
sintered Si
1-x
Ge
x
(x=50%) target was used, the pressure was lower than 5x10
-5
Pa, the wave
length of KrF pulsed laser beam was 248 nm, the deposition pulse rate was 2 Hz, and the
power of laser pulse was 180mJ. The deposition was conducted at room temperature for
10~30 minutes. Si/Ge alloy deposited at room temperature, which would act as scaffold in the
following process, was amorphous and had no contribution to the luminescence property.
Therefore, the thickness of this scaffold should be as thin as possible. After this procedure,
SiGe hemisphere shells were formed above the PS spheres and SiGe mesh was formed
between interstices of non-close-packed PS nanosphere arrays.
4) The template, PS nanosphere arrays, was removed by heating the substrate at 700~900
o
C for more than 30 minutes. During the elevation of temperature, PS spheres were removed
and SiGe hemisphere shells moved down to contact with SiGe mesh, leading to the formation
of continuous SiGe scaffold, as shown in Figure 1d.
Figure 1. Scheme for the fabrication procedures of Si/Ge HSSAs. Low-left part of d,e have been drawn
transparent to show clearly the shell structure. (Reprinted with permission from Ref. [31]. Copyright
AIP 2007).
5) The Si/Ge alloy was deposited at 700~900
o
C and proper duration, which is 55 minutes
for SL-/DL-HSSAs samples in this chapter, to obtain Si/Ge alloy with desired thickness.
Zhipeng Huang and Jing Zhu 462
Except for the deposition temperature and duration, the other parameter of PLD was identical
to what descript in step 3. After this step, a Si/Ge alloy film with hexagonal ordering protrude
arrays was formed, as shown in Figure 1e.
2.2. Characterization of Morphology
Surface morphologies of HSSAs were investigated by scanning electron microscope
(SEM). Large-area SiGe HSSAs could be seen on the surface of silicon substrate. Figure 2a
shows a low magnification bird-eye view SEM image of SL-HSSAs. The tilted angle of
sample was about 15
o
. HSSAs were a replication of the top surface morphology of PS sphere
arrays, and therefore exhibited highly hexagonal ordering. The number of layer in HSSAs
structure was tuned by that of the PS sphere arrays. By employing single layer template, SL-
HSSAs could be obtained, and DL-HSSAs by double layers or multilayer template. The
details of structures could be seen in bird-eye view and cross-sectional view SEM images of
SL- and DL-HSSAs. In single layer structure, the patterned film showed a hexagonal
ordering, and there was a hollow hemi-sphere in each protrudes. The center-to-center distance
between shells was about 400 nm, matched well the average diameter of untreated PS sphere.
For each hemi-sphere shell, the diameter was about 320 nm, and the thickness of the shell was
about 80 nm. The diameter and thickness of each shell was determined respectively by the
duration of RIE process and deposition time of SiGe alloy. Exposed to the Si/Ge flux during
the deposition, the interstice between non-close-packed PS spheres also filled with SiGe film.
Figure 2. SEM images of HSSAs. a, A low magnification image of monolayer HSSAs; b, High
magnification bird-eye view and c, cross-sectional view images of monolayer HSSAs. d, High
magnification bird-eye view and e, cross-sectional view images of double layers HSSAs. (Reprinted
with permission from Ref. [31]. Copyright AIP 2007).
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 463
Thus, in single layer each hemi-sphere shell was connected firmly to its nearest neighbors. In
double layers structure, each layer was also hexagonal arrays of hemi-sphere shell, and the
stacking manner of the two layers was similar to (111) plane stacking arrangement in FCC
structure. Different from single layer arrays, in the upper layer double layers structure the
shells were isolated to each other, while they were interconnected by flat film of SiGe in
single layer arrays. The other difference was that in lower layer of double layers structure, the
shell was not a complete hemi-sphere, as shown in Figure 2d and Figure 2e.
As shown in Figure 2a and Figure 2b, there were some little protrudes on the surface of
hemisphere shell. For sample presented in Figure 2, the deposition duration at room
temperature was 30 minutes. When the deposition duration of Si/Ge alloy at room
temperature was decreased to 10 minutes, HSSAs with different morphologies were obtained,
as presented in Figure 3. These SEM images exhibited distinguished elongated protrudes,
which had diameters of ca 70 nm. These structures will be termed nanoflower arrays in this
chapter. Figure 3 gives low and high magnification images for single layer and double layer
nanoflower arrays, from which morphology characters of nanoflower arrays can be found.
Similar to HSSAs, single layer and double layer nanoflower arrays could be obtained. White
broken circles in Figure 3a sketched up the hexagonal ordering of single layer nanoflower
arrays. As marked by white arrow in Figure 3c, nanoflower from bottom layer in double
layers structure were shown.
Figure 3. SEM images for single layer (a,b) and double layer nanoflower arrays.
Except for the deposition duration at room temperature, the other experimental
parameters of samples presented in Figure 3 were identical to those in Figure 2. Therefore,
the difference on the morphology between two samples should be caused by the deposition
duration at room temperature. The longer duration at room temperature, the thicker Si/Ge
alloy film would be deposited. In previous experiment, it was found that annealing at high
temperature (>700
o
C) would roughen the surface morphology of Si/Ge alloy film. A thinner
Zhipeng Huang and Jing Zhu 464
film would be more susceptible to high temperature treatment, and got rougher after high
temperature. We believe a rougher surface will be favorable for the growth of nanoflower
arrays.
2.3. Photoluminescence Properties
The room temperature photoluminescence (PL) of HSSAs and nanoflower arrays were
studied by a micro-raman spectroscopy (Renishaw RM2000). The wave length of exciting
laser was 514.5 nm, the power of exciting laser was 25 mW, and the spot diameter of exciting
laser was 4 m. Raman signals were measured in a back-scattering geometry and no polarizer
was used. A 50x objective lens was used. The optic microscope system of this instrument was
helpful to observe surface morphology and seek single layer structure region, double layer
structure region and flat film region, because different surface morphologies showed different
colors in the optic microscope. Aided by the optical microscope, the PL properties of single
layer, double layer structure, and flat film were studied.
The results of PL measurement were presented in Figure 4. Two kinds of reference
samples were measured. One was a flat Si/Ge alloy film deposited under the experiment
parameters identical to those of HSSAs, and the other was a flat region on the sample of
HSSAs. It was shown that two reference samples showed similar PL spectra at room
temperature. HSSAs and nanoflower arrays structure show stronger PL intensities and
different shapes of PL spectra, compared to the reference samples. The most intensive PL
spectrum came from DL-HSSAs. The spectra shapes were related to layer number of HSSAs
or nanoflower arrays structures. For single layer structures the PL spectra show the most
intensive peaks between 600~700 nm, while the most intensive peaks of PL spectra for
double layer structure lied between 800~900 nm. Beside the spectra shapes, the intensities of
PL spectra were also layer-number dependent. The double layer structure always showed PL
spectra more intensive than single layer structure.
Figure 4. Room temperature photoluminescence spectra for HSSAs, nanoflower arrays, and reference
samples. (Reprinted with permission from Ref. [31]. Copyright AIP 2007).
If the PL intensities of the strongest peaks were compared, the PL intensity from DL-
HSSAs is more than 50 folds of that from reference samples. If the PL intensities at the wave
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 465
length of 850 nm were compared, the PL intensity from DL-HSSAs is more than 700 folds of
that from reference samples. In recent publications concerning Si LED, the samples were
fabricated by expensive optical- or electron beam lithography, and SOI structure was
employed to facilitate the emission. The published enhancement of enhancement of Si LED
varied from 70 to 250 folds [28,29,30]. Here, enhancement more than 700 folds was easy to
obtain via a convenient and low cost method. Furthermore, this enhancement was obtained
from a Si-substrate structure.
2.4. Discussion
The obvious relationship between shapes and the most intensive peaks of PL spectra and
layer number of HSSAs and nanoflower arrays implies that the enhancements from HSSAs
and nanoflower arrays arise from some kind of optical effects. We will discuss in details each
parameter that will affect the PL behavior of HSSAs in this section, and show that the
enhancement is indeed an optical effect but not a quantum effect.
For PL spectra shown in Figure 4, no character of stimulated emission was found. Thus
the PL results should be studied in scenario of spontaneous emission. The luminescence
intensity of an object can be described by the flowing formula:
2
2
( ) ( ) ( ) [ | | ( )] ( ) I n n f H i = < > = equation 1
where I() is PL intensity, n is density of carriers in the structure, is the spontaneous
emission rate, is extraction efficiency of structure, is frequency of photon, f and i denote
respectively initial and final state of photon, H represents the Harmiltonian of transition
interaction,

is density of states (DOS) of emitted photons. The item in square brackets
describes spontaneous emission rate given by Fermis Golden Rule [33]. We will discuss the
difference concerning each term equation 1 between different samples, and find the origin of
the enhancement in intensities and difference in PL spectra shape.
Photogenerated carriers were the major source of carriers available for radiative transition
in our experiment. There were three factors that induced the difference of carrier density
among samples, which were the possibility that an electron would be excited to excited state
under the same illumination, the volume of materials within the illumined area of exciting
laser, and the interface within this area. More materials within the illumined area, more
photo-carriers generated. The interface of materials affected the diffusion of photo-carriers
and therefore the density of photo-carriers.
Because the HSSAs and the reference samples were fabricated with the identical
parameters, the microstructure of these samples should be identical, and then the possibility
that an electron will be excited to excited state under the same illumination should be
identical. The microstructure of HSSAs and reference sample were characterized by
Transmission Electron Microscope (TEM), and the results are presented in Figure 5. The high
resolution TEM (HR-TEM) images showed that Si/Ge nanocrystals were embedded in
amorphous Si/Ge matrix in two samples, and the microstructure of two samples was very
similar. The similarity was confirmed by counting of particle size distribution from a series of
HR-TEM images, which were shown in Figure 5c, and Figure 5d.
Zhipeng Huang and Jing Zhu 466
For the same projected illumined area, the volume of Si/Ge in DL-HSSAs and SL-HSSAs
was 1.85 and 1.17 times of that in flat film sample, respectively. While the enhancement of
PL spectra from SL- and DL-HSSAs exceeded 8 times of reference samples. Therefore, the
extra amount of Si/Ge within illumined area could not respond for the enhancement of PL
spectra.
Figure 5. HR-TEM images of HSSAs (a) and reference sample (b), and the corresponding particle size
distributions of HSSAs (c) and reference sample (d). (Reprinted with permission from Ref. [31].
Copyright AIP 2007).
Interfaces were common in reference samples, HSSAs, and nanoflower arrays. Interfaces
blocked the diffusion of excited carriers, or confined the excited carriers, increased the
carriers concentration, and therefore enhanced the PL intensity. For single layer structure and
reference samples, the interface that could confine the carriers was interface between film and
substrate, while another interface existed in double layers arrays structure, which was the
interface between unit in the upper layer and the bottom layer. The contact between
nanoshells in the upper layer and the bottom layer was not so firm, as shown in Figure 2d in
which the nanoshells in the upper layer were easily detached from the bottom layer. The weak
contact meant that the confinement effect of excited carriers was more pronounced in double
layers arrays structure, therefore the PL intensities of double layers structures should stronger
than that of single layer structure and reference samples. However, carriers confinement
could not induce the difference in shapes of PL spectra, because it increased PL intensity at
all photon frequencies, as predicted by equation 1 and shown in Figure 2 of Ref. 25.
Besides the carriers concentration, there was another electron-related factor that
impacted the PL intensity in equation 1, which was the transition ratio of carriers at excited
state. As shown in Figure 5, the microstructures of HSSAs and reference sample were similar,
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 467
and thus the transition ration of excited carriers in HSSAs and reference sample were similar.
Therefore, the Hamiltonian H in equation 1 was similar for HSSAs and reference sample, and
the transition ratio was not the origin of PL enhancement and PL shape difference.
The overall spontaneous emission efficiency, which was the term in bracket in equation
1, could be deduced from lifetime measurement of emitted photons. The lifetime
measurements of photons from HSSAs and reference sample were conducted on an
Edinburgh instruments (FLS 920) spectrometer. In the measurement, the excitation light
source was a Xe lamp, and the samples were placed in a 45
o
angle both with the incident and
emergent beam. The decay curves of PL intensities at 780 nm were recorded, as shown in
Figure 6. Lifetimes was obtained by fitting the PL decay curves using the expression
I=I
0
exp(-t/). Lifetime for shell sample was 6.36 s and lifetime for flat sample was 6.48 s.
There was no obvious difference between lifetime for SiGe nanocrystal in shell arrays and in
flat film. The measured PL lifetime (
measure
) was defined by the relative strength of radiative
(
r
) and nonradiative (
nr
) transitions: 1/
measure
=1/
r
+1/
nr
.
nr
for SiGe nanocrystal in shell
arrays and flat film should be similar, because the shell arrays and the flat film were deposited
with the same PLD parameter, and thus had the same microstructure, which was confirmed by
TEM characterization as shown in Fig. 4. Therefore, the radiative lifetime,
r
, of Si
1-x
Ge
x
nanocrystal in shell arrays and in flat films had no large difference. This meant that the
overall spontaneous emission efficiency of Si
1-x
Ge
x
in HSSAs and reference samples had no
obvious difference, and could not induce the PL enhancement and PL shape difference.
Figure 6. Decay spectra of PL intensities for HSSAs and reference sample. (Reprinted with permission
from Ref. [31]. Copyright AIP 2007).
The carriers concentration (n) and spontaneous emission efficiency (
2
2
| | ( ) f H i < > =
)
could not induce the shape difference of PL spectra from HSSAs and reference samples.
Therefore, the enhancement and shape difference of PL spectra should be ascribed to the
extraction efficiency of structure (), as shown in equation 1. It is well known that a rough
surface facilitates the extraction of photon from the surface. However, the enhancement and
shape difference of PL observed in our experiment should not be simply ascribed to the
roughness of surface, because it was obvious that the nanoflower arrays was rougher than
HSSAs, while the PL intensity of nanoflower arrays was weaker than that of HSSAs.
Zhipeng Huang and Jing Zhu 468
The enhancement and shape difference should originate from the arrays structures. In a
two dimensional pattern structure, when the wave vector satisfied certain Bragg diffraction
conditions, the lateral propagating wave could couple with ex-plane mode and then extracted
from the two dimensional structure. As discussed in Ref. [34], the direction in photonic
band diagram was particularly important because at this direction wave propagating in six
equivalent -X directions coupled each other and coupled to a mode normally diffracting
from surface. The normally diffracting mode remarkably enhanced the extract of light from
pattern structures. Ref. 28 also showed an extraordinary enhancement of PL intensity at
direction of photonic band diagram.
Photonic band diagram of SL- and DL-HSSAs were calculated using MEEP, an
implement of three dimensional (3D) Finite-Difference Time Domain (FDTD) method [35].
Due to the limit of MEEP, the basis vector of hexagonal array was re-defined in a Cartesian
coordinate system. The re-defined basis vector in patterned surface was illustrated in Figure
7a, in which a denoted center-to-center distance between nanoshells. In the 3D-FDTD
computation, the volume of unit cell was
3
(1 3 10)a , where
2
(1 3)a stood for
rectangular couple of re-defined basis vector lying on the surface of HSSAs structure, and
10a was the length of vector normal to surface of HSSAs structure, as the geometric models
shown in Figure 7b,c. Periodical boundary condition was adopted for vectors parallel to the
surface of HSSAs, and Perfectly Matched Layers (PML) were adopted for vectors normal to
the surface of HSSAs. The geometry parameters of HSSAs were measured from SEM
images. The center-to-center distance a was 400 nm, the outside diameter of nanoshell was
320 nm, and the thickness of nanoshell was 80 nm.
a
a
2
a
1
3d view
3. Side view
2. Front view
1. Top view
2
3
1
d
3d view
3. Side view
2. Front view
1. Top view
2
3
1
c
3d view
3. Side view
2. Front view
1. Top view
2
3
1
c
3d view
3. Side view
2. Front view
1. Top view
2
3
1
b a
a
a
2
a
1
3d view
3. Side view
2. Front view
1. Top view
2
3
1
d
3d view
3. Side view
2. Front view
1. Top view
2
3
1
c
3d view
3. Side view
2. Front view
1. Top view
2
3
1
c
3d view
3. Side view
2. Front view
1. Top view
2
3
1
b a
Figure 7. a, illustration of re-defined basic vector in lateral direction, where a is original basis vector,
and a
1
, a
2
are re-defined basis vectors. b, geometric model for band structure computation of SL-
HSSAs. c, geometric model for band structure computation of DL-HSSAs. b and c only draw the
interface of different refractive index.
Photonic band diagram of SL- and DL-HSSAs were presented in Figure 8, accompanied
with the corresponding PL spectra. Hatched regions were drawn to highlight the relation
between PL peaks and direction in photonic band diagram. For both single layer structure
and double layers structure, the wave frequencies of PL peaks were close to frequencies at
direction in photonic band diagram. The computation implied that the positions of peaks in
PL spectra were determined by the photonic band structure in arrays structures.
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 469
Figure 8. a, photonic band diagram of SL-HSSAs and PL spectra of single layer arrays structure; b,
photonic band diagram of DL-HSSAs and PL spectra of double layer arrays structure.
However, the origin of shapes of PL spectra, or the relative intensities between peaks in
PL spectra, was still not clear. Further investigation of PL properties was conducted by
simulating the light propagating in and extracting out the SL-HSSAs, DL-HSSAs and flat
film, and obtaining enhancement factor of SL-HSSAs and DL-HSSAs. MEEP was employed
to perform the simulation. The geometric model of DL-HSSAs for the simulation was shown
in Figure 9. The geometric model of SL-HSSAs was similar, except that there was only one
layer of nanoshell arrays. The geometry size of simulation was 3.2x3.2x2.4 m
3
, and the grid
size was 25 nm. The boundary condition was PML, and the thickness of PML layer was 0.4
m. A Gaussian pulse was used as radiating source, and was placed at the center for the flat
film and center of SL- and DL-HSSAs. The radiating source was lighted, and light began to
propagate in the structures. The lights extracting from the structure were recorded at 5
observation planes, which was 5 planes surrounding the blue volume in Figure 9, and were
summed as PL intensity.
Figure 9. Geometric model of DL-HSSAs used in the simulation of light propagation. (Reprinted with
permission from Ref. [31]. Copyright AIP 2007).
The enhancement factor was defined as the ratio of the PL intensity from the HSSAs to
that from flat film. The simulation results were presented in Figure 10. It was shown by
simulation that both SL-HSSAs and DL-HSSAs enhanced the extraction of photons, and that
the enhancement of extraction from DL-HSSAs was stronger than that from SL-HSSAs. The
Zhipeng Huang and Jing Zhu 470
simulation predicted that the greatest enhancement of PL from DL-HSSAs occurred at
wavelength of ca. 850 nm, which matched well the experiment. The simulation results
qualitatively explained relative intensity of PL between SL-HSSAs and DL-HSSAs, and
predicted the wavelength of strongest PL peaks from SL-HSSAs and DL-HSSAs. As shown
by simulation, the patterned surface structure remarkably enhanced the light extracting, and
therefore induced enhanced light emission.
Figure 10. The simulated enhancement factor of PL. (Reprinted with permission from Ref. [31].
Copyright AIP 2007).
Each term in equation 1 was discussed, and the origin of enhancement and shape
difference of PL spectra was ascribed to the difference in the abilities of extracting light from
difference structures. The reference samples, flat films, suffered the internal reflection which
blocked the light extraction in many high refractive index LED device, and therefore had low
extraction efficiency. After patterned into hemisphere shell or nanoflower arrays, some lateral
propagating light waves coupled each other and coupled to light wave normally extracting
from the surface. Thus, periodically patterned surface facilitated the light extraction. In
nanoflower arrays, the surfaces were rough, the symmetry of arrays was disturbed by the
elongated protrudes on the surfaces of repeating unit. Accordingly, the couples in laterally
and normally propagating light wave were weaker than those in HSSAs. Therefore, the PL
intensities of nanoflower arrays were weaker than those of HSSAs, while they have very
similar shape of PL spectra. Double layers structures could extract more light, because more
couple of light waves took place.
In conclusion, light extraction ability was important for the PL properties. It was also
emphasized by Yablonovitch et al. that In most cases of room temperature LEDs, it appears
that the light extraction effect, will be more important. (than Purcell spontaneous emission
rate enhancement ) [36].
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 471
3. Controllable Multilayer Hemisphere Shell Arrays on Different
Substrate
3.1. Background
As introduced in section 2, HSSAs remarkably enhanced the PL intensities of Si/Ge
alloy, and DL-HSSAs showed enhancement far beyond SL-HSSAs. However, it is lack of
convenient method to control layer number in PS arrays. So to obtain DL-HSSAs, great
efforts have to pay to prepare double layer PS arrays as template. Further more, the results
introduced in section 2 imply that the enhancement of PL intensity is closely related to layer
number in HSSAs, and that more remarkable enhancement can be obtained if further increase
the layer number.
In this section, we will introduce the preliminary results concerning the fabrication of
layer-number-controllable multilayer hemisphere shell arrays (ML-HSSAs) and
corresponding PL properties. Our attempts followed a layer-by-layer assembly scheme, which
had been successfully demonstrated on incorporating defects into 3d colloid crystal
[37,38,39].
The key point of layer-by-layer assembly is to control layer number of arrays in each
round of assembly. Our effort is schematically presented in Figure 11. After self-assembly by
a simple drop coating method, PS arrays might showed different layer numbers at different
region, as shown in Figure 11a. Without etching by RIE process, the PS arrays were used as
scaffold to deposit a thin layer of Si/Ge by PLD at room temperature. After this process, only
the utmost top surface of PS arrays was covered by Si/Ge, as shown in as shown in Figure
11b. Thus, only one layer of Si/Ge alloy was obtained despite what is the layer number of PS
arrays. In succession, the PS arrays were removed by heating at high temperature, 700
o
C for
example. After the removal of PS arrays, SL-HSSAs were obtained, as shown in Figure 11c.
Finally, Si/Ge alloy was deposited at desired temperature for appropriate duration to
demanded thickness, as shown in Figure 11d.
Figure 11. Experimental scheme for the control of layer number in an assembly round.
The sample after procedures listed in Figure 11 was used as substrate for the self-
assembly of PS sphere, and then began to be initiated another round of fabrication. Because
the layer number of HSSAs can be controlled in single round, the overall layer number of
HSSAs is well controlled just by repeating the round for desired repeats.
Zhipeng Huang and Jing Zhu 472
3.2. Geometry Characterization
Surface morphology of SL-HSSAs fabricated by the new scheme was characterized by
SEM, and the results were presented in Figure 12. SEM images were taken from the sample
after the removal of PS by heating. Large area homogeneous ordered thin Si/Ge HSSAs were
obtained, as shown in Figure 12a. Different from what was introduced in section 2, nanoshells
fabricated by new scheme were close packed. Figure 12b shows cross-sectional view SEM
image of SL-HSSAs, and Figure 12c shows a high resolution image corresponding to region
enclosed by white rectangle in Figure 12b. It is shown by Figure 12c that the PS sphere had
been totally removed, and the thickness of nanoshell was less than 10 nm.
Figure 12. SEM images of thin Si/Ge alloy HSSAs.
Figure 13. Cross-sectional view SEM image of FL-HSSAs (a,b,c) and the formation scheme of AB
stacking (d,e,f) and AA stacking.
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 473
Four-layers HSSAs (FL-HSSAs) had been fabricated by repeating 4 times procedures
shown in Figure 11. Figure 13a-c presented cross-sectional SEM images of FL-HSSAs. As
shown by SEM images, the layer number was homogeneous in the samples. There were two
kinds of stack manner between nanoshell in adjacent layers, which were AB type as shown in
Figure 13b and AA type as shown in Figure 13c. Because each layer of nanoshell was a
replica of top surface of PS arrays, so the stacking manner between adjacent layer of
nanoshells was determined by the relative position between the top layer PS spheres in PS
arrays and the latest layer of nanoshell. If the top layer PS spheres were located at the
interstice of nanoshells after self-assembly, as shown from Figure 13d to Figure 13e, the latest
deposited nanoshells also located at the interstice of nanoshells in previous nanoshell arrays,
as shown from Figure 13e to Figure 13e. Figure 13f to Figure 13g illustrated the process
leading to AA type stacking.
3.3. Photoluminescence Properties
The photoluminescence properties of FL-HSSAs were investigated by a micro Raman
spectroscopy. The details about experiment setup and parameters were the same as what
introduced in section 2.3. For the evaluation of enhancement properties, SL-HSSAs were
fabricated with the same experimental parameter as each single round for FL-HSSAs. The
results were presented in Figure 14. It was shown that the PL intensities of FL-HSSAs were
about 7 times higher than those of SL-HSSAs.
Figure 14. Photoluminescence spectra of FL-HSSAs and SL-HSSAs on Si substrate (The sharp peaks
marked by the circle are Raman scattering peaks).
The amount of Si/Ge alloy in FL-HSSAs within the projected illumined area during PL
measurement was four times that of SL-HSSAs. Thus the actually enhancement arisen from
structure difference was about 2 times. The enhancement in this approach was lower than
what was introduced in section 2. There were two possible reasons. The structural difference
may be one reason. As shown by SEM images, in ML-HSSAs, the hemisphere nanoshell is
closed-packed to each others, while the hemisphere nanoshell is non-close-packed in samples
introduced in section 2. The variation of refractive index was more pronounced in non-close-
packed arrays, and had more powerful ability to tune the optical properties. This opinion was
also implied by the difference between positions of strongest peaks from close-packed SL-
Zhipeng Huang and Jing Zhu 474
HSSAs, as shown in Figure 14, and non-close-packed SL-HSSAs, as shown in Figure 4. The
disorder in the stacking manner between adjacent layers in ML-HSSAs, as shown in Figure
13, can also contribute to the low enhancement ability.
3.4. ML-HSSAs on Different Substrates
All samples introduced above were fabricated directly on Si substrate, which has a
relative high refractive index. The higher refractive index of substrate makes smaller the total
reflection angle of substrate, and makes lower the extraction efficiency of device. Thus, many
published Si LED devices were fabricated on a low refractive index SiO
2
film [28,29,30]. We
also tried this scheme to further enhance the luminescence behavior of HSSAs.
Multi-layers SiO
2
nanosphere arrays were used as substrate for the fabrication of ML-
HSSAs. The SiO
2
nanosphere arrays self-assembled to substrate often show (111) direction
normal to the substrate surface. Because SiO
2
nanosphere array has an optical band gap along
(111) direction, the crystalline orientation of SiO
2
nanosphere array relative to substrate helps
to block the light propagating normally deep into the substrate and facilitate the extraction of
light from the substrate [40].
Figure 15. Plan view (a), low magnification (b) and high magnification (c) cross-sectional view SEM
image of FL-HSSAs.
The SiO
2
nanospheres had a nominal diameter of 500nm, and were assembled to arrays
by drop-coating technique. SEM images of FL-HSSAs on SiO
2
nanosphere arrays were
shown in Figure 15. Region 1 in Figure 15a showed top surface of FL-HSSAs, while region 2
showed SiO
2
nanosphere arrays. Because diameter of SiO
2
nanosphere was larger than that of
PS sphere used as mask for the deposition of Si/Ge nanoshell, the ordering of PS sphere on
SiO
2
nanosphere arrays was a little bit bad, as shown in Figure 15a. From the cross-sectional
view image, Figure 15b, different layers of structure was easy to be distinguished, which were
1 for Si substrate, 2 for SiO
2
nanosphere arrays, and 3 for FL-HSSAs. SEM images showed
Nanoshell Arrays: Fabrication and Enhanced Photoluminescence 475
that multi-rounds of fabrication for ML-HSSAs did not disturb the original ordering of SiO
2
nanosphere arrays and the ordering of HSSAs fabricated by previous step.
PL spectra of FL-HSSAs on Si substrate and SiO
2
nanosphere arrays substrate were
presented in Figure 16. The SiO
2
nanosphere substrate increased 4 times the PL intensities. It
should be noticed that the order of FL-HSSAs on SiO
2
nanosphere arrays was not good and
the diameter of SiO
2
nanosphere had not been designed to open the band gap at the wave
length coincided to the strongest peaks of FL-HSSAs. The order of FL-HSSAs can be
improved by using PS nanosphere and SiO
2
nanosphere with the same diameter. Combining
the practicable design of photonic band gap, the enhancement effect can be further improved.
Figure 16. PL PL spectra of FL-HSSAs on Si substrate and SiO
2
nanosphere arrays substrate.
4. Conclusion
In this chapter, we introduce the fabrication and the PL properties of HSSAs. Remarkably
enhancement, as high as 700 folds, can be obtained by DL-HSSAs. By the TEM, SEM,
photon lifetime measure, and electromagnetic simulation, we ascribe the origin of PL
enhancement to the improvement of extraction efficiency in HSSAs. Basing on this finding,
we conducted preliminary research on the fabrication and PL properties of controllable ML-
HSSAs. The enhancement of PL from controllable ML-HSSAs proved the practicability of
this idea. We also tried to incorporate controllable ML-HSSAs to SiO
2
nanosphere arrays
substrate, and obtained 4 times further enhancement of PL intensity. The results presented in
this chapter shows that HSSAs is a promising route for Si based LED device.
Acknowledgement
The authors are grateful to National 973 Project of China, Chinese National Nature
Science Foundation and National Center for Nanoscience and Technology of China.
476 Zhipeng Huang and Jing Zhu

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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 479-508 2010 Nova Science Publishers, Inc.
Chapter 15
A STRATEGY FOR THE INCORPORATION
OF TRIVALENT LANTHANIDE IONS
INTO ANATASE TIO
2
NANOCRYSTALS
Wenqin Luo,
a, b
Chengyu Fu,
a, b
Renfu Li
a, b
and Xueyuan Chen
1,a, b
a
Key Laboratory of Optoelectronic Materials Chemistry and Physics,
Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China
b
State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, P.R. China
Abstract
Trivalent lanthanide (Ln
3+
) ion-doped semiconductor nanocrystals have attracted extensive
attention due to the ability to tailor their optical properties via size control and to achieve
highly efficient luminescence through sensitization by the host. To date, finding a way to dope
the undopable Ln
3+
ions into semiconductor nanomaterials via chemical methods remains a
challenge. In this chapter, recent progress in the doping of Ln
3+
ions in TiO
2
nanomaterials has
been reviewed. A novel sol-gel-solvothermal method has been developed to effectively
incorporate Ln
3+
ions (Eu
3+
, Er
3+
, Nd
3+
and Sm
3+
) into anatase TiO
2
nanoparticles via the self-
assembly and crystallization process of previous amorphous nanoparticles, in spite of a large
mismatch in ionic radius and charge imbalance between Ln
3+
and Ti
4+
. The crystallization
process of Ln
3+
doped TiO
2
nanoparticles were systematically studied by means of
thermogravimetric-differential thermal analyses (TG-DTA), powder X-ray diffraction (XRD),
and transmission electron microscope (TEM). Photoluminescence (PL) spectra of Ln
3+
:TiO
2
samples exhibit resolved and sharp emission and excitation lines from the intra f-f transitions
of Ln
3+
ions (Ln=Nd, Sm, Eu, Er), indicating regular crystalline surroundings of Ln
3+
ions.
Multiple sites of Eu
3+
, Sm
3+
and Nd
3+
ions in anatase TiO
2
were detected by means of high-
resolution site-selective spectroscopy at 10K, whereas only single site emission of Er
3+
in
TiO
2
were observed. Very intense near-infrared luminescence around 1.53 m was also
observed, which originated from the single lattice site of Er
3+
ions incorporated in TiO
2
nanocrystals. The luminescence dynamics and CF levels of Ln
3+
at different sites have been
analyzed. Highly efficient emissions of Nd
3+
and Sm
3+
sensitized by the TiO
2
host were
observed upon the excitation above the TiO
2
band gap energy at room temperature (RT),

1
E-mail address: xchen@fjirsm.ac.cn. Author to whom correspondence should be addressed.
Wenqin Luo, Chengyu Fu, Renfu Li et al. 480
which is of particular interest for material applications. A growth mechanism for the
incorporation of Ln
3+
in the anatase lattice is also suggested.
1. Introduction
Recently, Ln
3+
ion-doped semiconductor nanocrystals have attracted extensive attention
due to their potential applications in photoelectric devices, flat plane displays, solid state laser
materials and bio-labels [1-6]. One of the advantages offered by these materials is the ability
to tailor their optical properties via size control and to achieve highly efficient luminescence
through the sensitization by the host. Moreover, they provide the possibility of excitation with
electrical current. Titania is a well-known wide band-gap semiconductor (band-gap of 3.2 eV
for anatase [7]) and a good candidate to be used as the host material of Ln
3+
ions because of
its good chemical, mechanical, optical and thermal properties. There are three crystalline
forms of TiO
2
, i.e., anatase (tetragonal), rutile (tetragonal) and brookite (orthorhomibic).
Anatase is a main phase of TiO
2
when synthesized via soft chemistry from titanium
tetravalent precursors. After high temperature calcination, anatase phase can be transformed
to rutile, which is the most stable phase of titania. However, due to a large mismatch in ionic
radius between Ln
3+
and Ti
4+
(0.0860.103 nm vs. 0.061 nm, respectively, for coordination
number VI [8]), charge imbalance and the existence of intrinsic self-purification processes at
the nanoscale [9-10], it is difficult to incorporate Ln
3+
ions into the TiO
2
nanocrystal lattice
through chemical methods. The means to effectively accommodate Ln
3+
ions in TiO
2
systems
is a precondition to achieving high luminescence performance of this kind of material. In the
past few years, many efforts have been made to synthesis Ln
3+
ion-doped TiO
2
nanomaterials
in order to yield intense and host-sensitized Ln
3+
emissions in various forms of the materials
[11-22]. Although whether Ln
3+
ions could be incorporated into the semiconductor lattice is
controversial, some important results have been achieved. These results indicated that
trivalent Ln
3+
ions can be introduced into the TiO
2
nanocrystals, and energy transfer (ET)
from the host to Ln
3+
ions can be achieved if the synthesis method is well designed.
In this chapter, different chemical approaches to accommodate Ln
3+
ions in anatase TiO
2
host have been reviewed. Much attention is focused on a new approach recently developed by
us to incorporate Ln
3+
in TiO
2
nanoparticles lattice. The crystallization behavior of Ln
3+
doped TiO
2
nanoparticles was systematically studied. Recent progress on the PL properties of
Ln
3+
ions (Ln=Eu, Sm, Nd and Er) in anatase TiO
2
nanocrystals prepared by sol-gel-
solvothermal method has been reviewed. A mechanism for the incorporation of Ln
3+
ions into
TiO
2
lattice is presented.
2. Progress in the Doping of Lanthanides in TiO
2
Nanomaterials
2.1. Amorphous-Crystalline Composites
Amorphous phase, such as glass, is a relatively loose structure. The solid solubility of
Ln
3+
ions in amorphous phase is much larger than that in the crystalline counterpart.
Moreover, the lattice distortion caused by the replacement of Ti
4+
ions with the larger Ln
3+
ions and the charge imbalance can be easily compensated in amorphous phase. The
A Strategy for the Incorporation of Trivalent Lanthanide Ions 481
amorphous-crystalline composite material is a promising host for Ln
3+
ions with efficient PL,
in which the amorphous phase provides an ideal environment to accommodate Ln
3+
ions and
the crystallite with semiconducting nature acts as a sensitizer (energy antenna).
Figure 1. TEM and EDS of Eu
3+
-doped (8 mol%) cubic mesoporous titania thin films: a) view along the
[100] zone axis; b) magnified view along the [100] zone axis, c) view down the [111] zone axis, d) EDS
confirming the presence of europium in the mesopore walls. The measured europium content is 124
mol%; this is an average value taken over several large areas. (Reprinted with permission from [12],
Frindell, K. L. et al., Angew. Chem. Int. Ed. 41, 959 (2002). 2002, Wiley-VCH Verlag GmbH & Co.
KGaA.)
A cubic mesostructured matrix of titania with three dimensional array of embedded
anatase nanocrystals has been utilized to accommodate Ln
3+
ions, and the sensitized Ln
3+
emissions by TiO
2
host were obtained [12, 23]. Figure 1 shows the TEM images of Eu
3+
(8
mol%) doped cubic mesoporous titania thin films. The TEM images viewed along different
directions ([100] and [111]) revealed that the films have a cubic arrangement of pores with a
size of 7-8 nm. As shown in Figure 1d, the high content (124 mol%) of Eu
3+
present in the
walls of the sample is confirmed by energy dispersive X-ray spectroscopy (EDS)
measurements. The excitation and emission spectra of Eu
3+
(8 mol%) and Sm
3+
(2 mol%)
ions doped mesoporous titania films are shown in Figure 2a, b and c, d respectively [23].
Upon excitation above titania band gap, both samples exhibited intense red emissions due to
Wenqin Luo, Chengyu Fu, Renfu Li et al. 482
intra-4f transitions of Eu
3+
and Sm
3+
ions. The obtained emission lines are unresolved as a
result of the location of Ln
3+
ions in the amorphous titania regions. The excitation spectra of
both samples by monitoring the emissions at 614 nm for Eu
3+
ions and 601 nm for Sm
3+
ions
exhibited a broad band at 330 nm, which was associated with the band gap of titania films,
whereas excitation lines from intra-4f transitions of Eu
3+
and Sm
3+
can not be detected,
indicating that the main contribution to the excitation is from the band gap of the titania.
Figure 2. Excitation and PL spectra of (a, b) 8 mol% europium and (c, d) 2 mol % samarium doped
mesoporous titania films. (Redrawn after [23], Frindell, K. L. et al., J. Solid State Chem. 172, 81
(2003). 2003, Elsevier).
Similar amorphous-crystalline structure was also adopted to accommodate Eu
3+
ions in a
monodisperse spherical mesoporous TiO
2
particles prepared by a simple nonionic surfactant-
assisted soft-chemistry method [19]. Figure 3 shows the SEM and TEM images of Eu
3+
doped
TiO
2
nanoparticles. The SEM image (Figure 3a) reveals that the particles are spherical and
monodisperse with a mean size of 250 nm. The presence of Eu
3+
(4.95 mol%) was confirmed
by EDS in the inset of Figure 3a. The TEM image illustrated that the Eu
3+
doped TiO
2
nanoparticles possess mesoporous structure with the pore size of 710 nm. The high
resolution TEM (HRTEM) image (Figure 3c) reveals that the pore wall of the mesoporous
nanoparticles is semicrystallite and there are many anatase nanocrystallites embedded in the
amorphous titania regions. The RT PL spectra of the Eu
3+
doped nanoparticles under different
heat treatments are compared in Figure 4. Under ultraviolet excitation at 360 nm, broad
emission lines from the excited state of
5
D
0
to
7
F
1
,
7
F
2
and
7
F
3
states can be observed. As
shown in Figure 4, the sample calcined at 400 C shows more effective luminescence
compared to the as-prepared sample without further calcination. An important factor for the
increase of samples luminescence intensity may be the formation of titania nanocrystallites
in the pore walls under calcination which plays the role of sensitizer to transferring the
absorbed excitation energy to Eu
3+
ions. When the sample is further annealed at 500 C, the
PL intensity was found to decrease. This may be due to the fact that the amorphous titania
were completely transformed into anatase and thus the previously well dispersed Eu
3+
ions
tended to aggregate and the PL of Eu
3+
was quenched.
A Strategy for the Incorporation of Trivalent Lanthanide Ions 483
Figure 3. (Color online) (a) SEM image and EDS spectra, (b) low magnification TEM, and (c) HRTEM
images and corresponding selected area electron diffraction (SAED) pattern of monodisperse
mesoporous Eu
3+
doped TiO
2
phosphor particles after 400 C calcinations. (Reprinted with permission
from [19], Yin, J. B. et al., Appl. Phys. Lett. 90, 113112 (2007). 2007, American Institute of Physics).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 484
Figure 4. (Color online) RT PL spectra of the mesoporous Eu-doped TiO
2
phosphor particles (a) before
calcinations, (b) after 400 C calcinations, and (c) after 500 C calcinations. (The inset is the emission
photograph of the corresponding samples.) (Reprinted with permission from [19], Yin, J. B. et al., Appl.
Phys. Lett. 90, 113112 (2007). 2007, American Institute of Physics).
2.2. Aggregates of Layered Nanostructure
Layered oxide materials are repeating two dimensional units of host oxide layers between
which a guest cation exists to hold the layers together. The unique structure of the layered
oxides makes them an ideal host to accommodate the Ln
3+
ions. In this system, Ln
3+
ions are
not really incorporated into the TiO
2
lattice. As a consequence, no crystal-field (CF) transition
of Ln
3+
ions can be observed in PL spectra.
Xin et al. reported an exfoliation-restacking route to accommodate Ln
3+
ions in the
lamellar aggregates of titania nanosheets [24]. The TEM image (Figure 5a) clearly shows the
lamellar structure of these materials. The content of Eu
3+
ions in the flocculated sample can
be detected by EDS analysis (Figure 5b) and the concentration of the dopant can be roughly
determined to be 101 mol%. The PL spectra of ex-Ti
0.91
O
2
/H, ex-Ti
0.91
O
2
/Tb and e-
Ti
0.91
O
2
/Eu (ex- means exfoliated) samples are shown in Figure 6. Under the excitation
at 250 nm, ex-Ti
0.91
O
2
/Eu sample emits lights both from the Ti
0.91
O
2
host and Eu
3+
ions,
whereas only Ti
0.91
O
2
host emission is detected for ex-Ti
0.91
O
2
/Tb sample. Xin et al. ascribed
the broad band peaking at 250 nm (Figure 6c) to the Ti
0.91
O
2
host absorption. However, the
band gap of Ti
0.91
O
2
host was determined to be 380 nm by UV/VIS absorption spectra, which
deviates significantly from 250 nm. Instead, the charge transfer between Eu
3+
and O
2-
ions,
i.e., an electron transferring from the O
2-
(2p
6
) orbital to the empty orbital of Eu
3+
(4f
6
),
usually locates at 200290 nm [25]. Therefore it is likely that the observed excitation band
between 220 and 380 nm results from the Eu
3+
O
2-
charge transfer in ex-Ti
0.91
O
2
/Eu. Their
conclusion on the ET from Ti
0.91
O
2
nanosheet to Eu
3+
ions on the basis of the observation of
A Strategy for the Incorporation of Trivalent Lanthanide Ions 485
emissions of Eu
3+
under the excitation at 250 nm seems questionable and deserves further
evidence.
Figure 5. (a) TEM image and (b) EDS spectra of the composite ex-Ti
0.91
O
2
/Eu. (Reprinted with
permission from [24], Xin, H et al., Appl. Phys. Lett. 85, 4187 (2004). 2004, American Institute of
Physics)
Layered titanate oxides intercalated with hydrated Eu
3+
ions have been synthesized by
electrostatic self-assembly deposition (ESD) and layer-by-layer assembly (LBL) method [26-
27]. Figure 7 shows the XRD pattern of an as-deposited Eu/TiO film by ESD method, where
Eu
3+
ions and water molecules are sandwiched between titanate nanosheets. The interlayer
distance of TiO is 6.8 . The composition with content was determined to be
Eu
0.31
Ti
0.81
O
4
2.1H
2
O, indicating that the intercalated Eu
3+
ions exist as aqua ions and are
coordinated with 710 water molecules under ambient conditions. ET from TiO layer to
intercalated Eu
3+
ions has been achieved in this material. The interlayer water that contributed
to ET plays a key role in the sensitized emission of Eu
3+
ions. As shown in Figure 8, the
excitation spectra by monitoring the
5
D
0

7
F
2
transition at 614 nm exhibit a broad band at
Wenqin Luo, Chengyu Fu, Renfu Li et al. 486
250-350 nm, which was associated with the band gap of the titanate nanosheet. In addition,
the peak at 395 nm due to the
7
F
0

5
L
6
intra-4f transition of Eu
3+
ions is also observed. Upon
excitation above TiO band gap at 300 nm, emission lines at 570, 593 and 614 nm assigned to
the transitions from
5
D
0
to
7
F
0,

7
F
1
and
7
F
2
are detected, respectively. The intensities of
excitation and emission peaks of the as-deposited Eu/TiO film are stronger than that of
Eu/TiO film treated at 100 C for 1 h due to the elimination of some of interlayer water by
heat treatment. Emission intensity and layer distance are also found to decrease with the
decrease in humidity for the same reason as illustrated in Figure 8.
Figure 6. PL excitation and emission spectra of (a) ex-Ti
0.91
O
2
/H, (b) ex-Ti
0.91
O
2
/Tb and
(c) ex-Ti
0.91
O
2
/Eu. The excitation spectra were measured by monitoring the emissions at 395,
544 and 612 nm for ex-Ti
0.91
O
2
/H, ex-Ti
0.91
O
2
/Tb and ex-Ti
0.91
O
2
/Eu, respectively. The excitation
wavelengths are also shown. (Reprinted with permission from [24], Xin, H et al., Appl. Phys. Lett. 85,
4187 (2004). 2004, American Institute of Physics).
A Strategy for the Incorporation of Trivalent Lanthanide Ions 487
Figure 7. XRD pattern and structure model of as-deposited titanate layered oxide intercalated with Eu
3+
ions. (Reprinted with permission from [27], Ida, S. et al. J. Phys. Chem. B 110, 23881 (2006).
2006, American Chemical Society).
Figure 8. RT excitation (
em
=614 nm) and emission (
ex
=300 nm) spectra of Eu/TiO films of as-
deposited, treated at 100
o
C for 1 h and under 5% humidity for 2 days. (Reprinted with permission from
[27], Ida, S. et al. J. Phys. Chem. B 110, 23881 (2006). 2006, American Chemical Society).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 488
2.3. Sol-Gel Thin Films
Sol-gel method is commonly used to prepare Ln
3+
ions doped TiO
2
thin films due to the
possibility of architectural design of coating and multilayered thin films in several types of
geometries [11, 14, 28-29]. The substrate of the thin films may significantly affect the
crystallization and PL performance of the samples [11, 30]. Figure 9 shows the XRD patterns
of TiO
2
thin film deposited on glass and Si respectively. For thin films deposited on glass, a
broad diffraction peak at around 26 is observed, indicative of amorphous nature for the
sample. In contrast, the thin film deposited on Si substrates exhibits diffraction peaks of a
Figure 9. XRD of TiO
2
thin film deposited on (a) glass and (b) Si before and after annealing at 600 C.
Films deposited on Corning glass substrates are amorphous, while those deposited on Si present a
mixture of crystalline phases. After annealing, the rutile phase (see the peaks at * positions) is better
developed in films deposited on Si. (Redrawn after [30], Palomino-Merino, R. Thin Solid Films 401,
118 (2001). 2001, Elsevier).
A Strategy for the Incorporation of Trivalent Lanthanide Ions 489
mixture of crystalline phases (anatase, rutile and TiO). With the increase of annealing
temperature at 600 C, no improvement was achieved for the crystallinity of amorphous thin
film deposited on glass, while the crystallinity of the films deposited on Si was improved
slightly. Upon the excitation by a 325 nm Ar laser beam, Eu
3+
ions embedded in both samples
exhibit broad emission lines from the
5
D
0

7
F
J
(J=0, 1, 2, 3, 4). Moreover, for the same
nominal concentration of Eu
3+
and similar film thickness, a higher PL intensity is observed
for film deposited on Si than on glass substrate. A possible explanation of this effect was
ascribed to the non-negligible contribution from the reflected light of the PL signal at the
TiO
2
/Si interface, which was not present in the transparent TiO
2
/glass interface [11]. However
the contribution of better crystallinity of the TiO
2
on silicon to the improvement of PL
intensity should also be taken into account.
It was pointed out that the PL intensity of Ln
3+
in thin films can be enhanced by co-
doping some foreign cations such as Ce
3+
and Y
3+
[28]which act as dispersers of the
dopants and thus reduce the possibility for the cross relaxation of close Ln
3+
ions. Strong
visible luminescence of Tb
3+
ions due to intra-4f shell transitions were observed for Tb
3+
doped titania films under the excitation at 340 nm line of Xe lamp [28-29]. The excitation
spectrum presents a broad line ranging from 340390 nm with the strongest peak at 370 nm,
which is ascribed to the band gap absorption of TiO
2
host, suggesting that the emissions of
Tb
3+
are mainly achieved via ET from TiO
2
host to Tb
3+
ions. The PL intensity of Tb
3+
is
significantly enhanced by co-doping Ce
3+
ions (2.6 mol%) in the thin film. The Ce
3+
ions
bridged the ET from TiO
2
host to Tb
3+
ions, i.e., the energy absorbed by TiO
2
host is
transferred to Ce
3+
ions firstly and then to Tb
3+
ions. Furthermore, the co-doped Ce
3+
ions can
disperse the clustering of Tb
3+
ions, prevent nonradiative de-excitation among Tb
3+
ions and
enhance the PL intensity of Tb
3+
. The co-doping of Y
3+
ions was also found to enhance the
PL intensity of Er
3+
doped TiO
2
thin film [29]. With the increase of the co-doped Y
3+
ions (0-
30 mol%), the PL intensity of Er
3+
ions at around 1.54 m was gradually enhanced,
meanwhile the emission lines of Er
3+
were broadened as a result of worse crystallinity of TiO
2
host induced by the co-doping of Y
3+
ions.
2.4. Nanocrystals and Nanotubes
Besides the different ways to accommodate Ln
3+
ions in TiO
2
materials mentioned above,
Ln
3+
ions were also doped into the nanocrystals [13, 18, 20-21, 31] and nanotubes [25, 32].
Stouwdam and coworkers reported the sensitized emissions in Ln
3+
(Ln=Eu, Er, Nd, Yb) ions
doped TiO
2
nanoparticles with a size of 3-5 nm prepared by the thermal decomposition of
[Ti(O
i
Pr)
3
(dmae)] (
i
pr=isopropyl; dmae=dimethylaminoethoxide) in hot trioctylphosphine
oxide (TOPO). The sensitized emissions of Sm
3+
in TiO
2
nanoparticle aggregates prepared by
sol-gel method were also addressed [13]. As shown in Figure 10, the excitation spectra show
a broad band centered at 358 nm, which is assigned to titania band gap absorption, thus
verifying the ET from TiO
2
to Sm
3+
ions. The relatively weak band at 240 nm in the spectra
can be attributed to the charge transfer transition from the O
2-
ligand to the Sm
3+
ions. The
band gap of TiO
2
can be tailored by co-doping Bi
3+
and Zr
4+
ions. Upon excitation above the
TiO
2
band gap at 355 nm, slightly resolved emission lines from
4
G
5/2
state to
6
H
5/2
,
7/2,9/2
multiplets are detected, indicating that Sm
3+
ions were probably located at a quite regular CF
environment.
Wenqin Luo, Chengyu Fu, Renfu Li et al. 490
Recently, Wang et al. synthesized Eu
3+
doped nanocrystalline titania microspheres by
ultrasonic spray pyrolysis (USP) and solvent evaporation-induced self-assembly method [20].
As shown in Figure 11, the TiO
2
:Eu
3+
(8 mol%) sample heated at 400 C shows spherical
morphology with diameters ranging from 0.1 to 1.4 m. The spherical particles exhibit porous
structures (Figure 11b) and anatase polycrystalline nature (Figure 11c). Emission bands
centered at 590, 614, 651 and 698 nm corresponding to the characteristic
5
D
0

7
F
J
(J=1, 2, 3,
4) transitions of Eu
3+
are observed under the excitation at 330 nm. These lines are
inhomogeneously broadened suggesting that Eu
3+
ions were located at much distorted CF
environments. Due to the porous structure of the sample, high concentration of doped Eu
3+
ions up to 16 mol% can be achieved. The excitation spectra by monitoring the
5
D
0

7
F
2
transition at 614 nm exhibit a broad band at around 330 nm which can be associated with the
band gap absorption of TiO
2
host, verifying effective ET from TiO
2
host to Eu
3+
ions.
Figure 10. (a) Excitation spectra (
em
=610 nm) for (i) TiO
2
:Sm
3+
(0.75 mol%), (ii) TiO
2
:Sm
3+
(0.75 mol%), Zr
3+
(0.5 mol%), and (iii) TiO
2
:Sm
3+
(0.75 mol%), Bi
3+
(0.5 mol%). (b) Emission
spectrum of TiO
2
:Sm
3+
(
ex
=355 nm). (Redrawn after [13], Hu, L. Y. J. Lumin. 127, 371 (2007).
2007, Elsevier).
Intense PL of Eu
3+
ions was obtained in TiO
2
nanotubes prepared by hydrothermal
method in NaOH aqueous solution with the precursor of Eu
3+
:TiO
2
nanocrystals obtained by
the sol-gel method [25, 33]. Figure 12a shows the TEM image of the obtained nanotubes. It
can be seen that the outer diameters and lengths of the nanotubes are about 9 and 200 nm,
respectively. By further annealing at 700
o
C, as shown in Figure 12b, the nanotubes were
transformed to nanorods. The excitation spectra of precursor TiO
2
/Eu nanocrystals, nanotubes
and nanorods are compared in Figure 13. By monitoring the
5
D
0

7
F
2
emission of Eu
3+
ions at
612 nm, the excitation lines at about 394, 465 and 535 nm corresponding to the typical Eu
3+
f-
f transitions can be observed in all three samples. However, the shapes and positions of
excitation lines were quite different from each other. In addition to the above Eu
3+
characterized absorption lines, two intense broad excitation peaks with the maxima at about
A Strategy for the Incorporation of Trivalent Lanthanide Ions 491
275 and 312 nm are observed in Eu
3+
:TiO
2
nanotubes, which can be ascribed to the charge
transfer between Eu
3+
and O
2-
and the band gap absorption of titania host respectively,
illustrating the existence of ET from the TiO
2
nanotubes to Eu
3+
ions. In this preparation
method, the TiO
2
precursors may have great impact on the PL properties of final nanotubes.
The PL of titania nanotubes prepared via a two-step hydrothermal treatment [32] behaved
very differently from that of the counterparts above-mentioned, in that the ET from TiO
2
to
Eu
3+
ions was not observed and the PL lines were worse resolved.
Figure 11. Eu-doped nanocrystalline titania microspheres. a) SEM image. b) TEM image. c) SAED
pattern recorded on the sphere shown in b). The sample shown in a), b), and c) contains 8 mol % Eu.
d) PL spectra of the spheres doped with varying amounts of Eu. The excitation is at 330 nm.
e) Corresponding PL excitation spectra for the 614 nm emission. The samples were thermally treated
at 400 C. (Reprinted with permission from [20], L. Li et al., Adv. Mater. 20, 903, (2008). 2008,
Wiley-VCH Verlag GmbH & Co. KGaA.)
Figure 12. TEM images of Eu
3+
:TiO
2
: (a) nanotubes, (b) nanorods (Redrawn after [25], Zeng, Q. G. et
al., Scripta Mater. 57, 897 (2007). 2007, Elsevier).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 492
Figure 13. Excitation spectra of the Eu
3+
ions in TiO
2
nanotubes, nanorods and nanocrystals by
monitoring the 612 nm emission line. The inset is the ultravioletvisible spectrum of the nanotubes.
(Redrawn after [25], Zeng, Q. G. et al., Scripta Mater. 57, 897 (2007). 2007, Elsevier).
3. Sol-Gel Solvothermal Approach for Incorporation of
Lanthanides in TIO
2
Nano-Lattices
3.1. Synthesis and Characterization Experiments of Ln
3+
:TiO
2
Nanoparticles
Recently, we have developed a facile sol-gel solvothermal approach to incorporate Ln
3+
ions into anatase TiO
2
nano-lattices [34-35]. In this method, we take advantages of the
hydrolysis and condensation reactions of tetra(n-butyl)titanate to precipitate TiO
2
nanoparticles from the solution in the absence of catalyzers such as acid or alkali. During the
sol-gel process, Ln
3+
ions can be co-precipitated with the TiO
2
nanoparticles. In detail, 1 mL
tetra(n-butyl)titanate was dissolved in 20 mL ethanol, to which was added the required
amount of Ln(CH
3
COO)
3
6(H
2
O) solution in 0.2 mL diluted de-ionized water and 20 mL
ethanol. After stirring for about 30 min, white particles began to precipitate from the solution.
Under continuous stirring for 3 h, the obtained cloudy solution was transferred into 20 mL
Teflon-lined autoclaves and subjected to solventhermal treatment for 5 h at 120 C. The final
obtained precipitates were isolated by centrifugation, washed with ethanol several times, and
dried at 40 C. The as-prepared sample was further annealed in air for 2 h at 400, 500, 600,
and 700 C, respectively, with a heating rate of 5 C/min to get the final products.
TG-DTA experiments were conducted on a Netzsch STA449C thermal analysis system
with pure air flow of 20 cm
3
/min. The sample was heated at a rate of 10C/min. XRD patterns
were collected using a PANalytical XPert PRO powder diffractometer with Cu K1
radiation (=0.15187 nm). The morphology of the sample was characterized by a JEOL-2010
A Strategy for the Incorporation of Trivalent Lanthanide Ions 493
TEM equipped with the EDS detector. Samples for TEM studies were prepared by dispersing
Ln
3+
:TiO
2
powders onto a holey carbon support.
Emission and excitation spectra and transient decays were recorded on an Edinburgh
Instruments FLS920 spectrofluorimeter equipped with both continuous (450 W) and pulsed
xenon lamps. For low temperature measurements, samples were mounted on a closed cycle
cryostat (10-350 K, DE202, Advanced Research Systems). For site-selective spectroscopy,
the excitation (or emission) monochromators slits were kept as small as possible to improve
the instrumental resolution. The best wavelength resolution is 0.05 nm. The line intensities
and positions of the measured spectra were calibrated according to the FLS920 correction
curve and standard mercury lamp. Laser spectroscopic measurements were carried out upon
excitation by a mode-locked ps Ti: sapphire laser (Spectra-Physics, Tsunami), which provides
a pulse width of 1.5 ps, a repetition rate of 82 MHz and a tunable range from 700 to 1000 nm.
The sample was mounted on an optical cryostat (Janis SHI-950, 4-300 K). The fluorescence
was dispersed by a 1-meter monochromator (Jobin-Yvon 1000M) and detected with a cooled
Hamamatsu R943-02 photomultiplier (PMT) or InGaAs detector. The signals were recorded
by SpectrAcq2 data acquisition system with DM302 photon counting module (Jobin-Yvon).
3.2. Crystallization Behavior
It has been revealed that the crystallization process has great effect on the incorporation
of Ln
3+
ions into TiO
2
lattice sites [34]. So the systematic study of crystallization behavior of
nanoparticles is of great importance to achieving high performance of nanophosphors. In the
following, the Eu
3+
doped TiO
2
system is used as an example to study impact of dopant
concentration on the crystallization and the thermodynamics of TiO
2
nanoparticles.
3.2.1. Effect of Dopant Concentration on the Crystallization of Nanoparticles
Figure 14 shows the TG-DTA curves of the as-prepared Eu
3+
:TiO
2
(x=2, 4, 6 mol%)
nanoparticles. The weight loss between 50150 C can be ascribed to the evaporation of
absorbed water and ethanol in nanoparticles, and the weight loss between 150400 C
accompanying with an exothermal peak at around 250 C may be due to the decomposition of
organic residues such as butyl alcohol byproduct. The exothermic peaks at approximately
400, 520, and 560 C are related to the crystallization temperatures for samples with Eu
3+
contents of 2, 4 and 6 mol% respectively, suggesting that the crystallization of TiO
2
was
hindered by the doping with Ln
3+
ions.
Figure 15 shows the XRD patterns of Eu
3+
:TiO
2
annealed at 400 C for 2 h with different
dopant concentrations. As revealed in patterns, under annealing at 400 C for 2 h, the samples
with nominal Eu
3+
concentration below 6 mol% exhibit pure anatase phase (JCPDS No. 71-
1166, space group I4
1
/amd), and the higher Eu
3+
contents the worse crystallinity of the sample
is observed. The sample of Eu
3+
:TiO
2
(6 mol%) shows amorphous structure, which indicates
a higher crystallization temperature required for its heat-treatment, in consistence with the
results obtained by TG-DTA experiments.
Wenqin Luo, Chengyu Fu, Renfu Li et al. 494

Figure 14. TG-DTA curves of the as-prepared xEu
3+
:TiO
2
(x=2, 4, 6 mol%) nanoparticles.
Table 1. Lattice parameters of Eu
3+
:TiO
2
(x=0, 1, 2, 4 mol%) nanoparticles
annealed at 400C
Samples a (nm) c (nm) Volume (nm
3
)
Bulk
a
0.37845 0.95143 0.13627
TiO
2
:Eu
3+
(0%) 0.37864 0.94186 0.13503
Eu
3+
:TiO
2
(1%) 0.37893 0.94254 0.13534
Eu
3+
:TiO
2
(2%) 0.37909 0.94527 0.13584
Eu
3+
:TiO
2
(4%) 0.38009 0.95240 0.13759
a
Calculated from JCPDS No. 71-1166. See also Ref. [36]
Because of the large ionic radius of Eu
3+
, the occupation of Eu
3+
at Ti
4+
site may lead to a
slight lattice expansion and lattice strain. The crystal lattice parameters of Eu
3+
:TiO
2
(x=0, 1,
2, 4 mol%) nanoparticles annealed at 400 C are calculated from the (101) and (200) planes
of XRD patterns, which are compared to the values of the bulk anatase in Table 1. Compared
to the bulk anatase, an increase of a and a decrease of c are observed for the undoped anatase
nanocrystals, where a and c denote the lattice parameters of the tetragonal unit cell. Similar
variation was reported by Swamy et al., where a nonlinear size dependence of lattice
parameters was observed for the neat anatase crystallites with a size less than ~15 nm [36].
For the samples doped with Eu
3+
ions, the lattice parameters of a and c and the unit cell
volume increase with the increase of Eu
3+
content (Table 1). This variation can be explained

Eu
3+
4 mol%
80
90
100

Eu
3+
6 mol%
T
G
D
T
A
Temperature (
o
C)
80
90
100
100 200 300 400 500 600

E
x
o
.
Eu
3+
2 mol%
80
90
100

A Strategy for the Incorporation of Trivalent Lanthanide Ions 495
by taking into account the fact that the higher Eu
3+
contents the more Ti
4+
ions could be
replaced by Eu
3+
. The slight lattice expansion for samples with high Eu
3+
content indicates
that Eu
3+
ions to some extent were incorporated into the TiO
2
lattice.
20 30 40 50 60 70 80
Eu
3+
6 mol%
Eu
3+
4 mol%
Eu
3+
2 mol%
2 (degree)
Eu
3+
1 mol%
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Figure 15. XRD patterns of xEu
3+
:TiO
2
(x=1, 2, 4, 6 mol%) nanoparticles annealed at 400 C for 2 h.
3.2.2. Effect of Annealing Temperature on the Crystallization of Nanoparticles
10 20 30 40 50 60 70 80

(
0
0
4
)
(
2
2
4
)
(
2
1
5
)
(
2
2
0
)
(
1
1
6
)
(
2
0
4
)
(
2
1
1
)
(
1
0
5
)
(
2
0
0
)
700
o
C
600
o
C
500
o
C
2 (degree)
as-prepared
400
o
C
(
1
0
1
)
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Figure 16. XRD patterns of Eu
3+
:TiO
2
(2 mol%) nanoparticles annealed at different temperatures.
(Reprinted with permission from [34], Luo, W. Q. et al., J. Phys. Chem. C 112 10370 (2008). 2008,
American Chemical Society).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 496
Figure 16 shows the XRD patterns of Eu
3+
:TiO
2
(2 mol% ) nanoparticles annealed at
different temperatures [34]. The as-prepared sample exhibits amorphous structure. Pure
diffraction peaks of anatase TiO
2
are obtained in the samples annealed at 400 to 700 C. With
the increase of annealing temperatures, the diffraction peaks become stronger and sharper,
indicating an improvement of crystallinity of the samples. By means of Debye-Scherrer
equation, the average sizes of samples annealed at 400, 500, 600, and 700 C are estimated to
be 12, 17, 19, and 27 nm, respectively.
Figure 17. TEM images of TiO
2
:Eu
3+
(2 mol%) at different experimental stages: (a) samples obtained
before solvothermal step; (b) samples obtained after solvothermal step (dried at 40
o
C); (c) samples
annealed at 400
o
C for 2 h; (d) samples annealed at 600
o
C for 2 h. The insets show the SAED patterns
of corresponding samples.
To investigate the growth process of nanoparticles, samples taken from different stages of
preparation process were subjected to the TEM characterization. Figure 17a shows TEM
image of the precursor prior to hydrothermal treatment, the morphology of the obtained
particles are irregular and the size is about 800 nm. The SAED pattern (inset of Figure 17a)
shows amorphous nature of the precursor. Near monodisperse spherical amorphous TiO
2
nanoparticles with the size of about 600800 nm are obtained after solvothermal treatment at
120 C for 5 h as shown in Figure 17b. After annealed at 400 C for 2 h, clear polycrystalline
rings indexed in anatase crystalline structure (inset of Figure 17c) is observed and the
morphology and size of particles remain unchanged. As revealed by HRTEM observation, the
A Strategy for the Incorporation of Trivalent Lanthanide Ions 497
spherical nanoparticles are the aggregates of 812 nm anatase TiO
2
nanocrystals [34]. When
the annealing temperature increases to 600 C for 2 h, clearer polycrystalline rings are
observed (inset of Figure 17d), suggesting a better crystallization of nanoparticles. The
spherical morphology of nanocrystals remains unchanged and the size of nanoparticles
slightly decreases to 500650 nm as a result of sample densification under higher temperature
heat treatment.
3.3. PL Properties of Ln
3+
:TiO
2
Nanoparticles
3.3.1. Eu
3+
Doped TiO
2
Nanoparticles
Recently, we have provided spectroscopic evidence of the multiple site structure of Eu
3+
ions incorporated in the 8-12 nm TiO
2
aggregates [34]. By means of site-selective
spectroscopy at 10 K, as shown in Figure 18, three kinds of luminescence sites of Eu
3+
are
identified. One site (site I) exhibits broadened fluorescence lines with most intense emission
at 613.3 nm similar to that of Eu
3+
ion in glasslike phase, which is associated to the distorted
lattice sites near the surface. The other two sites (Sites II and III) exhibit sharp emission and
excitation lines with most intense emission lines at 616.7 and 618.1 nm respectively, which
600 650 700

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)
10K Emission
(X8)
(d)
(c)
(b)
(a)
7
F
4
7
F
3
7
F
2
7
F
1
7
F
0
Figure 18. (Color online) The 10 K emission spectra of Eu
3+
:TiO
2
(2 mol%) annealed at 400 C, with
(a)
exc
=343.0 nm, corresponding to the band-gap excitation; (b)
exc
=464.6 nm for Site I; (c)
exc
=470.7
nm for Site II; (d)
exc
=472.1 nm for Site III. Color photographs of Eu
3+
:TiO
2
and Eu
3+
:Y
2
O
3
(2 mol%)
are compared in (e) and (f), respectively. Both nanophosphors were excited with a xenon lamp at 465
472 nm under the same experimental condition. To eliminate the influence of excitation light, a 495-nm
long-pass glass filter was used when taking these photos. (Reprinted with permission from [34], Luo,
W. Q. et al., J. Phys. Chem. C 112 10370 (2008). 2008, American Chemical Society)
Wenqin Luo, Chengyu Fu, Renfu Li et al. 498
0.0 0.5 1.0 1.5 2.0 2.5 3.0
10
100
1000

SiteIII
=(0.39ms)

Site II
=(0.33ms)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
time (ms)
Exp.
Fit

Site I
=(0.37ms)
T=10 K
Figure 19. (Color online) The 10 K luminescence decays of
5
D
0
for Eu
3+
at Sites I, II and III
respectively. (Reprinted with permission from [34], Luo, W. Q. et al., J. Phys. Chem. C 112 10370
(2008). 2008, American Chemical Society).
are ascribed to the lattice site with ordered crystalline environment. The value of full width at
half maximum height (FWHM) of Sites II and III is much smaller than that of Site I,
decreasing from ~9.0 nm (the 613-nm peak) to 0.58 nm (the 617-nm peak). As shown in
Figure 18a, Eu
3+
luminescence from sites II and III plus other minor sites can be observed
when excited above TiO
2
band-gap at 343 nm, indicating a weak ET from TiO
2
host to Eu
3+
ions. The weak ET can be understood because of the energy mismatch between TiO
2
band
gap and Eu
3+
ion excited states. Since no energy level of Eu
3+
is located in an energy range
approximately from 28,500 to 31,000 cm
-1
and thus this nonresonant host-to-Eu
3+
ET can
only be accomplished with the assistance of lattice phonons [37].

The PL intensity of
Eu
3+
:TiO
2
is comparable to that of Eu
3+
:Y
2
O
3
(2 mol%) nanophosphors (prepared by sol-gel
combustion method) under the xenon light excitation as shown in the inset of Figure 18. Note
that the Eu
3+
:Y
2
O
3
is a commercial red phosphor. The decay curves of
5
D
0
for Eu
3+
at sites I,
II and III are plotted in Figure 19. The three curves can be well fitted with single exponential
and similar
5
D
0
lifetimes of 0.37, 0.33 and 0.39 ms for sites I, II and III are obtained,
respectively.
Eu
3+
ion is a sensitive optical probe to detect local symmetry around Eu
3+
ions. By
carefully analyzing the high resolution emission and excitation spectra of Eu
3+
ions at three
sites, the local symmetries of three sites can be determined. The intensity ratio of
5
D
0

7
F
2
lines of Eu
3+
with electric-dipole (ED) nature to that of
5
D
0

7
F
1
lines with magnetic-dipole
(MD) nature can provide some structural information such as distortion of ligand environment
and site symmetry of local environment around Eu
3+
ions. As shown in Figure 18, the ED
transitions of Eu
3+
ions at three sites are all much stronger than the MD transitions, suggesting
that Eu
3+
ions occupy low-symmetry sites without an inversion center. Ti
4+
ions sit at a D
2d
site in the anatase lattice. The substitution of Ti
4+
with larger Eu
3+
leads to a descent of the
A Strategy for the Incorporation of Trivalent Lanthanide Ions 499
intrinsic D
2d
to a lower site symmetry (S
4
, C
2v
or D
2
), according to the branching rules of the
32 point groups [38]. Theoretically, if Eu
3+
ions situate at D
2d
or S
4
lattice sites, only two lines
for J=0 to J=1 transition and three lines (S
4
) or two lines (D
2d
) for the J=0 to J=2 CF transition
are theoretically allowed. However, three lines for
5
D
0

7
F
1
transition and four lines for the
5
D
0

7
F
2
transition of Eu
3+
ions at Site II can be clearly identified. Moreover, according to the
ED selection rule, the
5
D
0

7
F
0
(0-0) transition is only allowed in the following 10 site
symmetries, C
s
, C
1
, C
n
and C
nv
(n=2, 3, 4, 6) [39-40]. The appearance of the 0-0 line suggests
that Eu
3+
ions at Site II may occupy a C
2v
symmetry. By contrast, for Eu
3+
at Site III, the
absence of 0-0 emission and three resolved lines from the emission of
5
D
0

7
F
1
plus three
lines from the emission of
5
D
0

7
F
2
indicate a possible D
2
site symmetry for Site III.
Furthermore, according to the high resolution spectra, Eu
3+
ions at Site II (or III) are very
likely located at a distorted C
2v
(or D
2
) site, since one of the
5
D
0

7
F
2
lines was observed to
be split into two neighboring peaks for Site II (or III). As for Eu
3+
at site I, it resides in a
disordered environment, therefore, should have the lowest site symmetry C
1
. Consistently, we
observed all three lines for
5
D
0

7
F
1
of Eu
3+
at site I.
Figure 20. Illustration of the site symmetry of (a) pure anatase nanocrystal, where Ti
4+
occupies a D
2d
symmetry; (b) Eu
3+
doped anatase nanocrystal, where Eu
3+
occupies a C
2v
symmetry (Site II); (c) Eu
3+
doped anatase nanocrystal, where Eu
3+
occupies a D
2
symmetry (Site III). The six nearest neighboring
oxygens are labeled as O1 to O6. The top-view projection plane of these nearest neighboring atoms and
the positions of symmetry operators (C
2
and
v
) are schematically plotted. Lattice expansion is vividly
represented by slightly moving outward O1, O2, O3, O4, O5 and O6 in (b) and (c).
A possible model describing the lattice distortion from D
2d
site symmetry to C
2v
or D
2
is
depicted in Figure 20. Recently, a charge transfer vibronic exciton (CTVE) model was
proposed to interpret the multi-site formation in Eu
3+
:BaFCl crystals [40]. Similarly, an
Wenqin Luo, Chengyu Fu, Renfu Li et al. 500
oxygen vacancy or self-trapping CTVE may be formed to compensate for the charge
imbalance when a trivalent Eu substitutes for the tetravalent Ti in the anatase, accompanied
by a lattice relaxation. As shown in Figure 20b, the lattice expansion occurs evenly at various
directions and an oxygen vacancy is created around Eu
3+
ion at Site II, thus a C
2v
site
symmetry is formed. For Site III, however, an oxygen vacancy is not physically formed;
instead, the charge compensation may be collectively accomplished by CTVE. As shown in
Figure 20c, two vertical symmetric planes (
v
) at the original Ti
4+
location were broken due
to the uneven lattice expansion along specific directions when Ti
4+
is replaced by Eu
3+
, thus a
D
2
site

symmetry is formed.
The thermal stability of Eu
3+
in sites I, II and III was investigated by site-selective
spectroscopy experiments at RT. Figure 21 shows the influence of annealing temperature on
the emission intensities of
5
D
0

7
F
2
transition, which is highly sensitive to the local
environment, of Eu
3+
at three different sites. Multiple sites can be observable for the sample
annealed at a temperature up to 700 C. Whereas, the emission intensity of Eu
3+
in sites I and
III increased gradually with the annealing temperature increased up to 600 C at the expense
of the decrease of emission intensity of Eu
3+
at site II, illustrating a site transition of site II to
site I and III. When the annealing temperature increased above 700 C, only emission lines
from site I can be observed. The above facts indicate that Eu
3+
ions at sites II and III in the
samples annealed at high temperature are unstable, and may be expelled from the lattice to the
grain or surface site.
400 500 600 700

Site I
Site II
Site III
Annealing temperature(
o
C)
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Figure 21. Influence of the annealing temperature on the emission intensities of
5
D
0

7
F
2
transitions of
Eu
3+
at different sites in Eu
3+
:TiO
2
(2 mol%) nanocrystals.
A Strategy for the Incorporation of Trivalent Lanthanide Ions 501
3.3.2. Sensitized Emissions of Sm
3+
, Nd
3+
Doped TiO
2
Nanoparticles
Sensitization is an important process for the efficient PL of Ln
3+
ions, which can
overcome the inefficient direct excitation of parity forbidden intra-4f transition. Unlike Eu
3+
ions doped samples, due to the match between the energies of the TiO
2
band gap and Sm
3+
,
Nd
3+
excited states, the efficient sensitization emission of TiO
2
host to Sm
3+
or Nd
3+
can be
expected [41-42]. Figure 22 shows the RT excitation spectra of Sm
3+
and Nd
3+
doped TiO
2
nanoparticles annealed at 500 C for 2 h. Both samples exhibit broad bands at around 340 nm,
which are associated with the band-gap of TiO
2
nanoparticles, whereas only weak excitation
lines originating from the f-f transitions of Sm
3+
and Nd
3+
ions are detected, suggesting more
efficient PL of Sm
3+
and Nd
3+
ions by ET from TiO
2
host to Ln
3+
ions than direct excitation
of Ln
3+
ions. Upon the excitation above the TiO
2
band gap at around 340 nm at RT, as shown
in Figure 23a and c, intense sensitized emissions from Sm
3+
and Nd
3+
ions are observed. As
shown in Figure 23b, upon excitation above TiO
2
band gap at 10 K, sharp CF splitting
emission lines related to the transition from
4
G
5/2
to
6
H
5/2
,
6
H
7/2
,
6
H
9/2
and
4
H
11/2
multiples of
Sm
3+
centered at 584.1, 612.8, 664.1 and 727.0 nm are obtained, indicating that Sm
3+
ions
were incorporated into a regular environment at TiO
2
nanocrystal matrix. Due to Kramers
degeneracy for f 5 configuration, 3, 4, 5 and 6 emission lines from the lowest CF level of
4
G
5/2
to
6
H
5/2
,
6
H
7/2
,
6
H
9/2
and
6
H
11/2
are theoretically expected respectively for Sm
3+
ions sit at
a lattice site. As clearly identified in Figure 23b, more emission lines (i.e. at least 5, 6, 7 and 4
lines for the transitions from
4
G
5/2
to
6
H
5/2
,
6
H
7/2
,
6
H
9/2
and
6
H
11/2
respectively) than expected
are detected, indicating that at least two different CF environments around Sm
3+
ions exist in
200 250 300 350 400 450 500 550
0
100
200
300
400
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Wavelength (nm)
(a) TiO
2
:Nd
(b) TiO
2
:Sm
(a)
(b)
RT
Figure 22. RT excitation spectra of (a) TiO
2
:Nd
3+
(2 mol%) annealed at 500
o
C for 2 h by monitoring
4
F
3/2

4
I
11/2
transition at 1094 nm; (b) TiO
2
:Sm
3+
(2 mol%) annealed at 500
o
C for 2 h by monitoring
4
G
5/2

6
H
7/2
transition at 612.8 nm. (Redrawn after [42], Luo, W. Q. et al., J. Phys. Chem. C 113 8772
(2009). 2009, American Chemical Society).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 502
500 550 600 650 700
900 1000 1100 1200 1300 1400
I
n
t
e
m
s
i
t
y

(
a
.
u
.
)
RT
10K
(a)
TiO
2
:Sm
3+
6
H
11/2
6
H
9/2
6
H
7/2 4
G
5/2

6
H
5/2

RT
10K
(b)
TiO
2
:Nd
3+
Wavelength (nm)
(c)
(d)
4
I
13/2
4
I
11/2
4
F
3/2

4
I
9/2
Figure 23. Emission spectra of Sm
3+
and Nd
3+
ions doped TiO
2
nanoparticles annealed at 500 C for
2 h upon excitation above TiO
2
band gap. (a) RT emission spectrum of TiO
2
:Sm
3+
(2 mol%) under
excitation at 343 nm; (b) 10 K emission spectrum of TiO
2
:Sm
3+
(2 mol%) under excitation at 332 nm;
(c) RT emission spectrum of TiO
2
:Nd
3+
(2 mol%) under excitation at 338 nm; (d) 10 K emission
spectrum of TiO
2
:Nd
3+
(2 mol%) under excitation at 339 nm. (Redrawn after [42], Luo, W. Q. et al., J.
Phys. Chem. C 113 8772 (2009). 2009, American Chemical Society).
the samples. The multiple site emissions are also detected in Nd
3+
doped TiO
2
nanoparticles.
As shown in Figure 23d, upon excitation above TiO
2
band gap at 339 nm at 10K, at least 9, 7
and 4 emission lines centered at 915, 1094 and 1385 nm for the transitions from the lowest
CF level of
4
F
3/2
to
4
I
9/2
,
4
I
11/2
and
4
I
13/2
can be clearly identified respectively, more than that
theoretically expected due to Kramers degeneracy for f
3
configuration (i.e., 5, 6 and 7
emissions for
4
F
3/2
to
4
I
9/2
,
4
I
11/2
and
4
I
13/2
respectively).
3.3.3. Er
3+
Doped TiO
2
Nanoparticles
By modifying the synthesis condition, single site emissions of Er
3+
in TiO
2
with a
nominal dopant concentration of 0.75 mol% were obtained [35]. Figure 24 shows the 10 K
excitation spectrum of Er
3+
doped TiO
2
by monitoring the near-infrared (NIR)
4
I
13/2

4
I
15/2
emission at 1532.6 nm. Abundant sharp excitation lines centered at 380.6, 407.6, 489.4,
523.4, 550.5, and 654.0 nm can be assigned to the direct excitation from ground state of
4
I
15/2
to the upper excited states of
4
G
11/2
,

2
H
9/2
,

4
F
7/2
,

2
H
11/2
,
4
S
3/2
and
4
F
9/2
, respectively. Fine CF
splitting of the excited states of Er
3+
can be easily identified, indicating that Er
3+
ions are
incorporated into a regular TiO
2
nanocrystal lattice. It should be noted that a broad excitation
band centered at 358 nm can be observed, which is associated with the band gap of anatase
TiO
2
nanocrystals, indicating the ET from TiO
2
host to Er
3+
ions. According to the Kramers
A Strategy for the Incorporation of Trivalent Lanthanide Ions 503
degeneracy for the f
11
configuration, two excitation lines from the lowest CF level of
4
I
15/2
to
4
S
3/2
are theoretically expected for Er
3+
ions sit at a lattice site at low temperature. As clearly
seen in the inset of Figure 24, there are only two lines assigned to the excited state of
4
S
3/2
(with an energy gap of 18 cm
-1
) and no trace of CF splitting due to another site can be
observed. The CF splitting of other excited states in Figure 24 is also in good agreement with
theoretical analysis, indicating that the doped Er
3+
ions were very likely located at the same
site in TiO
2
nanocrystals.
300 400 500 600 700
0
200
400
600
544 548 552 556 560
4
G
1
1
/
2

4
I
1
5
/
2
2
H
9
/
2

4
I
1
5
/
2
4
F
7
/
2

4
I
1
5
/
2
2
H
1
1
/
2

4
I
1
5
/
2
4
F
9
/
2

4
I
1
5
/
2
4
S
3
/
2

4
I
1
5
/
2
4
F
3
/
2
,
5
/
2

4
I
1
5
/
2
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Wavelength (nm)
T=10K




4
S
3/2

4
I
15/2
Figure 24. Excitation spectrum of Er
3+
:TiO
2
nanocrystals at 10 K, and the inset enlarges the excitation
lines for the transition of
4
I
15/2

4
S
3/2
. (Reprinted with permission from [35], Fu, C. Y. et al. Opt. Lett.
33, 953 (2008). 2008, Optical Society of America).
As shown in Figure 25a and b, similar NIR emission lines are obtained upon excitation
either to the
2
H
11/2
state of Er
3+
or above the TiO
2
band gap, suggesting a homogeneous CF
environment for the doped Er
3+
ions. When excited above the band-gap energy, as shown in
Figure 25c, a broad band (peaking at ~550 nm) attributed to defects is observed. These defects
may be related to oxygen vacancies originating from the substituting Er
3+
for Ti
4+
[15]. In
addition, sharp emission lines from
4
S
3/2

4
I
15/2
are observed being superimposed on the broad
band. The eight CF levels of
4
I
15/2
are experimentally determined to be located at 0, 15, 95, 166,
210, 378, 454 and 504 cm
-1
according to the
4
S
3/2

4
I
15/2
emission at 10 K. Interestingly, self
absorption lines correspond to the hypersensitive transition of
4
I
15/2

2
H
11/2
are observed due to
the large rank-2 reduced matrix elements (RMEs) of the unit tensor of the transition which
could result in strong absorptions. Similar self absorption lines were also observed in Er
3+
doped
Gd
2
O
3
nanocrystals [43]. Figure 25d shows the upconversion luminescence of Er
3+
under a 976
nm laser excitation at RT. An intense green emission due to the transition from
2
H
11/2
and its
thermally coupled
4
S
3/2
states to
4
I
15/2
is observed. As illustrated in the inset of Figure 25, the
Wenqin Luo, Chengyu Fu, Renfu Li et al. 504
fluorescence decay curve of
4
I
13/2
is slightly deviated from a single exponential under the
excitation of 523.4 nm, which may be caused by a nonradiative ET process from Er
3+
to the
neighboring defects that have close energy levels to the
4
I
13/2
state. Assuming the electric dipole-
dipole interaction between donor and acceptor, the decay curve can be well fitted by the
Inokuti-Hirayama model [44]: ( ) ( ) [ ]
2 / 1
0 0 0
/ / exp t C t I t I = , where I is the time
dependent PL intensity and I
0
is the initial intensity, C is a freely varied parameter, t is the time
and
0
is the intrinsic luminescence lifetime. The intrinsic fluorescence lifetime of
4
I
13/2
is fitted
to be 1.56 ms at 10 K.
1500 1520 1540 1560 1580 1600
0
100
200
300
0 1 2 3 4 5 6
10
100
1000
400 450 500 550 600 650 700
0
100
200
300
400 450 500 550 600 650 700
0
40
80
120
t (ms)

Wavelength (nm)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
(b)
(a)
T=10K
4
I
13/2

4
I
15/2
t=1.56ms




t
2
H
11/2

4
I
15/2
4
S
3/2

4
I
15/2
T=10K
(c)

RT
(d)
4
F
9/2

4
I
15/2
2
H
11/2
,
4
S
3/2

4
I
15/2


Figure 25. (Color online) NIR (a) (b), visible (c), and upconverted (d) luminescence spectra of
Er
3+
:TiO
2
nanocrystals, where (a)-(c) were measured under the 523.4, 358 and 358 nm excitation at 10
K and (d) was measured under the 976 nm laser excitation at RT, respectively. The inset shows the
luminescence decay curve of (a), with the experimental (dotted) and fitted (solid) results. (Reprinted
with permission from [35], Fu, C. Y. et al. Opt. Lett. 33, 953 (2008). 2008, Optical Society of
America).
A Strategy for the Incorporation of Trivalent Lanthanide Ions 505
3.4. Growth Mechanism of Ln
3+
Doped Nanoparticles
For material synthesis, the study of growth mechanism of the materials is of great
importance for the material design and performance. It has been demonstrated that, in the sol-
gel solvothermal method, Ln
3+
ions can be incorporated into the anatase TiO
2
lattice and
intense emission lines of Ln
3+
ions can be obtained by either directly excited of Ln
3+
ions or
energy transfer from host matrix. However, Ln
3+
ions in TiO
2
lattice are metastable and will
be expelled to the surface of TiO
2
nanocrystals under the high temperature annealing (above
700
o
C). Moreover, the solvothermal temperature was found to play a vital role in the PL
performance of the samples. For example, the emission intensity from Eu
3+
at TiO
2
lattice
gradually weakened with the increase of solvothermal temperature above 160
o
C and
eventually vanished at 170
o
C, under which condition, TiO
2
nanoparticles has been
crystallized to anatase phase. No improvements in PL performance were achieved even after
further annealing the nanocrystals at high temperature (above 400
o
C), indicating that the
crystallization process of amorphous TiO
2
nano-aggregates plays a important role in the
successful incorporation Ln
3+
ions into TiO
2
lattice. Based on the experiment results of TG-
DTA, TEM, XRD and PL, we have proposed a mechanism to illustrate the growth process of
Eu
3+
doped TiO
2
nanoparticles, as shown in Figure 26 [34]. First, the hydrolysis of tetra(n-
butyl)titanate followed by the condensation of the resulting titanium hydroxide species
affords the -Ti-O-Ti- and -Ti-O-Eu- clusters which undergo the further condensation to form
amorphous TiO
2
nanoparticles with their surfaces covered with hydroxyl and Eu
3+
ions which
hindered the crystallization of the nanoparticles under post heat treatment. After solvothermal
treatment, the amorphous TiO
2
nanoparticles are coalesced to form amorphous submicron
spherical aggregates (Figure 17b). By further heat-treatment (above 400 C), two or more
neighboring TiO
2
nanoparticles are merged into one single anatase nanocrystals, and those
Eu
3+
ions originally embedded in the interfaces between nanoparticles may enter the Ti lattice
Figure 26. A schematic illustration showing the growth mechanism of Eu
3+
doped TiO
2
nanocrystals.
(Reprinted with permission from [34], Luo, W. Q. et al., J. Phys. Chem. C 112 10370 (2008). 2008,
American Chemical Society).
Wenqin Luo, Chengyu Fu, Renfu Li et al. 506
to lower the interfacial energy of nanoparticles during the crystallization process. However,
compared to the surface site, the compatibility of Eu
3+
ions at lattice sites II and III is
relatively poor. If provided enough thermal energy, Eu
3+
ions at the lattice site are prone to be
expelled from the TiO
2
matrix during the crystal growth.
4. Conclusion
Ln
3+
ion-doped anatase TiO
2
nanoparticles are promising materials for phosphor devices.
Various approaches to accommodate Ln
3+
ions into TiO
2
host materials have been reviewed.
ET from TiO
2
host to Ln
3+
ions was observed in different TiO
2
nanomaterials, illustrating that
TiO
2
is a good host and sensitizer for Ln
3+
ions. However, in most cases, only unresolved PL
lines were obtained due to the poor incorporation of Ln
3+
into TiO
2
lattice. A facile sol-gel
solvothermal approach was proposed for the synthesis of Ln
3+
doped TiO
2
nanocrystals.
Through the sol-gel process and self assembly of the nanoparticles, the Ln
3+
ions can be
doped into the nanoparticles. With the crystallization of the nanoparticles, the Ln
3+
ions can
be metastably incorporated into TiO
2
lattices. The strategy in this method provides a possible
way to design the syntheses of other semiconductor nanocrystals with Ln
3+
ions incorporated
into the lattice, which is usually difficult to do in other methods. The lattice incorporation of
Ln
3+
ions in TiO
2
nanocrystals and efficient host-to-Ln ET obtained in these systems is of
great significance for further material applications in the fields of optics and electronics.
Moreover, the nearly monodisperse spherical morphology is ideal for luminescence devices
because high packing densities and scattering of light can be obtained.
Although some advances have been made in Ln
3+
doped TiO
2
nanomaterials, to gain deep
insight into the understanding of chemistry and physics of Ln
3+
ions in TiO
2
nanocrystals,
there is still much work to be done in further research in the future, such as the band gap
engineering of TiO
2
via size control, to achieve more efficient host-to-Ln PL, and systematic
CF analysis of local environment and distortion around lanthanides.
Acknowledgements
This work is supported by the One Hundred Talents Program of the Chinese Academy of
Sciences (CAS), Knowledge Innovation Program of CAS for Key Topics (No. KJCX2-YW-
358) and Young Scientists, Instrument Developing Project of CAS (No. YZ200712), the
NSFC (Nos. 10504032, 10774143 and 10804106), the 973 program (No. 2007CB936703),
the National High-Tech R&D Program of China (863 Program, No. 2009AA03Z430), Fujian
Provincial Science Fund for Distinguished Young Scholars (No. 2009J06030), and the Key
Project of Science and Technology Foundation of Fujian Province (No. 2007I0024).
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 509-524 2010 Nova Science Publishers, Inc.
Chapter 16
NANOCRYSTALLITE SUPERHARD
TITANIUM NITRIDE FILM IN MULTI-ARC
ION PLATING
Xiang Yu
1
, Chengbiao Wang
1
, Meng Hua
2
, Yang Liu
3
and Shengli Ma
4
1
School of Engineering and Technology, China University of Geosciences,
Beijing100083, China
2
MEEM Department, City University of Hong Kong, 83 Tat Chee Ave.,
Kowloon Tong, Kowloon, Hong Kong, China
3
Beijing Powertech Co. Ltd., Beijing 100072, China
4
State-Key Laboratory for MBM, Xians Jiaotong University,
Xian 710049, China
Abstract
Titanium nitride (TiN) films synthesized by multi-arc ion plating (AIP) normally have a
columnar microstructure, and are likely to induce surface defects due to the formation of
macroparticles and neutral particles in the vicinity of cathode arc sources. Hence, the
achievable microhardness of the normal AIP TiN films only ranges between 20~30 GPa. A
systematic study for fabricating an adherent nano-superhard titanium nitride (TiN) film on M2
high speed steel substrate by a vacuum cathode multi-arc ion-plating (AIP) system was
initiated. To understand the relationship of the film processing-structure-property, their
microhardness, film-to-substrate adhesion, frictional property, and microstructure of the film
were investigated using Vickers hardometer, scratch tester, ball-on-disc tester, X-ray
diffractometer, and transmission electron microscope. Results show that: (i) the achievable
film microhardness ranges between 35 GPa and 45 GPa; (ii) the critical load (Lc) of the
superhard TiN film is at 64 N approximately; (iii) the friction coefficient, under a high-load
and a high rotating-speed, of the film is ranging from 0.5 to 0.8; and (iv) the nm scale mean
main grain-sizes of the film are approximately 12.7 nm for TiN
111
, 19.7 nm for TiN
200
and 9.6
nm for TiN
220
. The maximum achievable microhardness 45 GPa is more than twice of the 22
GPa for standard TiN film. Such hardness enhancement is anticipated as mainly due to: (a) the
formation of nanoscaled crystalline grains; (b) the preferential orientation and growth of
Xiang Yu, Chengbiao Wang, Meng Hua et al. 510
grains in the close-packed plane (111); and (c) the induced residual stress within the film by
ion bombardment.
Keywords: Superhard TiN film; mechanical property; crystalline size; preferential orientation
1. Introduction
TiN film has been extensively studied and successfully used for decades due to its
favorable properties of high melting point, high hardness and high thermal conductivity [1].
Its application ranges from hard and protective coating on mechanical tools to decorative
coating, and diffusion barriers in microelectronic components [2,3]. Currently, the rapid
development of engineering and high technologies brings strict demand on the quality of TiN
film, and therefore the performances of the film still need to be improved further. Multi-arc
ion plating (AIP) with features of high ionization rate, ion kinetic energy and deposition rate
has been rapidly developed in the last two decades. During depositing AIP TiN film,
macroparticles and neutral particles are usually accompanied with the ions in the vicinity of
cathode arc sources. This subsequently roughens relatively the TiN film structure with the
presence of columnar grains and other defaults. Hence, this type of films has low erosion and
corrosion resistance, and poor brightness. Their microhardness is normally in the order of
20~30 GPa [4,5].
Conventionally, the approach to improve the hardness, wear and corrosion resistance
performances is to increase the thickness of the film. However, this may not be usually
effective. Improvement of the film intrinsic and/or extrinsic properties like grain size,
morphology, texture, etc. can also be the alternative approach to enhance these performances
[6]. Resent interest in nanotechnology stimulates numerous studies in films, specifically
aiming at understanding the atomic level of their formation and growth mechanisms. The
growing demand for superior protective coatings to operate in severe conditions results in the
novel development of hard and superhard coatings like multilayered coatings, and super-
lattices and/or heterostructures, nanostructured composite coatings [7,8]. This study was
initiated to synthesize an adherent superhard TiN film on the substrate of M2 high-speed steel
using multi-arc ion-plating coater. It also investigated the relationship among the deposition
parameters, the mechanical properties and the nanostructure so as to understand the forming
mechanism of the film.
Recent research in preparation of industrial materials has led to coatings with hardness
comparable to diamond and cubic boron nitride. This has subsequently aroused a

great deal of
interest in synthesizing nanostructured superhard TiN films with Vickers hardness 40 GPa.
The nanostructures of these superhard materials are identified to be either ternary or
quaternary. However, techniques to synthesize these films are generally rather complex
because the films usually: (i) constitute of alternating layers of nm-scale transitional metal
nitrides [9] and (ii) are embedding the transitional metal nitride nanocrystals within the
amorphous phase of a covalent nitride (e.g. nc-TiN/a-Si
3
N
4
, nc-(Ti
1-x
Al
x
)N/a-Si
3
N
4
, nc-TiN
/TiB
2
, nc-TiN/BN, etc.) with the element-doped nanocomposites [10]. As binary TiN films
become outmoded and replaced by superhard films, it is difficult to achieve microhardness as
beyond 40 GPa due to inadequate control of the film processing parameters. Our recent
deposition method has allowed superhard nanocrystallite TiN films to be accomplished with
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 511
microhardness values consistently up to 45 GPa, with none of the complexity (i) and (ii) as
mentioned above.
Figure 1. Schematic cross-sectional view of SP0809AS coater.
2. Experimental Details
2.1. Coating Equipment and Sample Preparation
Table 1 tabulates the operating conditions of the SP0809AS type vacuum coater
(Figure1) used in fabricating the films. The surface of steel substrate was firstly polished to an
average surface finish of Ra=0.08 m, and was thoroughly cleaned in an acetone ultrasonic
bath for 15 min and blow-dried with nitrogen. The so-prepared steel coupons were hung
vertically on the steel racks of a rotational substrate holder in the centre area of the vacuum
coater. Eight Ti rod targets were fixed around the vacuum chamber. Ar gas was injected to
each of the two vertically collocated arc evaporation sources from the 1 mm diameter holes
uniformly arranged on a double-layer steel bar, and nitrogen gas was injected towards the
substrate from the two ion sources for improving ionization efficiency. The flow of Ar and N
2
gases was controlled by two mass flowmeters. The bias voltage and the bias current to the
substrate were controlled by a unipolar pulse DC bias power supply. The duty ratio of the
pulsed bias voltage in Ar ion cleaning was 70% and in deposition was 50 %. The temperature
of vacuum chamber before deposition was raised up gradually to 300
o
C by two 4 KW group
heaters, followed by further cleaning the coupon surfaces for 15 min by bombarding Ar ion at
a bias voltage of 1200 V in a 4 Pa argon atmosphere. By maintaining the depositing pressure
at 210
-1
Pa in the argon atmosphere, Ti ion etching was performed for 5 min under the
1000 V bias voltage, which was followed by 10 mins pre-deposition of a 0.2 m Ti interlayer
Xiang Yu, Chengbiao Wang, Meng Hua et al. 512
using the eight Ti rod targets with 80 A arc current and under 300 V. The deposition of TiN
layer was initiated for accomplishing a film thickness of approximately 3 m by introducing
nitrogen gas with the target voltage stabilized at 20 V. A PLC (Programmable Logical
Controller) system was used to control automatically the process parameters in each coating.
TiN layers were deposited with individual bias voltages varying from 100 V to -600 V in
step of 100 V under the 210
-1
Pa depositing pressure.
Table 1. Setting of operational conditions of deposition equipment
Deposition method Vacuum cathode multi-arc ion-plating
Arc target Ti8, purity of 99.99%
Substrate Cr12Mo4V high-speed steel, 20205 mm
3
Working gases Ar + N
2
, purity of 99.999%
Substrate bias power 01500V (unipolar DC pulse), 595% (duty ratio),
020 A (bias current)
Base pressure 1.010
-3
Pa
Arc current /Target voltage 80 A/20 V
Heating temperature 300
o
C
Ar ion bombardment Bias voltage -1200 V and duty ratio 70%, 4 Pa, 15 min
Ti ion etching Bias voltage -1000 V, duty ratio 50%, 5 min, 0.2 Pa
Ti interlayer 0.2 Pa (Ar 80 Sccm) Depositing
pressure TiN layer 0.2-0.6 Pa (Ar/N
2
, Ar 80 Sccm, N
2
0-165 Sccm)
2.2. Methods of Surface Analysis
A MH-6 microhardness tester with a Vickers indenter under 20 g loading was used to
measure the hardness of the films. A MS-S3000 scratch tester with initial load 3 N, loading
rate 100 N/min and transverse speed 4 mm/min was used to investigate the adhesion between
the steel coupons and the TiN films in air atmosphere. Optical microscope with a video
camera was used to observe the wear traces in scratch-testing. A DD-92 ball-on-disc tester
was used to investigate the frictional property of the films. Toughness was evaluated by ball-
pressing test under a vertical force of 100 kg with a 12 SiC ball pressing and dwelling onto
a TiN filmed disc coupon for 5 mins. A JEM3010 high-resolution transmission electron
microscope (HRTEM) and a Xpert Pro X-ray diffractometer (XRD) were used to investigate
the crystallographic structures of the TiN film. A CuK radiation operating at 40 kV and 40
mA was used to record the scanning results in the 2 range from 20
o
to 75
o
(by XRD
detection) with a step size of 0.02
o
and a dwell time of 4 s. All results were taken with a
sampling depth of 200 nm and the sampling area of about 1010 mm
2
. Subsequently, the
level of preferred orientation (POD) of the TiN films was determined by the following
formulae [11].
[ ]

=
n
k
s
k
k
s
k
k
k
I
I
n I
I
POD
o o
o
0 0
0
1
(1)
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 513
Where: I
k
0
is the relative intensity measured at an orientation angle of =0
o
; I
k
s
is the
relative intensity in the same plane of the standard PDF (which is the abbreviation of Joint
Committee for Powder Diffraction Standards-International Centre for Diffraction Data
(JCPDS-ICDD)) card; and n is the total number of reflection peaks obtainable from the film.
Figure 2. Bias voltage vs. microhardness of TiN films.
3. Results and Discussions
3.1. Mechanical and Tribological Properties
3.1.1. Microhardness
To measure accurately the Vickers microhardness of TiN film thickness in micron-scale,
the mathematical mean of five measurements, under the same measuring condition, at four
different points was taken as the experimental value. Figure 2 shows the relationship of the
bias voltages and the micorhardness of the TiN films. The micrographs in Figure 2 illustrate:
(1) the specimen of the intended superhard TiN film of 45 GPa and (2) the pressing-ball used
to perform the indentation. The achievable microhardness values, indented under 20 g
loading, of the TiN film coupons deposited with a bias voltage in the range from -100 to -600
V were between 35 GPa and 45 GPa. The largest limit of 45 GPa was above twofold of the
films deposited by the arc-ion-plated TiN films [10]. The morphology of the film surface was
clearly seen on the indentation micrograph (1). The micrograph (2) for the ball-pressing test
Xiang Yu, Chengbiao Wang, Meng Hua et al. 514
suggested that the toughness of the film was high and beneficial in accomplishing good
adhesion. The high ion current used in the deposition of the TiN films resulted in high
substrate bias current. Typical substrate bias current was in range of 6 A ~14 A, which was
almost fourfold that in the magnetron sputtering [11]. The deposition pressure in scale of 10
-1
Pa was low, and would provide purer space and longer mean free path for the film-to form
ions than that in several-Pascal scale as in the ordinary arc ion-plating process. This activated
high-energy ion bombardment in scale of several-hundred Volts for forming fine and dense
structure to enhance the microhardness of the films. Biasing the substrate increases the
density of excited radicals and brings along high-energy suitably for ion bombardment onto
the substrate. This also strengthens the microhardness of the films. However, the
magnification of residual stress in the TiN films [12] when the bias voltage is too large,
typically beyond -350 V, may degrade the film mechanical properties. Hence, the
achievement of superhard TiN films requires the adequate optimization of the process
parameters like the substrate bias voltage and the gas pressure. Following analyses were
performed on a 45 GPa TiN film deposited with a -200 V substrate bias voltage and a 0.2 Pa
gas pressure.
3.1.2. Film-to-Substrate Adhesion
The surface of the specifically deposited superhard TiN film was scratch-traced across by a
diamond stylus under the condition of gradually increasing the normal loading. During the
loading process, the noise signals and images of the friction force produced in the scratch test
were monitored and plotted (Figure 3). Subsequently, the critical load (Lc) was determined by
studying the variation of the curves for the friction forces and noise signals along with the
images of typical morphologies, and the scratch history was calculated from the images of
typical scratch traces (Figure3). The flat trend with very mild variation of the scratch trace in
the image 1 of Figure 3 resulted in the relatively low friction force and friction noise. A few
Figure 3. Curves of changes of friction forces and acoustic signals during scratching test and typical
morphology images of superhard TiN film.
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 515
wear cracks in those visible scratch traces were observed on the morphology of the image 2
(Figure 3) when the loading was increased. These cracks were not large enough to propagate
through the thickness of the TiN film layer and they did not break the film. Under such
circumstance, the friction force and noise were gradually increased. Increasing further the
loading would lead to the commencement of forming chip in the film, as seen on the image 3
in Figure 3. When the applied load was approaching the critical breaking value Lc 64 N of
the film, some visible traces of peeling were detected on the film surface and sudden raise in
the friction force and noise was observed. When the applied load was increased beyond this
critical value, enlargement of cracks and chips along the scratch trace (see Image 4 in Figure
3) took place. Such scratching phenomena led the curves of friction forces and noise to
fluctuate sharply. The film was peeled off at the end stage when a large load of 100 N was
applied.
3.1.3. Tribological Property
In order to investigate the frictional property of the superhard TiN film working under
high load and high-speed conditions, ball-on-disc tests were performed loaded under 10g and
20g, respectively, were performed. Such loading conditions were generally considered as
relatively high. The Al
2
O
3
ceramic ball used in the tests was 8 cm and the rotating test-speed
was 2000 revolutions/min. The two curves of friction coefficients of the superhard TiN film
under the two individual loads were shown in Figure 4. The image inserted in the figure
illustrates the morphology of the disc wear track under the corresponding loading conditions.
Figure 4. Change curves of friction coefficients of superhard TiN film under different loads.
Xiang Yu, Chengbiao Wang, Meng Hua et al. 516
The frictional coefficients of superhard TiN film were found to be between 0.5 and 0.8. The
high coefficients of friction would be due to the formation of macroparticles during AIP
deposition. The average friction coefficient under the 10 g loading was 0.56 and that under
the 20 g was 0.67. This confirms that larger load is susceptible to frictional deterioration. The
inserted image shows sight of some small cracks in the wear areas. Such cracks may be
brought along by the drop-out and repetitively frictional rubbing of the ball against those tiny
asperity peaks on the film surface. Tests under the high-speed and high-load conditions
indicated that the superhard TiN film: (i) did not fail in the one-hour testing; and (ii) did give
a normal range of friction coefficients. Such noteworthy results imply that using the suprhard
TiN film can improve the wear-resistant performance of the steel substrate.
3.2. Microstructure
The microstructure analyses of the superhard TiN film for comparing with those of
standard TiN film in PDF card 6-642 were performed by XRD technique. The XRD spectrum
(Figure 5) of the superhard TiN film displayed a strong preferred crystalline orientation in the
(111) orientation plane and weak ones in the orientation planes of (200) and (220). The
relative intensity I/I
o
values of the standard TiN film in PDF card 6-642 showed: (I) the
maximum characteristic peak of 100 for the (200) plane at 2 42.4
o
; and (ii) the decreasing
of individual intensities for the other two characteristic peaks from 75 for the (111) plane to
55 for the (220) plane. The XRD analyses showed that the relative intensity of the maximum
characteristic peak for the superhard TiN film was 100 for the (111) plane at 2 36.5
o
and
its minimum characteristic peak was 2.5 for the (200) plane. Obviously, the comparison
Figure 5. XRD spectrum of superhard TiN film.
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 517
illustrates that for the superhard TiN films deposited using AIP system: (I) has given a
preferred orientation of (111) plane; (ii) has moved its maximum characteristic peak to 2
73.7
o
in the (111) plane instead of at 2 42.4
o
in the (200) plane for the standard TiN film;
and (iii) has resulted in more striking intensity difference between the maximum and
minimum characteristic peaks.
As the structure of TiN material belongs to a NaCl face-centred cubic type in which Ti
atoms constitute mainly to the skeleton of the crystal lattice with N atoms filling into its
interspaces, the TiN films hence share the densest structure at (111) plane rather than in the
planes of (200) and (220) [13].The formation of the preferred orientation and preferred
growth at (111) plane for the superhard TiN film may thus be due to concentrating the
crystalline grains at the plane (111) that subsequently constituting orderly and uniform
arrangement. However, their arrangement at the planes of (200) and (220) is less uniform.
Such orderly and preferred orientation greatly contributes to the super-hardness.
When the crystal sizes of the deposited TiN films are larger than 10
-4
cm, the depths of
their diffraction peaks become insensitive to the change of crystal sizes. But, the broadened
diffraction peaks of the films are sensitive with the decrescent crystal sizes when their sizes
are below 10
-5
cm. Consequently, the crystal sizes can be calculated using Scherrer formula
[15]:

cos
2 / 1
B
K
D
hkl
= (2)
Where: D
hkl
is the crystal size along a direction normal to the plane; K is the Scherrer
constant; = 0.154nm and is the X-ray wavelength of CuK radiation; B
1/2
is the full-width
at half maximum of a Bragg peak; and is Bragg angle. Calculation gave the values of the
mean nm-scale grain-sizes of the film as 12.7 nm for TiN
111
, 19.7 nm for TiN
200
, and 9.6 nm
for TiN
220
. All these values are smaller than that of the other AIP TiN films as reported in
[16]. The layer number of TiN grain lapped normal to plane (111) was determined by N
111
=
D
111
/d
111
= 12.7/ 0.244 =52 (layers). The calculation gave 52 layers of crystallographic plane
normal to plane (111) to constitute a TiN
111
grain for the deposited TiN film. Their mutual
interaction subsequently re-enforced the strength of the so deposited film.
Figure 6. Superhard TiN films (a) conventional TEM micrograph and (b) HRTEM micrograph.
Xiang Yu, Chengbiao Wang, Meng Hua et al. 518
For illuminating further the film microstructure, TEM and HRTEM analyses (Figure 6)
on the nanocrystalline superhard TiN film were conducted. The conventional TEM
micrograph (Figure 6(a)) suggested that the nanometer scale crystal grains were finely and
uniformly distributed. The HRTEM micrograph (Figure 6(b)) revealed clearly the distribution
of the preferred orientation in most area on the plane (111) of the nanocrystalline. The above
TEM analysis and the XRD analysis mutually and supportively confirm the existence of a
microstructure characteristic of the preferred crystalline orientation in nanometer scale on the
plane (111) of the superhard TiN film. Such nonopolycrystalline structure and preferred
orientation at the adjacency of crystal growth create barriers to restrain the dislocation sliding
and plastic deformation of crystal grains. As a result, it induces the superhardness in the film.
3.3. Hardness Enhancement Mechanism
All the mean micorhardness values, as obtained by four data points method, for the
coated TiN samples were in the range of 34 45 GPa. Since some of these hardness values
are above 40 GPa that is almost twice the reported value for tranitional arc-ion-plated TiN
films, they are thus considered as super-hard coatings. As a result, it also confirms that the
AIP techniques we used are able to produce super-hard coating under the properly controlled
conditions. High ion current and ion energy values were generated in the filming process. The
bombardment of these high-energy ions under several-hundred volts facilitates the deeper
penetration and better fusion so that fine and dense structure can be formed. Our testing
results also showed that the film microhardness varied notably within certain ranges of the
depositing pressure and bias voltage. Such finding suggests that the depositing pressure and
the bias voltage are the two major parameters influencing the formation of the film
microstructure that, in turn, determines the microhardness of the film.
Table 2. Comparison of XRD data of nano-superhard film with standard TiN film
k (hkl) 6-642 Superhard TiN film
I/I
o

k

k
()
d(nm) D
111
(nm) N(layer)
111 75 100 18.25 0.244
12.7 52
200 100 2.5 21.20 0.212
19.7 93
220 55 3.5 30.76 0.1496
9.6 64
Keynotes: I is for intensity, is the angle and subscript k stands for superhard film.
Table 2 compares the XRD data of the superhard TiN film with the standard TiN film in
PDF card 6-642. Generally, the magnitude of the diffraction peaks is insensitive to the
changes in crystal size when the crystal size is beyond 10
-4
cm. But the broadening of the
diffraction peaks is sensitive to the sizes of crystallites when their sizes are below 10
-5
cm.
Calculation based on the measured B
1/2
gave the mean grain-sizes of the film as 12.7 nm for
TiN
111
, 19.7 nm for TiN
200
, and 9.6 nm for TiN
220
. However, the peak of XRD spectrum for
the (200) plane is much broader than that for its (111) plane as shown in Figure 7 for the
XRD spectra obtained from a nanocrystalline superhard TiN film. This seems to contradict
with the experimental result that has shown the grain-size for (200) plane to be larger than the
grain-size for (111) plane. The peak broadening of a spectrum may have been resulted from
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 519
the effect of either one or the combination of the three factors: (i) instrumental broadening,
(ii) smaller-grain and (iii) microstrain. Identification of the respective contribution of these
three factors to the broadening generally requires a series of carefully planned and tedious
experiments. Analysis of the results (Figures 7 and 8) indicates that: (a) the peak intensity of
TiN
200
and TiN
222
(Figure 7) is much weaker than TiN
111
reflecting a larger attribution from
the grain size to the peak broadening; (b) the influence of K
2
on K is negligible at low 2
and becomes obvious at 2 > 45
o
implying the instrumental broadening is more significant
for the (200) plane spectrum rather than for the (111) plane spectrum (Figure 7); (c) there is
not any obvious plane distortion and bending respectively for the (111) and (220) planes in
the HR-TEM micrograph (Figure 8(a)) implying the negligible attribution from microstrain
broadening. The above analyses therefore suggest that the peak broadening is mostly
attributed to the smaller-grain size. They also affirm that the calculation by Eq.(2) really gives
a reliable guide to the trend of the grain-sizes. The layer number N lapped normal to a
crystalline plane can also be calculated theoretically. The calculated N lapped normal to the
(111) plane of the TiN grain by N
111
=D
111
/d
111
=12.7/0.244 =52 (layer) implies the structure of
a TiN
111
grain in a crystallographic plane normal to the (111) plane to be constituted by 52
layers. Such structure gives the highest density for the atomic arrangement and induces
hindering to the dislocation within the TiN nano-crystallines so as to enhance the film
macroscopic mechanical behaviors.

Figure 7. XRD spectra of nanocrystalline superhard TiN film.
Xiang Yu, Chengbiao Wang, Meng Hua et al. 520
The XRD spectra (Figure 7), HR-TEM micrograph (Figure 8(a)) and electron diffraction
pattern (Figure 8(b)) confirmed the three main crystallographic planes (111), (200) and (220)
of the TiN films. Our study (Table 2) showed that: the obtained value of the relative intensity
I/I
o
of the maximum characteristic peak for a standard TiN film was 100 for the (200) plane at
2 42.4
o
, 75 for (111) plane, and 55 for (220) plane; whereas the obtained intensity value I
k
for a superhard TiN film was 100 for the (111) plane at 2 36.5
o
, and the minimum
characteristic peak of 2.5 for the (200) plane. Hence, it is derived that the superhard TiN films
deposited by the ion-plating system have a preferred orientation in (111) plane. Moreover, the
maximum characteristic peak is shifted to the plane (111) at 2 36.5
o
for the superhard TiN
film from the (200) plane at 2 42.4
o
for the standard TiN film in PDF card 6-642.
Comparing the relative intensity I/I
o
values in the column 6-642 for the standard TiN film and
in the column I
k
for the superhard TiN film (Table 2), it shows a striking difference of the
intensity between their maximum and minimum characteristic peaks. Typically, their
respective planes have mutually swapped over. The preferential crystalline orientation of the
nano-crystalline TiN film is strong on the plane (111) and weak on the planes (200) and
(220).
With the aim of alleviating the effect of steel substrate on the diffraction peaks, STD
diffraction at
o
0.6, 3 and 5 were respectively conducted and their XRD spectra were
correspondingly labeled as (2), (3) and (4) in Figure 7. The location of lower azimuth angle
and the shallower penetration depth in Figure 7 suggests that the elimination of the substrate
effect was advantageous for the analyses. It can be observed from Figure 7 that: (i) there is an
obvious peak for the substrate in the case (1); (ii) a reduction in substrate peak intensity, in
cases (2) to (4), can be clearly seen; (iii) the lowest X-ray depth observed in the case (4),
which suggests its substrate effect is minimum. The difference in intensities for
crystallographic planes (200), (220) and (311) of the superhard TiN film as seen from the
STD diffractions confirms that preferred growth has taken place at the close-packed plane
(111) for the superhard TiN film.
The TiN material belongs to NaCl type face-centred cubic structure that has a skeleton of
Ti atoms as the crystal lattice and N atoms in its interstices. The densest film structure is in
the (111) plane rather in the planes (200) and (220). The preferred orientation and preferred
growth being in the close-packed plane (111) of the superhard TiN film may mainly be due to
the concentration of crystalline grains at the (111) plane and its associated uniform
arrangement. Such a high degree of order plane subsequently provides the densest and hardest
structure when compared with the planes (200) and (220).
Figure 8 shows the HRTEM micrograph and the electron diffraction pattern of a selected
area of the multi-grains on a deposited TiN film. It illustrates the existence of preferred
crystalline orientation on plane (111) and the occurrence of local orientation at the grain
interface on (220) (Figure 8a). The electron diffraction pattern of the correspondingly selected
area (Figure 8b) confirms the existence of an obvious nano-polycrystalline character for the
deposited TiN film. As distinguished from the ring-shaped diffraction rings obtained from
amorphous grain planes, Figure 8b shows a distinct arc-shape cluster of diffraction rings for
the crystalline planes (111), (200) and (220) with the brightest ring being for the (111) plane.
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 521
( c)
1m
Figure 8. (a) HR-TEM micrograph, (b) selected area electron diffraction pattern and (c) cross-sectional
micrograph of the TiN film.
It is thus reasonable to derive that these planes, particularly the close-packed (111) plane, are
those for the TiN nanocrystalline grains to grow. Figure.8c shows a cross-sectional
micrograph of a TiN film. It can be seen that the film has a dense and fine microstructure, and
there is no sight of a columnar character. The HRTEM micrograph shows a fine, uniform and
nanometer-scale crystalline size for the superhard TiN film, which is consistently in
agreement with the traces of XRD analysis in Figure 7. During the formation of the film, the
high flux and energy of the energetic ion bombardment enhances the mobility and dispersive
capacity of the adsorptive particles and consequently facilitates the arrangement of the orderly
atoms.
Calculation by Eq.(1) with the relevant measurements gave the degree of preferred
orientation (POD) on the plane (111) of the deposited superhard TiN film as 3.59. This
calculated POD value is much higher than that for the reported sputtered TiN film [17] and
serves to verify the methods used for the accomplishment of a preferred orientation of the
TiN film.
Xiang Yu, Chengbiao Wang, Meng Hua et al. 522
Figure 9. Correlation among film hardness, PODs and gas pressures & bias voltages.
To reveal the natural characteristics of the nanocrystalline TiN film, a correlation of the
experimental hardness and structure to their process parameters was performed.
Experimentally, it was found that by varying the process parameters of substrate bias voltage
and gas pressure a superhard TiN film was produced which exhibited a microstructure with (i)
a preferred orientation and preferred growth in the close-packed plane (111) (that can be
expressed in terms of POD) and (ii) gave mean grain-sizes on a nm scale. A typical
correlation among the TiN film microhardness, the PODs of TiN
111
, the gas pressure as well
as the bias voltages is shown in Figure 9, on which an indent image illustrates the geometry
and dimensions of an indented superhard TiN film having hardness of 45 GPa. The depth of
indentation was made specifically in the range of 0.140 0.34 m so as to minimize the
influence of substrate on the measured film hardness. The deviation of the microhardness
measurements so obtained was estimated and found in an order of 10 %. The result in Figure
9 shows that: (i) the superhard TiN films have the structure character of POD beyond 3.1; and
(ii) suitable selection and simultaneous adjustment of gas pressure (in the range of 0.10 Pa ~
0.30 Pa) as well as pulsed bias voltages (in the range of -100 ~ -250 V) allowed the formation
of superhard TiN films with the required structure. The AIP deposition method is likely to
activate high ionization in the vacuum chamber. Hence, biasing the substrate leads to the
generation of a glow discharge surrounding the ion sources and the substrate holder. The
effect is to enhance further the ionization and reactivity of nitrogen gas. The majority of the
nitrogen under such circumstance reacts with titanium atoms in substrate surface, and with
Nanocrystallite Superhard Titanium Nitride Film in Multi-arc Ion Plating 523
discharging plasma and target surface. Although the application of biasing increases the
density of excited radicals on the substrate and suitably activates high-energy ion
bombardment to the substrate, it may however increase the residual stress in the TiN films
and result in the loss of the required special structural properties when the bias voltage is
above -350 V. Consequently, it degrades the mechanical properties of the film. In our
experiment, the AIP deposition was set to a steadily low gas pressure of 0.1 Pa. It thus gave a
relatively pure deposition environment and it also increased the mean free paths of the
favorably excited particles. Optimization of the process parameters like the substrate bias
voltage and the gas pressure thus facilitates the formation of superhard TiN films. The results
of this study therefore indicate that the PODs of TiN
111
are a good indication for judging
whether the microhardness of the TiN films will increase or decrease.
The phenomenon of hardness enhancement of the nanocrystalline TiN film is closely
related with the ion flux and energy associated with the bombardment by the energetic
particles in the film growing process. Estimation by Veprek et al [18]

indicated that such a
type of induced film superhardness would degrade the TiN film intrinsic hardness to, or
below 22 GPa when its residual stress was reduced after the deposition period by an
annealing treatment. Data in our experiments suggested that there was no visible decrease in
the hardness values of the TiN films after one-month deposit under room temperature. Our
experiments showed that a 45 GPa TiN film reduced its hardness to 36 GPa (i.e. 21 percent
decrease) when it was annealed in a furnace at 600
o
C for 0.5 h. It was only 21 percent
decrease and the hardness value after annealing was still much higher than the intrinsic
hardness of a standard TiN counterpart. The measured value of the residual stress of the film
before and after annealing was 2.43 GPa and 1.54 GPa, respectively. Such a reduction
suggests that annealing may result in grain growth and an associated decrease in hardness of
the film. Consequently, it leads us to conclude that the residual stress induced in the film by
the energetic ion bombardment can also make a partial contribution to the film hardness
enhancement.
4. Conclusion
An adherent nanocrystalline superhard TiN film was deposited on the substrate of M2
high-speed steel using a multi-arc ion plating system that was operated under (i) a low
depositing pressure of 0.2 Pa and (ii) the energetic bombardment of the high ion flux and ion
energy. The nanocrystalline superhard TiN film so deposited possesses a microstructure
characteristic of nanometer scale preferred crystalline orientation on the plane (111), which is
subsequently inducing superhardness of the film, as confirmed by the analyses of both XRD
and TEM. Our studies have illustrated that it is possible to produce superhard naonosrystallite
TiN films with microhardness of 45 GPa. The studies have also indicated that it is possible to
correlate the preferred orientation on the close-packed plane (111) and the growth of TiN
layers with the film hardness. Furthermore, the results of TEM studies on superhard TiN film
are consistent with that of XRD analysis This supports that our approach in using AIP
system for producing superhard TiN film is feasible and that the relevant mechanisms found
are valid. We believe that such findings contribute significantly to the scientific
understanding in the field of thin film hardness enhancement.
Xiang Yu, Chengbiao Wang, Meng Hua et al. 524
Acknowledgments
The support from (i) Supported by Program for New Century Excellent Talents in
University (NCET), (ii) A Foundation for the Author of National Excellent Doctoral
Dissertation of PR China, (iii) Strategic Research Grant of City University of Hong Kong
(CityU: 7002235), (iv) Major Project of International Scientific Cooperation Plan of China
(2006DFB51260) is greatly acknowledged and (v) Open Research Foundation of National
Scientific Drilling Laboratory of China University of Geosciences (NLSD200705).
References
[1] G.S. Kim, S.Y. Lee, J.H. Hahn, B.Y. Lee, J.G. Han, J.H. Lee and S.Y. Lee, Surf. Coat.
Technol. 2003, 171, 83-90.
[2] W.M. Posadowski, Thin Solid Films 2001, 392 (2), 201-207.
[3] U. Krause, M. List and H. Fuchs, Thin Solid Films 2001, 392, 196-200.
[4] X.Yu, C. B.Wang, Y. Liu and D. Y. Yu, Acta. Metall. Sin. 2006, 42 (6), 662-666.
[5] T. Hanabusa, K. Kusaka, T. Matsue, M. Nishida, O. Sakata and T. Sato, Vacuum 2004,
74, 571-575.
[6] T. Nishikiori, T. Nohira and Yasuhiko Ito, Thin Solid Films 2002, 408, 148-154.
[7] P. F. Mcmillan, Nature 2004, 430, 738.
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[9] K. Reuter and M. Scheffler, Phys. Rev. B 2002, 65, 035406.
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Coat. Technol. 2005, 194, 143-148.
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[13] X.Yu, C. B.Wang, M. Hua, P. Tam, Y. Liu and D. Y. Yu, Surf. Rev. Lett. 2007, 14(4),
789-793. .
[14] Ming-Hua Shiao, Sui-An Kao and Fuh-Sheng Shieu, Thin Solid Films 2000, 375, 163-
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[15] T. Matsue, T. Hanabusa and Y. Ikeuchi, Vacuum 2004, 74, 647-653.
[16] X.Yu, M.Hua, C. B. Wang, Z. Q. Fu and Y. Liu, Appl. Surf. Sci. 2007, 253 (7), 3705-
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2005, 476, 1-29
In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 525-557 2010 Nova Science Publishers, Inc.






Chapter 17



EMBEDDED OPTICAL-ELECTRICAL
NANOMATERIALES FABRICATED BY ION
IMPLANTATION


X.T. Zu and X. Xiang
Department of Applied Physics, University of Electronic Science and Technology of
China, Chengdu, 610054, Peoples Republic of China
S. Zhu and L.M. Wang
Department of Nuclear Engineering and Radiological Sciences, University of Michigan,
Ann Arbor, MI 48109-2104, USA
Abstract
Ion implantation provides a versatile and powerful technique for synthesizing nanometer-scale
clusters embedded in the near-surface region of a variety of host materials. The embedded
nanoparticles have attracted considerable attention because of their unique optical-electrical
properties that are different from those of the bulk matrix. Metallic nanoparticles embedded in
insulators have pronounced optical effects, including surface plasma resonance (SPR)
absorption, and strong third-order nonlinear optical (NLO) susceptibility. The former suggests
applications as optical filters, including eye-glass coatings. The latter has potential application
in all-optical-memory or switching devices. Oxide nanoparticles have good
photoluminescence. They have promising application in light-emitting devices. Magnetic
metallic nanoparticles often show a ferromagnetic behavior with a larger coercivity than that
of the corresponding bulk materials, which may provide potential application of the
nanocomposite as magneto-optical materials for a high density magnetic data storage device.
In this data review, nanoparticles embedded in insulators, e.g., Al
2
O
3
, MgO, YSZ and
TiO
2
single crystals, were fabricated by ion implantation and subsequent thermal annealing,
including metallic Ni, Zn and their oxides, and intermetallic nanoparticles. Optical, magnetic
and mircostructural properties of nanoparticles have been studied. The metallic nanoparticles
have surface plasmon resonance absorption, and oxide nanoparticles show good
photoluminenscence. The magnetic nanoparticles, e.g., metallic Ni and intermetallic Co
x
Ni
1-x
nanoparticles, show strong ferromagnetism behaviors. The ion fluence can affect the
concentrations and the intensities of the surface plasmon absorption of metallic nanoparticles.
Ion flux is another important parameter to fabricate nanoparticles. An example of effects of
ion flux on the nanoparticles has been presented in this data review. The relationship between
X.T. Zu, X. Xiang, S. Zhu et al. 526
annealing temperature and optical, magnetic and microstructural properties of nanoparticles
has also been systematically studied.
IIntroduction
Nanostructured materials are promising to play a dominant role in future technology as
they possess different, and often unique, properties relative to their macroscopic counterparts.
There has been a great deal of recent interest in the incorporation of nanoparticles into
dielectric and semiconductor materials to form nanocomposites. Metallic nanoparticles
embedded in insulators have been extensively studied because of pronounced optical effects,
including surface plasmon resonance (SPR) absorption and strong third-order nonlinear
optical (NLO) susceptibility [1]. These composites have drawn much attention due to
applicability for all-optical-memory or switching devices and single electron transistors [2],
etc. Magnetic metallic nanoparticles often show a ferromagnetic behavior with a larger
coercivity than that of the corresponding bulk materials. Ferromagnetic nanoparticles have
potential application in magnetic storage devices [3, 4]. Oxide nanoparticles have good
photoluminescence. They have promising application in the light-emitting devices.
Various synthesis methods have been attempted to synthesize these nano-phases, such as,
surface sputtering [5], pulsed laser deposition [6, 7], solgel [8] and ion implantation [912].
Among these techniques, ion implantation is one of the most reliable and effective methods
for the synthesis of nano-scaled particles. The implanted ions frequently precipitate as nano-
particles in controlled concentrations in the near surface regions of the host materials. Almost
any element in the periodic table can be implanted into virtually any selected host material.
The average precipitate size can be controlled by varying the implantation and annealing
conditions (such as dose, dose rate, energy, temperature and annealing time) at pre-calculated
depths of the host matrices [1]. Oxide crystals are often stable substrates used in a large range
of technological applications. These high stabilities make them suitable candidates to allow
the controlled formation of colloidal dispersions of metallic precipitates using ion
implantation.
In general, ion implantation techniques used to form nanoclusters may be categorized as
follows [13]: (1) room temperature implantation, followed by high temperature annealing; (2)
room temperature implantation at dosage above the threshold dose for spontaneous
nanocrystals formation; (3) ion implantation at elevated temperatures. In this data review,
metallic nanoparticles were prepared by means of the second; oxide nanoparticles were
prepared by the second method of ion implantation and thermal annealing; the intermetallic
nanoparticles participated spontaneously by sequential implantation of two ions at a high
dose.
This data review will be concerned primarily with the optical, magnetic and
microstructural properties of metallic, oxide and intermetallic nanoparticles prepared in single
crystals by room temperature ion implantation combined with subsequent thermal annealing.
The substrates, metallic ion sources and implantation parameters used in this data review are
listed in Table 1. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and
transmission electron microscopy (TEM) analyses are used to characterize microstructural
properties of nanoparticles. Optical absorption and room temperature photoluminescence (PL)
measurements are used to obtain the optical properties of nanoparticles. The magnetic
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 527
properties of the samples were characterized by a MPMS superconducting quantum
interference device (SQUID) magnetometer.
Table 1. Substrate and ion implantation parameters
Material
Ion
species
Ion energy
(keV)
Ion fluence (cm
-2
)
Flux (A/cm
2
) or dose rate
(ions/cm
2
s)
Reference
-Al
2
O
3

(0001)
Ni 64 110
17
5, 10 A/cm
2
[14, 15]
Zn 48 0.1, 0.5, 1, 510
17
5 A/cm
2
[16, 17]
TiO
2
(001) Ni 64 110
17
5 A/cm
2
[18]
MgO (100) Ni 64 110
17
5 A/cm
2
[19,20]
YSZ (001)
Ni 64 110
17
5 A/cm
2
[21]
Co+Ni 90 110
17

2.9310
13
ions/cm
2
s for Co,
2.6310
13
ions/cm
2
s for Ni
[22]
Abbreviations in This Data Review
BF bright-field
EDS energy dispersive spectroscopy
EELS energy electron-loss spectroscopy
FC field-cooling
HAADF high-angle annular dark-field
HREM high-resolution electron microscopy
MEVVA metal vapor vacuum arc
MPMS magnetic property measurement system
NLO nonlinear optical
PL photoluminescence
SAED selected area electron diffraction
SPR surface plasma resonance
SQUID superconducting quantum interference device
STEM scanning transmission electron microscopy
TEM transmission electron microscopy
UV-VIS ultraviolet-visable
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
YSZ yttria-stabilized zirconia (with 9.5 mol. % Y
2
O
3
in this datareview)
ZFC Zero-field-cooling
IIConclusion
2.1. Ni and NiO Nanoparticles Embedded in Single Crystals
Ion implantations were conducted at room temperature using a metal vapor vacuum arc
(MEVVA) implanter. The samples were tilted off-axis by around 7 degrees to avoid
channeling implantation. After Ni ion implantation, the Al
2
O
2
and YSZ samples were
X.T. Zu, X. Xiang, S. Zhu et al. 528
annealed in oxidization in order to study the formation of oxide nanoparticles, and the MgO
sample was annealed in reducing atmosphere to study growing up of metallic nanoparticles.
2.1.1. Chemical Charge States of As-Implanted and Annealed Samples

XPS measurements were performed to characterize chemical charge states of Ni element
in as-implanted and annealed crystals. The C
1S
peak at 285.0 eV is used to calibrate the
spectra. The samples had been etched 2 nm with Ar
+
ion before measurements in order to
remove surface contamination.
2.1.1.1. XPS Results of Al
2
O
3

Figure 1 shows the XPS spectra of Ni
2p3/2
energy level of the as-implanted and annealed
Al
2
O
3
crystals at etching depth of 2 nm, respectively [14]. The as-implanted spectra can be
resolved into two Gaussian components. The peak at 852.3 eV (Figure 1a) is attributed to
metallic Ni
0
, and the peak at 854.4 eV (Figure 1b) is due to Ni
2+
(NiO). It is clear that the Ni
element is prominent in charge state of metallic Ni
0
in as-implanted crystals and Ni
2+
in
annealed crystals at 900
o
C in ambient atmosphere. After etching 12 nm, there is no obvious
change for the as-implanted and annealed samples.


Binding Energy/eV
864 856 848 864 856 848
b a

Figure 1. XPS spectra of Ni2p3/2 core level of Ni+-implanted Al2O3 at an ion flux of 5 A/cm2 before (a)
and after annealing at 900o for 1h in ambient atmosphere.
The XPS results above are obtained from the Ni-ion-implanted samples at ion flux of
5A/cm
2
. The XPS result from Ni-ion-implanted Al
2
O
3
at ion flux of 10A/cm
2
is shown in
Figure 2. The peak at a binding energy of 856.6 eV can be attributed to Ni
2+
in NiAl
2
O
4
and
the one at 862.8 eV is assigned to the well known shake-up satellite peak of Ni
2+
. The two
peak positions and their energy difference 6.2 eV are just consistent with the previous study

[23]. Thus, the XPS result indicates the formation of NiAl
2
O
4
with the spinel structure when
ion implantation conducted at a flux of 10A/cm
2
.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 529
873 864 855 846
Binding Energy/eV

Figure 2. XPS spectra of Ni2p3/2 energy level of Ni+-implanted Al2O3 crystals at a flux of 10A/cm2.
2 nm
864 855 846
12 nm
2 nm
864 855 846
12 nm
a b
Binding Energy/eV

Figure 3. XPS spectra of Ni2p3/2 energy level of Ni ion-implanted (a) and annealed (b) YSZ crystals at
900oC in ambient atmosphere.
X.T. Zu, X. Xiang, S. Zhu et al. 530
2.1.1.2 XPS Results of YSZ

Figure 3 shows the XPS spectra of Ni
2p3/2
energy level of the as-implanted and annealed
YSZ crystals at different etching depths, respectively [21]. The spectra can be resolved into
Gaussian components. In the as-implanted spectrum at etching depth of 2 nm, the peak at
852.5 eV is attributed to metallic Ni
0
, the peak at 855.6 eV may be due to Ni
2+
(NiO) or Ni
3+

(Ni
2
O
3
), and the peak at 860.6 eV could be assigned to the shake-up satellite peak of Ni
0
, Ni
2+

or Ni
3+
. But after etching 12 nm, the charge state of Ni is only Ni
0
. These results show that the
implanted Ni in the surface is easy to be oxidized. This is not same as the Ni ion implanted -
Al
2
O
3
single crystals, whose Ni on the surface are mainly in charge state of metallic Ni
0
[14].
In the annealed spectrum at etching depth of 2 nm, the peak at 855.5 eV shows Ni is only in
charge state of Ni
2+
(NiO) or Ni
3+
(Ni
2
O
3
). The implanted Ni ion had entirely been oxidized in
the surface of YSZ matrix. However, the metallic Ni
0
(the Gaussian peak at 853.0 eV)
appeared after etching 12 nm. This result shows that there is still some metallic Ni
0
retained
in the YSZ matrix even after annealing at 900
o
C in ambient atmosphere. For the as-implanted
and annealed TiO
2
crystals, the XPS spectra of Ni are similar to those of YSZ.
2.1.1.3. XPS Results of MgO

Figure 4 shows the XPS spectra of Ni
2p3/2
energy level of the Ni ion implanted MgO
crystals after annealing at 700 and 900 C in Ar+4% H
2
atmosphere, respectively [20]. There
is no obvious difference between the Ni
2p3/2
energy level spectra at 700 and 900 C, i.e., the
charge state of Ni did not change with the increasing annealing temperature. The peak at
852.9 eV is attributed to metallic Ni
0
, and the peak at 859.1 eV could be assigned to the
shake-up satellite peak of Ni
0
. These results show that the implanted Ni is only in the charge
state of Ni
0
and the charge state of Ni was still metallic Ni
0
after annealing at 900 C in
Ar+4% H
2
atmosphere.


864 855 846
a
864
855 846
b
Binding energy/eV

Figure 4. XPS spectra of 11017 cm-2 Ni ion implanted MgO samples after annealing at 700 oC (a) and
900 oC (b) in Ar+4% H2 atmosphere, respectively.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 531

30
40
50
I
n
t
e
n
s
i
t
y
/

a
.
u
.

as-received
as-implanted
600
o
C
700
o
C
800
o
C
900
o
C
5A/cm
2

A
l
2
O
3

<
0
0
6
>

N
i
O

<
2
2
2
>

N
i

<
1
1
1
>

u
n
i
d
e
n
t
i
f
i
e
d


2/deg
Figure 5. XRD traces (-2) of Al2O3 single crystals implanted at 5A/cm2 and after annealing at
different temperatures.
2.1.2. XRD Spectra of As-Implanted and Annealed Al
2
O
3
Samples

X-ray diffraction measurement was used to clarify the formation of metallic Ni, NiO and
NiAl
2
O
4
at ion flux of 5 and 10A/cm
2
, respectively [15]. XRD traces (-2) of some samples
were collected with a Cu K

line of 1.54056 . Figure 5 shows XRD traces (-2) of as-

received and as-implanted crystals at a flux of 5A/cm
2
and annealed crystals at temperatures
from 600 to 900
o
C. In all the spectra, two diffraction peaks can be observed at ~40.6 and
~41.7, which were assigned to unidentified and (006) planes of the as-received Al
2
O
3

crystals, respectively. For the as-implanted sample, a broad diffraction peak of metallic Ni
appeared at ~44.3 indicating the formation of metallic Ni nanoparticles during ion
implantation. After annealing at 600
o
C in air, the XRD spectra show coexisted diffraction
peaks of both Ni and NiO nanoparticles. As the annealing temperature increased, NiO
nanoparticles grew up at the expense of Ni nanoparticles. When the annealing temperature
reached 900
o
C, most of the Ni nanoparticles were oxidized into NiO nanoparticles. The trace
of the Ni nanoparticles was hardly detectable based on the XRD spectrum. This is consistent
with the XPS result above.
X.T. Zu, X. Xiang, S. Zhu et al. 532

20 30 40 50 60 70
I
n
t
e
n
s
i
t
y
/
a
.
u
.

A
l
2
O
3

<
0
0
6
>
10A/cm
2
N
i
A
l
2
O
3

<
4
4
0
>

N
i
A
l
2
O
3

<
1
1
1
>


2/deg
Figure 6. XRD traces (-2) of Al2O3 single crystals implanted at 10A/cm2 and after annealing at
different temperatures.
In order to evaluated the mean grain size of Ni and NiO nanoparticles, the Scherrer
formula

[24] was used


) cos(
9 . 0
B
B
D

=
,

where ,
B
, and B are the X-ray diffraction wavelength (1.54056 ), Bragg diffraction angle
and the full width at half maximum (FWHM) of diffraction peaks, respectively. The
calculated grain sizes of Ni and NiO nanoparticles are listed in Table 2 for as-implanted and
annealed samples. For the as-implanted sample, Ni nanoparticles have mean dimension of 4.9
nm, which will be proved by the following TEM measurement. The annealing effect on the
growth of Ni nanoparticles is not obvious before the annealing temperature up to 800
o
C,
which is similar to Ni nanoparticles in the silica glass [9, 25]. The growth of NiO
nanoparticles mainly occurred at annealing temperature above 800
o
C. These results just
explained the shift towards longer wavelength of UV absorption band, i.e., the optical band
gap of NiO nanoparticles shifted towards lower energy due to quantum confinement effect as
the grain size increased.
Table 2. Average dimensions of Ni and NiO nanoparticles calculated from the XRD
spectra after Ni ion implantation with an ion flux of 5A/cm
2
.
samples Ni particle size (nm) NiO particle size (nm)
as-implanted 4.9
annealed at 600C 5.1 10.8
annealed at 700C 5.5 11.6
annealed at 800C 9.2 19.9
annealed at 900C 21.5

Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 533
Figure 6 shows XRD traces (-2) of as-implanted crystal at an ion flux of 10A/cm
2
.
After ion implantation, two new diffraction peaks appeared at ~20.58 and ~64.56,
respectively. According to the JCPDS card (No. 78-1601), these two diffraction peaks may be
corresponding to (111) and (440) planes (2 = 19.08 and 65.545) of NiAl
2
O
4
. The peak
shifts with respect to the powder diffraction data may suggest an existing stress due to the
lattice distortion after the Ni ion implantation. This XRD result proved the formation of
NiAl
2
O
4
spinel structure.
2.1.3. TEM Results of As-Implanted and Annealed Samples

Nanoparticles of Ni precipitated spontaneously during ion implantation. In TEM
measurements, a HAADF STEM (high-angle annular dark-field scanning transmission
electron microscopy) technique was used besides a conventional bright-field imaging
technique. For HAADF STEM imaging, intensity in the image is approaching a Z
2
dependence on atomic number Z [26]. As an example, for the Ni ion implanted Al
2
O
3
, the
local area where Ni element distributed will show brighter contrast because Ni has a larger Z
than both Al and O. This suggests a HAADF STEM image provides chemical information on
element distribution by its contrast (so called Z- contrast image).
2.1.3.1. Ni and NiO Nanoparticles in Al
2
O
3

Figure 7 shows a bright-field and a HAADF STEM cross-sectional image indicating size
and distribution of Ni nanoparticles embedded in Al
2
O
3
formed by ion implantation at an ion
flux of 5A/cm
2
. In this study, Ni has a much higher Z than both Al and O; therefore the
nanoparticles of Ni show bright contrast. As is shown in Figure 2, nearly spherical embedded
nanoparticles are distributed from the surface to 30 nm below the surface, consistent with
calculation results by SRIM 2000 code [27]. The size of nanoparticles ranges from 1 to 5 nm
in diameter, which is consistent with the XRD result. Figure 8 is a HREM image showing the
crystalline structure of nanoparticles of Ni in the surface of Al
2
O
3
matrix. The image shows
clearly the Ni-ion implanted area is amorphized entirely [14].

15 nm
surface
Ni
Al2 O3
surface
Ni
15 nm Al2O3
a b

Figure 7. A bright-field (a) and a HAADF STEM (b) cross-sectional image in the near surface of as-
implanted Al2O3 matrix.
X.T. Zu, X. Xiang, S. Zhu et al. 534
2 nm
Ni
Al
2
O
3
2 nm 2 nm 2 nm
Ni
Al
2
O
3
2 nm
Al
2
O
3
Ni

Figure 8. A HREM image showing structure of Ni nanoparticles in the near surface of Al
2
O
3
matrix.
5 nm
NiO nanoparticle
Al
2
O
3
matrix
b
25 nm 25 nm 25 nm
a
NiO
nanovoids
Al
2
O
3
matrix

Figure 9. A cross-sectional bright-field and a high-resolution TEM image from a sample annealed at
900
o
C after Ni ion implantation with an ion flux of 5A/cm
2
.
Figure 9 shows a cross-sectional bright-field (BF) and a high-resolution electron
microscopy (HREM) image from a sample annealed at 900
o
C after Ni ion implantation with
an ion flux of 5A/cm
2
. In the BF imaging (Figure 9a), the NiO nanoparticles grew to 6-20
nm in diameter with irregular shape, which is consistent with the XRD result. In addition, the
nanoparticles migrated towards the surface of the crystal after annealing. A high density of
voids formed below the nanoparticles during the thermal annealing process. The amorphous
area of Al
2
O
3
matrix was partially recrystallized. The HREM image (Figure 9b) demonstrates
the single crystalline nature of the NiO nanoparticle [15].
2.1.3.2. Ni and NiO Nanoparticles in YSZ

TEM measurement showed that no obvious nanoparticles precipitated after Ni ion
implantation. And YSZ matrix did not amorphize after ion implantation. Although XPS
measurements have detected the metallic Ni, TEM measurement did not observe
nanoparticles precipitated in as-implanted YSZ matrix. This may be due to the very small
crystals or none, and even show amorphous conditions. Figure 10 shows a cross-sectional
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 535
bright-field transmission electron microscopy image of the annealed sample at 900
o
C. After
thermal annealing at 900
o
C for 0.5 h, nanoparticles with size ranging from 4 to 12 nm can be
observed. The large particles distributed in the surface of the YSZ crystal. Figure 11 is a high-
resolution electron microscopy (HREM) image clearly showing the crystalline structure of
nanoparticles in the surface of YSZ matrix. The nanoparticles are nearly in shape of sphere.
In order to clarify which oxide the nanoparticles are, the selected area electron diffraction
(SAD) pattern had been obtained in Ni-implanted region in YSZ sample after annealing at
900
o
C (shown in Figure 12). After indexing the SAD pattern (the circled spots in Figure 12)
the nanoparticles were identified to be NiO [21].

25 nm
surface
NiO

Figure 10. A cross-sectional bright-field transmission electron microscopy imaging of the annealed
sample at 900
o
C.
3 nm 3 nm
NiO NiO
YSZ YSZ
3 nm 3 nm 3 nm 3 nm
NiO NiO
YSZ YSZ

Figure 11. A HREM image showing the crystalline structure of nanoparticles in the surface of annealed
YSZ matrix.
X.T. Zu, X. Xiang, S. Zhu et al. 536
111
NiO
202
NiO
200
YSZ
022
YSZ
111
NiO
202
NiO
200
YSZ
022
YSZ

Figure 12. A SAD pattern of the annealed YSZ matrix showing the formation of NiO nanoparticles.
2.1.3.3. Ni Nanoparticles in MgO


Figure 13. A cross-sectional HAADF STEM images indicating the nanoparticles of Ni in the surface
region of the MgO single crystal after Ni ion implantation (a) and followed by annealing at 900
o
C for
0.5 h under Ar+4%H
2
atmosphere.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 537

Figure 14. Composite selected area electron diffraction (SAED) patterns indicating orientation
relationship between Ni nano-particles and the MgO matrix (a); A high resolution TEM (HREM)
micrograph showing the crystalline characteristics of Ni nano-particles in the annealed MgO single
crystal (b).
Figure 13 shows HAADF images in MgO matrix after Ni ion implantation (a) and
subsequent annealing at 900
o
C under Ar + 4% H
2
atmosphere (b), respectively. In as-
implanted MgO, the formation of Ni nano-particles is evident and the particle ranges 35 nm
in size. The grown and coalescence of these nanoparticles occurred, after thermal annealing
and the particles size increased to 810 nm. Moreover, larger rods of Ni with 20 nm in length
precipitated in the surface of MgO matrix. Besides, the nanoparticles spread into the deeper
regions of MgO matrix after thermal treatment.
The Ni nanoparticles have specific orientation relationship with the MgO matrix in both
of as-implanted sample and thermal annealed sample after ion implantation. As indicated by
the composite selected area diffraction (SAD) pattern in Figure 14 (a), the orientation
relationship between the Ni particles and MgO matrix was determined as:
<001>
Ni
<001>
MgO
and {010}
Ni
{010}
MgO
. Extra satellite spots also appear around the
strong spots from the original MgO single crystal in the composite SAD patterns. These
satellite spots result from reflections attributable to double diffraction since Ni particles were
embedded in the MgO single crystal with the same orientation relationship but different
lattice spacing. The double-diffraction reflections are directly responsible for the Moir
fringes in the high resolution TEM images (Figure 14 (b)). As shown in Figure 14 (b), Mori
fringes appeared in the place where embedded Ni particles were overlapped with the MgO
matrix, due to lattice spacing mismatch between the two phases. The spacing of Mori
fringes, d
m
, can be calculated by the following equation:


1
2
2
1
d
d
d
d
m

=
,
X.T. Zu, X. Xiang, S. Zhu et al. 538
where d
1
and d
2
are lattice spacings of two overlapping crystals. The lattice spacing for
Ni(002) is d
Ni,002
= 0.176 nm (lattice parameter a
Ni
= 0.352 nm), and for MgO(002) d
MgO,002
=
0.211 nm (lattice parameter a
MgO
= 0.422 nm). Thus according to the equation above, d
m
is
1.06 nm, which is consistent with the measured value in the image [19].
2.1.3.4. Ni Nanoparticles in TiO
2

Ni Nanoparticles precipitated spontaneously during ion implantation from the surface of
TiO
2
matrix to a depth of 50 nm, as revealed by the cross-sectional HAADF Z-contrast image
shown in Figure 15(a). In this HAADF STEM image, Ni has a higher Z than both Ti and O,
so the nanoparticles of Ni show a brighter contrast. The dimensions of nanoparticles ranged
from 3 nm to 10 nm. Some elongated precipitates up to 20 nm in length were observed in the
near surface of TiO
2
. These elongated Ni precipitates are observed with the round shape in a
plan-view TEM image. The implantation region of TiO
2
matrix has been damaged and
amorphized to 60 nm in the depth below the surface. Figure 15(b) is a HREM image of Ni
nanoparticles embedded in the TiO
2
matrix, revealing a well-developed crystalline structure
of Ni nanoparticles after ion implantation without a thermal treatment [18].


Figure 15. A cross-sectional HAADF STEM image of Ni nanoparticles in the near surface of a TiO
2

single crystal (a); and a HRTEM micrograph showing a crystalline Ni nanoparticle in the amorphous
TiO
2
matrix (b).
2.1.4. Optical Absorption of As-Implanted and Annealed Samples

The optical absorption spectra were measured by a SHIMADZU UV-2550
spectrophotometer at room temperature, with a deuterium lamp for UV and a tungsten
halogen lamp for the visible region. The wavelength used in the experiment ranged from 200
to 1000 nm.
2.1.4.1. Optical Absorption of Ni-Implanted and Annealed Al
2
O
3

The optical absorption spectra of as-received, as-implanted, and annealed Al
2
O
3
single
crystals with an ion flux of 5A/cm
2
are shown in Figure 16. The spectra have vertically been
offset to avoid overlapping except that of the as-received crystal. The absorption spectrum of
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 539
the pure crystal was a smooth line in the visible waveband due to a wide band gap ~9 eV. A
broad absorption band peaked at 400 nm in the as-implanted crystal [14]. According to the
XPS, XRD and TEM results above, the absorption band can be ascribed to the surface plasma
resonance absorption of metallic Ni nanoparticles. As the annealing temperature increased,
the absorption band shifted towards the longer wavelength. After annealing at 800
o
C, this
absorption band was absent. At the same time, the crystals turned colorless. However, a new
absorption shoulder in the UV region began to appear after annealing at 600
o
C. As the
annealing temperature reached 800
o
C, the UV absorption shoulder peak evolved into an
absorption band and its peak position shifted to the longer wavelength of 306 nm (4.05 eV).
There is no detectable change for the peak position of the absorption band after annealing at
higher temperatures. This UV absorption band was related to the formation of NiO, since NiO
is an insulator with a band gap of ~4eV (310 nm)

[9]. These results have been proved by the
XPS and XRD results. And TEM showed the microstructure of NiO and the recrystalization
of Al
2
O
3
matrix [15].

as-implanted
400
o
C
500
o
C
600
o
C
700
o
C
800
o
C
as-received
0
0.2
0.4
0.6
250 400 600 800
Wavelength/nm
A
b
s
o
r
b
a
n
c
e
/
a
.
u
.
5A/cm
2
900
o
C
1000
o
C

Figure 16. Optical absorption spectra of Al
2
O
3
single crystals after Ni ion implantation at 5A/cm
2
and
annealing at different temperatures.
2.1.4.2 Optical Absorption of Ni-Implanted and Annealed YSZ

The optical absorption spectra of Ni-implanted and annealed YSZ single crystals are
partly shown in Figure 17. The spectra have vertically been offset to avoid overlapping except
X.T. Zu, X. Xiang, S. Zhu et al. 540
that of the annealed crystal at 900 C. In the spectrum of as-implanted crystal, there is a very
broad and weak absorption band ranging from 400 to 700 nm. The absorption curves of
annealed crystals are similar to that of as-implanted crystal up to 200
o
C. The absorption
intensity begins to decrease after annealing at 200
o
C, and the absorption band disappears
after 250
o
C. There is no change for the absorption spectra at annealing temperature of
300~900
o
C, similar to that of as-received YSZ [21].

200 400 600 800
0
0.2
0.4
0.6
0.8
1.0
1.2
wavelength/nm
a
b
s
o
r
b
a
n
c
e
/
a
.
u
.
as-implanted
200
o
C
250
o
C
300
o
C
900
o
C

Figure 17. Optical absorption spectra of Ni ion-implanted and annealed YSZ crystals at different
annealing temperatures.
YSZ is known to have a band gap of 5.6 eV (222 nm). So its absorption spectrum is
nearly a line in the visible region. According to the TEM results above, the broad and weak
absorption band ranging from 400 to 700 nm is not due to the SPR absorption of metallic Ni
nanoparticles. Although XPS measurements have detected the metallic Ni, TEM
measurement did not observe nanoparticles precipitated in as-implanted YSZ matrix. This
may be due to the very small crystals or none, and even show amorphous conditions. So the
metallic Ni in the as-implanted crystals does not show metallic behavior. In addition, the
broad absorption band disappeared just after annealing at 250
o
C. At this temperature the
metallic Ni clusters did not begin to grow. So the broad absorption band can be ascribed to
the point defects and their clusters induced by ion implantation. Just as the Xe ion-implanted
YSZ

crystals [28], this absorption band may be associated with the combination of electrons
trapped at oxygen vacancies and oxygen ions with trapped holes. Metallic Ni clusters grow
with the increasing annealing temperature. At the same time, metallic Ni clusters are partly
oxidized into NiO nanoparticles. However, the optical absorption spectra did not detect the
absorption of Ni or NiO nanoparticles. A possible reason is that the Ni and NiO coexist in the
YSZ single crystals and each concentration is low.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 541
2.1.4.3. Optical Absorption of Ni-Implanted and Annealed MgO

The optical absorption spectra of as-implanted and annealed MgO single crystals are
shown in Figure 18. The spectra have vertically been offset to avoid overlapping except that
of the annealed crystal at 900 C. In the spectrum of as-implanted crystal, there are two weak
absorption bands centered at ~360 nm and ~575 nm, respectively. They have been identified
with the F
2
centers and the V-type centers in magnesium sublattice (magnesium vacancies),
respectively, which is consistent with the Ag
+
and Ni
+
ion implanted MgO single crystals
[29,30]. Upon heat treatment above 700 C these two absorption bands are completely
annihilated by the recombination of point defects. During the annihilation of centers, a new
absorption band at ~430 nm formed gradually. Form the XPS and TEM results, it can be
concluded that the broad absorption band is related to the metallic Ni nanoparticles, i.e., the
surface plasmon resonance (SPR) absorption. After annealing above 700 C, the absorption
maximum shifts to a longer wavelength with the increasing annealing temperature, which is
related to the growth of Ni nanoparitcles [20].


A
b
s
o
r
b
a
n
c
e
/
a
.
u
.

as-implanted
400 C
900 C
600 C
800 C
700 C
0
0.5
400
Wavelength/nm
200 600 800 1000
1.0
1.5
200 C

Figure 18. Optical absorption spectra of MgO

single crystals after Ni ion implantation and annealing at
different temperatures.
X.T. Zu, X. Xiang, S. Zhu et al. 542
2.1.5. Magnetic Properties of Ni Nanoparticles

The magnetic properties of the samples were characterized by a magnetic property
measurement system (MPMS) superconducting quantum interference device (SQUID)
magnetometer at 10 and 300 K. The zero-field-cooling (ZFC) and field-cooling (FC) curves
for detecting superparamagnetism of the nanoparticles were measured in an applied magnetic
field of H = 100 Oe. The ZFC curve was achieved by cooling the sample initially in a zero
field to 10 K, and magnetization was recorded in an applied magnetic field where H = 100 Oe
as the temperature increased. The FC magnetization was measured by gradually cooling the
sample from 300 K to 20 K, and the magnetization was recorded in the presence of a 100 Oe
field.
2.1.5.1. Magnetic Ni Nanoparticles in MgO

Figure 19 shows a magnetization plot as a function of magnetic field at 10 K in the Ni-
implanted MgO sample. The applied magnetization field H is parallel to (100) plane of the
MgO single crystal, i.e. (100) of Ni nano-particles (Figure 14), owing to their orientation
alignment. As shown in the hysteresis loop measured at 10 K, the coercivity, H
c
, was about
195 Oe, which is larger than ~150 Oe of randomly oriented Ni particles in Al
2
O
3
[31],
because crystallographically oriented particles have stronger tendency to retain its magnetic
moments than that of randomly oriented particles under a reversing magnetic field [31]. The
magnetization curves at 10 K were completely saturated as the applied field increased to H =
5000 Oe (not shown in the figure). No coercive force H
c
was observed in the sample at 300 K
[19].


Figure 19. A magnetic hystersis loop of Ni nanoparticles in the MgO single crystal at 10 K after ion
implantation. The coercivity H
c
was about 195 Oe at this temperature.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 543

Figure 20. ZFC and FC magnetizations as a function of temperature for Ni nanoparticles in as-
implanted and after subsequent annealed MgO samples. Curves were taken in the ZFC and FC
processes at H=100 Oe.
The zero-field-cooled (ZFC) and field-cooled (FC) magnetization as a function of
temperature are shown in Figure 20 for both as-implanted and the annealed samples. As
shown in Figure 20, the FC magnetization increases monotonically with the decrease of
temperature. However, the magnetization increases at first, then decreases with an increasing
of temperature in ZFC curve. The temperature, at which the maximum in ZFC magnetization
occurs, is characterized as the blocking temperature (T
B
). The blocking temperature T
B
of Ni
nanoparticles was determined to be ~35 K in the as-implanted sample and above 300 K in the
annealed MgO sample, respectively. These Ni nanoparticles exhibit superparamagnetic
properties above the blocking temperature. This behavior is consistent with the result from the
as-implanted sample that shows almost immeasurable coercivity and remanence at 300 K.
However, superparamagnetism of the Ni nanoparticles in the annealed MgO sample persists
to above 300 K, and these Ni nanoparticles remain ferromagnetic at room temperature [19].
T
B
has a relation with particle size, based on the equation: T
B
= K
eff
V/25k
B
, where K
eff

the effective anisotropy related to the magnetocrystalline anisotropy and to the shape
anisotropy, V is the volume of a particle, k
B
is Boltzmann constant [32]. If we use the
magnetocrystalline anisotropy K
1
value (-810
5
erg/cm
3
) in [32] to replace K
eff
, the Ni
particles size that contributed to the measured magnetic property can be roughly calculated to
be ~3.3 nm in as-implanted sample and 6.8 nm in thermal annealed sample. This is close to
X.T. Zu, X. Xiang, S. Zhu et al. 544
the TEM observations above. It should be noted that the calculation neglects the shape
anisotropy caused by large rod-shape Ni precipitates in the annealed sample, which may
cause magnetic anisotropy and increase average particles size contributing to the magnetic
property.
2.1.5.2. Magnetic Ni Nanoparticles in TiO
2


Figure 21 shows the ZFC and FC magnetization as a function of temperature of Ni
nanoparticles in TiO
2
matrix. Figure 21 clearly shows the non-zero difference between the FC
and ZFC data, indicating the hysteresis while eliminating any para- and diamagnetic
contributions. In these ZFC/FC curves, the blocking temperature, T
B
, is ~85 K. Above the
blocking temperature, the magnetization is unstable and the sample loses all its hysteric
responses. The two insets in Figure 21 showing magnetization plots as a function of magnetic
field (M-H) at 10 K and 300 K, respectively. The applied magnetization field H is parallel to
(100) of the TiO
2
single crystal. The magnetic hysteresis loop at 10 K after correcting
paramagnetic contribution from TiO
2
matrix shows a ferromagnetic behavior with coercivity,
H
c
, equal to ~ 210 Oe [18]. This value is larger than that of Ni nanoparticles in MgO (195 Oe)

above. In addition, a coercivity, H
c
, equal to ~ 270 Oe was obtained at 10 K in Ni-implanted
YSZ crystal when the applied magnetization field H is parallel to (001) of the YSZ single
crystal [21]. The variation of coercivity strongly depends on the grain size. Since
nanoparticles less than a critical size are in single domain states, their coercivities are higher
than that of a common bulk sample [33]. This large coercivity can be explained by the nano-
size effect and the single domain structure (the critical size of the single domain for spherical
Ni particles was ~ 42 nm) [34, 35]. The magnetization curves at 10 K was completely
saturated at applied fields H = 4000 Oe. The remnant magnetization of the saturation
magnetization (M
r
/M
s
) is about 40% at this temperature. The coercive force and remnant
magnetization of Ni nanoparticles were not observed as the temperature increased to 300 K,
confirming the superparamagnetic behavior of the nanoparticles above the blocking
temperature. Since some nano-particles are not truly spherical, the shape anisotropy has
contribution to the superparamagnetism.
Langevin function can be used to calculate the true magnetic moment of each particle for
superparamagnetic particles as [36]:


)] / ( ) / [coth( ) / (
0 0 0
mH M T k T k mH M M T H M
B B
=


where, M
0
is the saturation magnetization (emu/g), m is the mass of individual particle
(gram), and k
B
is Boltzmann constant. The saturation magnetization in our sample was about
25 emu/g from the hysteresis loop at 300 K. Figure 22 shows magnetization vs. applied
magnetic field of Ni nanoparticles at 300 K (solid circles) and the best fit for the Langevin
function (solid line). From the data fitting, we calculate the average grain size of 9.4 nm for
the Ni nanoparticles contributing to magnetic moment, which is in the range of particle size
measured by TEM observation. The mean-magnetic moment per particle of the sample was
calculated to be 11064
B
[18].

Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 545
0
FC
ZFC
Temperature (K)
0 50 100 150 200 250 300
2.0
4.0
6.0
M
a
g
n
e
t
i
z
a
t
i
o
n

(

1
0
-
5
,

e
m
u
)
-3 -1 0 1 2 3
1
-2
0
1
M

(

1
0
-
4
e
m
u
)
H (kOe)
T= 10 K
-3 -2 -1 0 1 2
0
0.5
1
-0.5
-1
3
T=300K
M

(

1
0
-
4
e
m
u
)
H (kOe)
0
FC
ZFC
Temperature (K)
0 50 100 150 200 250 300
2.0
4.0
6.0
M
a
g
n
e
t
i
z
a
t
i
o
n

(

1
0
-
5
,

e
m
u
)
-3 -1 0 1 2 3
1
-2
0
1
M

(

1
0
-
4
e
m
u
)
H (kOe)
T= 10 K
-3 -1 0 1 2 3
1
-2
0
1
M

(

1
0
-
4
e
m
u
)
H (kOe)
T= 10 K
-3 -2 -1 0 1 2
0
0.5
1
-0.5
-1
3
T=300K
M

(

1
0
-
4
e
m
u
)
H (kOe)
-3 -2 -1 0 1 2
0
0.5
1
-0.5
-1
3
T=300K
-3 -2 -1 0 1 2
0
0.5
1
-0.5
-1
3
T=300K
M

(

1
0
-
4
e
m
u
)
H (kOe)

Figure 21. Temperature dependence of the ZFC and FC magnetization curves for the Ni implanted TiO
2

sample with magnetic hysteresis loops at 10 K (bottom inset) and 300 K (top inset).
-20 -10 0 10 20
Applied Magnetic field (kOe)
M
a
g
n
e
t
i
z
a
t
i
o
n

(
e
m
u
/
g
)

-30
-20
-10
0
20
10
T=300K
-20 -10 0 10 20
Applied Magnetic field (kOe)
M
a
g
n
e
t
i
z
a
t
i
o
n

(
e
m
u
/
g
)

-30
-20
-10
0
20
10
T=300K

Figure 22. Measured (solid circle) and the Langevin function fitted (solid line) magnetization (M) vs.
magnetic filed (H) at the room temperature.
X.T. Zu, X. Xiang, S. Zhu et al. 546
2.2. Zn and ZnO Nanoparticles Embedded in Al
2
O
3

Ion implantations were conducted at room temperature using a metal vapor vacuum arc
(MEVVA) implanter. The samples were tilted off-axis by around 7 degrees to avoid
channeling implantation. After Zn ion implantation, the Al
2
O
2
samples were annealed in
oxygen atmosphere in order to fabricate zinc oxide nanoparticles. ZnO is well-known as a
versatile wide band gap (~3.3 eV) semiconducting material with a large exciton binding
energy of 60 meV, which allows excitonic recombination and optically pumped laser
oscillations even at the room temperature. Following the demonstration of blue-green light
emitting diodes (LEDs) and lasers using IIVI compounds, ZnO has been intensively studied
for optoelectric applications in both the visible and ultraviolet (UV) regions. Optical
absorption and TEM measurements are same as those of the Ni-ion-implanted samples above.
2.2.1. Optical Absorption of Zn Nanoparticles Fabricated with Different Fluences

The optical absorption spectra of as-implanted -Al
2
O
3
single crystals at fluences of
110
16
, 510
16
, 110
17
, and 510
17
cm
-2
are shown in Figure 23. The spectra have been offset
to avoid overlapping except that of the as-implanted spectrum at fluence of 110
16
cm
-2
. After
Zn
+
ion implantation at a fluence of 110
16
cm
-2
, a weak absorption peak appeared at ~260
nm. This absorption peak becomes clear gradually with the increasing fluences. At the same
time, the peak wavelength shift to longer wavelength linearly (dash line in Figure 23). The
absorption peak shifts to ~285 nm when the ion fluence up to 510
17
cm
-2
. The strong and
broad peak at 260-285 nm is due to surface plasma resonance absorption of metallic Zn
nanoparticles [16]. Actually, the similar absorption peaks have been observed in SiO
2
glass
and MgO single crystal matrices (listed in Table 3).

200 400 600 800
0.2
0
0.4
0.6
0.8
A
b
s
o
r
b
a
n
c
e
/
a
.
u
.
Wavelength/nm
510
17
110
17
510
16
110
16

Figure 23. Optical absorption spectra of Zn
+
-implanted Al
2
O
3
single crystals at different fluences.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 547
As a whole, the SPR peaks in -Al
2
O
3
and MgO lie at longer wavelength than that in
SiO
2
matrix. This is because that -Al
2
O
3
and MgO have larger refractive indexes (1.76 for -
Al
2
O
3
and 1.74 for MgO) than SiO
2
(1.52). According to the Maxwell-Garnett (MG) [41] and
Mie [42] theory, the SPR peak would shift towards low energy with increasing refractive
index of surrounding medium. The size of nanoparticles is another factor to influence the SPR
peak wavelength, which will shift to a longer wavelength with the increasing crystalline size.
The SPR absorption peaks in Table 3 are observed in the as-implanted matrices except that in
MgO which was observed after annealing at 1150 K, which shift to a longer wavelength due
to the growth of nanoparticles.
Table 3. SPR peaks of metallic Zn nanoparticles in several insulator matrices
matrix Zn
+
ion/cm
-2
SPR peak reference
SiO
2
110
17
4.8 eV/259 nm [10]
110
17
4.86 eV/255 nm [37]
110
17
5.3 eV/234 nm [38]
310
17
4.86 eV/255 nm [39]
MgO

110
17
4.2 eV/295 nm [40]
-Al
2
O
3

110
17
4.56 eV/272 nm
[17]
510
17
4.35 eV/285 nm
2.2.2. Optical Absorption of Zn-Ion-Implanted and Annealed Al
2
O
3

The optical absorption spectra of the as-received, as-implanted with a fluence of 110
17

cm
-2
and annealed -Al
2
O
3
single crystals are shown in Figure 24. The spectra have been
shifted vertically to avoid overlapping except that of the as-received sample. The SPR
absorption peak slightly shifted towards the longer wavelength due to the growth of
nanoparticles with the increasing annealing temperature. The spectrum of annealed sample
at 500 C is a transition one because it includes both the absorption peak of Zn
nanoparticles and the absorption edge of ZnO nanoparticles. After annealing at 600 C for 1
h, the SPR absorption peak disappears and a clear absorption peak appears at ~360 nm,
which is consistent with the exciton absorption of ZnO [10, 17, 40]. The intensity of this
exciton absorption peak decreases with the further increasing annealing temperature.
Apparently, this intensity decrease does not indicate a decrease of Zn content in the sample.
It may be due to the decreased concentration of ZnO nanoparticles because of the formation
of ZnAl
2
O
4
spinel during thermal annealing in O
2
atmosphere [43]. The microscopic
morphology of Zn and ZnO nanoparticles has been characterized by TEM imaging with the
main results shown below.

Observed after annealing at 1150 K.

X.T. Zu, X. Xiang, S. Zhu et al. 548
200 400 600 800
0.2
0
0.4
0.6
0.8
1.0
A
b
s
o
r
b
a
n
c
e
/
a
.
u
.
Wavelength/nm
as-implanted
400
o
C
500
o
C
600
o
C
700
o
C
800
o
C
900
o
C
300
o
C

Figure 24. Optical absorption spectra of Zn
+
-implanted and annealed Al
2
O
3
single crystals at different
temperature.
5 nm
surface
amorphous
Crystalline matrix
20 nm

Figure 25. A cross-sectional bright-field TEM image (a) and a high resolution TEM (HREM) image (b)
of Zn nanoparticles embedded in -Al
2
O
3
formed by Zn
+
ion implantation at a dose of 110
17
cm
-2
. The
polycrystalline ring in the bottom inset in (a) showing the random orientation of the Zn nanopartilces
precipitated after the ion implantation.
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 549
2.2.3. TEM Results of Zn and ZnO Nanoparticles

Figure 25 shows a cross-sectional bright-field TEM image (a) and a high resolution TEM
(HREM) image (b) of Zn nanoparticles embedded in -Al
2
O
3
formed by Zn
+
ion implantation
at a dose of 110
17
cm
-2
. Nearly spherical embedded Zn nanoparticles of 3-10 nm in diameter
are observed and the ion-implanted area is amorphized. The insert one in Figure 25a is a
selected area electron diffraction (SAD) pattern. The polycrystalline ring can be observed in
the SAD pattern showing the random orientation of the Zn nanopartilces precipitated after the
ion implantation [16].

20 nm
crystalline matrix
recrystallized Al
2
O
3
ZnO
voids
surface
a
100
101
b

Figure 26. A cross-sectional bright-field TEM image (a) and selected area electron diffraction (SAED)
pattern (b) of ZnO nanoparticles embedded in -Al
2
O
3
formed after annealing at 600 C.
Figure 26 contains a cross-sectional bright-field TEM image (a) and selected area
electron diffraction (SAED) pattern (b) of ZnO nanoparticles embedded in -Al
2
O
3
formed
after annealing at 600 C. The ZnO can be confirmed by the SAED pattern. Figure 27 is a
high resolution TEM image of ZnO nanoparticles, showing the nanoparticles of 10-12 nm in
dimensions. The mori fringes indicate the precipitation of ZnO nanoparticles after annealing.
It is clear that the ZnO nanoparticles formed close to the surface of the -Al
2
O
3
single crystal,
with a depth shallower than the projectile range of implanted Zn atoms. It indicates that the
Zn atoms migrated towards the surface of the crystal during the annealing in oxygen
atmosphere. At the same time, some high density of large voids (labeled in Figure 26a) is
observed in the near-surface region due to the migration and precipitation of irradiation
induced vacancies.
The recrystallized Al
2
O
3
grains have different orientation relationship with the original
matrix, which can be observed in Figure 28. However, the recrystallization was not complete
after annealing at 600 C for 1 h. The front surface area (labeled in Figure 28) remained
amorpous. Apparently, longer annealing time or higher annealing temperatures are needed to
complete the recrystallization [17].

X.T. Zu, X. Xiang, S. Zhu et al. 550
5 nm

Figure 27. A high resolution TEM image of ZnO nanoparticles, showing the nanoparticles of 10-12 nm
in dimensions.
2 nm
Al
2
O
3
matrix
recrystallized Al
2
O
3
amorphous Al
2
O
3

Figure 28. A high resolution TEM image showing the recrystallized Al
2
O
3
with different orientation
relation with the matrix.
2.2.4. PL of ZnO Nanoparticles

Figure 29 shows the photoluminescence (PL) spectra of the as-implanted crystal and the
annealed crystal at 600 C using a HeCd laser excitation at 325 nm line at room temperature.
There is a very weak PL band peaked at ~470 nm in the as-implanted crystal. It may be due to
the photoluminescence combination of both F (PL at 3.0 eV) and F
2
(PL at 2.4 eV) centers
coexisted in Al
2
O
3
induced by ion implantation [44]. PL spectrum of the annealed crystal
shows two PL peaks, one at 370 nm, and the other at 500 nm, which have also been observed
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 551
in Zn
+
ion implanted SiO
2
and CaF
2
[37, 39]
.
The UV emission is the characteristic PL peak
ascribed to ZnO free-exciton recombination at room temperature, which confirms the
formation of ZnO nanoparticles after thermal annealing. The green emission at ~500 nm may
originate from the deep levels [45, 46]. The deep-level emission at around 2.5 eV is
associated with either surface state emission or excess Zn interstitials (or oxygen vacancies).
Up to now, both UV and green PL peaks of embedded ZnO nanoparticles have been
observed in SiO
2
, CaF
2
and Al
2
O
3
matrices by ion implantation and thermal annealing (listed
in Table 4).

Wavelength/nm
350 400 450 500 550 600 650 700 750 800
0
100
200
300
400
a
b
P
L

i
n
t
e
n
s
i
t
y
/
a
.
u
.

Figure 29. Photoluminescence spectra of the as-implanted (a) and the annealed (b) crystal at 600 C at
room temperature.
Table 4. PL of ZnO nanoparticles embedded in several insulator matrices
SiO
2

700
o
C 1h 375 500 1:2 [37]
700
o
C 2h 377 500 1:7
[39]
400
o
C 45min 384 500 2:1
CaF
2

500
o
C 45min 372 - -
[47]
700
o
C 45min 379 - -
Al
2
O
3
600
o
C 1h 370 500 3:1 [17]
2.3. Intermetallic Co
x
Ni
1-x
Nanoparticles Embedded in YSZ
Sequential ion implantation in dielectric matrix determines three different cluster
morphologies: separated systems, alloy clusters and coreshell clusters. Sequential ion
implantations with different elements were performed mostly on silica substrates, but also on
quartz and sapphire [48]. In this data review, the intermetallic Co
x
Ni
1-x
nanoparticles
embedded in YSZ were synthesized by sequential implantation of 90 keV Co and Ni ions at
room temperature. TEM and magnetic measurements were utilized to analyses the magnetic
Co
x
Ni
1-x
nanoparticles [22].
X.T. Zu, X. Xiang, S. Zhu et al. 552
2.3.1. TEM Images of Co
x
Ni
1-x
Nanoparticles

A bright field cross-sectional TEM image (Figure 30a) shows that the nanoparticles
precipitated spontaneously during ion implantation in the near surface of the YSZ matrix. The
typical nanoparticle size ranged from 3 to 10 nm. In the high concentration region of
implanted Co and Ni ions (~2540 nm below the surface, consistent with the results from
SRIM 2000 code [27]), some large precipitates up to 25 nm in length formed parallel to the
surface of YSZ. High-resolution TEM images clearly revealed that the elongated particles
consisted of individual crystals joined across twin boundaries. The (111) twin planes are
shown in Figure 30b. The selected area diffraction pattern inserted in Figure 30a exhibits
obvious extra diffraction spots from the precipitates, which are circled in the SAD pattern.
The precipitates are cubic with a>0.35 nm. The phases consistent with this lattice parameter
include cubic Co, Ni, solid solution Co
x
Ni
1-x
, as well as intermetallic phases, CoNi and
Co
3
Ni
7
[49].


Figure 30. Bright-field cross-sectional TEM (a) and high resolution TEM (b) micrographs showing
nanoparticles of Co
x
Ni
1-x
in YSZ single crystal; SAD pattern (inset in (a)) indicating the orientation of
the nanoparticles to the matrix.
Energy filtered elemental mapping images of Co, Ni, and O using the L
2,3
or K edges in a
corresponding energy electron-loss spectroscopy (EELS) spectrum, are shown in Figure 31.
The bright contrast of the nanoparticles in the Co and Ni maps indicates that the nanoparticles
contained both Co and Ni. These nanoparticles do not contain oxygen as indicated by the dark
contrast in nanoparticles in the O map image. Energy dispersive spectroscopy (EDS) analysis
showed the composition ratio of Co over Ni ranges from 0.8 to 1. Therefore, the nanoparticles
are Co
x
Ni
1-x
solid solution. The orientation relationship between aligned nanoparticles and the
YSZ matrix are (200)
YSZ
(200) Co
x
Ni
1-x
, and [011]
YSZ
[011] Co
x
Ni
1-x
. Based on calculations
using the SRIM code, the maximum level of damage reached 300 dpa in the YSZ matrix;
however, the YSZ matrix still retained its crystallinity.

Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 553

Figure 31. (a) Bright-field image and elemental mapping images of (b) Co, (c) Ni, and (d) O,
respectively, indicating the compositional distribution of the nanoparticles.
2.3.2. Magnetic Properties of Co
x
Ni
1-x
Nanoparticles

Magnetization plots as a function of magnetic field at both 10 and 300 K are shown in
Figure 32. The magnetization field H applied is parallel to (001) of the YSZ single crystal, i.e.
(001) of Co
x
Ni
1-x
, due to its orientation alignment. The coercivity, H
c
, at 300 K was measured
to be ~100 Oe. The coercivity increased to 260 Oe as the temperature decreased to 10 K.


Figure 32. Magnetization vs field applied at temperatures of 10 and 300 K. The field applied is parallel
to the (001) plane of the YSZ matrix.
X.T. Zu, X. Xiang, S. Zhu et al. 554
These values are consistent with previously reported particle-size dependent coercive forces
in CoNi alloys [50, 51]. The magnetization curves at 10 and at 300 K were completely
saturated at applied fields of H = 800 and 5000 Oe, respectively. The saturation
magnetization, Ms, increased 15% as the temperature decreased from 300 to 10 K. The
remanent magnetization M
r
/M
s
was 0.41 at 300 K and its value increased to 0.77 at 10 K.
The variation of coercivity strongly depends on the grain size. Since nanoparticles less
than a critical size are in single domain states, their coercivities are higher than that of a
common bulk sample [33]. Previous investigations reported that the critical size with the
largest coercivity lies in the 3040 nm range for Co
50
Ni
50
[50]. The coercivity of our samples
can be attributed to this nanostructural effect. The mismatch between the matrix and the
implanted Co
x
Ni
1-x
particles probably induces stress, which also affects the coercivity [52].
Nanoparticles are expected to illustrate superparamagnetic properties.


Figure 33. Temperature dependence of the magnetization. The curves show that in the ZFC and FC
processes at H = 100 Oe.
The blocking temperature can be readily characterized by ZFC and FC magnetization.
Figure 33 shows the temperature dependent magnetization curves under ZFC and FC
processes at H=100 Oe. No blocking temperature within 300 K was observed. Since TEM
analysis has confirmed that the nanoparticles are not oxidized, the results from the ZFC and
FC curves suggest that the sample might not be blocked at low temperature. This is
reasonable if particle-size and shape effects are considered. As observed in the TEM
micrograph (Figure 30), the particle size is widely distributed from 3 to 10 nm, and some
longer particles up to 25 nm have formed from a sequence of twin planes roughly
perpendicular to the length of the particle. They might not be in single domain states. The
blocking temperatures therefore are different and may overlap.
The critical temperature, i.e., the blocking temperature, T
B
, is also roughly given as the
equation: T
B
= K
eff
V/25k
B
[32]. Based on this equation, T
B
= ~227 K, if we use the
magnetocrystalline constant K
1
value (1.510
5
J/m
3
) from Ref. [53] for K
eff
and a maximum
diameter of 10 nm for the nanoparticles. The result of this calculation differs from the
experimental observation because K
1
only represents the magnetocrystalline anisotropy
contribution. Since some nanoparticles are not truly spherical, the contribution by shape
Embedded Optical-electrical Nanomateriales Fabricated by Ion Implantation 555
anisotropy to K
eff
should also be considered. On the other hand, the elongated particles
formed by repeating twins may result in interparticle dipolar interactions. Thus,
supermagnetism of the Co
x
Ni
1-x
nanoparticles may persist to above 300 K, and the
nanoparticles will remain ferromagnetic at room temperature.
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In: Nanotechnology...
Editors: C.J. Dixon and O.W. Curtines, pp. 559-602
ISBN 978-1-60692-162-3
c 2010 Nova Science Publishers, Inc.
Chapter 18
STRUCTURAL, DYNAMICAL AND OPTICAL
PROPERTIES OF SELF-ASSEMBLED PORPHYRINS
AT THE MESOSCOPIC SCALE
Valentina Villari
1,
, Norberto Micali
1
and Luigi Mons u Scolaro
2
1
CNR-Istituto per i Processi Chimico-Fisici,
S.ta Sperone C.da Papardo, I-98158, Messina, Italy
2
Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica,
Universit a di Messina Salita Sperone 31,
I-98166 Vill. S. Agata, Messina, Italy
Abstract
Organized self-assembly of molecules, driven by noncovalent intermolecular interac-
tions, is the most versatile tool for accessing new materials with desired optical and
electronic properties. Porphyrins are particularly attractive species to incorporate into
supramolecular assemblies because their rich photochemistry may impart functional-
ity, provide insight into the mechanisms of biological processes such as photosynthe-
sis, serve as probes into the features of self-assembled structures and as models for
molecular organization and energy/electron transfer processes. The close molecular
packing in a self-assembled porphyrin aggregate leads to different electronic coupling
and delocalization of the excitation energy, which can be exploited for applications in
non-linear optical devices, photoelectric cells, recording devices. The possibility to
control and tune either shape and size of the porphyrin clusters opens the way for their
use as potential nanodevices. This review aims to collect some recent developments
in the eld of porphyrin self-assembly and to frame all the reported topics into the
current theories.
1. Introduction
Porphyrins constitute a wide class of natural and synthetic molecules whose photophys-
ical properties can be modulated by changing the peripheral substituent groups and/or by

E-mail address: villari@me.cnr.it; valentina.villari@cnr.it. (Corresponding author)

560 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
inserting metal ions in the central core of the macrocycle.[1, 2] In nature, for instance,
porphyrins are present under different forms and are responsible of many biochemical pro-
cesses in animal and vegetable kingdom: specic examples are furnished by hemoglobin or
by chlorophyll, as well as by many other biological molecules whose building blocks are
porphyrin residuals, like cytochromes and hemocyanines.
Along with natural porphyrins many synthetic porphyrins are exploited in biological and
medical research for the study of nucleic acid conformation, of intercalation phenomena[3,
4, 5, 1, 6] and as drugs in anticancer photodynamic therapy.[7, 8] Moreover, the stabil-
ity of these systems makes them especially interesting for photoionization processes, en-
ergy/electron transfer, photocatalysis and nonlinear optical properties.[9, 10, 11, 12]
Numerous studies, for instance, have been carried out to investigate the DNA structure, by
exploiting the ability of some porphyrin derivatives of intercalating into DNA of appropri-
ate composition, while other porphyrins, depending on the nature of peripheral substituents
or inserted metals, are limited to external, groove binding.[3, 4, 5, 1]
The interaction of porphyrin-based moieties with different chemical species makes them
useful for molecular recognition processes in the sensor eld.[13, 14, 15] One important,
promising, and newly developed practical application is the determination of the absolute
conguration of various chiral compounds, even of biological importance like amino acids,
and of the enantiomeric excess.[16, 17] In addition, the chemo-responsive behaviour of
metalloporphyrins provides a way of reporting the presence of odors by changes in color;
two-dimensional display of metalloporphyrins, as an example, was employed as sensor for
the visual identication of a wide range of olfactants and solvent vapors.[18, 19]
One of the most challenging aspect for specic application in materials science, con-
densed matter science, engineering, farmaceutics (drug delivery) as well as in nano-science
and nanotechnology, consists in using porphyrins and their derivatives as buildingblocks for
designing and accessing to supramolecular systems, by means of controlled self-assembly.
From a general point of view, self-assembly is the autonomous organization of components
into patterns or structures; it involves components from the microscopic to the macroscopic
scale and many different kinds of non-covalent interactions, like van der Waals, electro-
static, hydrophobic interactions, hydrogen and coordination bonds. Thanks to the wide
range of interactions when using components larger than molecules, often it is possible to
adjust interactions themselves over wide ranges of strength and selectivity. Nonmolecular
systems are, thus, in many aspects more versatile in their design than molecular systems. It
is often easier to build-up nonmolecular components than it is to synthesize molecules, and
easier to observe the process and products of self-assembly using conventional experimen-
tal techniques (like, for instance, scattering).
Depending on their geometrical disposition in the assembly, porphyrins can form differ-
erent kinds of aggregates called H- (face-to-face interactions) and J-type (side-by-side in-
teractions). J aggregates have attracted a great deal of interest for their nonlinear optical
properties originating from the close molecular packing: the stacking interactions together
with electrostatic and hydrogen bonding interactions, in fact, leads to electronic coupling
and delocalization of the excitation energy.
Among different kinds of porphyrins the water soluble moieties are very interesting because
their self-aggregation can be conveniently controlled by screening the charge repulsion
through the ionic strength and pH and by varying concentration.[20, 21] More precisely,
Self-assembled Porphyrins at the Mesoscopic Scale 561
acting on the intermolecular interaction potential leads to structures which are different not
only at a mesoscopic scale but also locally. Furthermore, porphyrin self-assembly on the
DNA surface[22, 23, 24, 25, 26] or engineered viral particles[9] has been reported as a
convenient method to control the size and extent of supramolecular porphyrin assemblies.
Resonant energy transfer to the interacting porphyrins in these self-assembled structures
has been also observed, occurrence which is of crucial importance in the design of new
efcient articial antenna systems.
The local structural organization of self-assembled porphyrin aggregates can be conve-
niently studied by exploiting the features of the supramolecular chirality, which can arise
from intrinsically chiral assemblies[27, 28, 29, 30, 31, 32] or from aggregation onto chiral
templates.[34, 35, 36, 37] Selection of the chirality of a supramolecular structure, in the
absence of any templating agents, was carried out by means of macroscopic chiral elds
(i.e. vortex motion) during the aggregation process.[32, 33] Such an occurrence suggested
to speculate about the role played by the sign of vorticity in relation to the origin of biolog-
ical chirality. Also intriguing is the possibility to induce chirality on porphyrin aggregates
which self-replicate in solution, that is retain the memory of their imprinted chirality.[37]
These systems are useful in understanding the transfer of information in biologically rele-
vant aggregation processes.
The huge literature reporting the mesoscopic self-assembly of porphrins suggests that the
shape and size of the mesoscopic (and also local) structure, as well as the aggregation kinet-
ics and physico-chemical properties, of porphyrin aggregates in solution are not an intrinsic
property of porphyrin itself. Rather they depend on the proper choice of the thermodynamic
parameters of the solution and templating agent, which can be easily tuned and controlled.
For these reasons porphyrin assemblies are extremely good candidates for applications in
nanodevices, photoelectric cells, recording devices and as model for light harvesting in an-
tenna systems.
In this review article some recent developments in the eld of porphyrin self-assembly is
presented within the following topics:
theoretical and experimental aspects related to the characterization of structural and
dynamical properties of the aggregating species;
kinetic mechanisms of the aggregation process and the consequent structure of the
nal aggregate;
dependence of the mesoscopic structure and geometry of the aggregates on the ther-
modynamic parameters of the solution (like porphyrin concentration, ionic strength
and pH);
analogy between nonlinear optical properties of porphyrin aggregates and those of
metal composites: delocalization of the excitons in submicrometric zones (hot
zones) generating Raman and Rayleigh scattering enhancement;
supramolecular chirality induction by a templating agent or by an external eld and
dependence of the symmetry factor on aggregates size.
All these subjects will be discussed and supported by numerous examples and experimen-
tal techniques (Static and Dynamic Light Scattering, Raman Scattering, Uv-Vis, Circular
562 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Differential Extinction and Circular Intensity Differential Scattering). Attention will be de-
voted to the experimental aspects concerning the mesoscopic systems like for instance the
inuence of the scattering on the absorption and circular dichroism measurements.
2. Exciton Delocalization
In a porphyrin assembly the strong interactions give rise to the coupling between excited
states (excitons) of the contituent molecules. The optical properties of these structures are
described by the Frenkel exciton model, according to which the extent of the exciton wave
functions is determined by the competition between intermolecular transfer interactions
and (static) disorder. According to a purely exciton model, in fact, the energy and the
broadening of the band for an aggregate of N two-level molecules can be obtained by the
excitation Hamiltonian:
H =
N

m=1
(E
mon
+ E
m
)b
+
m
b
m
+
N1

m=1
J(b
+
m
b
m+1
+b
+
m+1
b
m
) (1)
Here, b
+
m
and b
m
are the Pauli creation and annihilation operators for de-excitation and ex-
citation on the site m, J is the nearest-neighbour excitation transfer interaction, E
mon
=
hc
mon
is the molecular (monomer) two level excitation energy and E
m
represents the en-
ergy offsets introduced by the static disorder. For perfectly ordered aggregates (distribution
width of E
m
being zero), the exciton wave functions are delocalized along all the length of
the aggregate. The one-exciton states, |k (the ground state being |0), which determine the
absorption spectrum, and their k-th exciton energy are given by:
|k =
N

m=1
sin
_
km
N + 1
_
b
+
m
|0 (2)

k
=
mon
+ 2Jcos
_
k
N + 1
_
(3)
If molecules are arranged in a J-structure the exciton coupling constant J is negative, which
leads to red-shifts in the spectrum relative to the monomer. By contrast, J is positive for
H-type aggregates, with resultant blue-shifts in the spectrum.
In disordered aggregates the exciton states are mixed due to the broken translational sim-
metry, and localize on a part of the aggregate; these states, which can be visible as separate
lines when the disorder is small, merge into one broader line when the disorder increases.
The width (half-width-at-half-maximum) of this absorption line, , is directly related to the
nite number of molecules over which delocalization occurs:[39, 38]
N
del
=
_
3
2
|J| / 1 (4)
2.1. Resonance Light Scattering Effects
Exciton coupling and electronic communication among the molecules in an aggregate
(especially in a J-type aggregate) can cause extraordinary optical effects: one example is
resonance light scattering (RLS), i.e., an increase in the intensity of scattered light at the
Self-assembled Porphyrins at the Mesoscopic Scale 563
Figure 1. Experimental extinction (plot a) and scattering (plot b) spectra of an aggregated
H
2
TPPS
4
solution ([H
2
TPPS
4
]=3 M, pH=1).
wavelength where the aggregate has an electronic absorption transition. For aggregates of
sufcient size, the enhanced scattering overwhelms the absorption and a peak in the scat-
tering spectrum appears.
Besides in solutions of porphyrin aggregates[40], the phenomenon is observed also in a va-
riety of small chromophores in solution[41, 42], chromophore-protein complexes[43, 44],
chromophore-nucleic acid complexes[45, 46] and chlorophyll a aggregates[47].
Figure 1 displays, as examples, the absorption and scattering spectra of an aggregated
porphyrin solution (H
2
TPPS
4
of gure 2). The isolated porphyrin has a Soret band
at the frequency
mon
, corresponding to 1/
mon
=
mon
= 434nm, whose width is

mon
= 875cm
1
, and the J-aggregate a peak at
J
= 490nm (J = 1275cm
1
),
with 100cm
1
. According to the exciton theory the resonant band width leads to a
delocalization over few tens of porphyrins.
Even though the exciton theory allows for a calculation of the delocalization length from
the spectral width of the absorption band of the aggregate, for large aggregates the scatter-
ing component affects the absorption spectra signicantly. As a consequence the evaluation
of the band width can be misleading. The distinction between scattering and absorption can
be conveniently done by measuring independently the extinction and RLS spectra on the
same sample and by performing a linear regression analysis of the data in the region close
to the resonance.[48, 49, 50]
By assuming that only a single excited state of the monomer contributes to the polarizability
around the lower energy absorption frequency, (), the quantum mechanical expressions
564 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 2. Scheme of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin ( H
2
TPPS
4
) struc-
ture.
for the absorption and scattering cross-section are:
C
abs
= 2Im()
C
sca
= 8/3
3

4
_
(Re())
2
+ (Im())
2
_
(5)
Re() and Im() being the real and imaginary parts of the polarizability for a system
where the dipole moment vector has one component[48, 51, 52].
According to this theory, the scattering cross-section C
sca
depends on the number N of in-
teracting chromophores and the calculation for a J-aggregate can be performed according to
the point dipole approximationas described in the literature.[51] Figures 3a) and b) describe
the calculated dependence of the absorption and scattering cross-section, respectively, on
the number of interacting chromophores. This approach was particularly useful for obtain-
ing the size and the structure of a J-aggregate inside the water pool of a microemulsion on
increasing the size of the inner core[48], as shown in the next subsection.
2.2. Geometrical Arrangement of Porphyrins in a J-aggregate
Porphyrin molecules are optically isotropic, but when they aggregate in a J-
arrangement, the large interaction between porphyrins (coherence length of the exciton
coupling) makes the free displacements of electrons under incident radiation asymmetric,
giving rise to optical anisotropy[21, 48, 51] and depolarization ratio
dep
= I
V H
/I
V V
= 0
(I
V V
and I
V H
being the polarized and depolarized scattered intensity, respectively).
Unlike the scattering cross-section, the depolarization ratio is not dependent on the size of
the aggregate, but it is related only to the principal values of the polarizability tensor at the
resonance wavelength[51, 52]:

dep
=
3
_

//

_
2
45
_
1/3
_

//
+ 2

__
2
+ 4
_

//

_
2
(6)
being
//
and

the parallel and ortogonal component of the polarizability, respectively,

for an axially-symmetric molecule.
Self-assembled Porphyrins at the Mesoscopic Scale 565
Figure 3. Dependence of the absorption (upper plot) and scattering (lower plot) cross-
section on the number of constituting monomers (curve a: N=1, curve b: N=2, curve c:
N=5, curve d: N=10, curve e: N=20), calculated by using the RLS theory[51] for a J-type
aggregate of H
2
TPPS
4
.
In practice, the depolarization ratio depends on the slip angle between adjacent porphyrin
planes (see inset of gure 4) and can give information on the geometry of the excited state
of an aggregated species. By assuming a parallel arrangement of the transition moments of
the exciton-coupled chromophores, in the case of J-aggregates conned in a water pool of a
microemulsion the slip angle decreases on increasing the droplet size, as reported in Figure
4.
On considering that aggregates grow in the water pool and the dimensions are limited by
the conned environment, it is possible to combine the calculated angles with simple ge-
ometrical analysis and estimate the aggregation number, N
aggr
, and the length of the por-
phyrin clusters in the inner water compartments. Assuming the model recently proposed in
the literature[53], in which the porphyrins form monodimensional arrays, we can calculate
the coherence length as L = (N
del
+ 1)R (where R is the radius of a single molecule).
The ratio r = (N
del
+ 1)/(N
aggr
+ 1) indicates the quality of the exciton delocalization,
being close to unity for an ideal J-aggregate. The maximum value for this parameter re-
ported so far has been 0.25, for J-aggregates obtained in acidic aqueous solutions, using
ammonium chloride as the nucleating agent.[53] For J-aggregates in a microemulsion the r
values obtained range between about 1 and 0.35 for the smallest core and the largest one,
respectively, suggesting a high level of coherence for these aggregates.[48]
566 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 4. Slip angle between porphyrins as a function of the droplet radius of the wa-
ter/AOT/decane microemulsion (experimental conditions: volume fraction = 0.05,
[H
2
O/AOT]=5 65), [acetate buffer]=25mM, pH=2.7, TPPS stock solution at 80M ).
The inset reports the depolarization ratio dependence on the slip angle, calculated from the
RLS theory for a TPPS4 solution with N=50.
3. Kinetics of Self-assembly
Aggregation of porphyrins (particularly in water solutions) can be induced acting on
many parameters, so that the mesoscopic and local arrangement of the nal structures vary
signicantly depending on the induced kinetic mechanism and rate.
The rate of aggregation of particles depends on frequency of collision and probability of
sticking after collision. These factors are related to the solution parameters such as temper-
ature, pH or other chemical properties that affect particle correlations, and on the presence
of an external eld. In 1917 Marian Smoluchowski introduced his kinetic expression for the
time evolution of particle aggregation; it relates the concentration changes of the species i
and j to form species i+ j due to binary collisions.[54] This equation is based on a mean eld
theory of identical particles (namely it assumes that the probability of two particles meeting
is simply proportional to the product of their concentration) and includes a kernel, which
depends on the physical properties of the system like shape and size of particles, compo-
sition, and interaction potential. The kernel can take many forms, depending on collision
interactions among the particles, and in recent years many different forms of the kinetic
prole have been obtained analytically and numerically for different systems[55, 56].
For a nite system the Smoluchowski equation takes the form of a system of coupled ordi-
nary differential equations:
P
i
+ P
j
K(i,j)
P
i+j
dc
k
dt
=
1
2

i+j=k
c
i
K(i, j)c
j
c
k

j=1
K(k, j)c
j
(7)
where P
j
denotes an aggregate containing j monomers, K(i, j) is the reaction kernel of
creation and destruction of the aggregate and c
k
is the concentration of the species k. By
Self-assembled Porphyrins at the Mesoscopic Scale 567
considering dilute solutions, in which only binary collisions are relevant, Kernels are con-
gurational and orientational averages of the reaction rates between two colliding species.
Smolukowski equation is analytically solvable only for few kernels like the constant kernel
K(i, j) = K(1, 1) (i.e. same probability of collision for all clusters and monomers), the
sum kernel K(i, j) i + j, the product kernel K(i, j) ij and their linear combinations.
Another particular case was suggested by Smoluchowski, who obtained an explicit form for
the Kernel K(i, j) 4(R
i
+R
j
)(D
i
+D
j
), by solving the diffusion equation, R
i
and D
i
being the radius and the diffusion coefcient of the aggregate constituted by i monomers,
respectively.
No general solution exists and for real systems the reaction kernel depends on many pa-
rameters, making it difcult to know its form. However, in the case of kinetic mechanism
of aggregation driving to clusters with specic properties, like scaling, self-similarity and
universality, some considerations and simplications can be done.
For self-similar structures, for example, namely those structures which are space scale-
invariant (like fractals for which R
i
= R
mon
i
1/D
f
, with D
f
dened as fractal dimension),
the homogeneity relation for the kernel holds:[57, 58]
K(ai, aj) = a

K(i, j) (8)
with the condition that the kernel for the collision between the species i and j is K(i, j) =
i

, with j >> i and 1. The quantity = + 2 describes the tendency of a large

cluster to join with another large cluster, so determining the overall rate of aggregation; ,
on the other hand, governs the aggregation rate between big clusters and small clusters. The
occurrence > 1 describes a gelation process which gives rise to an innite-size cluster
in nite time. In this frame, for different values of the quantities and , different fractal
structure of the aggregate is obtained.
Among the numerous collision mechanisms which can be considered, particular attention
has to be devoted to the diffusion driven collisions. If the sticking probability between
smaller and bigger clusters is predominant ( = 0 or, more generally < ) the ag-
gregation process gives rise to monodisperse Diffusion Limited Aggregates (DLA) with
D
f
= 2.5, whereas higher sticking probability between bigger clusters ( > 0) gener-
ates polydisperse Diffusion Limited Cluster-Cluster Aggregates (DLCCA) characterized
by D
f
= 1.75.
In the case of the Smoluchowski kernel, for example, the self-preserving shape implies:
K(i, j) (i
1/D
f
+ j
1/D
f
)(i
1/D
f
+j
1/D
f
). (9)
where the Einstein-Stokes relation D = k
B
T/(6R) was used (however, a more general
dependence D
i
i

can be also considered[59]). The kernel used by Smoluchowski rep-

resents an example of DLA mechanism in which = 0.
From the mean eld and Smoluchowski treatment it is clear that in colloidal systems the
kinetics of growth and the relative mechanism drive the morphology of the resulting aggre-
gate.
Examples of fractal structures built through different aggregation mechanisms in a lattice
can be obtained by numerical calculation and molecular dynamics, giving to each lattice
site a probability p to be occupied. In a real system p is represented by the probability that,
568 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 5. Numerical calculation for fractal structure originating from DLA (at left) and
percolation (at right) mechanism.
under collision, two species stick together. In gure 5a) the fractal structures originating by
the diffusion-limited aggregation mechanisms is sketched, as an example.
A quantitative description of the aggregation process can be done by considering that the
distribution of fractal clusters with different mass (or size) is an homogeneous function
evolving in a self-preserving form[60], independently of the initial distribution:[61]
c
i
(t) = i
2
f(i/

S(t)) (10)
where c
i
is the concentration of clusters constituted by i monomers and

S(t) t
z
is the
average aggregation number of clusters (or in terms of mean cluster radius

R(t) t
z/D
f
),
with z = (1 )
1
. For the Smolukowski kernel given in eq. 9 it is z = 1 which corre-
sponds to the result otained for a DLA growth mechanism.
Because it is easy from an experimental point of view to monitor the time dependence of
the monomer concentration (an example is reported in the following subsection), let us con-
sider the kernel for the reaction involving only collisions between clusters and monomers:
K(1, j) = j

. The Smoluchowski equation 7 becomes:

dc
1
dt
= c
1

j=1
j

c
j


S(t)
1
(11)
the last proportionality being obtained by using eq. 10 for c
j
(t). By integrating previous
equation, the time dependence of the monomer concentration results in a stretched expo-
nential:
c
1
(t) = Aexp
_
t
()/(1)
_
(12)
According to the mean-eld theory[54] and to Molecular Dynamics simulations[57, 62], a
reaction-limited (RLA) early stage of the fractal aggregation (with D
f
= 2.1) is expected to
precede the diffusion-limitedregime described above. In this early stage the clustering pro-
cess is hindered by short-range high repulsive barrier, so that many collisions are required
before aggregation occurs (low sticking probability). For reaction limited aggregation the
Self-assembled Porphyrins at the Mesoscopic Scale 569
dynamic scaling law of the mean cluster radius is described better by an exponential in-
crease

S(t) exp(bt), where b depends on the experimental conditions.
Due to its transient regime, it is difcult to observe the RLA early stage experimentally, but
in the subsection 4.2 and 6.2 it will be shown how to obtain the required information in the
case of porphyrin solutions.
Another mechanism originating fractal structures is percolation, a model which represents
a powerful tool for the study of many physical processes like second order phase transitions
or gelation in complex uids, as well as of porous materials, biological structures, polymers,
just to cite some examples. This model assigns a critical threshold concentration (called site
percolation probability) at which the largest cluster includes almost all the molecules and
spatially extends to all the space[63], as sketched in Figure 5b).
3.1. Experimental Observation of Porphyrin Fractal Structures
The fractal structure of colloidal aggregates can be studied experimentally by means of
Elastic Light Scattering experiment, which measures the zero-time autocorrelation function
of the scattered eld, E
S
:[65]
G
1
(Q, 0) = E

S
(Q, 0)E
S
(Q, 0) = I(Q) = KM
w
cP(Q)S(Q) (13)
in which P(Q) and S(Q) are the normalized formfactor and the structure factor, respectively,
M
w
the weight average molecular weight of the particle, c the mass concentration, Q =
(4n/
0
)sin(/2) and K = [4
2
n
2
/(N
A

4
0
)](dn/dc)
2
the optical constant (
0
being the
incident wavelength, the scattering angle, N
A
the Avogadro number, n the refractive index
and dn/dc the refractive index increment)[64]. The factorization in the product between
P(Q) and S(Q) is performed under the hypothesis of independence of intermolecular and
intramolecular averages.
The form factor, P(Q), represents the intra-particle interference and is related to the spatial
Fourier transform of the particle mass distribution, w(r), all over the volume of the particle:
P(Q) =

_
V
w(r)exp (iQ r) dr
_
V
w(r)dr

2
(14)
For particles smaller than the wavelength (tipically smaller than
0
/20) P(Q) 1.
The structure factor, S(Q), is dened as the Fourier transform of g(r
1
, r
2
) 1, where
g(r
1
, r
2
) = (r
1
)(r
2
) is the number density correlation function. In the case of self-
similar systems this function is homogeneous, that is:
(r
1
)(r
2
) =
A

(r
1
)(r
2
) (15)
where (r
1
) is the number density of monomers at the position r
1
.
For an homogeneous and isotropic system the number density correlation function depends
only on the distance between two particles g(r
1
, r
2
) = g(|r
2
r
1
| , 0), simply indicated as
g(r). Therefore, the structure factor can be written as:
S(Q) = 1 +
_
[g(r) 1]exp (iQ r) dr (16)
570 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
For self-similar structures eq.15 implies that (r)(0) r
A

, A

being related to the

space dimension d and to the fractal dimension D
f
as A

= d D
f
. As already seen in the
previous section, the fractal dimension is dened through a scaling law between the number
of monomers constituting the cluster with radius R and the radius itself: N(R) = R
D
f
. By
using the power-dependence of the number density correlation function on r, the structure
factor is easily calculated:[60]
S(Q) = Q
D
f
(17)
Previous equation is valid for describing ideal fractals, i.e. clusters extending all over the
space scale; real fractal systems, however, have a nite size and at Qvalues lowenough they
must obey a Gaussian law (Guinier limit)[66]. Chen and Teixeira[67] proposed a structure
factor suitable for describing a nite fractal aggregate constituted by m

monomers, encom-
passing Gaussian and fractal behavior. The nite extension of the aggregate is taken into
account by an exponential cut-off exp(r/), with a cutoff correlation length:
S(Q) = m

sin[(D
f
1)arctan(Q)]
(D
f
1)Q(1 +Q
2

2
)
(D
f
1)/2
(18)
Previous equation reduces to eq. 17 if Q >> 1 and /R
mon
> 50.
The theoretical approach described above, along with the experimental results obtained by
light scattering, turns out to be extremely powerful in showing that the kernel of the kinetic
equation can be easily modied by means of pH, ionic strength and concentration to give
rise to aggregates with different fractal morphology.
In gure 6, as examples, the intensity proles of porphyrin solutions at different pH values
are reported. By considering that the smallness of porphyrin monomers makes the form
factor be approximately unity, the measured intensity prole is directly related to the
structure factor.
The porphyrin aggregation process is driven by the interparticle potential which can
be described through the well-known Derjaguin-Landau-Verwey-Overbeek potential
(DLVO),[68] related to the presence of a diffuse double layer surrounding colloidal
particles.
For H
2
TPPS
4
4
solutions containing [HCl] < 0.01 M the protonation of the core
(giving rise to the diacid form H
4
TPPS
2
4
) originates the zwitterionc form. Under these
conditions the electrostatic repulsion between negative charges of the SO

3
perypheral
groups is still high and is responsible for the high kinetic barrier to the approach of
monomers and the low probability of aggregation, so that light scattering experiments do
not reveal any detectable amount of aggregates.
On increasing the acid concentration (0.1M < [HCl] < 4M) negative charges are
progressively screened by H+ ions and the sticking probability increases accordingly.
At [HCl] 0.1M the interaction between diacid porphyrins is still repulsive (charge
2-) with a long screening length and the weak attractive van der Waals forces ( r
6
)
are scarcely effective, leading to a small probability of interaction. Therefore, after an
induction period due to the small sticking probability, the DLVO potential, whose attractive
component depends on the third inverse power of the interparticle distance, favors the
adhesion between clusters ( > 0). As shown in Figure 6, the scattered intensity prole
follows a power law with D
f
= 1.75, indicating that small clusters are able to self-interact
Self-assembled Porphyrins at the Mesoscopic Scale 571
Figure 6. Absolute scattered intensity prole of aggregated H
2
TPPS
4
in water solu-
tion under strongly acidic conditions (at the end of kinetics). Experimental conditions:
[H
2
TPPS
4
]=3M and [HCl]=0.1 M (squares), [HCl]=1 M (circles), [HCl]=2 M (trian-
gles),
0
= 532nm. The continuous line has slope equal to -1.75 and the dashed one slope
equal to -2.5.
leading to larger aggregates with a DLCCA mechanism. For [HCl] 1M the net charge
of the molecules is small enough to lower the screening length and to increase the sticking
probability between clusters and monomers ( < 0); aggregation takes place according to
a DLA mechanism (D
f
= 2.5).
At [HCl] 4M, the net charge on the monomer becomes very small and the ionic strength
is large enough to almost reduce to zero the screening length. The aggregation process
is driven almost entirely by attractive forces and it takes place by nucleation, without
any fractal arrangement. Any further increase of the acid concentration leads to the full
protonation of the sulfonate end groups and to the disruption of the aggregates. Because of
the presence of the two positive charges, the H
8
TPPS
2+
4
porphyrin does not self-interact
even under these extreme ionic strength conditions.
3.2. Monitoring of the Fractal Growth
As the structural information on the formed fractal cluster can be obtained by Static
Light Scattering, the size distribution and dynamic scaling properties can be studied by
Quasi-elastic Light Scattering. In fact, by considering that the form factor of monomers is
unity, the autocorrelation function of the scattered eld contains information on the dynam-
ics of the growing aggregates:
G
1
(Q, ) = E

S
(Q, 0)E
S
(Q, ) = a

i
M
2
i
N
i
S
i
(Q)exp(
i
) (19)
where a is a factor depending on the experiment geometry, M
i
, N
i
and S
i
represent the
mass, number and structure factor of the i-th cluster with radius R
i
and the decay rate
i
=
572 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 7. Diffusion coefcient of a fractal aggregate of H
2
TPPS
4
at 3M with [HCl] =
1M as a function of the exchanged wave vector (at the end of kinetics). The dashed line
indicates the Q
2
dependence. The incident wavelength is
0
= 532nm.
D
i
Q
2
+A(QR)
i
(D
i
and
i
being its translational and rotational diffusion, respectively,
and A(QR) being related to the anisotropy of the cluster). The initial decay rate of the
correlation function is given by:
=
1
G
1
(Q, 0)
_
M
2
i
N
i
(t)S
i
(Q)(D
i
Q
2
+ A(QR)
i
)dM
i
(20)
In the QR << 1 limit, the amplitude A(QR) is small and the translational term is domi-
nant, so that
i
R
1
i
. The mean radius

R(t) =

i
R
i
(t)N

(R
i
, t) (N

(R
i
, t) being the
size distribution), obtained from the mean decay rate of the correlation function, allows for
the check of the dynamic scaling of the aggregate size.[69]
More generally the relaxation rate of the correlation function can be written as =
DQ
2
F(QR), where the function F(Q, R) takes into account aggregate internal motions. In
the limiting case of QR << 1, F(QR) = 1 and contains information only on the trans-
lational diffusion, as previously seen; in the opposite case, when QR >> 1, F(QR) Q
3
and no diffusion coefcient can be extracted. For fractal systems, for which the condition
QR >> 1 is fulllled, the diffusion coefcient (and hence the size) are obtained only for
rigid structures (absence of internal motions). Thanks to the strong inter-porphyrin interac-
tions inside the aggregate, fractals constituted of porphyrins are rigid, as put in evidence by
the dynamic light scattering measurements (see Figure 7).
From a practical point of view, although dynamic light scattering is able to measure the
mean radius of the growing clusters for the cheking of the dynamic scaling, in the case
of porphyrin solutions the rate of the kinetic process is faster than the time required for
data aquisition. Alternatively, UV-vis measurements guarantee a higher dynamic range and
allow for the determination of the time-dependence of the monomer concentration and an
estimation of that of the mean cluster mass.
Figure 8a) reports the time evolution of the spectral contribution of monomeric t H
2
P
agg
Self-assembled Porphyrins at the Mesoscopic Scale 573
Figure 8. Integrated area of the absorption band of the monomeric t H
2
P
agg
, centered at
420 nm (plot a), and of the extinction band of the aggregated form, centered at 452 nm (plot
b). Experimental conditions: [t H
2
P
agg
]=5M, [NaCl] = 0.1M. The continuous line
in plot a) represents the t according to eq. 21 and that in plot b) a power law with exponent
z 1.
porphyrins (see gure 9 for the structure) which are depleted from solution to originate
clusters. The theoretical prediction of a stretched exponential (eq. 12) is valid in the late
aggregation stage and it cannot describe the whole kinetic. As already pointed out a com-
plete description of the measured monomer concentration must take into account the RLA
early stage, during which the depletion of monomers follows an exponential form[70]. So
that the time dependence of the monomer concentration can be represented by:[71, 72]
c
1
(t) = A
0
+ A
1
exp
_
(k
1
t)

+A
2
exp(k
2
t) (21)
where k
1
and k
2
are two observed time constants, = ()/(1 ) and each process is
weighted by a proper amplitude factor. The continuous line in Figure 8a) represents the t
Figure 9. Scheme of the trans-bis(N-methylpyridinium-4-yl)diphenylporphyine ( t
H
2
P
agg
) structure.
574 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
with eq. 21 and shows a very good agreement with the experimental behaviour.
On the other hand, by following the time evolution of the increasing spectral contribution
ascribed to porphyrins in the aggregated form, it appears that it is obeying (at least before
the levelling off due to nite concentration constraints) the power law of the mean cluster
mass, with z

= 1 (see Figure 8b). This implies a value 0 and suggests that, after the
very early stage driven by RLA, a DLA growth mechanism occurs. The dynamic scaling
of the cluster mass is fulllled likely due to the predominance of resonant scattering, which
depends on the weight average molecular mass of the aggregate, on the absorption at the
characteristic wavelength of the J aggregate.
4. Tuning and Control of the Aggregate Mesoscopic Structure
A careful survey of the literature about aggregation of the anionic TPPS4 por-
phyrin shows that different authors found different structural arrangements for the nal
aggregate[73, 74, 75, 76], especially regarding structure and size. In this section it will be
shown that structural changes of porphyrin aggregates can occur in aqueous solutions by
simply changing porphyrin concentration and ionic strength. These parameters, acting on
the interaction potential and on the aggregation kinetic rate, lead to nal aggregates with
different structure and size. The resonant scattering allows for collecting experimental data
with a good signal to noise ratio even in the depolarized conguration and for determining
the reorientational motions of the porphyrin aggregates.
To this aim all the components of the polarizability tensor, in principle, must be measured,
but, for sake of simplicity, let us assume a cylindrical symmetry of the polarizability ten-
sor. For a dilute solution of monodisperse noninteracting N particles, resulting from the
aggregation of small molecules (small with respect to the wavelength of radiation), the
Rayleigh-Debye-Gans approximation can be used. Thus, the normalized polarized and de-
polarized eld autocorrelation functions in the absence of correlation between translational
and rotational motions are:[64, 66, 77, 78]
G
V V
(Q, t) = NS(Q)
_

2
iso
+
4
45

2
exp (6t)
_
exp
_
DQ
2
t
_
(22)
G
V H
(Q, t) = NS(Q)

2
15
exp (6t) exp
_
DQ
2
t
_
(23)
where
iso
is the isotropic excess polarizability of the particle ( 1/3Tr()) with respect to
the solvent, the anisotropy of the particle polarizability and D and the translational
and rotational diffusion coefcient, respectively. The latter two coefcients can be obtained
experimentally from the initial decay rate of the eld correlation functions, as follows:

V V
(Q) = DQ
2
+
6
45
2
iso
4
2
+ 1
(24)

V H
(Q) = DQ
2
+ 6 (25)
From equations 22 and 23 taken at t=0, the depolarization ratio is written as
dep
=

2
/(15
2
iso
+ 4/3
2
), indicating that the intensity of the depolarized scattering becomes
Self-assembled Porphyrins at the Mesoscopic Scale 575
relatively more important the larger the optical anisotropy of the scattering object.
The hypothesis of independence of rotational and translational motions leading to eqs. from
22 to 25 remains valid for dilute solutions until the coupling parameter Q
2
D/ < 5
(where D = D
//
D

is the anisotropy in the translational diffusion motion).

4.1. From Fractal to Rod-Like Structures
As it was already shown, in dilute solution of water soluble porphyrin aggregation is
triggered by lowering pH enough to shield the charged sulfonate groups and allow a closer
approach of molecules to occur; the same effect is obtained by increasing ionic strength. In
both cases extended fractal structures are formed.[20, 21]
In the presence of salt the autocorrelation function relaxation rate in polarized and depolar-
ized conguration does not indicate any difference, as shown in Figure 10a) and b). This
nding indicates that rotational motions do not contribute to the width of the quasielastic
optical spectrum and eqs from 22 to 25 are not distinguishable one from another. Indeed,
although aggregates are optically anisotropic, the rotational diffusion of the whole aggre-
gate is too slow to be detected. Moreover, the Q
2
-dependence of the relaxation rate proves
that, despite their large size (R
H
0.85m), the strong intermolecular interaction gives
rise to internally rigid structures.
The intensity prole shown in Figure 10c) clearly indicates a fractal arrangement of por-
phyrins. The Q-range investigated by a combination of data at wide and small angles is
wide enough to display the bending at small Q values, representing the effect of the cutoff
of the density correlation function described in eq. 18. From the t it results that this cutoff
is 0.7m and the fractal dimension is D
f
2.2 (consistent with that found for an
analogous system[79]).
It has been shown recently[80] that the fractal dimension of a DLCCA and an RLCA aggre-
gate is an increasing functionof the monomer aspect ratio, so that aggregation of rod-shaped
building blocks leads to a loss of distinction between the two kinetic mechanisms of growth
as the axial asymmetry increases. By considering that the building blocks of the fractal are
the strongly exciton coupled porphyrins, their nonspherical shape can be responsible of the
underestimated value of the fractal dimension deriving from a DLA growth mechanism.
The gyration radius of the aggregates, R
g
=

3

= 1.2m, along with the value of the
hydrodynamic radius, allows for an estimation of the fractal porosity through their ratio
R
H
/R
g

= 0.7; this value is in good agreement with that expected for fractals with an ex-
ponential cutoff in the density correlation function.[81, 82]
When salt is not added to the solution, aggregation of TPPS4 is fostered at mild acidic
conditions by increasing porphyrin concentration[21, 75]; under this condition porphyrins
aggregate in rod-like mesoscopic structures. In the concentration range from 40 up to 500
M, polarized and depolarized autocorrelation functions have signicatively different re-
laxation rates one from another, as shown with some examples in Figure 11. From eqs.24
and 25 it is clear that the zero-Q value of the depolarized relaxation rate gives the rotational
diffusion coefcient, whereas the slope of the Q
2
-dependence of both polarized and depo-
larized relaxation rate furnishes the translational diffusion coefcient.
In order to adopt a reasonably corrected model for calculating the aggregate size, let us
consider that the structure factor of molecules in the aggregate can be regarded as the form
576 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 10. Relaxation rate of the polarized (plot a) and depolarized (plot b) correlation
function; the continuous lines represent the Q
2
-dependence with the same slope. Plot c)
reports the whole intensity prole along with the t with eq. 18, typical of nite fractals.
Experimental conditions: [H
2
TPPS
4
]=3M, pH=2.7, [NaCl]=1.5M,
0
= 532nm
factor P(Q) of the aggregate itself; moreover, if solution is diluted enough to neglect inter-
actions between aggregates the structure factor can be approximated to unity. In this frame
the form factor is simply proportional to the measured intensity prole through eq.13. Fig-
ure 12 displays that the scattered intensity of the concentrated porhyrin solutions (in the
absence of added salt) can be well tted by a rod form factor with length L, described by:
P(Q) =
2
QL
_
QL
0
sin(x)
x
dx
_
2
QL
sin
_
QL
2
__
2
(26)
Then, for a diffusion coefcient of a rod the following Broesmas equations hold:[83, 84]
=
3k
B
T
L
3
_

_
(27)
D =
k
B
T
3L
_

1/2
_

//
+

__
(28)
with
D =
D
//
+ 2D

3
(29)
Self-assembled Porphyrins at the Mesoscopic Scale 577
Figure 11. Relaxation rate of the polarized (plot a) and depolarized (plot b) correlation
functions at pH=2.7 for two concentration values: [ H
2
TPPS
4
]=40M (squares),
0
=
532nm and [H
2
TPPS
4
]=500M (circles),
0
= 780nm. The continuous lines represent
the Q
2
-dependence with the same slope for the same symbols and the dashed lines indicate
the zero-Q value of the depolarized relaxation rate.
Figure 12. Absolute scattered intensity prole for the H
2
TPPS
4
solutions for differ-
ent concentration values: 40M (squares) at
0
= 532nm, 250M (diamonds) at

0
= 780nm, 500M (circles) at
0
= 780nm, all at pH=2.7. The continuous lines
are the t according to the rod form factor (eq. 26).
D
//
=
k
B
T
2L
(

//
) (30)
D

=
k
B
T
4L
(

) (31)

= ln
_
2

_
(32)
578 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
being the ratio between diameter and length of the rod and ,
//
,

functions of the
parameter

[83, 84].
By inserting the measured values of the translational and rotational diffusion coefcients
in the Broesmas equations, the solution of the non-linear systems of equations gives the
geometrical parameter of the rod (L and ). Both static and dynamic measurements agree
in indicating that the length of the rod depends on porphyrin concentration and in particular
from 40M to 250M it is about 0.5 m and then decreases to about 0.2 m at 500M;
moreover, the dynamic measurements add information on the rod diameter, L

= 10nm.
The decrease of the length with increasing concentation can be attributed to the lower steric
hindrance of a large number of shorter rods with respect to a small number of longer rods.
The increase of absorbance, and hence of the local heating of the sample upon irradiation,
makes it more difcult to investigate higher concentration values by means of light scatter-
ing; however, X-ray measurements on the same porphyrin by Gandini et al.[75] showed
that, at concentration values ten times higher and above, porphyrins are arranged in even
shorter rods (about 35 nm). These authors proposed two plausible structures for the rods:
one consisting in planar association (sheets) into a ringlike conguration (hollow cylinders)
and the other deriving by the formation of a continuous shallow helix without disruption
into separate layers. This tubular structure has been found also for other self-assembled
bio-systems like bacterial antenna chlorophyll[85], guanosine nucleoside[86] and melanin
particles[87]. Also porphyrin derivatives under proper conditions were proved to form
ber-like aggregates[88, 89] with only one molecule per cross section.
In section 7.1 it will be shown that, in the presence of a chiral templating agent, rod-like
H
2
TPPS
4
J-aggregates are more consistent with an helical arrangement for which the
projection of the transition dipole moment is mostly perpendicular to the long axis of the
rod,[90] as also observed for other J-aggregate wires.
4.2. Effects of Initial Conditions in the Diffusion-Limited Aggregation Kinet-
ics
The kinetic prole of a real diffusion controlled aggregation process is strongly depen-
dent not only on the initial concentration of the reactant but also on their order of mixing
(i.e. initial spatial distribution of reactants).[91] Another important factor inuencing the
aggregation kinetic prole is the presence of nucleation centres, for example small aggre-
gates (seeds) already formed in an aged stock reactant, which represent a divergence in the
spatial distribution of reactant itself.
As far as self-assembly of porphyrins in solution are concerned, dramatic effects on kinetics
(and also on the structure) are observed varying the initial spatial distribution of reactants
(or using aged stock concentrated porphyrin solution). It was suggested that a protocol to
mix the reagents must to be set up in order to get reproducible results, besides a careful con-
trol of the thermodynamic conditions.[92, 93] Pasternack et al., for instance, put in evidence
the importance of the mixing order in studying the kinetic of supramolecular assembling of
the t H
2
P
agg
porphyrin onto the surface of DNA[94] and the formation of J-aggregates
fromH
2
TPPS
4
[93]. Also the relative concentrations of the stock solution of reagents play
an important role, as well as the lag time between injecting a reagent and mixing the solu-
Self-assembled Porphyrins at the Mesoscopic Scale 579
tion.
This peculiar behaviour is also characteristic of most simple reactions as bimolecular diffu-
sion limited reaction (A+ B C) were an anomalous rate law is observed[95, 96, 97].
The anomalous effects result from the preservation of a memory of the initial spatial reac-
tant distribution, which can be minimized by thorough continuous randomization (stirring).
In many diffusion limited reactions, however, the reaction progresses very quickly (at nite
reactant concentrations), so that it is difcult to randomize the reactant distribution. In such
a case it is difcult to x a well dened initial time for the reaction since the mixing itself
takes time. Also for this reason in realistic case of diffusion limited reaction, the inadequate
mixing and the initial reactant distribution effects are dramatic.
The effects of the initial distribution of reactants on the kinetics is explicity taken into
account in the differential equation describing the time evolution of the density of a
pair of species in the simpler case of the bimolecular diffusion limited reaction (e.g.
recombination):[98]

t
= L = (L
0
+k
r
S) (33)
where k
r
is the rate of reaction of pairs, S is a term containing information on the efciency
of reaction at different distances of the two species and their mutual orientation, and, for
diffusive processes it can be written L
0
= D
2
. In the absence of reaction the density
of pairs in the volume V is at the equilibrium =
eq
g(r)/V and L
0

eq
= 0.
By transferring the space-time dependence of the density of pairs to the probability that the
pair survive at time t[98], P(t) =
_
dr (r, t), equation 33 becomes:
dP
dt
=
_
t
0
V
1
k
r
()P(t )d k
eq
I(t) (34)
with I(t) a term depending on the rate constant at equilibrium, on the efciency of reaction
and on the ratio (0)/
eq
((0) being the initial distribution).
Equation 34, therefore, takes into account the initial distribution of reactants through the
term I(t),which is equal to zero only when (0) =
eq
. In the next subsections some ex-
amples of the effects of zero-time conditions on the aggregation of porphyrins are reported.
4.2.1. Effects of Mixing Order and Aging in Porphyrin Aggregation
Two different mixing methods can be adopted in preparing H
2
TPPS
4
aqueous solu-
tions in the presence of other reagents required for triggering aggregation: adding a stock
solution of concentrated porphyrin as last reagent (porphyrin-last mixing, PL) or as rst
reagent at the desired concentration in water (porphyrin-rst mixing, PF). Although UV-vis
measurements do not distinguish between the two nal solutions, being sensitive only to the
local molecular arrangement, light scattering puts in evidence two signicatively different
mesoscopic structures. In fact, as previously seen, the kinetics of growth and the relative
mechanism drive the morphology of the resulting aggregate.
The intensity proles reported in Figure 13 put in evidence that at higher pH aggregates
exhibit a fractal structure when the porphyrin is added in an acidic environment (PL mix-
ing), while they form statistical isotropic objects using the PF mixing. The structure of such
580 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 13. Absolute scattered intensity prole for the H
2
TPPS
4
solutions
([H
2
TPPS
4
]=3M) at different concentration of hydrochloric acid ([HCl]=0.1 M (plot
a) and [HCl]=2 M (plot b)) for PL (squares) and PF (circles) mixing order (
0
= 532nm).
isotropic objects can be described by the Ornestein-Zernike behavior:
I(Q)
_
1 +
2
c
Q
2
_
1
(35)

c
being the correlation length.
In the PF mixing case there is no fractal arrangement in the whole investigated Q range.
At lower pH, but still high enough not to break the aggregates (see section 4.1), the dis-
tinction between the structures formed with the two mixing methods is progressively lost.
All these occurrences can be ascribed to the inevitable concentration gradient of the added
last reagent, which causes different nucleation probability in some parts of the system. In
the case of the acidic porphyrin solutions this effect becomes more important when the nal
concentration of acid is not high and is mainly due to the large volumetric ratio between the
reagent solutions to be mixed.
Another example is given by the porphyrin aggregation in the presence of a polyamine,
spermine; also in this case the mixing order is a key parameter. In gure 14 the intensity
proles shows that, in the PF mixing, aggregates take a fractal structure with a fractal di-
mension of D
f
2.5 and radius of 3m (as obtained by the tting with eq. 18), whereas
in the PL mixing no fractal arrangement is observed (aggregate radius 0.6m).
The presence of small aggregates pre-formed in the porphyrin solution before adding the
reactant and inducing aggregation can act as nucleation centers. The number and the size of
these pre-existent aggregates affect, in a uncontrolled way, the features of the aggregation
Self-assembled Porphyrins at the Mesoscopic Scale 581
Figure 14. Absolute scattered intensity prole for the H
2
TPPS
4
solutions
([H
2
TPPS
4
]=3M,
0
= 532nm) in the presence of 30-fold higher spermine concen-
tration for PF (plot a) and PL (plot b) mixing order.
kinetics, e.g. the induction time and rate. The induction time is the apparent initial reac-
tion inactivity, often observed experimentally in porphyrin aggregation[94], which makes
sigmoidal-shaped the kinetic prole. An example of the aging effect on induction time and
rate of aggregation is displayed in gure 15.
5. Formation of Organic Fractal Composites
The resonance properties of porphyrin J-aggregates have proved to be extremely use-
ful for the study of their structure and dynamics, as well as for insights in the aggregation
kinetic mechanisms of fractals. But porphyrin fractals reserve other interesting electro-
magnetic phenomena, like the scattering enhancement with scaling properties analogous to
fractal metal composites.
In composites (thin lms, colloidal aggregates, etc...), which are formed by non-linear ma-
terial embedded in a host medium (either linear or non-linear), the enhancement of the
linear and non-linear optical response originates from the strongly uctuating local elds,
E
i
, which exceed the applied one, E
0
.[99, 100, 101, 102] The local eld enhancement is
described by the factor
G =
1
N |E
0
|
2
N

i=1
|E
i
|
2
. (36)
N being the number of monomers constituting the cluster.
By considering the composite constituted by N polarizable small (with respect to incident
wavelength) monomers with short range dipole-dipole coupling, the local eld, acting on
the i-th monomer is a superposition of the incident and all the scattered waves:[103, 104]
E
is
=
1
mon
d
is
= E
0s
exp(ik
0
r
i
)
N

j=i=1
W
sl
(r
i
r
j
)d
jl
(37)
582 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 15. Kinetic proles of t H
2
P
agg
aggregation ([t H
2
P
agg
]=5M with
[NaCl]=0.1M) obtained by starting from a freshly prepared (within a week) stock solution
(continuous curve) and from the same stock aged more than one month (dashed curve).
with
mon
the isolated monomer polarizability, and s and l indicate the different orientation
in the space. Previous coupled-dipole equation means that the amplitude of the transition
dipole moment d
i
at the i-th monomer within the composite is related to the external eld
E
0
through a light-induced dipolar interaction W.
The condition of short range dipole-dipole coupling is not so restrictive for fractal compos-
ites because of the strong localization which makes the interaction of monomers at distances
greater than the excitation wavelength negligible.
The dipole-dipole interaction, expressed in eq. 37, can be synthetically written as:
(Z +W)|d >= |E
0
> (38)
where Z =
1
mon
and |d > is the state of the light-induced dipolar moments.
Because polarizability is, in general, complex, let us dene X = Re (1/
mon
) and
= Im(1/
mon
) its real and imaginary part, respectively. The parameter X has the
meaning of a relative frequency detuning and determines the resonance width (related to
the dissipation within a cluster).
The optical properties are easily related to the polarizability of the system, =
1/N

N
i=1

i
,
i
(omitting indeces s and l for sake of brevity) being obtained through the
solution of equation 38 as
i
=

nj
[(< is|n >< n|jl)/(Z +w
n
)]. The eigenvalues w
n
of W (with eigenvectors |n >traditionally called surface plasmons) contribute to the width
of the resonant band.
With these denitions the enhancement described by equation 36 becomes:[104]
G =
_
1 + (X/)
2
_
Im(). (39)
The ratio |X| / is called quality factor, because, when |X| >> , the enhancement factor
can be very large. Dynamic simulations showed that enhancements and uctuation of local
elds in non-fractal composites are signicantly lower than for fractals.[105]
Self-assembled Porphyrins at the Mesoscopic Scale 583
The enhancement in a composite concerns both non-linear (e.g. harmonic generation phe-
nomenon and Kerr effect) and linear (e.g. scattering, absorption and uorescence) optical
response and is dened as the ratio between the optical response from monomers in a clus-
ter and that of the same number of isolated monomers. As far as linear properties are con-
cerned, Rayleigh scattering enhancement factor, for instance, is G
R
=
s
/
_
N
(0)
s
_
, where

s
is the scattering cross-section of the composite and
(0)
s
that of the single monomer.
For Raman scattering, on the other hand, the enhancement factor depends also on the Raman
shift. By considering that the dipole moment d
(S)
i
induced at the Stokes-shifted frequency

S
on an isolated monomer (with Raman polarizability
(S)
i
) interacts, besides with the
local eld, with other dipoles, the enhancement of the Raman scattering is:
G
RS
=
_

i
d
(S)
i

2
_
N ||
2
|E
0
|
2
(40)
where || is the Raman polarizability of the monomer (due to the incoherent nature of the
Raman scattering

j
=

ij
) and averages are over orientations.
For very large Stokes shift, outside the aborption band of the cluster the enhancement factor
is due only to the local eld and G
RS
reduces to eq. 39. But when the Stokes shift is small
also the Raman amplitudes are enhanced according to:
G
RS

_
|E
i
|
4
|E
0
|
4
_

_
|
i
|
4
_

1
0

4
. (41)
More in general for a non-linear optical process E
n
the enhancement can be written as:
G =
1
N |E
0
|
n
N

i=1
|E
i
|
n
|X|
n

1n
Im() (42)
where the right-hand of the previous equation follows from eq.39 under the condition
|X| >> .
The enhancement of the optical response is expecially high in composites with fractal mor-
phology for which the breaking of the translational invariance causes the localization of
the excitations (eigenmodes) in subwavelength regions; in these hot zones absorption by
monomers is much higher than by other monomers in a fractal composite. Moreover, the
scale invariance gives to the optical response of these composites interesting scaling prop-
erties provided that the eigenmodes delocalization (i.e. coherence length) occurs over a dis-
tance in between the characteristic spacing between the nearest monomers and the radius of
the cluster (R
0
<< L << R, where for fractals it has to be recalled that (R/R
0
)
D
f
= N).
In a self similar composite any physical quantity obeys a scaling law in Z with some scaling
index and, under the condition |X| >> , the following scaling law was derived:[100, 104]
Im() R
3
0
_
R
3
0
|X|
_
d
0
1
(43)
with 0 d
0
1 the optical spectral dimension, which is analogous to the spectral dimen-
sion appearing in the scaling law for the vibrational density of states. Also the coherence
584 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
length of dipolar excitations obeys a scaling law involving the same optical spectral dimen-
sion L R
0
_
R
3
0
|X|
_
(d
0
1)/(3D
f
)
.
From eqs. 42 for Rayleigh scattering (n=2) and 43 it follows[103] that the Rayleigh scat-
tering enhancement of a fractal composite obeys the scaling law
G
R

N
R
3
0

_
R
3
0
|X|
_
d
0
+1
(44)
for clusters smaller than the excitation wavelength ( kR << 1, with k = 2/
0
).
For larger clusters eq. 44 becomes:[103]
G
R

C
R
R
3
0

_
R
3
0
|X|
_
d
0
+1
. (45)
Previous equation indicates that the enhancement comes from the resonance of the scat-
tering by dipolar eigenmodes (i.e. from
1
) and from the prefactor C
R
, representing the
coherence due to fractality, which takes different form depending on the fractal dimension
D
f
.[100]
It is worth to note that when a fractal tends to an homogeneous system ( D
f
=3) the |X|
range in which the enhancement occurs reduces to the frequency of isolated monomer (for
metal particles it is the surface plasmon frequency).
Numerical simulations of optical properties in some fractal composites showed that
the scaling behaviour of the quantities discussed is obeyed.[100, 103, 106] On the
other hand some experimental investigations have been carried out on clusters of metal
particles.[107, 108, 109] Recent experimental works[110, 111] proved that porphyrin
fractals embedded in a polyamine matrix (spermine) give rise to scattering enhancement
phenomena, which nd a natural framework, as organic fractal composite, in the theory
described above. In the next subsections it will be shown that absorption and elastic
scattering of this organic composite obey the scaling laws of fractal composites and that
the enhancement of the Raman scattering is a powerful tool for the study of the very early
stage of porphyrin aggregation.
5.1. Rayleigh Enhancement in a Porphyrin Composite
In typical J aggregates the exciton dipoles are delocalized over about a few tens of
molecules; under this condition there is a resonant scattering at the J-aggregate absorption
band and optical properties are well described by the Frenkel theory. Local eld enhance-
ment has been obtained only in the presence of metal tip in near-eld optical microscopy
(e.g. ref. [112]).
Unlike H
2
TPPS
4
aqueous solution in acidic conditions, for which the width of the J-
aggregate extinction band is narrow, when a ligand molecule (i.e. a polyamine) is added
in excess concentration a signicant broadening occurs, as displayed in Figure 16. By
applying the Frenkel model, the spectral width of the J-aggregate resonant peak would cor-
respond to N
del
< 3, which is inconsistent with the measured resonance wavelength; in
fact, the expected value from the resonant light scattering theory for a small number of cou-
pled excitons is close to E
mon
(for N
del
=3 it should be
J
=470 nm[93]).
Self-assembled Porphyrins at the Mesoscopic Scale 585
Figure 16. Extinction spectra of H
2
TPPS
4
in the presence of hydrochloric acid (curve
a: Experimental conditions [H
2
TPPS
4
]=3 M and [HCl]=0.1M) or of spermine (curve
b: Experimental conditions [ H
2
TPPS
4
]=3 M, [spermine]=100 muM, pH=2.7, [citrate
buffer]=10 mM).
Rather, the broadening extending in the long wavelength region well outside the absorp-
tion frequency of the J aggregates suggests that porphyrins can interact through dipolar
coupling, giving rise to scattering enhancement. Moreover the enhancement is particu-
larly high since, as seen at the end of section 5, the aggregates formed in the presence of
polyamine possesses a fractal structure (when porphyrin is added as rst reagent).
The proposed model for the structure of the present system[110] can be sketched by con-
sidering the formation of an intermolecular network of porphyrins (in an edge-to-edge ar-
rangement); in such a network the ligand induces the branching through interactions be-
tween the protonated nitrogen atoms of the polyamine and the negatively charged sulfonate
end groups of the porphyrin not involved in the porphyrin-porphyrin contacts. In this het-
erogeneous system the ligand is directly involved in the formation of the fractal and, be-
sides the exciton coupling inside the J aggregate, the porphyrin molecules (embedded in the
polyamine matrix and not involved in the J aggregate) interact through dipolar coupling.
In order to discriminate between absorption and scattering contribution in the extinc-
tion spectra, two independent measurements of extiction and absorption (see Figures 16
and 17) were performed using a homemade spectrophotometer.[110] Absorption can be re-
lated to the imaginary part of the polarizability (see eq. 5) as kIm() and plotted against
|X| = |
mon
|,
mon
being the frequency of the porphyrin monomer absorption band.
In gure 17 data fullll the scaling law of eq. 43 with slope -0.7. This value is in a very
good agreement with the d
0
= 0.3 found through numerical simulation in DLCCA metal
fractal composites.[103]
The enhanced scattering contribution can be calculated as the difference between the ex-
tintion and absorption spectra.[113] Figure 18 clearly shows the monotonic increase of the
enhanced scattering with the wavelength for the solution in the presence of polyamine; for
the acidic solution in the absence of polyamine the resonance[94] is limited in the wave-
length range close to the J-aggregate absorption band.
586 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 17. Scaling law for the absorption, A kIm() (see eq. 43), obeyed with d
0
=
0.3, both for positive and negative values of X. In the inset the absorption spectrum of
H
2
TPPS
4
aggregates is reported in the presence of spermine.
In the inset of gure 18 the Rayleigh scattering enhancement is reported against X; it is
well represented by eq. 45, valid for large fractals (kR 45). The optical spectral dimen-
sion obtained by the slope shown in the inset of gure 18 is d
0
= 0.3. The explicit form
used for the prefactor C
R
is C
R
= Q
sc
R
2
(Q
sc
being the scattering efciency factor of
nonabsorbing spherelike aggregates).
These results suggests that, in order to explain the broadening of the absorption band, the
energy shift observed experimentally, and the wavelength dependence of the scattering, the
porphyrin-spermine system should be regarded as a fractal nanoparticle composite.
5.2. Identication of the RLA Early Stage in Porphyrin Aggregation
In the H
2
TPPS
4
-spermine composite the Raman scattering enhancement aids the
identication of the early stage of the porphyrin aggregation.[111] We have shown that
the diffusion-limited kinetics describe well the late stage of the aggregation leading to the
nal fractal structure, but it should be preceeded by a reaction limited early stage during
which the seeds triggering the extended aggregation are formed. This occurrence was sug-
gested experimentally (in section 4.2) by the presence of an additional exponential decay in
the time dependence of the depleting monomer concentration.
The frequency shifts in the low frequency Raman spectrum, shown in Figure 19, are very
similar to those reported in the literature for the aggregated diacid H
4
TPPS
4
. In particular,
the two bands at 242 and 316 cm
1
were previously assigned to vibrational motions of the
aggregated porphyrin[114]. Because both the excitation wavelength and the low-frequency
Stokes shifts belong to the scattering enhancement region, the Raman scattering is strongly
enhanced.
The Raman intensity increase with elapsing time is directly related to the concentration
increase of porphyrins involved in the growing aggregate. As it is shown in the main plot
of gure 19, the time evolution of the two characteristic bands is complete in about 60 s.
Self-assembled Porphyrins at the Mesoscopic Scale 587
Figure 18. Scattering enhancement for the aggregate formed in the presence of spermine.
In the inset the scaling law (see eq. 45) is shown for positive values of X.
Figure 19. The main gure reports the time evolution of the integrated area (
[c
1
(0) c
1
(t)]) of the low frequency Raman spectrum (from 180 to 340 cm
1
); the con-
tinuous line is the t according to Eq. 47 with a
2
= 0.01s
2
. Figures from a) to d) show
the characteristic Raman shifts of the aggregated diacid porphyrin ( H
4
TPPS
4
) at different
elapsed time starting from mixing of reagents. Note that the Y-axis scale are the same for
all the plots a) to d). The used excitation wavelength is 514 nm.
588 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
During this time the Rayleigh scattering prole is at and no resonance light scattering ap-
pears, due to the smallness of the aggregates (initial seeds).
Afterward, the crossover toward an almost constant Raman scattered intensity and the ap-
pearance of an increasing scattering signal suggest the beginning of the typical slower ki-
netics (tens of hours) leading to the larger DLA aggregates. According to the von Smolu-
chowski theory we can identify this early stage of the aggregation with the predicted RLA
mechanism.
In order to make this discussion more quantitative let us use the form of Di Biaso et al.[62]
for the reaction kernel to be introduced in the von Smoluchowski equation:
K(i, j) =
_
p
s
for i = j = 1
p
s
for i, j = 1
(46)
where p
S
is the sticking probability and 0 < < 1.
The analytical solution of Eq. 9 obtained for monomers becomes:
c
1
(t)
_
4 + 4at +(at)
2
_
1

_
4 + (at)
2
_
1
(47)
with at a scaled adimensional time depending on p
s
and on the initial monomer concen-
tration; the last equality derives from the negligibility of the linear term, that in the present
case is at least three orders of magnitude smaller than the quadratic term.
This approach takes into account the low sticking probability of monomers and the
crossover from RLA to DLA mechanisms. As already observed, the Raman intensity is
proportional to c
1
(0) c
1
(t), c
1
(0) being the known initial porphyrin concentration. In the
main plot of Figure 19 the continuous line represents the result of the tting procedure with
eq. 47.
Complementarily, monomer depletion can be monitored in real time by the uorescence
quenching of the typical two-band emission of the diacid porphyrin upon aggregation (see
the inset of Figure 20). In fact, although the enhancement is expected also in the uores-
cence signal, it cannot be observed experimentally because porphyrin aggregates do not
emit, as shown in the spectra of gure 20. The kinetic trace of uorescence quenching is
also well tted by eq. 47, with the same values of the parameter a
2
. Trying to t data with
an exponential behaviour does not give satisfactory result.
The very good agreement between the two independent data sets and the theoretical ap-
proach of Di Biaso et al.[62] gives an experimental prove of the existence of the theoreti-
cally expected crossover between the two aggregation regimes.
The induction time often observed in the UV-visible and light scattering kinetic proles of
porphyrin solutions[94] could be due to the nondetectable RLA initial stage.
All the peculiar features of the porphyrin-spermine composite are retained when samples
are dried after the DLA aggregation process is completed. Aggregates are embedded in a
polyamine matrix (halo in Figure 21A) and their fractal morphology is visible in the optical
image.
A micro-Raman map, collected for a generic cluster and reported in Figure 21B), clearly
puts in evidence the spatial distribution of the Raman intensity. The brighter zones of the
image, i.e. those zones with higher Raman intensity, enclose the single inhomogeneities of
the localized eld which are averaged out due to the low resolution of the micro-Raman
spectroscopy.
Self-assembled Porphyrins at the Mesoscopic Scale 589
Figure 20. Fluorescence bands of the diacid H
4
TPPS
4
in the monomeric form(continuous
line) and upon aggregation (dashed line). The inset reports the time-dependence of the
uorescence intensity ( c
1
(t)) at 700nm, with excitation at 488 nm. The continuous line
is the t obtained with eq. 47, with the same values of the parameter a
2
as in gure 19.
Figure 21. A) Optical microscopy image of a sample of TPPS4-spermine composite de-
posited on a glass cover slide after evaporating the solvent (the bar is 10 m). B) Micro-
Raman image collected as intensity at 242 cm
1
(the explored surface is 7 7m
2
).
(Reprinted gures with permission from N. Micali, V. Villari, A. Romeo, M.A. Castri-
ciano, and L. Mons u Scolaro, Physical Review E 76, 011404 (2007). Copyright (2007) by
the American Physical Society. http://link.aps.org/abstract/PRE/v76/e011404).
590 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
6. Supramolecular Chirality
Chirality is the properties of optically active particles to display different optical re-
sponse to the handedness of the incident circularly polarized light and is widely exploited,
through the circular dichroism(CD) spectroscopy, to investigate structure and conformation
of molecules, inclusion complexes and macromolecules of biological relevance.
Chirality can also occur at supramolecular level (i.e. the nonsymmetric arrangement of
molecules in a noncovalent assembly) because chiral assemblies can be obtained through
chiral units, through interaction with chiral matrixes or be originated from macroscopic chi-
ral eld (vortex motion). In this sense, many chiral templates have been used to produce
the induced supramolecular chirality. In the literature beautiful examples of noncovalent
systems have been described in which the process of self-assembly is fully controlled and
intriguing concepts such as chiral memory[37] and chiral amplication[115] have emerged
with very promising consequences.
Many studies have been carried out on porphyrins binding to both condensed and noncon-
densed DNA or helical polypeptides[23, 34, 40]. Through the study of the supramolecular
chirality it is possible to investigate the biopolymer structure, as well as to identify and con-
trol the formation of long-range, organized porphyrin assemblies on the biopolymer, which
serves as a template.
Other species of chiral templates was proved to give the chiral imprinting in the very
rst step of the formation of chiral aggregates of porphyrins, but, once formed, these ag-
gregates seem to retain memory of the chiral arrangement despite the removal of the
template[36, 37]. It was also proved that the stored chiral information can be removed
with increasing temperature or just with time, so that it is possible to accurately design
supramolecular systems for which a complete cycle of imprinting, storing, releasing, and
restoring of the memorized chirality can be performed[116].
Symmetry breaking and evidence of the role of asymmetric forces in the process of chiral
selection were also obtained by promoting aggregation under gentle rotary evaporation of
dilute porphyrin solutions.[32, 33]
Much interest is recently devoted to the supramolecular chirality and the recent experimen-
tal results open the way towards the design of chiral soft materials that could be used for
symmetry amplication, for chemical sensing and enantioselective catalysis.
In the next subsections, by using self-assembled porphyrins, a brief outline of the differ-
ential scattering in chiral supramolecular assemblies will be reported; moreover, a relation
between mesoscopic structure and supramolecular chirality will be shown.
6.1. Scaling of the Asymmetry Factor in Porphyrin J-aggregates
Beyond the investigation of the different structures of porphyrin aggregates obtained
under different experimental conditions, it is important to know if correlation there exists
between the fractal-to-rod change of the mesoscopic arrangement and changes in the local
porphyrin arrangement. The supramolecular chirality induced by a chiral acidic template
during the aggregation process can be exploited for this aim, since the aggregate meso-
scopic nal structure is not affected by the chiral acid used.
The induced circular dichroism (ICD) bands are displayed in Figure 22 for both fractal and
Self-assembled Porphyrins at the Mesoscopic Scale 591
Figure 22. Circular dichroism spectra of fractal (dashed line) and rod-like (continuous
line) H
2
TPPS
4
aggregates in solution (Experimental conditions: [ H
2
TPPS
4
]=3M,
[NaCl]=1.5M, [L-tartaric acid]=25mM, pH=2.7 for fractals and [H
2
TPPS
4
]=40M, [L-
tartaric acid]=25mM, pH=2.7 for rods.
rod-like aggregates and appear in correspondence with the monomer and J-aggregate ab-
sorption bands (see also Figure 1). As it will be better explained in the next subsection, the
strong scattering contribution causes a broadening of the ICD bands.
The occurrence that linear dichroism can affect data interpretation can be excluded due to
the exactly specular behaviour obtained in the presence of the two opposite enantiomers of
the templating agent.
The spectra of gure 22 have opposite sign, indicating the unexpected opposite
supramolecular chirality for the fractal and the rod-like aggregates. Such a result can be
rationalized by considering that the presence of added salt in solution has manifold effects:
screening the high electrostatic repulsion between porphyrins favouring their approach, in-
creasing consequently the kinetic rate driving towards the fractal morphology, allowing an
unconstrained local arrangement. In the absence of salt, on the other hand, aggregation is
forced by increasing concentration but the repulsive barrier between monomers is still high.
This implies that the local arrangement is strongly dependent on those congurations which
minimize the repulsion.
Analogous considerations can be done for porphyrin aggregates formed in the aqueous in-
terior of microemulsions; despite the low concentration of the microemulsion droplets in
the continuous medium, the connement of porphyrins in the water pool simulates a high
concentration enviroment.[48] The sign of the circular dichroism signal obtained for the
conned rods is the same as that of the rod-like aggregates in bulk and the strength increases
with increasing the rod length. This occurrence indicates an effect of chirality amplication
due to the long-range chiral order of the strongly exciton-coupled porphyrins (high coher-
ence length)
It is worthnoting that the choice of the circular dichroism band of the monomer (instead
of that of the aggregate) was done in order to avoid the contribution of the resonance scat-
tering. As it will be shown in the following, the contribution from scattering can affect
592 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 23. Circular dichroismspectra of an aggregated t CuPagg solution obtained by
placing the sample near (continuous curve) and far (dashed curve) from the detector. Exper-
imental conditions: [t Cu Pagg]=5M, [polyGlutammate]=500M, [NaCl]=0.15M,
[buffer]=2 mM, pH=5.5.
signicantly the shape and the intensity of the circular dichroism spectrum.
6.2. An Outline of Differential Scattering in Porphyrin Aggregates
The circular dichroism spectrum of a chiral particle is essentially dominated by differ-
ential absorption when particle size is smaller than
0
/20, but in the case of large aggregates
the differential scattering, namely the ability of long-range chiral macrodomains to scatter
preferentially one or the other circular polarizations of light, can affect signicantly the
shape of CD bands. In particular, contributions in the CD spectrum at wavelengths outside
the absorption bands appear[117, 118, 119] and the magnitude of the signals inside the ab-
sorption band can be up to 1000 times larger than those observed for small systems.[120]
These effects, originally referred to as anomalous behaviour, allows for obtaining rele-
vant information on the structure of a chiral system. In gure 23 the reported CD spectra
have been obtained by placing the sample near and far from the detector; with these two
different experimental geometries it is possible to collect transmitted light under different
angular acceptance, putting in evidence the contribution of differential scattering (see eq.
48 reported in the following). The dependence of the measured spectrum on the sample
position clearly shows how the differential scattering affects signicantly both shape and
intensity of CD bands in an aggregated porphyrin solution.
A thorough quantum mechanical treatment of the differential scattering was done by some
authors[121, 122], but in the following the main points of the classical approach by Busta-
mante et al.[123] are recalled.
The signal measured in a standard CD spectrophotometer along the transmission beam con-
tains both the transmitted and the zero-degree scattered light:
I
L
I
R
I
L
+I
R
=
2.303(
L

R
)cl
2
+

L
(0)
R
(0)
2r
2
+
L
(0) +
R
(0)
(48)
Self-assembled Porphyrins at the Mesoscopic Scale 593
where I
L
and I
R
indicate the intensities measured when the incident light is left and right
circularly polarized, respectively, c is the concentration, l the optical path length, (0) the
scattering cross section in the forward direction and r the distance between the scattering
volume and the detector. In this equation the attenuation of the incident beam before reach-
ing the scattering volume and that of the scattered beam before leaving the cell was taken
into account. From a practical point of view the second term of equation 48 can be made
small enough to be neglected (for instance by placing the detector far from the sample and
by decreasing the angular acceptance for the detector). In the absence of the scattering con-
tribution, the rst term is the usual circular dichroism, but in the more general case it must
be written as
L

R
= (a
L
a
R
) + (s
L
s
R
), with a
L
a
R
the differential absorption
coefcient and
s
L
s
R
=
N
2.303
_
2
0
d
_

0
[
L
()
R
()] sind (49)
the differential scattering coefcient, which is dependent on the scattering all over the an-
gles. The sign of s
L
s
R
, which is not simply related to the sign of the circular intensity
differential scattering, depends on the relative orientations of the individual scattering el-
ements constituting the particle and on the particle size. It has been shown[123] that the
relative contribution between the circular differential scattering and absorption is related to
the third power of the ratio between the distance among the individual scattering elements
(and hence the particle size) and the wavelength of the incident light.
At any other angle, except zero, the detected signal contains only the circular intensity
differential scattering (CIDS):
I
L
I
R
I
L
+I
R
=
2.303(
L

R
)cl
2
_
(1 + cos)
2
2(1 +cos
2
)
_
+

L
()
R
()

L
() +
R
()
(50)
In the rst concentration-dependent term the differential attenuation of the scattered beam,
due to the circular differential absorption and scattering, is taken into account. The square
brakets contains the dependence of the polarization on the scattering angle, written for the
case of point-like scatterers; in most cases this dependence can be also used for an arbitrary
scatterer since the deviation from the point-like case is smaller than 5 percent. More gener-
ally, however, this dependence, if known, can be explicity considered in eq. 50.
The second term characterizes the dependence of the differential scattering cross section on
the scattering angle.
The two terms of eq. 50 can be separated by changing concentration or by measuring the
scattering in the backward direction; indeed, the rst term goes to zero at zero concentration
or at = 180
o
because the right circularly polarized light becomes left circularly polarized
when it is scattered backwards.
The CIDS proles are expecially useful in the determination of the supramolecular structure
of self-assembled or organized systems[124, 125, 126]. For helical structures, for instance,
according to this approach, the differential scattering displays intense lobes with alternat-
ing signs as a function of scattering angle, as also conrmed by experimental observation
in different helically organized biological structures[127, 128]. Position, sign, and number
of lobes are sensitive indicators of the sense of handedness of the chiral structure for wave-
length outside the absorption bands.[129]
594 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
Figure 24. a) Intensity prole of a t H
2
P
agg
aggregate in the presence of poly-L-
glutammate (PLGA) with M
w
= 13600 (
0
= 632.8nm). The straight line is a power
law t with a slope D
f
2.5. b) Circular differential absorption spectrum in the forward
direction and circular differential scattering spectrumat 0.5 5
o
. Experimental condi-
tions: [PLGA]=20M, [t H
2
P
agg
]=5M, [NaCl]=0.1M, [acetate buffer]=5mM, pH=4.5.
It is worthnoting that differential scattering effects can also appear for non chiral aggregates
and are due, for instance, to the alignement of non isotropic particles or to a not exactly cir-
cular polarization of the incident light. Therefore, in differential scattering experiments care
must be taken in order to avoid any unwanted artifacts not originating from the supramolec-
ular chirality.
As it was discussed at the beginning of the section, aggregation of porphyrins in the pres-
ence of chiral templates is a powerful tool for the investigation of the memory effects of
chiral imprinting on the aggregate structure. Fractal aggregates of t H
2
P
agg
, whose
formation is induced by the ionic strength, take a chiral arrangement when the aggregation
process occurs in the presence of a polypeptide as templating chiral agent. Figure 24a)
displays the intensity prole of the t H
2
P
agg
aggregated according to a DLA mechanism
of growth, whereas gure 24b) displays the circular differential extinction coefcient (i.e.
the rst term of equation 48) and the circular differential scattering coefcient of eq. 49
integrated over 0.5 5
o
and 0 2. The latter coefcient can be approximated
with the theoretical one (integrated all over the range) if considering that almost all the
intensity is scattered at small angle, as indicated by the intensity prole of Figure 24a).
In order to obtain the spectra in Figure 24b) a home-made experimental apparatus was
Self-assembled Porphyrins at the Mesoscopic Scale 595
Figure 25. Circular intensity differential scattering against the scattering angle of a
t H
2
P
agg
aggregate in the presence of poly-L-glutammate (PLGA) with M
w
= 1000
(
0
= 633nm). The inset reports the intensity prole at the same excitation wavelength;
the curve represents the t according to eq. 18 with D
f
2.2. Experimental conditions:
[PLGA]=20M, [t H
2
P
agg
]=5M, [NaCl]=0.1M, [acetate buffer]=5mM, pH=4.5.
designed: as light source and electronic processing a JASCO 500A spectropolarimeter was
adopted and a spatial Fourier transformoptics was interposed between sample and detector.
Just before the detector a spatial lter was placed in the conjugate Fourier plane of the sam-
ple, so that circular differential extinction and scattering coefcients were obtained when a
pinhole or a beamstop were used as spatial lter, respectively.
As far as the differential scattering prole is concerned, it was shown that for helix struc-
ture smaller than the wavelength of light CIDS possesses one lobe; in this case it is easier
to relate the change in its sign with the change in the long-range chiral arrangement of con-
stituting entities. In the case of aggregated t H
2
P
agg
in the presence of polypeptide the
measured CIDS angular prole (eq. 50) is reported in Figure 25 for excitation wavelength
outside the absorption band. It is obtained by replacing the Fourier transform optics with a
relay optics in which the image of the sample is formed onto the detector; both optics and
detector are placed in a rotating goniometer. In the inset of gure 25 the intensity prole,
showing a DLA mechanism of growth, is reported; the bending at low Q values is to be
attributed to the nite size of the aggregates.
Independently from structural information, however, measurements of the differential scat-
tering are extremely useful as sensitive probe of supramolecular chirality. The higher sen-
sitivity of CIDS with respect to CD for chiral aggregates originates from the fact that the
former is a relative measurement of the polarized to the total scattering (see the second term
of eq. 50) and the latter an absolute difference of extinction (see the rst term of eq. 48).
Therefore, small differences in the extinction and scattering cause a small CD signal, but a
large CIDS signal, when also the total scattering is small.
In this respect porphyrins interacting with chiral biopolymer or self-assembled in the pres-
ence of chiral templates constitute a valid system for the detection of supramolecular chi-
596 Valentina Villari, Norberto Micali and Luigi Monsu Scolaro
rality due to the high extinction coefcient in the visible range and the resonance scattering
effects.
7. Conclusion
The non-covalent nature of self-assembly, and of porphyrin self-assembly in particular,
is the key of the huge variety of structural and optical properties of the formed aggregates.
As it has been shown, these properties crucially depend on the kind of intermolecular inter-
action potential. This review aimed to show that the phenomenology observed in porphyrin
solutions and some apparently anomalous experimental results, like different shape of
the nal aggregates, mixing order effects, broadening of the absorption bands or unex-
pected chirality inversion, can be well framed theoretically. The knowledge of the molec-
ular mechanisms underlying the aggregation process helps to drive the system towards the
desired target: through the control and tuning of the aggregates shape and size, as well as
of the optical response, porphyrin aggregates represent a promising and versatile tool for
applications in material sciences, sensor elds and nanotechnology.
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SHORT COMMUNICATIONS
In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 605-613 2010 Nova Science Publishers, Inc.






Short Communication A



THE INFLUENCE OF THIOPHENE ADDITION
ON CATALYTIC PYROLYSIS OF POLY
(DIMETHYL SILOXANE)


K.F. Cai
*,1
, C.W. Zhou
1
, A.X. Zhang
1
and J.L. Yin
2

1
Tongji University, Functional Materials Research Laboratory, 1239 Siping Road,
Shanghai 200092, China
2
Tongji University, Shanghai Key Laboratory of Development and Application for
Metal-Functional Materials, 1239 Siping Road, Shanghai 200092, China
Abstract
The influence of thiophene addition on the pyrolysis of poly(dimethyl siloxane) catalyzed by
ferrocene at ~1050
o
C in Ar was studied. The as-synthesized product was characterized by X-
ray diffraction, scanning electron microscopy, transmission electron microscopy and high-
resolution transmission electron microscopy. The thiophene addition caused several changes.
Firstly, the yield of the product was increased by several times and the diameters of the
product were somewhat increased. Secondly, the product was changed from only SiC/SiO
2

nanocables to a mixture of SiC/SiO
2
nanocables and SiC-SiO
2
side-by-side nanowires. Thirdly,
more Y type nanostructures were found. Finally, the growth process of the product was
altered as the nanostructures each had a polyhedral FeS nanoparticle rather than spherical Fe
nanoparticle. However, lengths of the product were still on the millimeter scale. The
promotion mechanism of thiophene addition was also analyzed.

Keywords: synthesis; nanocables; nanowires; pyrolysis; silicon carbide; silicon oxide.
1. Introduction
Because nanocables have one-dimensional (1D) features of both nanowires and
nanotubes in axial direction and are ideal heterostructures in radial direction, they are

*
E-mail address: kfcai@tongji.edu.cn. Corresponding author, Tel.:/Fax: +86-21-65980255.
K.F. Cai, C.W. Zhou, A.X. Zhang et al. 606
excellent candidates for fundamental scientific research and potential applications in
nanodevices. Recently, nanocables have attracted great attention. Until now, many kinds of
nanocables, including Zn/ZnS [1], Zn/ZnO [2,3], SnO
2
/Sn [4], In
2
O
3
/Sb [5], C/SiO
2
[6],
ZnSe/SiO
2
[7], Ge/SiO [8], Ge/SiCN
x
[9] ZnO/ZnS [10], CdS/TiO
2
[11], ZnS/SiC [12],
CdS/Si [13], Ag/peptide/Au [14], SiC/SiO
2
/C [15], Si
3
N
4
/Si/SiO
2
[16], and so on have been
synthesized. SiC/SiO
2
nanocable system is one of the most extensively studied ones. Up to
now, many methods, such as laser ablation [15, 17], arc discharge [18, 19], carbon thermal
reduction [20-23], chemical vapor reaction [24], and others [25-27] have been developed for
synthesis of SiC/SiO
2
nanocables.
Recently, we developed a simple route to SiC/SiO
2
nanocables of a few millimeters in
length by pyrolysis of poly(dimethyl siloxane) (PDMS) at 1050
o
C in a flowing Ar atmosphere
[28]. Moreover, we [29] investigated the pyrolysis of PDMS catalyzed by ferrocene at
1050
o
C in a flowing Ar atmosphere. The yield was increased by several times and the
nanocables synthesized became very uniform with a spherical iron nanoparticle at their tips.
Most nanocables were about 5 to 10 nm in diameter. This improvement owes to the iron from
ferrocene.
When ferrocene is used as a catalyst precursor to synthesize carbon nanotubes, thiophene
is usually added for promoting the growth of carbon nanotubes [30-32]. However, the exact
promotion mechanism of thiophene has not been reported yet. In this work, the pyrolysis of
PDMS catalyzed by ferrocene and thiophene has been investigated in order to know the
influence of thiophene addition.
2. Experimental Procedure
The synthesis was carried out in the same system as that for the synthesis of SiC/SiO
2

nanocables described in our previous work [28, 29] (see schematic diagram of the system in
reference [33]). Briefly, the system contained a quartz tube (inner diameter ~85 mm) with a
sealed end. The sealed end was put in the hot zone of a muffle furnace. In a typical synthesis,
about 6 ml analytical pure PDMS and 0.1g ferrocene were placed in a 10-ml corundum
crucible and the crucible was put on a mullite substrate (~1508012 mm
3
). A 5-ml
corundum crucible loaded with ~2 ml thiophene (99% purity, Alfa Aeser) was placed on the
mullite substrate beside the 10-ml crucible at the downstream side. The substrate was
carefully pushed into the hot zone of the quartz tube. The open end of the big quartz tube was
sealed with a rubber stopper for gas inlet and outlet. After completely eliminating the air in
the tube furnace, the furnace was heated up to ~1050
o
C at a rate of 10
o
C/min, and held at
1050
o
C for 2h, in flowing Ar at a rate of ~8 ml/min. The furnace was cooled from 1050
o
C to
700
o
C in 10 h, and then cooled naturally to room temperature. White wool-like product was
observed on the surface of the substrate and the thickness of the product was about 2 mm.
The size, structure, and composition of the product were examined by powder X-ray
diffraction (XRD, Rigaku, D/max2550), scanning electron microscopy (SEM, JSM5510),
transmission electron microscopy (TEM, H-800), and high-resolution TEM (HRTEM, JEM-
2100F, JEOL) equipped with energy dispersive X-ray spectroscopy (EDS), respectively.
The Influence of Thiophene Addition on Catalytic Pyrolysis 607
3. Results and Discussion
With the help of thiophene, the yield of the product was about ten times higher than that
of the product from pyrolysis of PDMS catalyzed by only ferrocene, which indicates that
thiophene is a good promoter.



Figure 1. (a) XRD pattern of the as-synthesized product, (b) a typical SEM image of the product.
Figures 1(a) and (b) are XRD pattern and typical SEM image of the product, respectively.
The XRD pattern (figure 1(a)) of the as-grown product has a hillside background and the
peaks corresponding to SiC (JCPDS card file, No.29-1129), which is very similar to that for
SiC/SiO
2
nanocables shown in reference [29]. However, several additional peaks indicated by
asterisks appear in figure 1(a). These peaks can be indexed to FeS (JCPDS card file No.23-
1120), which should be resulted from the addition of the ferrocene and thiophene. SEM
image (figure 1(b)) shows that the product mainly consists of nanowires. Unlike the entangled
K.F. Cai, C.W. Zhou, A.X. Zhang et al. 608
SiC/SiO
2
nanocables from pure PDMS as shown in reference [28], the nanowires are mainly
straight, which is similar to the SiC/SiO
2
nanocables from pyrolysis of PDMS catalyzed by
ferrocene as shown in reference [29]. The nanowires are dense and fine. The lengths of the
nanowires are too long to be measured under SEM. They are estimated to be on the
millimeter scale with an optical microscope.
TEM observations at low magnifications reveal that most of the nanowires have
diameters in the range of 5 to 25 nm and that a small amount of the nanowires are thick with
diameters up to 70 nm (see figure 2(a)), which are somewhat thicker than those from
pyrolysis of PDMS catalyzed by only ferrocene. Some of the nanowires have Y junction.
The Y-junction usually accompanies twin structure whose twin plane is along the central line
of one branch of the junction, shown clearly as in the inset of figure 2(b).




Figure 2. Continued on next page.
The Influence of Thiophene Addition on Catalytic Pyrolysis 609

Figure 2. (a) A typical TEM image at low magnification of the product, small black arrow indicates a
faceted nanoparticle, (b) TEM image showing a Y-junction, the inset is an HRTEM image of the zone
marked by a white square in (b), showing one branch of the Y-junction contains a twin and the twin
plane is in the central of the branch indicated by arrows, (c) HRTEM image of a SiC/SiO
2
nanocable,
clearly showing the lattice spacing of about 0.25 nm, which corresponds to the distance between (111)
planes of SiC, and the growth direction is indicated by the long arrow, (d) typical EDS spectrum
recorded on the rod part of the nanocable, (e) TEM image of the product at low magnification, the
thicker 1D nanostructure looks like a nanocable, (f) HRTEM image of the thicker 1D nanostructure,
revealing that it is a side-by-side biaxial nanowires, an array of small arrows indicate the crystal defects.
TEM observations at high magnifications indicate that all the nanowires have a core-shell
structure. Usually a thicker core has a thicker shell. The thickest shell is about 5 nm. The
shells are much thinner than those synthesized from pure PDMS and are similar to those from
pyrolysis of PDMS catalyzed by only ferrocene. HRTEM observation reveals that the cores
are single crystalline and that the shells are amorphous, shown as in figure 2(c). The hillside
background of XRD pattern in figure 1(a) should be related to the amorphous shell. The
distance between two adjacent lattice planes is about 0.25 nm, which corresponds to the
spacing between (111) lattice planes of cubic SiC (JCPDS card file No. 29-1129), suggesting
that the core is -SiC with <111> growth direction. EDS analysis reveals that the nanocables
are composed of C, O and Si (see figure 2(d)). The Cu peaks are from the copper grid of TEM
sample holder. Besides the nanocables, side-by-side SiC-SiO
2
composite nanowires are
occasionally observed under HRTEM. Figure 2(e) shows a low-magnification TEM image of
the product. The thickest 1D nanostructure in figure 2(e) looks like a nanocable with a 5-nm
thick shell. However, it is observed under HRTEM (figure 2(f)) that there does have an
amorphous layer (~5 nm) at its right side, while no amorphous layer at its left side. That looks
like (but in fact not) an amorphous layer at its left side under TEM results from many lattice
defects. The defects form into a line that is parallel to the growth direction of the 1D
nanostructure. Namely, it is a side-by-side SiC-SiO
2
biaxial nanowire. Wang et al. [21] have
also synthesized such nanowires as well as SiC/SiO
2
nanocables using amorphous SiO and
carbon/graphite as starting materials at ~1500
o
C for 12h. Like nanocables, the side-by-side
nanowires could be potentially useful for high-strength composites [21].
K.F. Cai, C.W. Zhou, A.X. Zhang et al. 610
Therefore, the product is composed of SiC/SiO
2
nanocables and side-by-side SiC-SiO
2

biaxial nanowires. For simplicity, we call them composite nanowires hereinafter.




Figure 3. (a) another TEM image at low magnification of the product, clearly showing a faceted
nanoparticle at the tip of a nanocable, the inset is HRTEM image of the zone marked by a white square
on the nanoparticle, showing that the nanoparticle is single crystalline coated with a thin amorphous
layer, (b) EDS spectrum recorded on the nanoparticle, (c) TEM image of a separated nanocable with a
faceted nanoparticle at its tip, the inset is SAED pattern taken on the nanoparticle, indicating the
nanoparticle is cubic FeS.
Figures 3(a) to (c) show TEM images and EDS spectrum of the composite nanowires.
Figure 3(a) shows a faceted nanoparticle at a tip of a thick nanowire (see faceted nanoparticle
also in figure 2(a)). The HRTEM image (inset in figure 3(a)) of the zone marked by a white
square in figure 3(a) reveals that the faceted nanoparticle is single crystalline coated with a
thin amorphous layer. EDS analysis (figure 3(b)) shows that the nanoparticle contains Fe and
The Influence of Thiophene Addition on Catalytic Pyrolysis 611
S. The C and Cu peaks in figure 3(b) originate from the TEM sample holder, and the Si and O
peaks are from the thin amorphous SiO
2
layer at the surface of the nanoparticle (see the inset
of figure 3(a)). Figure 3(c) shows a TEM image of a separated nanowire with a faceted
nanoparticle at its tip. SAED pattern (inset in figure 3(c)) taken on the nanoparticle indicates
that the nanoparticle is cubic FeS (JCPDS card, No. 23-1123). The 1D nanostructures have
faceted FeS tips, indicating that the growth of the composite nanowires is governed by the
conventional vapor-liquid-solid (VLS) mechanism [34].
The growth process of the composite nanowires is obviously different from that of the
nanocables from pure PDMS, and it is also somewhat different from that of the nanocables
from pyrolysis of PDMS catalyzed by only ferrocene since the nanoparticle at the tips of the
nanostructures is faceted FeS rather than spherical Fe. Based on the above results, we propose
the growth process of the composite nanowires as follows. Ferrocene begins to vaporize at
about 185
o
C and decomposes above 400
o
C [31]. PDMS vaporizes above 200
o
C and as the
temperature is high enough the cleavage of the Si-C bond occurs to produce methyl (-CH
3
)
groups, and the methyl groups decompose to form CH
4
, C
2
H
6
, C and H
2
below 600
o
C [35].
As all the methyl groups are separated from the PDMS and the temperature is high enough,
SiO vapor forms [28]. The decomposed ferrocene is reduced by the H
2
to form atomic iron,
and thiophene decomposes to produce atomic sulfur around 600
o
C. The iron atoms and sulfur
atoms, carried by Ar gas mixed with hydrocarbon gases to the downstream site, react with
each other to produce FeS species that agglomerate into FeS clusters. At high temperatures
the clusters become FeS droplets and deposit on the substrate. The droplets serve as
preferential sites for absorption of the hydrocarbon gases and SiO vapor. Hydrocarbon gases
are catalytically decomposed into carbon atom and the carbon atom diffuses into the FeS
droplet and then FeS-Si-O-C alloy forms. As the FeS-Si-O-C alloy becomes supersaturated,
SiC and SiO
2
concurrently segregate from the alloy droplet by the reaction: 2SiO+C
SiC+SiO
2
. Because the melting point of SiC is much higher than that of SiO
2
, SiC solidifies
earlier. A SiC nanorod is formed along <111> direction, and then amorphous SiO
2
is
nucleated on the outer surface of the newly formed SiC nanorod. The growth of the
composite nanowires continues as long as the catalyst alloys remain in a liquid state and the
reactants are available. Finally, the composite nanowires with cubic FeS (JCPDS card, No.
23-1123) nanoparticles at their tips form. Note that the phase structure of the faceted FeS
nanoparticles is different from that of the FeS revealed by XRD. This is probably because the
amount of both ferrocene and thiophene is overmuch used. Earlier deposited FeS droplets are
covered by the later deposited ones; therefore, the former droplets have no chance to absorb
the reactant gases to become FeS (JCPDS card, No. 23-1123) nanoparticles but to form FeS
(JCPDS card, No. 23-1120) nanoparticles. The SEM and TEM samples could be
contaminated by such nanoparticles. This could be the reason that some flocky dots and some
agglomerated nanoparticles appear in the SEM image (see figure 1(b)) and TEM images (see
the nanoparticles indicated by the white arrows in figures 2(a), 2(b), 2(e) and 3(a)),
respectively. On the other hand, the FeS in the FeS-Si-C-O alloy finally crystallizes into cubic
phase (JCPDS card, No. 23-1123) due to the droplet contained Si, C and O.
What is the promotion mechanism of thiophene addition? It can be described as follows.
The Fe from ferrocene and S from thiophene react with each other at high temperature to
form FeS. The melting point of FeS (~1190
o
C) is much lower than that of Fe (1534
o
C);
therefore, the FeS-Si-C-O alloy solidifies at lower temperature than Fe-Si-C-O alloy. Namely,
K.F. Cai, C.W. Zhou, A.X. Zhang et al. 612
the nucleation and growth process of the composite nanowires will last longer, and the as-
synthesized product has a higher yield than the product from pyrolysis of PDMS catalyzed by
only ferrocene.
More 1D nanostructures with Y-junction are found in the present product (see figure 2(a))
than in the product from pyrolysis of PDMS catalyzed by only ferrocene. This implies that
the formation of the Y-junctions is related to the thiophene (sulfur). Deepak et al. [36] have
also found that thiophene (sulfur) plays an important role in the formation of carbon
nanotubes with Y-junction. The semiconductive Y-junctions could render them useful for
exploitation in nanoelectronics.
The composite nanowires are not as uniform as the nanocables from pyrolysis of PDMS
catalyzed by only ferrocene. This is probably related to the amount of catalyst precursors used.
The influence of adjusting the amount of catalysts on the product will be further studied.
4. Conclusion
Pyrolysis of PDMS catalyzed by ferrocene and thiophene is investigated. Compared with
the case of pyrolysis of PDMS catalyzed by only ferrocene, the present case has much higher
yield. The product consists of SiC/SiO
2
nanocables and side-by-side SiC-SiO
2
biaxial
nanowires. The product has more Y-junctions and the nanoparticles at the tips of the 1D
nanostructures are cubic FeS. Thiophene is a good promoter for the growth of SiC/SiO
2

nanocables and side-by-side SiC-SiO
2
biaxial nanowires.
Acknowledgment
This work was partly supported by Shanghai Pujiang Program and Natural Science
Foundation of China (50371062, 50872095).
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In: Nanotechnology ISBN: 978-1-60692-162-3
Editors: C.J. Dixon and O.W. Curtines, pp. 615-620 2010 Nova Science Publishers, Inc.






Short Communication B



NANOFINISHING OF COTTON TEXTILES


N. Vigneshwaran
*
and Virendra Prasad
Chemical and Biochemical Processing Division, Central Institute for Research on Cotton
Technology, Adenwala Road, Matunga, Mumbai 400 019, India
Abstract
Nanotechnology revolutionized every field in science and technology. Recently, its usefulness
in nanofinishing of cotton fabrics by imparting functional properties like antimicrobial, UV-
resistance, self-cleaning and drug-delivery is well documented. In addition, enhancement in
comfort properties of cotton textiles is also being evaluated with the help of nanofinishing.
With judicial use of nanomaterials, keeping in view their bio-safety and environmental impact
issues, nanofinishing will be a great boon to the users of cotton textiles.


With the advancement in science and technology, a new era has emerged in the realm of
textile processing. Apart from the regular finishing of textile materials for colour and handle,
functional properties like antimicrobial, UV-resistant, stain and water repellent, wrinkle
resistant, flame resistant, moisture control and drug delivery need to be imparted through
novel finishes for high-end applications. Nanofinishing or nanocoating the surfaces of textiles
and clothing is one approach to the production of highly active surfaces to have UV-blocking,
antimicrobial, and self-cleaning properties [1,2]. Fabrics are an excellent medium for the
growth of microorganisms when the basic requirements such as nutrients, moisture, oxygen
and appropriate temperature are present. Compared to synthetic fibres, natural fibres like
cotton are more susceptible to microbial attack resulting in yellowing, bad odour and strength
loss of the fabric. Also, cotton textiles are not resistant to ultraviolet (UV) radiation and
highly susceptible to fire hazard. Hence, there is a need for functional finishing in cotton
textiles to overcome the above mentioned problems.
Among the various metal salts, silver nitrate is the commonly used antibacterial agent
[3,4]. Silver nitrate has been used historically as an antiseptic agent. They bind to protein
molecules inhibiting the cellular metabolism, and eventually the microorganisms die. A

*
E-mail address: nvw75@yahoo.com (Corresponding author)
N. Vigneshwaran and Virendra Prasad 616
major disadvantage of silver nitrate is that it stains everything it touches to brown-black
when exposed to light [5]. Silver nanoparticles, in contrast, does not produce stains while
retaining their antibacterial property. In our earlier article, [6] we have reported a novel, in
situ synthetic route to prepare silver nanoparticles on the surface of cotton fabrics. These
silver nanoparticles impregnated cotton fabrics showed excellent antibacterial activity
against Staphylococcus aureus and bacteriostasis activity against Klebsiella pneumoniae
(Figure 1).


Figure 1. Cotton fabrics impregnated with silver nanoparticles. The increasing colour intensity
corresponds to increasing concentration of nano-silver.
Scanning electron microscopic analysis revealed the presence of silver nanoparticles on
the surface of cotton fibre (Figure 2).
In addition, nano-impregnated fabrics were yellow to pink coloured due to surface
plasmon resonance of silver nanoparticles and provided better protection against UV radiation
due to its absorption in the near-UV region. Another research group from the Hanyang
University, Korea [7] padded the colloidal silver solution onto the textile fabrics, including
cotton, polyester, cotton/polyester and cotton/spandex blended fabrics. They have also
reported efficient antibacterial activity against both Staphylococcus aureus and Klebsiella
pneumoniae.with good laundering durability. Duran et. al. [8] demonstrated the dip-coating of
silver nanoparticles produced by fungal process on textile fabrics and their effluent treatment.
The silver ions were reduced extracellularly by Fusarium oxysporium to generate stable silver
nanoparticles in water. These nanoparticles were coated onto cotton fabrics by dip coating
and the coated fabrics showed excellent antibacterial activity. Simultaneously, the effluent
generated was treated with Chromobacterium violaceum to reduce the silver nanoparticles
Nanofinishing of Cotton Textiles 617
concentration. Nano-silver particles are widely applied to socks in order to avoid growth of
bacteria. In addition, nano-silver can be applied to a range of other healthcare products such
as dressings for burns, scald, skin donor and recipient sites. In silver containing wound care
devices, the silver in contact with wound enters it and becomes absorbed by undesirable
bacteria and fungi, so that those organisms get killed [9].


Figure 2. Scanning electron microscopic image of cotton fibre surface deposited with silver
nanoparticles.
ZnO nanoparticles score over nano-silver in cost-effectiveness, whiteness, and UV-
blocking property. The UV-blocking property of a fabric is enhanced when a dye, pigment,
delustrant, or UV absorber finish is present that absorbs UV radiation and blocks its
transmission through the fabric to the skin [10]. Metal oxides like ZnO as a UV-blocker are
more stable when compared to organic UV-blocking agents. Hence, the nanoform ZnO will
really enhance the UV-blocking property due to the increased surface area and intense
absorption in the UV region. Our research finding [11] proved the excellent antibacterial
activity against two representative bacteria, Staphylococcus aureus and Klebsiella
pneumoniae and promising protection against UV radiation by the nano-ZnO impregnated
cotton textiles. Figure 3 shows the process for coating of cotton fabrics with nano-ZnO
prepared in our laboratory.

N. Vigneshwaran and Virendra Prasad 618

Figure 3. Schematic representation of nano-coating process for cotton fabrics.
The Ultraviolet Protection Factor (UPF) was calculated using the following equation as
per the AATCC test method number 183-2004 [12]:

400
= 280

400
= 280
E

-----------------------------------
E

UPF =

where, E

is relative erythermal spectral effectiveness, S

is solar spectral irradiance, T

is
average spectral transmission of the specimen, is measured wavelength interval (nm). The
UPF equation weighs the UV-B radiation more heavily than UV-A. Apart from nano-ZnO,
nano-silver coating onto cotton fabrics was found to increase the UPF factor due to their
absorption in the near-UV-region. [6,13]
Nanocrystalline titanium dioxide coatings have received much attention as photocatalysts
in practical applications such as environmental purification, deodorization, sterilization, anti-
fouling and self-cleaning glass due to their high oxidizing ability, nontoxicity, long term
stability and low cost. Among the different crystalline phases of titania, anatase is reported to
have the best performance. Daoud and Xin [14] successfully grown anatase nanocrystallites
on cotton fabrics and these fabrics could be made into self-cleaning clothes that tackle dirt,
environmental pollutants and harmful microorganisms. Also, they have reported [15] a
transparent thin layer of nanocrystalline titania coating on cotton textiles by a dip-paddry-
cure process. These titania coated cotton textiles possess significant photocatalytic self-
cleaning properties, such as bactericidal activity, colorant stain decomposition and
degradation of red wine and coffee stains. Figure 4 shows the photo catalytic activity of
titania nanoparticle.
Nanofinishing of Cotton Textiles 619

Figure 4. Photo catalytic activity of titania nanoparticles.
New generation medical textiles are important growing field that require functional
properties like bacteriostatic, anti-viral, fungistatic, non-toxic, high absorbent, non-allergic,
breathable, haemostatic and biocompatible. So, apart from metal and metal oxide
nanomaterials, nanoscale biological materials like enzymes and drugs are necessary to add
specific functionality to medical textiles [16]. Specialized nanomaterials functionalized with
ligands can be introduced on the surface of cotton textiles with the aim to absorb odours,
provide strong and durable antibacterial property, smooth pain and relieve irritation. Also,
such value added textiles could be of immense use in tissue engineering, drug delivery and
protective clothing.
References
[1] Bozzi, A; uranova, TY; Kiwi, J. J. Photochem. Photobiol. A, 2005, 172, 27.
[2] Qian, L. AATCC Review, 2004, 4, 14.
[3] Purwar, R; Joshi, M. AATCC Review, 2004, 4, 22.
[4] Ramachandran, Y; Rajendrakumar, K; Rajendran, R. Institution of Engineers (India)
Journal, 2004, 84, 42.
[5] Parikh, DV; Fink, D; Rajasekharan, K; Sachinvala, ND; Sawhney, APS; Calamari, TA.
Textile Res. J., 2005, 75, 134.
[6] Vigneshwaran, N; Kathe, AA; Varadarajan, PV; Nachane, RP; Balasubramanya, RH.
Functional Finishing of Cotton Fabrics Using Silver Nanoparticles. J. Nanosci.
Nanotechnol., 2007, 7, 1-5.
[7] Lee, HJ; Yeo, SY; Jeong, SH. Antibacterial effect of nanosized silver colloidal solution
on textile fabrics. J. Mater. Sci., 2003, 38, 2199-2204.
[8] Duran, N; Marcato, PD; Souza, GIHD; Alves, OL; Esposito, E. Antibacterial Effect of
Silver Nanoparticles Produced by Fungal Process on Textile Fabrics and Their Effluent
Treatment. Journal of Biomedical Nanotechnology, 2007, 3, 203-208.
N. Vigneshwaran and Virendra Prasad 620
[9] Forner-Cordero, I; Navarro-Monsolu, R; Munoz-Langa, J; Alcober-Fuster, P; Rel-
Monso, P. Use of nanocrystalline silver dressing in lymphatic ulcers in patients with
chronic lymphoedema. Journal of Wound Care, 2007, 16, 235-238.
[10] Hustvedt G; Crews PC. J. Cot. Sci., 2005, 9, 47.
[11] Vigneshwaran, N; Sampath kumar; Kathe, AA; Varadarajan PV; Virendra Prasad.
Nanotechnology, 2006, 17, 5087-5095.
[12] AATCC Test Method 183-2004, AATCC Technical Manual, 2005, 338.
[13] Gorensek, M; and Recelj, P. Nanosilver Functionalized Cotton Fabric. Textile Res. J.,
2007, 77(3), 138-141.
[14] Daoud, WA; and Xin, JH. J. Am. Ceram. Soc., 2004, 87, 953.
[15] Qi, K; Daoud, WA; Xin, JH; Mak, CL; Tang, W; Cheung, WP. Self-cleaning cotton.
Journal of Materials Chemistry, 2006, 16, 4567-4574.
[16] Petrulyte, S. Advanced textile materials and biopolymers in wound management.
Danish medical bulletin, 2008, 55(1), 72-77.













INDEX


3
3,4-ethylenedioxythiophene, 31
A
A, 348, 349, 572
AAS, 139
absorption coefficient, 117, 118, 123
absorption spectra, 145, 484, 538, 539, 540, 541, 546,
547, 548, 563, 585
accelerator, 392
acceptor, 291, 504
access, xi, 18, 27, 293, 295
accessibility, 85
accommodation, 389, 390, 391
accuracy, 19, 77, 108, 171, 177, 189, 299, 376
acetate, viii, 51, 53, 67, 129, 246, 566, 594, 595
acetic acid, 140
acetone, 129, 439, 511
acid, viii, 12, 16, 17, 30, 32, 33, 38, 51, 53, 59, 113,
120, 121, 129, 140, 143, 247, 318, 320, 323, 328,
412, 492, 560, 563, 570, 571, 580, 585, 590, 591
acidic, 33, 111, 114, 115, 126, 140, 245, 312, 565,
571, 575, 579, 580, 584, 585, 590
acoustic, 436, 453, 514
acoustic signals, 514
acquisitions, 74, 99
acrylate, 310, 316, 318
acrylic acid, 53, 120, 318
ACS, 108, 140
activation, 148, 172, 246, 331, 332, 333, 340, 343,
345, 347, 348, 349, 350, 352, 353, 354, 362, 363,
364, 365, 366, 367, 368
activation energy, 172, 246
active transport, 114
actuators, 77, 332, 339, 342, 347, 349
acute, 126, 127, 147
acute myeloid leukemia, 127
additives, 8, 245, 347, 355
adenine, 38, 103
adenocarcinoma, 123
adhesion, xv, 108, 137, 147, 148, 149, 509, 512, 514,
570
adlayers, 38
adsorption, 9, 103, 122, 144, 302, 328, 395
aerosols, 52
aerospace, 311
Ag, ix, 8, 10, 20, 24, 33, 53, 71, 72, 73, 74, 75, 76,
77, 79, 82, 84, 85, 86, 87, 88, 90, 93, 95, 96, 98,
99, 100, 194, 195, 217, 279, 280, 281, 282, 283,
284, 285, 286, 287, 288, 290, 320, 321, 355, 361,
541, 606
age, 425, 535
agent, 8, 112, 115, 119, 127, 148, 335, 561, 578, 591,
594, 615
agents, x, 107, 114, 115, 119, 120, 123, 125, 127,
134, 140, 142, 561, 617
aggregates, 393, 395, 410, 418, 422, 430, 431, 484,
489, 497, 505, 560, 561, 562, 563, 565, 569, 570,
571, 574, 575, 576, 578, 579, 580, 581, 584, 585,
586, 588, 590, 591, 592, 594, 595, 596
aggregation, 121, 131, 312, 315, 376, 415, 421, 425,
561, 565, 566, 567, 568, 570, 571, 573, 574, 575,
578, 579, 580, 581, 582, 584, 586, 588, 589, 590,
591, 594, 596
aggregation process, 561, 567, 568, 570, 571, 578,
588, 590, 596
aging, 117, 119, 145, 146, 149, 246, 335, 412, 581
aging process, 246
aid, 95, 108, 261
AIP, xv, 461, 462, 464, 466, 467, 469, 470, 509, 510,
516, 517, 518, 522, 523
air, 7, 11, 14, 32, 33, 56, 91, 92, 93, 121, 247, 282,
283, 284, 335, 350, 370, 412, 413, 414, 415, 416,
419, 420, 422, 423, 425, 426, 427, 428, 429, 492,
512, 531, 606
albumin, 130
alcohol, viii, 51, 53, 130, 131, 493
alkaline, 16, 17, 135
alkane, 38, 39
alloys, 7, 39, 102, 137, 152, 332, 354, 554, 611
alternatives, 294, 295, 297, 298
aluminum, viii, 4, 6, 8, 9, 24, 25, 27, 31, 247, 248
aluminum oxide, viii, 4, 31, 247
amine, 245, 320
Index

622
amino, 321, 327, 560
amino acid, 560
amino groups, 321
ammonia, viii, ix, 51, 53, 64, 66, 68, 411, 412, 413,
415, 418, 421, 422, 423, 424, 425, 426, 427, 428
ammonium, 130, 321, 565
ammonium chloride, 565
amorphization, 332, 343, 351, 354, 369
amorphous, xiv, 5, 27, 35, 126, 277, 282, 337, 343,
344, 351, 354, 355, 356, 363, 364, 368, 397, 461,
465, 479, 480, 481, 482, 488, 489, 493, 496, 505,
510, 520, 534, 538, 540, 548, 550, 609, 610, 611
amorphous carbon, 35, 126, 397
amplitude, 20, 21, 91, 93, 333, 375, 401, 572, 573,
582
analytical models, 386
anatase, xiv, xv, 31, 338, 479, 480, 481, 482, 489,
490, 492, 493, 494, 496, 497, 498, 499, 500, 502,
505, 506, 618
angiogenesis, 110, 111, 143, 144
Angiogenesis, 110, 141
angiopoietin, 111
aniline, 13, 24, 31, 33, 34, 40
animals, 128, 133
anisotropy, 153, 161, 165, 167, 168, 207, 212, 255,
277, 278, 291, 335, 543, 544, 554, 555, 572, 574,
575
annealing, xvi, 7, 161, 167, 224, 344, 345, 357, 361,
362, 373, 463, 488, 489, 490, 493, 495, 496, 497,
500, 505, 523, 525, 526, 528, 530, 531, 532, 534,
535, 536, 537, 539, 540, 541, 547, 549, 551
annihilation, 171, 541, 562
anode, 17, 28, 249, 252, 267
anomalous, 261, 579, 592, 596
antenna, 481, 561, 578
antenna systems, 561
antibacterial, 615, 616, 617, 619
antibiotic, 128
antibody, 119, 120
anticancer, 139, 142, 147, 560
anti-cancer, x, 107, 108, 109, 111, 112, 127, 133,
134, 138
anticancer drug, 147
antiferromagnetic, 153, 345
antigen, 119, 141, 143
anti-HER2, 123
antioxidant, 133
antitumor, 142
apoptosis, 126, 147, 148
apoptotic, 142
aqueous solution, 23, 28, 30, 35, 36, 42, 144, 245,
246, 249, 252, 490, 565, 574, 579, 584
aqueous suspension, 420
ARC, 435
arc plasma jet, 455, 456
argon, 511
aromatic rings, 323
arsenic, 148
arsenide, 161, 276
ASI, 599
aspect ratio, 18, 20, 238, 245, 246, 269, 381, 382,
385, 387, 388, 394, 404, 575
ASTM, 171
astronomy, 404
asymmetry, 258, 287, 575
atmosphere, 11, 84, 287, 302, 422, 511, 512, 528,
529, 530, 536, 537, 546, 547, 549, 606
atomic force, 9, 73, 101, 105, 197, 282
atomic force microscope (AFM), 9, 11, 12, 13, 14,
15, 73, 74, 78, 79, 80, 81, 84, 87, 104, 105, 194,
195, 196, 197, 222, 253, 254, 282, 286, 315, 448,
449, 450
ATRP, 309, 310, 311, 312, 313, 314, 315, 316, 317,
318, 319, 320, 323, 324, 325, 326, 328
attachment, 119, 181, 218, 372, 416
Au nanoparticles, 33
Au substrate, 10
autocorrelation, 569, 571, 574, 575
Avogadro number, 569
B
backscattering, 74, 94, 256
bacteria, 617
bacterial, 578
bacteriostatic, 619
band gap, xiv, 5, 7, 29, 35, 258, 260, 261, 263, 269,
294, 301, 460, 474, 475, 479, 481, 482, 484, 486,
489, 490, 491, 501, 502, 503, 506, 539, 540
bandwidth, 460
barium, 156, 361, 367, 370
barrier, 25, 246, 265, 568, 570, 591
barriers, 11, 165, 263, 510, 518
basement membrane, 110
basic research, 144
batteries, 23, 31
beams, 104, 286, 392
behavior, xv, 148, 260, 263, 277, 278, 283, 285, 286,
288, 289, 312, 324, 346, 351, 355, 373, 393, 394,
395, 403, 456, 465, 474, 480, 493, 525, 526, 540,
543, 544, 570, 580
Beijing, 304, 309, 435, 453, 459, 509
bending, 25, 186, 194, 417, 455, 519, 575, 595
benefits, 97, 376, 450
benign, 42
bias, 11, 12, 14, 29, 75, 373, 395, 511, 512, 513, 514,
518, 522, 523
biaxial, 609, 610, 612
binding, 112, 128, 239, 240, 261, 376, 398, 528, 546,
560, 590
binding energies, 376, 398
binding energy, 239, 240, 261, 528
bioactive compounds, 129
biocompatibility, 109, 115, 119, 123, 128, 140, 328
biocompatible, 109, 114, 123, 128, 129, 144, 239,
319, 619
biodegradability, 128, 132
biodegradable, 109, 114, 129, 133, 142, 148, 149
Index

623
biological processes, xvi, 559
biomacromolecules, 310
biomaterials, xii, 148, 309
biomedical applications, vii, 239
biomolecules, 120, 143
biopolymer, 590, 595
biopolymers, 602, 620
biosensors, 22, 29, 31, 40
biotechnology, 146, 310, 311, 312, 314
bipolar, viii, 4, 41, 42
bismuth, xii, 331, 333, 351, 352, 367, 368
blends, 53
blocks, xiv, 238, 416, 459, 617
blood, 109, 110, 111, 112, 113, 115, 116, 118, 119,
123, 126, 128, 133, 140, 145, 147, 321
blood flow, 111, 126
blood stream, 111, 119, 126
blood supply, 111
blood vessels, 109, 110, 111, 112, 113, 118, 119, 128
bloodstream, 115
blueshift, 263, 264
body weight, 113
Bohr, 117, 476
boiling, 54, 152, 412, 460
Boltzmann constant, 287, 438, 543, 544
bonding, 55, 61, 63, 87, 404, 411, 416, 417, 424, 455,
560
bonds, 74, 165, 282, 310, 394, 399, 400, 401, 402,
412, 417, 560
bone cancer, x, 107, 108, 110
bone graft, 134
bone marrow, 110
boron-doped, 454
bottom-up, vii, viii, xi, 3, 4, 293, 300
bovine, 130
brain, 116
branching, 25, 111, 422, 499, 585
branes, 24
brass, 283
breast cancer, 120, 123, 127, 133
bromine, 280
buffer, ix, 38, 71, 72, 73, 74, 75, 76, 80, 81, 82, 86,
87, 88, 100, 175, 259, 322, 566, 585, 592, 594,
595
building blocks, xiii, 239, 409, 410, 411, 417, 425,
428, 430, 431, 560, 575
bulk crystal, 89, 97, 101
bulk materials, ix, xv, 72, 73, 184, 228, 361, 525,
526
by-products, 156
C
C++, 376
cables, 152, 605
cadherin, 110
cadmium, 4, 5, 117, 121
calcination temperature, 335, 336, 344, 345, 349
calcium, 108, 137, 248, 352, 368
calibration, 376
cancer, ix, x, 107, 108, 109, 110, 111, 114, 116, 117,
119, 120, 121, 123, 124, 126, 127, 128, 132, 133,
134, 138, 140, 141, 142, 143, 144, 145, 146, 147,
148, 149
cancer cells, ix, 107, 110, 116, 119, 123, 127, 132,
148
cancer treatment, 109, 114, 126, 127, 140
cancerous cells, 108, 110, 126
candidates, xi, xii, 38, 52, 111, 117, 119, 124, 291,
293, 299, 303, 331, 335, 342, 344, 357, 460, 526,
561, 606
capacitance, 19, 23, 33, 348
capacity, 52, 68, 130, 178, 320, 424, 431, 521
capillary, viii, 14, 36, 41, 42, 51, 52, 54, 56, 57, 67,
414, 429, 430
caps, 391
carbide, 173, 333, 334, 335, 338, 339, 343, 353, 361,
605
carbon atoms, 372, 373, 376, 377, 388, 402, 403
carbon film, 397
carbon materials, 379, 390, 392
carbon nanotubes, viii, 4, 9, 22, 24, 34, 41, 102, 238,
267, 298, 299, 315, 319, 320, 372, 381, 390, 391,
393, 397, 404, 606
Carbon nanotubes (CNTs), 33, 34, 298, 315, 316,
317, 318, 319, 320, 321, 322, 323, 324, 372, 373,
397, 400, 403
carbonates, 159, 332
carbonization, 126
carboxyl, 314, 320
carboxyl groups, 314, 320
carboxylic, 320
carcinogenesis, 133
carcinoma, 127, 141, 144, 146
carcinomas, 116, 132
cardiovascular system, 145
carefulness, 347
carrier, xi, 65, 114, 150, 240, 263, 275, 460, 465
Cartesian coordinates, 386
CAS, 506
case study, 365
casting, viii, 4, 355
catalysis, 239, 309, 590
catalyst, viii, xi, 51, 237, 239, 241, 242, 243, 269,
310, 326, 606, 611, 612
catalytic activity, 618, 619
catalytic system, 313
cathode, xv, 17, 31, 42, 247, 250, 252, 253, 267, 397,
509, 510, 512
cation, 342, 349, 393, 484
cavities, 37, 438
cell, 5, 10, 14, 15, 17, 22, 110, 112, 115, 116, 119,
124, 126, 127, 130, 133, 137, 139, 142, 143, 145,
147, 148, 153, 160, 161, 247, 255, 280, 302, 342,
412, 450, 468, 494, 593
cell culture, 139
cell cycle, 126
cell death, 110
Index

624
cell growth, 110
cell membranes, 115
cell surface, 119, 147
cellular phones, 276
centrifugal forces, 334
CH4, xiii, 435, 438, 440, 441, 442, 443, 444, 445,
446, 453, 611
chain transfer, 310
channels, 23, 25, 40, 238, 247, 248, 417
charge coupled device, 73
charged particle, 131
chemical approach, 480
chemical bonds, 121, 380
chemical composition, 238, 412
chemical kinetics, 600, 601
chemical properties, 566
chemical reactions, 245, 362, 369
chemical reactivity, 11, 374
chemical sensing, xi, 294, 590
chemical structures, 312
chemical vapor deposition, 241, 454, 456, 457
chemical vapour deposition, 410
chemicals, 239
chemisorption, 310, 381
chemoprevention, 134
Chemopreventive agents, 142
chemotherapeutic agent, 142
chemotherapy, ix, 107, 123, 124, 127, 128
Chemotherapy, 148
China, 51, 237, 309, 317, 331, 435, 459, 475, 479,
506, 509, 524, 525, 605, 612
chiral, 560, 561, 578, 590, 591, 592, 593, 594, 595
chirality, 561, 590, 591, 594, 595, 596
chitosan, 129, 130, 131
chloride, 27, 31, 245, 248, 313, 323
chloroform, 323
chlorophyll, 560, 563, 578
chopping, 85
chromatography, 311
circular dichroism, 562, 590, 591, 592, 593
circular dichroism (CD), 590
circularly polarized light, 590, 593
circulation, 111, 115, 119, 123, 144
cisplatin, 132, 140
classes, 132, 238, 412, 413
classical, 161, 189, 398, 402, 592
cleaning, 29, 374, 380, 511, 618
cleavage, 145, 450, 611
clinical trials, 128
clustering, 419, 489, 568
clusters, xv, xvi, 10, 11, 140, 253, 277, 375, 376, 377,
378, 388, 390, 397, 399, 400, 401, 404, 411, 505,
525, 540, 551, 559, 565, 567, 568, 570, 571, 572,
573, 584, 611
C-N, 416
CNS, 148
CO2, 140, 343
coagulation, 124, 126
coatings, xv, 29, 109, 111, 115, 121, 125, 127, 131,
456, 510, 518, 525, 618
cobalt, 36
coding, 143
coherence, 123, 153, 349, 564, 565, 583, 584, 591
collaboration, 291, 404
collisions, 334, 389, 397, 566, 567, 568
colloidal particles, 144, 429
colors, 461, 464
combustion, 332, 343, 354, 369, 498
commercialization, 18
communication, 108, 140, 562
communities, 372
community, 295, 333
compatibility, 191, 460, 506
compensation, 500
competition, 164, 263, 562
complement, 115, 119
complex systems, vii, 3
complexity, xii, 108, 258, 372, 409, 410, 425, 431,
511
compliance, 172
complications, 126, 174
components, xii, 108, 145, 173, 261, 294, 299, 331,
333, 341, 342, 343, 352, 361, 372, 410, 413, 418,
424, 430, 431, 510, 528, 530, 560, 574
composites, x, 34, 151, 161, 165, 207, 321, 358, 361,
526, 561, 581, 582, 583, 584, 585, 610
composition, xiii, 6, 103, 114, 117, 120, 132, 238,
247, 250, 263, 300, 340, 344, 350, 354, 358, 412,
435, 436, 444, 446, 485, 552, 560, 566, 606
compound semiconductors, 4, 5, 7
compounds, xii, 6, 7, 8, 115, 129, 135, 138, 154, 155,
161, 210, 213, 247, 276, 309, 326, 328, 331, 335,
338, 343, 347, 350, 352, 353, 354, 362, 369, 411,
546, 560
computer simulations, 380, 397
condensation, 245, 492, 505
condensed matter, 560
conductance, 301, 372, 373, 404
conducting polymers, viii, 4, 10, 13, 22, 23, 31, 34,
40
conduction, 263, 264, 265, 277, 278, 279, 280, 281,
282, 287, 301
conductive, 9, 15, 39, 122, 265, 277, 297
conductivity, viii, xi, 15, 30, 41, 51, 53, 66, 67, 169,
170, 240, 241, 275, 278, 279, 437, 510
conductor, 265, 279, 381
configuration, ix, 72, 73, 77, 89, 96, 97, 101, 266,
297, 373, 383, 384, 393, 397, 501, 502, 503, 560,
574, 575, 578
confinement, 18, 117, 257, 258, 466, 532, 591
conjecture, xii, 371, 372, 397
connectivity, 424
conservation, 74
constant load, 455
constant rate, 162
constraints, 239, 574
construction, viii, 4, 21, 152, 238
Index

625
consumer electronics, 294
consumption, 313, 344
contamination, 190, 298, 338, 339, 528
contrast agent, 119, 125, 149
control group, 123, 127
convective, 429
conversion, 27, 181, 313, 365
cooling, 159, 161, 165, 169, 224, 228, 230, 335, 339,
376, 390, 391, 542
cooling process, 376
coordination, 8, 282, 399, 410, 480, 560
copolymer, 40, 119, 129, 132, 311, 317
copolymers, viii, 4, 24, 40, 132, 147, 310, 313, 314
copper, vii, x, 3, 9, 10, 20, 39, 53, 126, 127, 151, 153,
168, 250, 251, 262, 278, 414, 609
copper oxide, 168
core-shell, 119, 301, 310, 313, 314, 319, 320, 326,
409, 414, 417, 418, 431, 609
correlation, 143, 372, 522, 569, 570, 572, 574, 575,
576, 577, 580, 590
correlation function, 569, 570, 572, 574, 575
correlations, 566
corrosion, 11, 510
cost-effective, 299, 300, 333, 339
costs, 23, 303
cotton, xvi, 615, 616, 617, 618, 619, 620
coupling, xvi, 14, 127, 258, 335, 340, 345, 347, 352,
559, 560, 562, 564, 575, 581, 582, 585
covalent, 115, 121, 165, 310, 510
covalent bond, 115, 310
covalent bonding, 310
coverage, 9, 28, 35, 134, 135
covering, 283, 377, 412
CPD, 412
CPU, vii, 3
crack, 161, 170, 184, 185, 186, 201, 203, 205, 216,
217, 335, 439, 447, 448, 449, 450
cracking, 168, 184, 185, 186, 335
CRC, 46, 270, 507
critical current density, 154, 159
critical temperature, 554
critical value, 515
crops, 142
cross-linking, 314
cross-sectional, 154, 155, 375, 403, 462, 472, 473,
474, 511, 521, 533, 534, 535, 536, 538, 548, 549,
552
crosstalk, 460
cryogenic, 194, 374, 375, 377, 390
crystal growth, 238, 245, 246, 251, 253, 438, 506,
518
crystal lattice, 494, 517, 520
crystal structure, 153, 161, 277, 278, 280, 288, 290,
348, 349, 416, 460
crystal structures, 277
crystalline solids, 191
crystallinity, 415, 428, 429, 489, 493, 496, 552
crystallites, 41, 352, 353, 413, 414, 415, 416, 494,
518
crystallization, xiv, 238, 246, 255, 351, 354, 356,
479, 480, 488, 493, 497, 505, 506
crystals, xiii, 37, 74, 90, 98, 153, 154, 158, 159, 161,
168, 181, 239, 245, 246, 255, 278, 282, 353, 354,
409, 416, 422, 438, 440, 499, 526, 528, 529, 530,
531, 534, 538, 539, 540, 552
Cu cluster, 10
cubic boron nitride, 510
culture, 137, 139
culture media, 139
current limit, 152, 170
current ratio, 277
cutting tools, 456
CVD, xiii, 241, 244, 435, 436, 437, 438, 439, 440,
441, 443, 445, 447, 449, 451, 452, 453, 454, 455,
456, 457
cycles, 5, 6, 34, 38
cyclic voltammetry, 34, 35, 37, 38
cycling, 170
cyclodextrin, viii, 4, 40
cyclodextrins, 40
cytokine, 126
cytometry, 143
cytoskeleton, 126
cytostatic drugs, 132
cytotoxic, 121, 132
cytotoxicity, 121, 142
D
data set, 176, 588
database, 292
death, 123, 124, 126, 149
decane, 566
decay, 467, 498, 504, 571, 572, 574, 586
decomposition, 9, 14, 156, 165, 245, 282, 283, 369,
388, 437, 489, 493, 618
defect formation, 56
defects, xv, 9, 41, 72, 80, 81, 154, 158, 161, 166, 210,
211, 224, 227, 228, 229, 250, 255, 258, 288, 290,
354, 362, 391, 403, 416, 417, 438, 460, 471, 503,
504, 509, 609
defense, 133
definition, 4, 16, 178, 345, 410
deformation, x, 56, 151, 161, 165, 171, 173, 174, 177,
178, 181, 184, 187, 188, 189, 190, 191, 192, 193,
211, 216, 217, 218, 221, 373, 397, 400, 401, 402,
518
degenerate, 90, 373
degradation, 12, 33, 114, 132, 140, 378, 618
degrading, 85
dehydration, 245
delivery, x, xvi, 85, 107, 114, 115, 116, 120, 140,
141, 142, 143, 144, 145, 146, 147, 148, 149, 437
delocalization, xvi, 559, 560, 561, 562, 563, 565, 583
demand, 173, 510
dendrites, 414
density functional theory, 103
density values, 154
Index

626
depolarization, ix, 72, 73, 89, 95, 96, 97, 98, 99, 100,
101, 564, 565, 566, 574
deposition rate, 6, 438, 441, 510
deposits, viii, 4, 5, 6, 7, 8, 14, 27, 42
derivatives, 13, 30, 560, 578
desorption, 66, 128, 282, 302, 378, 380, 395, 438
destruction, 126, 566
detection, 22, 24, 31, 40, 53, 65, 73, 76, 77, 82, 89,
93, 98, 103, 108, 110, 124, 300, 327, 370, 439,
441, 512, 595
deviation, 58, 62, 63, 80, 181, 522, 593
DFT, 103
diamond films, xiii, 435, 439, 443, 446, 447, 450,
451, 454, 455, 456
diamond grains, 440, 443
diamonds, 174, 186, 455, 456, 577
dielectric constant, 99, 335, 340, 342, 344, 345, 346,
347, 348, 357, 360, 363
differential scanning, 282
differential scanning calorimetry, 282
diffraction, ix, xi, xiv, 71, 72, 73, 76, 77, 80, 81, 87,
102, 237, 287, 288, 290, 327, 413, 417, 442, 468,
488, 496, 517, 518, 520, 531, 532, 533, 537, 552,
605, 606
diffusion, 17, 110, 114, 129, 145, 153, 156, 160, 161,
164, 167, 226, 228, 242, 246, 302, 345, 353, 417,
430, 431, 437, 465, 466, 510, 567, 572, 574, 575,
576, 578, 579
diffusivity, 438
dimensionality, 238, 239, 277
dimerization, 381
dimethacrylate, 326
diodes, 6, 7, 27, 239, 258, 301, 546
dipole, 99, 146, 240, 386, 504, 564, 578, 582, 583
dipole moment, 240, 564, 578, 582, 583
diseases, 108
dislocation, 157, 161, 162, 163, 165, 166, 167, 190,
191, 207, 211, 213, 451, 460, 518, 519
dislocations, 154, 157, 161, 162, 165, 167, 171, 190,
191, 210, 221, 354
disorder, 255, 474, 562
dispersion, 126, 147, 297, 310, 312, 352
displacement, 8, 171, 173, 175, 176, 179, 181, 189,
197, 218, 342
disposition, 560
dissociation, 162, 377, 388, 399, 400
dissolved oxygen, 27, 28
distilled water, 53
distortions, 354
disulfide, 314, 315
divergence, 578
DNA, 40, 110, 142, 147, 312, 560, 561, 578, 590
domain structure, 285, 544
dominance, 190
donor, 262, 263, 504, 617
donors, 262, 263
dopant, 31, 32, 74, 277, 341, 484, 493, 502
dopants, 6, 38, 240, 277, 335, 489
doped, xiv, 74, 81, 239, 262, 277, 303, 323, 341, 479,
480, 481, 482, 483, 488, 489, 490, 491, 493, 494,
499, 501, 502, 503, 505, 506
doping, xi, xiv, 6, 31, 73, 153, 238, 241, 265, 275,
277, 281, 291, 372, 394, 460, 479, 493
dosage, 526
drainage, 111, 112
drug carriers, 112, 120, 145, 149
drug delivery, vii, 108, 111, 114, 115, 122, 124, 128,
141, 143, 145, 146, 147, 148, 312, 313, 314, 560,
615, 619
drug delivery systems, 108
drug discovery, vii, 146
drug release, 128, 132, 133, 140
drug targets, 113
drug use, 132, 133
drugs, ix, x, 107, 109, 111, 112, 113, 114, 115, 116,
120, 122, 124, 127, 128, 129, 132, 133, 142, 143,
145, 313, 314, 560, 619
drying, 148, 412, 413, 414, 415, 417, 418, 419, 421,
422, 423, 425, 426, 427, 428, 429, 430, 431, 439
drying time, 412, 414, 415, 417, 421, 422, 423, 425,
428, 431
DSC, 282, 287
DTA curve, 338, 339
durability, 616
duration, 18, 19, 20, 21, 282, 287, 291, 342, 352, 375,
412, 461, 462, 463, 471
dyes, 31, 117, 118, 119
dynamic scaling, 569, 571, 572, 574
dynamical properties, 561
E
elastic constants, 179
elastic deformation, x, 151, 171, 191, 211
elasticity, 404
electric arc, 372, 437
electric charge, 287
electric conductivity, 53
electric current, 42, 170, 246, 278
electric potential, 131
electric power, 170
electrical characterization, 295
electrical properties, x, xi, xv, 117, 152, 277, 278,
281, 283, 285, 293, 294, 299, 300, 335, 342, 345,
347, 348, 361, 362, 364, 371
electrical resistance, 300
Electroanalysis, 49
electrochemical deposition, 15, 23, 27, 28, 36, 37, 38,
40, 245, 247, 249
electrochemical reaction, 10, 14, 18, 20, 42, 248
electrochemistry, viii, 4, 15, 16, 18, 37, 40, 41, 42,
248
electrocrystallization, 8
electrodeposition, vii, 3, 5, 6, 7, 8, 9, 17, 25, 26, 27,
31, 34, 37, 39, 42, 246, 247, 248
Index

627
electrodes, 4, 8, 18, 19, 20, 23, 24, 33, 34, 40, 41, 42,
53, 127, 247, 250, 268, 296, 299, 344, 361, 372,
384, 388, 389
electroluminescence, 29, 276
electrolysis, 9
electrolyte, 17, 18, 19, 20, 21, 22, 23, 24, 27, 28, 29,
32, 33, 41, 42, 246, 247, 248, 249, 250, 252
electromagnetic, xiv, 97, 122, 140, 404, 459, 460,
475, 581
electromagnetic waves, 140
electromigration, 373
electron beam, 9, 265, 286, 296, 298, 465
electron beam lithography, 9, 265, 465
electron density, 460
electron diffraction, 250, 254, 520, 549
electron microscopy, xi, xiv, xv, 32, 114, 135, 215,
237, 242, 321, 372, 373, 412, 413, 459, 526, 527,
533, 535, 605, 606
electron paramagnetic resonance, 261
electronic circuits, 372
electronic materials, 291
electronic structure, 5, 142, 280, 286, 326, 372, 394,
403, 456, 460
electronic systems, 294, 300
electrons, 38, 72, 122, 153, 260, 263, 264, 265, 266,
278, 279, 282, 288, 294, 297, 298, 373, 394, 540,
564
electrospinning, viii, 51, 52, 53, 54, 55, 57, 58, 61,
66, 67, 68
electrostatic force, 56, 255, 315
electrostatic interactions, 410
ELS, 552
emission source, 264
emitters, xii, 9, 267, 269, 371, 372, 373, 383, 384,
385, 388, 394, 397
Empedocles, 270
emulsification, 130, 145
emulsifier, 130
enantiomers, 591
encapsulated, 114, 115, 116, 119, 121, 142
encapsulation, 109, 116, 121, 130, 133, 141, 144
endoplasmic reticulum, 148
endothelial cells, 110, 111, 112, 119
endothermic, 339
energy transfer, 141, 480, 505, 561
enlargement, 515
entertainment, 16
entrapment, 130, 132, 156, 157
environment, 20, 114, 126, 133, 175, 312, 335, 350,
411, 425, 429, 431, 481, 489, 498, 499, 500, 501,
503, 506, 523, 565, 579
environmental conditions, 121, 332
environmental factors, 143
environmental impact, xvi, 615
environmental stimuli, 315
enzyme immobilization, 31
enzymes, 114, 115, 619
epitaxial growth, 243
epitaxy, viii, 4, 241
epithelial cell, 119
epithelial cells, 119
epoxy, 392, 402, 403
EPR, 111, 112, 115, 125, 261, 262, 263, 264
equality, 588
equilibrium, 52, 88, 160, 394, 399, 400, 454, 579
equilibrium state, 400
equipment, 42, 172, 173, 276, 295, 296, 334, 363,
410, 512
Erk, 292
erosion, 510
esterification, 316, 323
estrogen, 145
etching, 11, 16, 17, 25, 28, 30, 104, 134, 226, 311,
375, 390, 438, 443, 461, 471, 511, 512, 528, 530
ethanol, 11, 17, 29, 53, 54, 55, 56, 59, 439, 492, 493
ethyl alcohol, 226
ethylene, 30, 31, 111, 145, 148, 314, 326
ethylene glycol, 30, 31, 111, 132, 145, 326
ethylene oxide, 148
europium, 481, 482
evolution, 145, 198, 225, 252, 337, 338, 344, 347,
350, 351, 362, 367, 369, 422, 423, 424, 431, 566,
572, 574, 579, 586, 587
exciton, xi, 117, 237, 239, 258, 261, 499, 546, 547,
562, 563, 564, 565, 575, 584, 585
exothermic peaks, 493
experimental condition, 28, 39, 77, 310, 497, 566,
569, 590
exposure, 93, 113, 121, 124, 147, 297, 300, 301
extinction, 109, 118, 563, 573, 584, 585, 594, 595,
596
extraction, xiv, 459, 465, 467, 469, 470, 474, 475
F
fabricate, xiv, xvi, 9, 14, 22, 23, 24, 25, 26, 27, 42,
73, 158, 265, 277, 297, 299, 303, 348, 355, 359,
360, 410, 438, 440, 451, 453, 459, 460, 525, 546
face-to-face interaction, 560
failure, 399, 402, 403, 461
family, 42, 110, 299, 333, 347, 350, 351, 362, 386
fault current limit, 152, 170
faults, 154, 161, 162, 163, 402
FCC, 463
FCL, 170
feedback, 15
feeding, 20
FEM, 88
Fermi, 465
ferroelectrics, 331, 332, 333, 342, 343, 347, 348, 352,
362
ferromagnetic, xv, 525, 526, 543, 544, 555
Ferromagnetic, 526
ferromagnetism, xvi, 278, 525
FFT, 415, 416
FIB, viii, 4, 20, 42, 85, 295, 297, 298, 303, 375
fiber, 41, 42, 52, 55, 56, 61, 62, 65, 66, 77, 78, 84,
283, 377, 390, 391, 439
Index

628
fibers, viii, xii, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,
61, 62, 63, 64, 66, 67, 68, 371, 373, 375, 377, 390,
401
fibronectin, 137, 144
field emission scanning electron microscopy, 412
field-emission, 9, 391, 392
filament, 265, 381, 393
fillers, 311
film thickness, 7, 38, 444, 489, 512, 513
filters, viii, xv, 51, 525
filtration, 52, 119
finite element method, 88
fire hazard, 615
flame, 455, 615
flat-panel, xi, 237, 264
flexibility, 27, 299, 312
flexural strength, 453
flight, viii, 51, 54, 55, 56, 57, 375, 388
floating, 429
flow, 41, 65, 111, 126, 143, 153, 156, 188, 190, 191,
221, 224, 228, 278, 425, 437, 440, 454, 461, 492,
511
flow rate, 65, 425, 440, 461
fluctuations, ix, 71, 395, 397
fluid, 144, 425
fluorescence, 104, 113, 117, 119, 145, 326, 493, 497,
504, 583, 588, 589
fluorescence decay, 504
fluoride, 29, 30, 31
fluorinated, 30
fluorophores, 117
flux pinning, 154, 158
focused ion beam, viii, 4, 20, 42, 85, 297
focusing, ix, xiv, 107, 140, 374, 383, 404, 411, 459
foils, 30
folate, 113, 116, 145, 146, 147, 148
folic acid, 113, 143
Ford, 316, 317, 320, 329, 330
Fourier, 416, 569, 595
fractal cluster, 568, 571
fractal dimension, 567, 570, 575, 580, 584
fractal structure, 567, 568, 569, 575, 579, 580, 585,
586
fractality, 584
fractal-like, 73
fractals, 567, 570, 572, 575, 576, 581, 582, 583, 584,
586, 591
fracture, 170, 173, 174, 184, 185, 186, 190, 194, 195,
196, 197, 199, 201, 203, 204, 205, 213, 215, 216,
217, 224, 228, 373, 397, 403, 436, 439, 443, 447,
450, 453, 454, 455, 456
fracture processes, 190
fragility, 276
fragmentation, 142, 353, 377, 399
free energy, 4, 246, 251, 353, 354, 356, 429
free radical, 323
freedom, 17, 297
friction, xv, 172, 175, 190, 334, 509, 514, 515, 516
FTIR, 140, 412, 416
fullerene, 50, 391
functionalization, 34, 310, 316, 318, 324, 328, 372
fungal, 616
fungi, 617
Fusarium, 616
fusion, 145, 421, 425, 518
FWHM, 250, 258, 261, 264, 448, 450, 498, 532
G
GaAs, 7, 103
gadolinium, 125
gallium, 161, 239, 243, 276
gas, 7, 9, 27, 53, 64, 65, 66, 68, 238, 240, 247, 294,
300, 302, 303, 374, 375, 379, 383, 389, 390, 391,
392, 394, 395, 437, 438, 439, 443, 454, 455, 456,
461, 511, 512, 514, 522, 523, 606, 611
gas diffusion, 302
gas phase, 238, 394, 437, 439, 443, 454
gas sensors, 240, 300, 303
gases, 24, 65, 66, 239, 300, 302, 303, 374, 390, 511,
512, 611
gasification, 438
gastric, 133, 149
Gaussian, 87, 259, 260, 469, 528, 530, 570
gelatin, 129
gelation, 31, 567, 569
gels, 336, 363
gene, vii, 143, 144, 145, 147
gene therapy, vii, 143, 147
generation, xi, 7, 10, 40, 118, 171, 184, 216, 227,
293, 294, 299, 410, 522, 583, 619
Georgia, 140
germanium, 72, 73, 239, 244, 460
Germany, 293, 334, 433, 476
GFP, 118
Gibbs, 596, 597, 598, 601
glass, 6, 7, 28, 32, 34, 37, 41, 42, 246, 461, 480, 488,
489, 497, 546, 589, 618
glass transition, 461
glass transition temperature, 461
glasses, 354, 355
glow discharge, 522
glutathione, 135
glycerol, 318
gold, 9, 11, 14, 27, 33, 35, 36, 37, 38, 39, 40, 41, 42,
79, 104, 109, 121, 122, 123, 124, 242, 244, 247,
249, 250, 251, 256, 259, 261, 310, 314, 315, 372
gold nanoparticles, 121, 242, 250, 314, 315
grades, 454
grafting, 311, 324
grain boundaries, 154, 158, 161, 277, 336, 352
grains, xiii, xv, 73, 158, 159, 190, 208, 250, 253, 277,
332, 335, 336, 338, 353, 354, 355, 435, 440, 443,
444, 446, 448, 453, 509, 510, 517, 518, 520, 521,
549
graphene sheet, 381, 398, 399, 401, 402
Index

629
graphite, 7, 8, 9, 10, 13, 41, 139, 181, 372, 373, 376,
377, 378, 379, 380, 390, 391, 392, 395, 398, 399,
400, 401, 402, 403, 404, 411, 412, 418, 610
gravity, 56, 334
groups, xi, 11, 12, 24, 27, 112, 121, 123, 129, 173,
241, 245, 275, 278, 279, 311, 312, 314, 315, 316,
317, 320, 321, 337, 349, 402, 429, 499, 559, 570,
571, 575, 585, 611
growth factor, 110
growth mechanism, xi, 24, 153, 237, 238, 241, 247,
253, 269, 480, 505, 510, 568, 574, 575
growth rate, xiii, 110, 153, 156, 157, 168, 251, 435,
436, 437, 438, 441, 443, 446, 451, 453, 457
growth temperature, 242, 447, 448, 450
growth time, 252
guidance, 143
guidelines, 294
gyration radius, 575
H
H
2
, xiii, 21, 25, 376, 435, 438, 439, 440, 441, 442,
443, 444, 445, 446, 453, 530, 536, 537, 611
half-life, 115
halogen, 278, 279, 538
haloperidol, 141
Halothane, 147
Hamiltonian, 467, 562
handedness, 590, 593
handling, 158, 294
harvesting, 27, 239, 294, 301, 561
health, 108
healthcare, 617
heart disease, 149
heat, 124, 126, 127, 159, 284, 332, 354, 401, 453,
482, 486, 497, 505, 541
heating, 31, 41, 127, 143, 156, 161, 162, 224, 283,
284, 339, 363, 373, 402, 404, 437, 461, 471, 472,
492, 578
heating rate, 492
heavy metal, 120, 121
heavy metals, 120
height, 10, 13, 15, 27, 73, 80, 211, 224, 229, 230,
265, 266, 375, 377, 381, 438, 498
helium, 374, 375, 376, 378, 379, 380, 383, 390, 391,
392, 393, 394
helix, 578, 595
hematological, 133
hemisphere, xiv, 374, 381, 384, 386, 387, 459, 460,
461, 463, 470, 471, 473
hemoglobin, 560
hepatic injury, 149
hepatocyte, 121
hepatocytes, 148
hepatotoxicity, 147
HER2, 112, 119, 123, 124
hES, 569, 571
heterogeneity, 80, 81, 150, 190, 342
heterogeneous, x, 152, 156, 181, 311, 422, 585
heterostructures, 102, 320, 510, 605
hexafluorophosphate, 32
hexane, 126
high pressure, 153, 353, 411
high resolution, xii, 38, 39, 168, 371, 472, 498, 499,
537, 548, 549, 550, 552
high tech, 510
high temperature, xii, 152, 156, 159, 319, 331, 332,
335, 343, 344, 345, 346, 347, 348, 352, 353, 354,
355, 358, 373, 401, 411, 464, 471, 480, 500, 505,
526, 611
high-speed, 510, 512, 515, 516, 523
high-tech, 294
Hoechst, 120
Holland, 49, 273
homogeneity, ix, 71, 126, 210, 277, 333, 348, 392,
567
homogenous, ix, 71, 72, 159, 190, 349, 428
homopolymers, 314
Honda, 555
Hong Kong, 509, 524
hormone, 133
host, xiv, xv, 73, 479, 480, 481, 484, 489, 490, 491,
498, 501, 502, 505, 506, 525, 526, 581
House, 273
HRP, 31
HRTEM, 168, 250, 321, 323, 327, 416, 425, 426,
428, 429, 482, 483, 496, 512, 517, 518, 520, 521,
538, 606, 609, 610
human, vii, 108, 109, 119, 124, 142, 146, 150
humans, 128, 133
humidity, viii, 11, 13, 15, 51, 53, 54, 55, 56, 57, 59,
60, 61, 62, 63, 65, 66, 68, 486, 487
hybrid, xii, 31, 33, 299, 309, 310, 311, 312, 314, 318,
321, 326, 328, 363
hybridization, 122, 147, 355
hybrids, 314, 319, 321, 322, 326
hydro, 12, 109, 111, 114, 115, 119, 120, 129, 133,
318, 326, 390, 392, 460
hydrocarbons, 390, 392, 443, 611
hydrochloric acid, 580, 585
hydrodynamic, 127, 312, 313, 575
hydrofluoric acid, 16
hydrogen, vii, xiii, 9, 11, 12, 31, 280, 376, 383, 410,
435, 437, 443, 446, 453, 456, 560
hydrogen bonds, 410
hydrogen gas, 9
hydrogen peroxide, 12, 31
hydrolysis, 245, 246, 319, 323, 492, 505
hydrolyzed, 245
hydrophilic, 12, 109, 111, 114, 115, 119, 120, 129,
133, 318, 326, 460
hydrophilicity, 132
hydrophobic, 36, 111, 114, 115, 120, 313, 318, 326,
410, 560
hydrophobic interactions, 115, 560
hydrophobic properties, 115
hydrophobicity, 111
Index

630
hydrothermal, 244, 245, 332, 339, 350, 367, 410, 490,
491, 496
hydrothermal process, 367
hydroxide, 7, 8, 245, 310, 326, 327, 332, 505
hydroxyl, 40, 129, 320, 402, 505
hydroxyl groups, 320, 402
hyperbranched polymers, 328
hypersensitive, 503
hyperthermia, 109, 124, 126, 127, 140, 141, 142, 143,
144, 146, 312
hypothesis, 288, 569, 575
hypoxic, 111
hysteresis, 339, 359, 360, 542, 544, 545
hysteresis loop, 359, 360, 542, 544, 545
I
IBM, vii, 3, 43, 476
ICD, 590, 591
identification, 79, 118, 143, 176, 560, 586
IgG, 120
illumination, 17, 77, 85, 91, 93, 94, 95, 96, 97, 99,
100, 102, 119, 285, 287, 465
imaging techniques, 124
immersion, 73
immobilization, 143
immunodeficiency, 124
immunoglobulin, 115
immunopathology, 143
immunotherapy, 142
implants, 108, 146
imprinting, 590, 594
impurities, 211, 338, 339
in situ, xii, 7, 115, 148, 315, 316, 371, 373
in vitro, 113, 137, 138, 140
in vivo, 117, 119, 124, 127, 140, 143, 144, 145, 146,
147, 149
inactivation, 121
incidence, 90, 91, 92, 93, 94, 95, 96, 100, 133, 134,
142
inclusion, 153, 590
independence, 569, 575
indexing, 535
indication, 131, 346, 394, 523
indicators, 593
indium, 239
induction, 125, 154, 561, 570, 581, 588
induction period, 570
induction time, 581, 588
industrial, xi, 109, 116, 267, 270, 275, 276, 410, 510
industry, 190
inert, 7, 282, 372, 391, 392, 394
inert liquid, 372
infancy, 411
infinite, 178
inflammation, 148
inflammatory, 145
information and communication technology, 108
infrared, 117, 121, 122, 255, 282, 412, 416
infrared spectroscopy, 412, 416
infrastructure, 28
inherited, 325, 440, 441
inhibitor, 245
inhomogeneities, 263, 588
inhomogeneity, 211
initiation, 40, 315
injection, 28, 119, 124
Innovation, 506
inorganic, viii, xi, xii, 4, 9, 25, 33, 42, 117, 120, 275,
276, 277, 278, 295, 309, 310, 311, 312, 315, 326,
328, 411
InP, 7, 103
insertion, 98, 108
insight, xvi, 378, 506, 559
instabilities, 372, 394, 395, 396, 438, 454
instability, xiv, 52, 54, 57, 58, 67, 121, 283, 429, 436,
437, 438, 451, 453
instinct, 436
instruments, 173, 247, 300, 467
insulation, 18, 279
insulators, xv, xvi, 291, 525, 526
integrated circuits, vii, 294
integration, vii, 3, 23, 79, 301, 302, 303
integrity, 115
Intel, vii, 3, 72, 304, 476
intercalation, 560
interdependence, 394
interface, 40, 73, 74, 122, 153, 156, 157, 159, 161,
162, 163, 165, 168, 175, 185, 210, 217, 229, 238,
247, 250, 269, 286, 290, 299, 300, 301, 303, 314,
429, 437, 438, 439, 465, 466, 468, 489, 520
interface energy, 250
interference, 176, 190, 527, 542, 569
intermetallic nanoparticles, xvi, 525, 526
intermetallics, 332
intermolecular, xvi, 410, 559, 561, 562, 569, 575,
585, 596
intermolecular interactions, xvi, 559
internal environment, 114
internalization, 114
internalizing, 112, 114
interpretation, 288, 404, 591
interstitial, 36, 269
interstitials, 258, 551
interval, 118, 258, 283, 375, 618
intestine, 133
intravascular, 148
intrinsic, xi, 152, 167, 211, 237, 238, 239, 242, 258,
262, 277, 293, 295, 297, 303, 332, 388, 411, 450,
460, 480, 499, 504, 510, 523, 561
inversion, 498, 596
Investigations, 146, 213
ion beam, 24, 276, 297, 298, 305, 378, 389, 392
ion bombardment, xv, 297, 395, 396, 510, 512, 514,
521, 523
ion implantation, xvi, 525, 526, 527, 528, 532, 533,
534, 536, 537, 538, 539, 540, 541, 546, 548, 549,
550, 551, 552
Index

631
ionic, xi, xiv, 8, 17, 32, 34, 129, 153, 165, 275, 443,
479, 480, 494, 560, 561, 570, 571, 574, 575, 594
ionic liquids, 8, 32, 34
ionization, 282, 374, 376, 378, 389, 392, 394, 510,
511, 522
IOP, 326, 327, 415, 416
iron, 17, 18, 36, 125, 127, 128, 149, 323, 343, 344,
345, 362, 606, 611
irradiation, xi, 123, 275, 281, 282, 283, 284, 286,
287, 288, 289, 290, 291, 296, 397, 413, 549, 578
irritation, 619
island, 21, 74, 75, 76, 77, 380
isomers, 373
isostatic pressing, 161
isothermal, 158
isotropic, 212, 564, 569, 574, 579, 580, 594
Italy, 559
ITO, 6, 7, 28, 32, 34
ITT, x, 151, 152, 171, 172, 173, 174, 175, 176
I-V curves, 287
IVH, 564
J
Japanese, 68, 102, 103
J
c
, 154
Jordan, 109, 124, 126, 127, 144
Jung, 45, 235, 271, 507, 556
K
KBr, 412
kinases, 126
kinetic energy, 376, 378, 383, 389, 400, 510
kinetics, x, 41, 152, 156, 171, 242, 247, 313, 351,
400, 411, 561, 567, 571, 572, 578, 579, 581, 586,
588, 600, 601
KOH, 17, 25, 27, 323, 375
Korean, 102, 145
L
labeling, 118, 149
lactic acid, 129
lamellar, 484
Langmuir, 45, 47, 48, 49, 271, 433, 600
Langmuir-Blodgett, 239
lanthanide, xiv, 326, 479
lanthanum, 310, 326, 327, 341, 342
large-scale, 28, 247, 276, 295, 303, 460
laser, 73, 75, 77, 78, 79, 83, 84, 85, 87, 89, 91, 93,
105, 239, 256, 257, 258, 259, 282, 372, 376, 378,
409, 411, 412, 413, 414, 415, 418, 421, 422, 423,
424, 426, 427, 428, 448, 454, 461, 464, 465, 480,
489, 493, 503, 504, 546, 550, 606
laser ablation, xiii, 409, 410, 411, 413, 431, 606
lasers, 7, 127, 239, 240, 546
latency, 460
latex, viii, 4, 24, 35, 36, 37
lattice parameters, 494
lattices, 416, 426, 506, 510
laundering, 616
law, 6, 92, 100, 179, 190, 191, 396, 569, 570, 573,
574, 579, 583, 584, 585, 586, 587, 594
layer-by-layer growth, 3, 5
lead, xii, 130, 167, 184, 226, 247, 253, 254, 258, 277,
278, 302, 326, 331, 332, 333, 338, 342, 343, 344,
345, 348, 352, 353, 354, 362, 363, 364, 365, 366,
369, 403, 494, 515, 574
leakage, 109, 116, 133
LED, xiv, 28, 29, 239, 258, 459, 465, 470, 474, 475
Leibniz, 293, 303
lens, 73, 77, 78, 85, 93, 95, 97, 98, 412, 439, 464
LEO, 439
lesions, 110
leukemia, 127
lifespan, 116
lifetime, 110, 117, 467, 475, 504
ligand, 112, 113, 116, 120, 489, 498, 584, 585
ligands, 116, 119, 619
light beam, 291
light emitting diode, 7, 27
light scattering, 562, 570, 572, 578, 579, 584, 588,
599, 602
limitation, 128, 129, 133, 224, 295, 303, 460
limitations, xi, 7, 116, 124, 243, 293
linear, xii, 157, 179, 191, 218, 283, 324, 371, 372,
373, 383, 388, 389, 394, 395, 396, 397, 398, 399,
400, 401, 402, 403, 404, 438, 563, 567, 581, 583,
588, 591
linear regression, 563
linkage, 417
links, 402
lipid, 114, 115, 147
lipids, 114, 125, 143
lipopolysaccharide, 149
liposome, x, 107, 114, 115, 116, 140, 143
liposomes, 109, 113, 114, 115, 116, 140, 141, 142,
143, 144, 145, 147, 148, 149
liquid film, 429
liquid helium, 390
liquid nitrogen, 152, 171, 283
liquid phase, xiii, 153, 156, 164, 409
liquids, 8, 32, 34, 52, 411
lithium, xii, 31, 278, 331, 333, 368, 453
Lithium, 352
lithography, vii, viii, xiv, 3, 4, 10, 11, 13, 14, 15, 16,
17, 18, 24, 239, 242, 276, 277, 295, 296, 297, 298,
303, 431, 459
liver, 111, 113, 121, 133, 146
liver cells, 146
liver disease, 146
living radical polymerization, xii, 309, 310
L-lactide, 40
localization, 79, 132, 263, 269, 582, 583
location, 9, 10, 15, 127, 176, 379, 413, 482, 500, 520
London, 46, 270, 273, 306, 405, 406, 556, 599
long-term, 300, 302, 395, 411
low temperatures, 350, 361, 362, 375, 377
Index

632
low-temperature, viii, xii, 4, 42, 245, 362, 371, 373,
376, 377, 378, 379, 380, 390, 404
luminescence, xiv, 143, 258, 264, 461, 465, 474, 479,
480, 482, 489, 497, 498, 503, 504, 506
lung, 108, 116, 133, 150
lung cancer, 133, 150
lungs, 108, 111, 133
lying, 379, 422, 468
lymph node, 144
lymphatic, 111, 112, 620
lymphatic system, 112
lymphoma, 133
lymphomas, 132
lysosomes, 114
M
machines, vii, 3, 333, 402
macromolecules, 144, 324, 590
macrophages, 111, 119, 146
maghemite, 125
magnesium, 129, 343, 365, 366, 541
magnetic field, 124, 125, 127, 128, 144, 152, 159,
322, 335, 345, 542, 544, 553
magnetic fluids, 313
magnetic materials, 37
magnetic moment, 125, 544
magnetic particles, 128
magnetic properties, xi, 109, 124, 127, 152, 239, 275,
321, 326, 344, 345, 542
magnetic resonance, 124, 312
magnetic resonance imaging, 124
magnetism, xi, 275, 278
magnetite, 125, 127, 313, 314
magnetization, 127, 542, 543, 544, 545, 553, 554
magnetizations, 543
magnetron, 514
magnetron sputtering, 514
magnets, 109, 124, 127, 128, 170
mainstream, vii
management, 108, 117, 453, 620
manifold, 300, 591
manipulation, 5, 10, 172, 294
manufacturer, 183
manufacturing, vii, 3, 16, 17, 291
mapping, 81, 144, 552, 553
market, 16, 294
Markov, 598
mask, 9, 286, 296, 297, 303, 474
mass transfer, 17, 153
material sciences, 596
material surface, 10
materials science, 5, 310, 560
MBE, 241, 244
MBP, 347
mean-field theory, 568
measurement, ix, 66, 71, 72, 77, 80, 95, 97, 101, 172,
176, 179, 190, 198, 250, 253, 266, 282, 283, 284,
285, 339, 373, 378, 454, 455, 464, 467, 473, 527,
531, 532, 534, 540, 542, 595
measures, 172, 569
mechanical behavior, 519
mechanical properties, x, 134, 151, 152, 170, 171,
172, 173, 175, 176, 177, 181, 189, 194, 196, 201,
203, 206, 212, 225, 238, 276, 277, 340, 372, 398,
403, 404, 455, 456, 510, 514, 523
mechanical stress, 167, 169, 402
mechanical testing, 171, 402, 403
media, 24, 92, 139, 245, 314, 333, 334, 335, 339,
351, 352, 361, 411
median, 184, 185
medicine, 108, 147, 310
melanin, 578
melanoma, 148
melt, 52, 158, 159, 161, 165, 168, 207, 224, 225, 353,
354
melting, 127, 156, 159, 161, 265, 344, 355, 461, 510,
611
melting temperature, 344
melts, 52
membranes, viii, 4, 24, 27, 32, 40, 65, 66, 141, 311
memory, 33, 345, 351, 561, 579, 590, 594
MEMS, 21, 46, 190, 360, 369, 370, 436
men, 108
mercury, 117, 493
mesoporous materials, 143
mesoscopic, 224, 277, 380, 385, 388, 422, 561, 562,
566, 575, 579, 590
metabolic, 111
metabolism, 133, 148, 615
metal ions, 7, 8, 15, 245, 247, 315, 320, 560
metal nanoparticles, 8, 33, 320, 321
metal oxide, xi, 4, 8, 9, 293, 294, 295, 298, 300, 302,
315, 411, 619
metal oxides, 4, 9, 411
metal salts, 14, 615
metalloids, 133
metalloporphyrins, 560
metallurgy, 391
metal-oxide-semiconductor, 29, 101, 460
metals, viii, 4, 7, 8, 9, 10, 11, 14, 27, 35, 42, 73, 85,
109, 121, 133, 135, 147, 149, 172, 176, 190, 191,
211, 247, 278, 291, 316, 355, 376, 380, 411, 560
metal-semiconductor, 301
metastases, 116
metastasis, 110, 127
metastasize, 110
methane, xiii, 435, 443, 446, 453
methyl group, 611
methyl groups, 611
methyl methacrylate, 311, 313, 318, 326
Mg
2+
, 342
mica, 181
micelles, 121, 142
microcracking, 167, 335
microelectrodes, 20, 295, 297, 298
microelectronics, 29, 303, 305, 355
Index

633
microemulsion, 332, 350, 564, 565, 566, 591
microemulsions, 591
microenvironment, 118, 144
microfabrication, 17
micrometer, 108
microorganism, 29
microorganisms, 615, 618
microparticles, 141
microphotographs, 395
microscope, xii, xiv, xv, 10, 32, 41, 73, 84, 101, 102,
113, 197, 201, 226, 297, 371, 373, 374, 375, 378,
381, 383, 387, 390, 391, 404, 448, 451, 462, 464,
479, 509, 512, 608
microscopy, xi, xii, xiii, xiv, xv, 9, 41, 54, 72, 74, 77,
102, 103, 104, 105, 118, 131, 135, 164, 167, 226,
237, 321, 371, 372, 373, 374, 380, 383, 390, 404,
413, 435, 459, 527, 533, 534, 535, 584, 589, 605
microspheres, 140, 148, 254, 411, 490, 491
microstructure, xv, 158, 161, 207, 345, 359, 360, 362,
363, 364, 369, 460, 465, 467, 509, 516, 518, 521,
522, 523, 539
microstructures, xii, 16, 17, 18, 20, 181, 252, 331,
332, 453, 454, 466
microwave, 127, 438, 440, 443, 451, 455
microwave radiation, 127
migration, 396, 438, 549
minerals, 108
miniaturization, 17, 294, 355, 371
mining, 403
misfit dislocations, 157
misleading, 277, 563
mitochondrial, 121
mixing, 135, 276, 277, 333, 354, 578, 579, 580, 581,
587, 596
MLC, 349
MMA, 311, 313
mobility, 72, 165, 240, 425, 429, 431, 521
MOCVD, 244
modeling, 41, 303, 398
models, xvi, 153, 180, 212, 362, 372, 386, 468, 559
modulation, 24, 37, 460
modulus, x, 151, 165, 171, 172, 173, 174, 175, 176,
177, 178, 179, 181, 184, 186, 189, 194, 196, 197,
198, 199, 206, 207, 208, 209, 210, 212, 403, 404
moieties, 311, 560
moisture, 32, 300, 302, 303, 332, 615
molar ratios, 132, 337
molar volume, 438
molecular beam, 241
molecular beam epitaxy, 241
molecular biology, 410
molecular dynamics, 374, 398, 400, 567
molecular mass, 574
molecular mechanisms, 596
molecular structure, 278, 430
molecular weight, 130, 132, 313, 569
molecular weight distribution, 313
molybdenum, 9, 438
momentum, 74, 389
monochromator, 493
monoclonal, 119, 120
monoclonal antibody, 119
monolayers, viii, 4, 5, 6, 8, 11, 12, 14, 24, 38, 124,
311, 391, 462
monolithic, 171, 186
monomer, 21, 32, 33, 40, 129, 132, 313, 314, 316,
562, 563, 568, 571, 572, 573, 575, 581, 582, 583,
584, 585, 586, 588, 591
monomeric, 572, 573, 589
Monte-Carlo, 10
Moon, 69, 231, 369, 507
morphological, 144, 431, 437, 438, 454, 456
mortality, 133, 142
mortality rate, 133
motion, 171, 191, 333, 374, 384, 389, 425, 430, 431,
561, 575, 590
motives, 372
motors, xii, 170, 331
moulding, 17
mouse, 119
movement, 211, 213
MOVPE, 241, 244
MRI, 124, 125, 141, 145
MRS, 270
MTS, 218
multidisciplinary, 108
multiple factors, 121
multiples, 95, 258, 501
multiplier, 375
myeloid, 127
N
NA, 73, 77, 93, 569
NaCl, 24, 517, 520, 573, 576, 582, 591, 592, 594,
595
NADH, 38
nanobelts, 238, 315
nanobiology, 315
nanoclusters, 5, 109, 135, 137, 139, 526
nanocomposites, 144, 315, 321, 357, 363, 510, 526
nanocrystal, 117, 140, 412, 416, 417, 427, 429, 467,
480, 499, 501, 502
nanocrystalline, xiii, 5, 8, 9, 117, 344, 345, 347, 367,
369, 435, 454, 455, 490, 491, 518, 519, 521, 522,
523, 618, 620
nanocrystals, xiii, xiv, 6, 8, 140, 142, 145, 147, 246,
300, 409, 411, 422, 427, 429, 430, 431, 433, 465,
479, 480, 481, 489, 490, 492, 494, 497, 500, 502,
503, 504, 505, 506, 510, 526
nanodevices, xvi, 238, 239, 240, 248, 297, 299, 315,
372, 559, 561, 606
nanodots, viii, 4, 25, 37
nanoelectronics, 23, 371, 612
nanofabrication, vii, viii, xi, 3, 4, 9, 10, 13, 15, 21,
24, 38, 40, 42, 43, 293, 295, 298, 299, 315
nanofibers, viii, ix, xii, 31, 51, 53, 64, 65, 66, 67, 68,
371, 377, 403
Index

634
nanofibrous membranes, 65
nanoindentation, x, 151, 171, 173, 174, 175, 181,
186, 190, 191, 192, 193, 194, 197, 198, 199, 201,
202, 203, 204, 205, 212, 213, 216, 217, 219, 222,
228
nanolithography, 9, 11, 13, 14, 15, 40, 297, 298, 299,
303
nanomaterials, viii, xi, xii, xiv, xvi, 4, 11, 42, 88, 149,
246, 293, 294, 295, 297, 298, 299, 301, 303, 309,
310, 328, 372, 374, 388, 410, 414, 479, 480, 506,
615, 619
nanomedicine, 144, 147
nanometer, vii, ix, xv, 40, 71, 72, 73, 80, 81, 82, 108,
116, 201, 265, 294, 295, 333, 338, 349, 350, 442,
518, 523
nanometer scale, 72, 80, 81, 82, 108, 295, 338, 349,
518, 523
nanometers, 11, 52, 80, 117, 171, 172, 190, 250, 303
nanoparticle synthesis, 109, 128
nanoparticulate, 147, 148
nanoribbons, 411
nanorods, viii, xiii, 4, 26, 27, 238, 245, 246, 248, 249,
250, 254, 256, 258, 261, 263, 315, 409, 410, 490,
491, 492
nanoscale structures, xiii, 117, 409
nanoscience, 238, 294
nanosheets, 42, 252, 484, 485
nanostructured materials, 23, 24, 247, 332
nanostructures, 8, 11, 50, 270, 273, 315, 384, 411,
412, 413, 415, 417, 419, 421, 423, 425, 427, 429,
431, 433
nanotechnologies, 39
nanotechnology, vii, xvi, 3, 43, 52, 108, 141, 142,
144, 146, 147, 238, 294, 303, 392, 510, 560, 596
nanotube, 26, 27, 28, 29, 30, 31, 32, 34, 35, 41, 104,
144, 315, 323, 372, 373, 381, 389, 390, 391, 397,
403, 411
National Academy of Sciences, 140, 143, 144
National University of Singapore, 331
NATO, 405, 455, 599
natural, x, 107, 126, 397, 522, 559, 560, 584, 615
Nd, xiv, 412, 479, 480, 489, 501, 562, 565, 584
necrosis, 126
NEMS, vii, 3, 21
neovascular, 119
network, xiii, 110, 224, 228, 417, 436, 585
neural tissue, 40
neuroblastoma, 146
neuroendocrine, 116
neutrophils, 119
New York, 43, 141, 147, 272, 304, 305, 307, 405,
431, 476, 556, 596, 599, 600, 602
nickel (Ni), xvi, 8, 9, 19, 20, 21, 25, 26, 37, 127, 355,
525, 527, 528, 529, 530, 531, 532, 533, 534, 536,
537, 538, 539, 540, 541, 542, 543, 544, 545, 551,
552, 553, 571
NiO, 9, 527, 528, 530, 531, 532, 533, 534, 535, 536,
539, 540
NIR, 109, 122, 123, 124, 502, 503, 504
nitrate, 247, 252, 615, 616
nitride, xiii, xv, 14, 84, 99, 100, 140, 239, 243, 244,
245, 246, 263, 409, 411, 412, 413, 414, 416, 417,
419, 420, 421, 422, 425, 426, 427, 429, 431, 509,
510
nitrides, 510
nitrogen, 152, 171, 262, 280, 283, 350, 376, 416, 417,
511, 512, 522, 585
nitrogen gas, 511, 512, 522
NMR, 282, 287
noise, 514, 515, 574
non-destructive, 77
nonionic, 115, 129, 482
nonlinear, xv, 187, 494, 525, 526, 527, 560, 561
non-linear, xvi, 559, 578, 581, 583
non-small cell lung cancer, 133
nontoxic, 129
nontoxicity, 618
non-uniform, 397
non-uniformity, 397
normal, ix, xv, 26, 75, 89, 90, 91, 93, 94, 95, 100,
107, 110, 111, 112, 116, 126, 127, 250, 269, 345,
348, 361, 374, 381, 383, 388, 399, 438, 468, 474,
509, 514, 516, 517, 519
novel materials, 411
n-type, 7, 17, 24, 28, 240
nuclear, 124, 145, 238
nuclear magnetic resonance, 145
nucleating agent, 565
nuclei, 21, 22, 24, 120, 246, 250, 251, 253, 269, 353,
422, 443
nucleic acid, 146, 560
nucleus, 113, 126, 402, 403, 429
numerical aperture, 73, 77
nutrients, 110, 615
nutrition, 110, 142
O
observations, 53, 161, 216, 340, 343, 346, 378, 414,
429, 544, 608, 609
occlusion, 109, 128
odors, 560
oil, 35, 73, 248
oncology, 142
Oncology, 146, 149
one dimension, ix, 107, 108
optical activity, 602
optical anisotropy, 564, 575
optical fiber, 77, 78, 84, 283, 439
optical imaging, 104
optical microscopy, 102, 103, 104, 226, 584
optical phonon confinement, 257, 258
optical properties, xiv, 31, 122, 123, 124, 141, 258,
314, 321, 332, 473, 479, 480, 526, 560, 561, 562,
582, 584, 596
optical tweezers, 104
optics, 77, 93, 94, 95, 102, 103, 104, 309, 314, 506,
595
Index

635
optimization, viii, 51, 100, 126, 159, 514
optoelectronic, 239, 258, 300, 310, 460
opto-electronic, 339
optoelectronics, xi, 239, 294, 301
ordinary differential equations, 566
organic, viii, xi, 4, 11, 13, 14, 15, 25, 29, 30, 42, 109,
117, 119, 128, 129, 133, 141, 275, 276, 277, 278,
279, 280, 281, 291, 295, 297, 302, 309, 310, 311,
312, 313, 315, 316, 317, 328, 355, 493, 584, 617
organic polymers, 309
organic solvent, 109, 128, 129, 133, 295, 297, 310,
311, 313, 315, 316, 317, 328
organic solvents, 109, 129, 133, 295, 297, 311, 315,
328
organic thin films, 277
organization, xvi, 417, 431, 559, 560, 561
orthorhombic, x, 151, 152, 159, 161, 171, 199, 201,
206, 207, 208, 218, 224, 226, 228, 229, 230, 341,
343
oscillations, 122, 312, 401, 546
oscillator, 375
osmolality, 128
osteoblasts, 149
osteosarcoma, 110
ovarian cancer, 143
oxidation, 8, 11, 31, 38, 41, 103, 121, 247, 282, 283,
316, 402
oxidative, 33, 121, 149, 282
oxidative stress, 121, 149
oxide nanoparticles, xvi, 8, 310, 525, 526, 528
oxides, viii, xvi, 29, 125, 159, 190, 265, 332, 333,
337, 340, 341, 343, 354, 363, 364, 365, 366, 368,
484, 485, 525, 617
oxygenation, x, 152, 160, 164, 167, 170, 171, 199,
224, 225, 226, 227, 228, 229, 230
P
p53, 143
PAA, viii, ix, 38, 51, 53, 54, 55, 56, 58, 59, 60, 64,
65, 66, 68
paclitaxel, 142
pain, 619
paints, 311
palladium, 9, 36, 79
PAN, 318, 325
pancreatic, 133
PANI, 23, 24, 32, 33, 34, 37, 38
parabolic, 180, 381, 382, 393
paramagnetic, 261, 288, 289, 544
parameter, xvi, 56, 59, 73, 96, 153, 176, 177, 179,
183, 199, 302, 344, 346, 403, 437, 462, 465, 467,
473, 504, 525, 538, 552, 565, 575, 578, 580, 582,
588, 589
particle mass, 569
passivation, 17
passive, 7, 113, 116, 119, 125, 127
pathways, 144, 277, 278, 280, 281
patients, 128, 140, 143, 145, 620
pattern recognition, 300
patterning, 9, 11, 40, 297, 429, 431
Pb, xii, 120, 153, 331, 332, 333, 337, 339, 342, 343,
344, 345, 353, 356, 362, 363, 364, 365, 366, 367,
369
PCA, 335
PDMS, 606, 607, 608, 609, 611, 612
peptide, 147, 148, 149, 606
peptides, 120
percolation, 568, 569
performance, ix, xi, 20, 24, 71, 80, 171, 239, 270,
277, 291, 293, 294, 300, 342, 345, 347, 355, 361,
362, 460, 480, 488, 493, 505, 516, 618
pericytes, 110
periodic, 25, 27, 411, 416, 426, 526
periodic table, 526
periodicity, 9
permeability, 111, 140, 150
permeation, 111
permit, 9, 199
permittivity, 356
perovskite, 340, 341, 342, 343, 344, 345, 346, 347,
348, 350, 354, 365, 366, 367, 369
perovskites, 365
peroxide, 323
perturbation, 11, 102, 278
PET, 28
pH, 6, 7, 27, 31, 38, 114, 115, 128, 135, 143, 146,
147, 245, 247, 249, 252, 314, 315, 560, 561, 563,
566, 570, 575, 576, 577, 579, 580, 585, 591, 592,
594, 595
pH values, 570
phagocyte, 147
pharmaceutical, 148
phase diagram, 154, 155, 157, 341, 362
phase transformation, 167, 335, 342
phase transitions, 569
phenol, 316
phenomenology, 596
phonon, xi, 74, 75, 79, 80, 81, 82, 83, 84, 86, 87, 90,
94, 95, 96, 98, 100, 101, 102, 237, 255, 256, 257,
258, 269
phonons, ix, 71, 74, 75, 90, 102, 255, 258, 498
phospholipids, 112, 147
phosphor, 6, 483, 484, 498, 506
phosphors, 326
photobleaching, 109, 119
photocatalysis, 560
photocatalysts, 618
photochemical, xi, 30, 275, 278, 281, 283, 286, 287,
291
photodetectors, 294, 300, 301, 302, 303
photoelectron spectroscopy, 412, 527
Photoelectronic, 307
photoexcitation, 376
photographs, 497
photoionization, 560
photolithography, 297, 299
Index

636
photoluminescence, xi, xiv, xv, 237, 241, 269, 459,
460, 464, 473, 525, 526, 527, 550
Photoluminescence, xiv, 259, 461, 463, 464, 465,
467, 469, 471, 473, 475, 477, 479, 551
photoluminescence spectra, xi, 269, 464
photolysis, 29, 121
photon, 117, 258, 460, 465, 466, 467, 475, 493
photonic, 35, 36, 311, 460, 468, 469, 475
photons, xiv, 117, 459, 465, 467, 469
photosynthesis, xvi, 559
photovoltaic, 6, 7
photovoltaics, 6
physical properties, x, xi, 237, 239, 240, 241, 258,
269, 272, 275, 287, 411, 566
physicists, 410
physicochemical, 33, 121, 143, 149
physicochemical properties, 121
physico-chemical properties, 561
physics, 145, 233, 378, 404, 506, 599
physiological, 128, 133
physiology, 118
piezoelectric, xii, 27, 239, 331, 332, 335, 339, 340,
347, 349, 350, 351, 352, 354, 357, 359, 360, 362,
363, 366, 368, 369, 370
piezoelectric properties, 239, 347, 349, 350, 352, 362,
363
PL spectrum, 259, 260, 550
planar, 239, 269, 278, 352, 386, 429, 578
planetary, 333, 334, 335, 337, 340, 343, 351, 352,
353, 355
plasma, xv, 28, 126, 133, 336, 437, 438, 439, 443,
447, 454, 455, 456, 523, 525, 527, 539, 546
plasmons, 102, 123, 582
plastic, x, 14, 53, 151, 152, 161, 165, 171, 173, 174,
176, 177, 178, 181, 183, 184, 187, 188, 189, 190,
191, 192, 193, 197, 216, 217, 218, 276, 311, 373,
397, 402, 518
plastic deformation, x, 151, 161, 165, 171, 173, 177,
178, 181, 187, 188, 189, 190, 191, 216, 217, 218,
373, 397, 402, 518
plasticity, 188, 190, 210, 277
platforms, 13, 299
platinum, 14, 15, 17, 36, 369
plausibility, 373
play, 24, 158, 224, 238, 245, 278, 279, 505, 526, 578
PLC, 512
PLD, 241, 244, 461, 462, 467, 471
PLGA, 129, 130, 131, 132, 140, 145, 147, 148, 594,
595
PMMA, 311, 313, 317, 325
PN, 582
point defects, 354, 460, 540, 541
point-to-point, 172
Poisson, 179, 224
Poisson ratio, 224
polarity, 240
polarizability, 90, 91, 99, 563, 564, 574, 582, 583,
585
polarization, ix, 10, 41, 42, 72, 76, 77, 88, 89, 92, 93,
95, 96, 97, 98, 100, 101, 104, 239, 255, 287, 340,
342, 357, 366, 373, 394, 593, 594
polarized light, 77, 89, 164, 226, 590, 593
polarized light microscopy, 164
pollutants, 618
poly(lactic-co-glycolic acid), 129
poly(methyl methacrylate), 111, 326
poly(vinylpyrrolidone), 144
polyamine, 580, 584, 585, 588
polyaniline, 13, 22, 23, 24, 31, 32, 33, 37
polyaniline (PANI), 22, 31, 37
polycarbonate, 40
polycondensation, 40, 319
polycrystalline, 4, 5, 7, 15, 161, 194, 195, 247, 248,
289, 335, 362, 490, 496, 497, 548, 549
polydispersity, 310, 313
polyester, 616
polyethylene, 28
polymer chains, 310, 315, 317, 320, 324
polymer film, 9, 33
polymer materials, 171, 310
polymer matrix, 33, 122, 132
polymer solutions, 53, 57
polymer structure, 22, 324
polymer-based, x, 107
polymerization, 23, 31, 32, 38, 41, 129, 149, 309,
310, 311, 315, 316, 323, 324, 325, 327, 328
polymerization time, 31, 32, 38, 41
polymerizations, xii, 309, 310, 326
polymers, viii, 4, 10, 13, 21, 22, 23, 31, 33, 34, 35,
40, 42, 52, 68, 119, 123, 128, 129, 130, 132, 142,
172, 176, 309, 310, 311, 312, 313, 319, 328, 569
polypeptide, 594, 595
polypeptides, 590
polysaccharides, 129
polystyrene, viii, 4, 24, 28, 35, 36, 37, 318, 327, 460
polystyrene latex, 36
population, 110, 161, 171, 207, 263
pore, 6, 16, 17, 25, 27, 29, 30, 52, 63, 111, 112, 311,
482
pores, 16, 17, 24, 25, 27, 31, 40, 58, 63, 228, 311,
481
porosity, 199, 201, 205, 207, 208, 210, 213, 216, 217,
226, 227, 228, 345, 575
porous, 17, 22, 25, 31, 33, 36, 55, 66, 353, 419, 490,
569
porous materials, 569
porphyrins, 560, 561, 563, 564, 565, 566, 570, 572,
573, 574, 575, 578, 579, 585, 586, 590, 591, 594,
595
potassium, 31
potential energy, 400, 401
p-polarized, 89, 97, 98
precipitation, 6, 7, 27, 129, 343, 549
prediction, 263, 280, 291, 336, 411, 573
pre-existing, 110
pressure, 87, 88, 93, 100, 104, 129, 153, 154, 155,
158, 174, 182, 221, 223, 224, 276, 277, 353, 375,
Index

637
392, 396, 411, 437, 438, 440, 443, 451, 454, 461,
511, 512, 514, 518, 522, 523
prevention, 142, 144, 147
printing, 358, 431
pristine, 282, 283, 287, 320, 414, 418, 431
private, 294
probability, 375, 397, 437, 566, 567, 568, 569, 570,
571, 579, 580, 588
probe, vii, xi, 3, 9, 10, 11, 12, 42, 77, 79, 104, 177,
181, 237, 376, 377, 498, 595
process control, 335
process gas, 455
production, 17, 23, 27, 36, 159, 247, 276, 352, 354,
358, 362, 372, 411, 615
productivity, 269, 333, 337
progesterone, 313
program, 7, 506
proliferation, 108, 137, 148
promote, 108, 301, 356, 411
promoter, 607, 612
propagation, 14, 89, 160, 161, 170, 184, 187, 201,
216, 217, 228, 255, 439, 451, 469
property, xv, 179, 197, 199, 268, 280, 286, 287, 290,
436, 438, 461, 509, 510, 512, 515, 527, 542, 543,
544, 561, 616, 617, 619
proportionality, 568
propylene, 111
prostate, 108, 119, 133, 134, 142, 143
prostate cancer, 119, 133, 134, 142, 143
prostatectomy, 143
proteases, 110
protection, 119, 616, 617
protective clothing, 619
protective coating, 414, 510
protein, 9, 118, 143, 149, 615
proteins, 115, 119, 121, 125, 126, 129, 137, 146, 149
protocol, 296, 578
protons, 125
prototype, 42, 286
prototyping, 296, 299
pseudo, 155
PSS, 28, 29, 38, 320
PST, 343, 345, 346, 349, 405
PT, 335, 336, 337, 338, 339, 340, 343, 344, 347, 348,
350
p-type, 7, 12, 14, 17, 29, 240, 241, 412
public, 294, 304
publishers, 413, 425, 432
pulse, 18, 19, 20, 21, 42, 125, 207, 375, 376, 377,
378, 388, 395, 404, 412, 418, 425, 426, 461, 469,
493, 511, 512
pulsed laser, xiii, xiv, 241, 242, 243, 410, 431, 459,
461, 526
pulsed laser deposition, xiv, 241, 242, 243, 459, 526
pulses, 10, 11, 16, 18, 19, 20, 21, 300, 303, 376
pumps, 375
purification, 312, 410, 412, 618
PVA, viii, 51, 53, 66, 67, 68, 130, 131, 159
PVP, 315
pyramidal, 189
pyrolysis, xv, 325, 332, 390, 392, 490, 605, 606, 607,
608, 609, 611, 612
pyrolytic graphite, 8, 9, 13, 41
pyrrole, 13, 21, 32, 35, 41
Q
QDs, 117, 118, 119, 120, 121, 141
quadrupole, 146
quality control, 171
quantitative estimation, 283
quantum, viii, x, 4, 7, 8, 17, 107, 108, 109, 117, 118,
140, 141, 142, 143, 144, 145, 148, 149, 265, 267,
321, 372, 396, 465, 527, 532, 542, 563, 592
quantum confinement, 117, 532
quantum dots, viii, x, 4, 7, 8, 107, 108, 109, 140, 141,
142, 143, 144, 145, 148, 149, 321
quantum yields, 109, 118
quartz, 53, 283, 412, 439, 551, 606
R
R&D, 506
radial distribution, 417
radiation, ix, xiv, 18, 107, 111, 121, 124, 127, 397,
412, 436, 451, 452, 453, 492, 512, 517, 564, 574,
615, 616, 617, 618
radiation therapy, ix, 107, 111
radical, xi, xii, 143, 275, 278, 279, 282, 309, 310,
315, 316, 324, 441, 451
radical polymerization, xii, 309, 310, 315, 316, 328
radio, 125, 252
radiofrequency, 127
radiotherapy, 123
radium, 223
radius, xiv, 117, 122, 123, 176, 181, 182, 184, 190,
266, 269, 374, 375, 376, 379, 380, 381, 383, 384,
385, 386, 388, 389, 390, 393, 479, 480, 494, 565,
566, 567, 568, 569, 570, 571, 572, 575, 580, 583
Raman scattering, ix, 71, 72, 73, 74, 75, 77, 82, 85,
86, 90, 102, 103, 241, 255, 257, 258, 473, 583,
584, 586
Raman spectra, ix, xiii, 71, 73, 75, 80, 82, 86, 87, 90,
94, 95, 99, 100, 104, 284, 287, 435, 441, 445
Raman spectroscopy, ix, 71, 72, 75, 101, 102, 103,
104, 412, 439
Raman-scattering, 102, 103
random, 16, 17, 349, 379, 390, 416, 548, 549
Rayleigh, 52, 561, 583, 584, 586, 587, 588
reactant, 5, 7, 241, 242, 437, 456, 578, 579, 580, 611
reaction rate, 18, 567
reaction temperature, 340
reaction time, 412
reactivity, 11, 324, 333, 340, 345, 353, 362, 374, 522
reagent, 6, 578, 579, 580, 585
reagents, 145, 238, 578, 579, 587
real time, 380, 588
reality, 404
Index

638
receptors, 112, 113, 115, 116, 119, 147
recognition, 119, 152, 300, 560
recombination, 260, 263, 264, 541, 546, 551, 579
reconstruction, 397
recovery, 125, 126, 176, 187, 191, 192, 210, 212,
302, 354
recrystallization, 368, 549
recrystallized, 534, 549, 550
red shift, 260
red wine, 618
redox, 41, 133, 282, 291
redshift, 257, 259, 260, 261, 263, 269
reduction, ix, 8, 9, 15, 25, 27, 33, 36, 41, 52, 71, 72,
75, 86, 99, 101, 187, 207, 215, 229, 247, 334, 343,
344, 345, 350, 354, 355, 361, 520, 523, 606
reference frame, 90, 91
reflectance spectra, 286
reflection, 76, 77, 79, 85, 87, 91, 92, 102, 103, 286,
346, 470, 474, 513
refractive index, 73, 84, 92, 93, 468, 470, 473, 474,
547, 569
regression, 144, 563
regression analysis, 563
regular, xiv, 6, 37, 170, 380, 423, 429, 448, 479, 489,
501, 502, 615
regulation, 104
relationship, xv, xvi, 11, 146, 188, 191, 192, 215,
250, 265, 313, 345, 416, 447, 465, 509, 510, 513,
525, 537, 549, 552
relationships, 213
relative size, 121
relaxation, 125, 288, 290, 346, 403, 489, 500, 572,
575, 577
relaxation rate, 572, 575, 577
relevance, 294, 590
Reliability, 305remission, 127
renal, 116, 119, 141
renal cell carcinoma, 141
repair, 297
replication, 27, 462
research, vii, x, xii, 24, 88, 107, 108, 139, 144, 146,
239, 241, 276, 294, 299, 303, 312, 321, 324, 333,
337, 371, 374, 376, 397, 401, 404, 411, 430, 448,
475, 506, 510, 560, 606, 616, 617
researchers, 89, 118, 119, 121, 127, 140, 152, 160,
276, 295, 302, 303, 310, 351, 356, 410, 460
reservoir, 10, 153
reservoirs, 41, 42
residuals, 560
residues, 493
resin, 392
resistance, 19, 119, 169, 171, 184, 190, 191, 192,
193, 212, 300, 302, 303, 373, 403, 510, 615
resistive, 24, 373
resistivity, 17, 249, 252, 277, 278, 279, 282, 283,
284, 285, 286, 287, 288, 291, 302
respiratory, 133
responsiveness, 319
retention, 111
returns, 125
Reynolds, 273, 477
RF, 125, 461
rhombohedral, 340, 341, 343
RIE, 461, 462, 471
rings, 373, 380, 391, 410, 496, 497, 520
rods, 246, 394, 417, 427, 428, 429, 537, 578, 591
room temperature, 32, 42, 53, 77, 126, 159, 161, 169,
175, 197, 201, 218, 239, 265, 266, 283, 314, 333,
347, 348, 412, 460, 461, 463, 464, 470, 471, 479,
523, 526, 527, 538, 543, 545, 546, 550, 551, 555,
606
room-temperature, 239, 240, 248, 260
rotational matrix, 91
roughness, 20, 175, 254, 286, 448, 467
Rouleau, 271
Royal Society, 413, 418
RP, 619
rubber, 171, 311, 606
rubber products, 311
Russia, 456
rutile, 367, 480, 488, 489
S
SAD, 535, 536, 537, 549, 552
saline, 124
salt, 8, 129, 246, 332, 343, 344, 350, 575, 576, 591
salts, xi, 129, 245, 275, 277, 278, 280, 282, 332
samarium, 482
sampling, 512
sapphire, 101, 173, 242, 243, 259, 493, 551
sarcomas, 132
satellite, 528, 530, 537
saturation, 156, 242, 246, 265, 267, 269, 287, 378,
422, 544, 554
scaffold, 461, 471
scalable, 23
scaling, 567, 570, 581, 583, 584, 585, 587
scaling law, 570, 583, 584, 585, 587
scandium, 343, 345, 365
Scanning electron, 20, 21, 135, 286, 413, 616, 617
scanning electron microscopy, xiv, xv, 32, 215, 242,
412, 459, 605, 606
scanning electronic microscope, 439
scanning tunneling microscopy, 9, 374
scatter, 109, 123, 208, 592
scattered light, 97, 98, 562, 592
schema, 225
Schmid, 104, 234
Schottky, 291
scientific community, 295
scientists, vii, ix, xii, 3, 107, 120, 309, 310, 315, 316,
317, 325, 410
SCs, 152
security, xii, 331
sediments, 412
Index

639
seed, xiii, 158, 159, 161, 169, 208, 224, 238, 252,
254, 409, 412, 419, 420, 421, 422, 425, 427, 428,
429, 430, 431
seeding, 158, 159, 345
seeds, 28, 246, 251, 362, 423, 426, 427, 430, 578,
586, 588
selected area electron diffraction, 483, 521, 527, 535,
537, 549
selectivity, 11, 300, 303, 560
selenium, x, 107, 109, 133, 134, 135, 136, 137, 138,
139, 142, 144, 145, 146, 147, 148, 149
self-assembling, 299, 410
self-assembly, vii, viii, xi, xiii, xiv, xvi, 3, 4, 24, 40,
237, 238, 239, 241, 251, 254, 269, 276, 299, 319,
409, 410, 411, 424, 429, 430, 431, 460, 461, 471,
473, 485, 490, 559, 560, 561, 578, 590, 596
Self-cleaning, 620
self-organization, 411, 425, 430, 431
self-similarity, 567
SEM micrographs, 23
semiconductor, vii, x, xiv, 3, 5, 6, 7, 8, 11, 14, 22, 27,
29, 72, 121, 141, 142, 143, 149, 161, 237, 238,
239, 241, 264, 265, 266, 269, 299, 301, 414, 479,
480, 506, 526
semiconductors, xii, 4, 5, 7, 8, 10, 27, 37, 42, 72, 117,
247, 263, 276, 277, 278, 299, 301, 302, 309, 316,
354, 411
sensing, xi, 27, 34, 42, 65, 66, 123, 141, 149, 261,
294, 299, 300, 302, 314, 590
sensitivity, viii, 31, 40, 51, 66, 68, 77, 82, 84, 87, 88,
95, 100, 103, 255, 258, 278, 303, 332, 394, 595
sensitization, xiv, 479, 480, 501
sensors, viii, xii, 9, 23, 24, 27, 34, 51, 65, 66, 240,
276, 294, 300, 302, 303, 314, 328, 331, 332, 339,
342, 347
separation, viii, 19, 20, 51, 54, 57, 67, 68, 118, 301,
309, 312, 313, 380
series, 10, 177, 288, 291, 334, 380, 392, 465, 519,
599
serum, 130, 139, 149
serum albumin, 130
Shanghai, 51, 317, 605, 612
shaping, 17, 392, 393, 394
sharing, xiii, 409
shear, x, 151, 172, 174, 177, 191, 447, 450
Shell, 460, 471
short-range, 255, 258, 398, 568
shoulder, 75, 80, 86, 539
Si3N4, 84, 85, 87, 88, 98, 99, 100, 606
side effects, ix, 107, 112, 126, 140
Siemens, 16
sign, 193, 333, 561, 591, 593, 595
signals, ix, 71, 72, 73, 82, 85, 89, 94, 95, 98, 99, 103,
120, 125, 261, 375, 464, 493, 514, 592
signal-to-noise ratio, ix, 72, 99, 100
signs, 127, 593
silane, 327
silanol groups, 311
silica, 23, 40, 121, 122, 184, 311, 312, 326, 532, 551
silica glass, 532
silicon dioxide, 84, 310
siloxane, xv, 605, 606
silver, 102, 103, 104, 244, 278, 280, 283, 321, 615,
616, 617, 619, 620
simulated emission, 248
simulation, xiv, 276, 374, 376, 379, 399, 401, 404,
459, 460, 469, 470, 475, 585
simulations, xii, 10, 187, 371, 373, 380, 397, 398,
400, 401, 402, 404, 568, 582, 584
Singapore, 331
single crystals, xi, xvi, 153, 158, 159, 165, 211, 214,
275, 276, 277, 278, 281, 282, 286, 457, 525, 530,
531, 532, 539, 540, 541, 546, 547, 548
single walled carbon nanotubes, 34
single-crystalline, 16, 17, 28, 238, 246, 410
sintering, xii, 158, 331, 332, 335, 336, 338, 344, 346,
347, 349, 351, 353, 355, 358, 361, 362, 364, 367,
368
SiO2, viii, xv, 11, 51, 53, 67, 68, 84, 85, 312, 325,
326, 460, 474, 475, 546, 547, 551, 605, 606, 607,
608, 609, 610, 611, 612
sites, xiv, 22, 39, 112, 113, 116, 119, 127, 140, 156,
157, 161, 207, 241, 242, 399, 403, 423, 479, 493,
497, 498, 499, 500, 506, 611, 617
skeleton, 17, 228, 517, 520
skin, 148, 617
skin cancer, 148
Sm, xiv, 479, 480, 501
smooth muscle, 148
smoothing, 17, 377
SNR, ix, 71, 72, 99, 100
sodium, 135, 138, 318, 320
soft matter, viii, 4, 10, 31, 33
software, 197, 218, 300
SOI, 460, 465
solar, 27, 29, 31, 52, 240, 301, 302, 618
solar cell, 27, 29, 31, 52, 240, 301, 302
solar cells, 27, 29, 31, 52, 240, 301
solar energy, 301
sol-gel, 31, 40, 245, 332, 336, 337, 339, 342, 343,
350, 352, 357, 358, 359, 361, 369, 489, 490, 492,
498, 506
solid phase, 246
solid solutions, 339
solid state, xi, 275, 277, 278, 282, 287, 288, 344, 345,
367, 369, 480
solid tumors, 142, 145
solidification, 60, 156, 354
solid-state, xii, 165, 331, 332, 333, 335, 338, 342,
343, 344, 345, 346, 347, 349, 350, 352, 353, 354,
362, 367, 369
sols, 369
solubility, 129, 277, 310, 316, 317, 328, 332, 480
solution phase method, 241
solutions, 5, 24, 25, 27, 33, 38, 52, 53, 57, 66, 67,
128, 135, 136, 145, 239, 245, 246, 303, 316, 339,
347, 352, 358, 361, 563, 566, 567, 569, 570, 572,
575, 576, 577, 579, 580, 581, 588, 590, 596
Index

640
solvent, viii, 4, 7, 32, 52, 54, 55, 56, 57, 58, 59, 61,
65, 129, 130, 141, 147, 310, 422, 490, 560, 574,
589
solvents, viii, 30, 31, 51, 54, 55, 56, 68, 129
space-time, 579
Spain, 151, 170, 293
spatial, ix, 18, 71, 72, 77, 172, 186, 283, 294, 376,
403, 569, 578, 579, 588, 595
spatial confinement, 18
species, xvi, 147, 239, 241, 242, 245, 248, 277, 278,
282, 288, 291, 300, 302, 303, 324, 345, 372, 375,
376, 399, 411, 437, 438, 439, 454, 505, 527, 559,
560, 561, 565, 566, 567, 568, 579, 590, 611
specific heat, 143
specific surface, 68
specificity, ix, 107, 120, 143
spectral dimension, 583, 586
spectroscopic methods, 288
spectroscopy, ix, xiv, 9, 27, 71, 72, 93, 95, 102, 103,
104, 135, 139, 464, 473, 479, 481, 493, 497, 500,
527, 552, 588, 590, 606
speed, viii, ix, xv, 4, 11, 13, 14, 15, 20, 51, 55, 56, 60,
64, 66, 67, 71, 110, 333, 334, 335, 341, 351, 356,
402, 412, 414, 425, 431, 509, 512
spermine, 580, 581, 584, 585, 586, 587
spheres, viii, 4, 24, 36, 37, 140, 173, 280, 311, 383,
414, 418, 461, 462, 473, 491
spin, viii, 4, 125, 239, 296
spleen, 111, 133
SPR, xv, 525, 526, 527, 540, 541, 547
sputtering, 252, 266, 526
SQUID, 527, 542
S-shaped, 260, 263, 269
stability, xi, 10, 39, 102, 109, 116, 121, 123, 131,
134, 175, 251, 293, 300, 310, 312, 313, 317, 344,
348, 364, 366, 369, 373, 376, 377, 378, 397, 404,
411, 437, 500, 560, 618
stabilization, 66, 210, 368, 369
stabilize, 124, 278, 437
stabilizers, 130
stages, ix, 10, 20, 107, 108, 111, 140, 158, 172, 176,
210, 288, 290, 352, 385, 398, 422, 423, 424, 430,
496
stainless steel, 20, 108, 134, 135, 137, 138, 334, 343,
352, 412
stainless steels, 20
standard deviation, 63
Staphylococcus, 616, 617
Staphylococcus aureus, 616, 617
stars, 372
STD, 520
steel, xv, 108, 134, 135, 137, 138, 173, 333, 334, 343,
351, 352, 412, 456, 509, 510, 511, 512, 516, 520,
523
STEM, 323, 527, 533, 536, 538
stem cell therapy, 145
steric, 578
sterilization, 618
stiffness, 172, 175, 176, 177, 179, 181, 183, 198, 218,
219
stimulus, 115
STM, 9, 10, 11, 14
stock, 566, 578, 579, 582
stoichiometry, 352
Stokes shift, 583, 586
storage, xiii, xv, 109, 116, 152, 158, 172, 173, 190,
312, 342, 351, 409, 410, 525, 526
strain, ix, 71, 72, 73, 74, 75, 76, 77, 80, 81, 82, 84,
87, 88, 90, 92, 93, 100, 102, 103, 104, 165, 166,
175, 181, 182, 188, 190, 191, 218, 223, 240, 342,
400, 403, 494
strains, ix, 71, 72, 80, 81, 173, 187, 335, 342, 403
strategies, viii, 4, 16, 24, 25, 52, 109, 114, 245, 277,
297, 300, 431
stress level, 177
stress-strain curves, x, 151, 174, 181, 218
stretching, 372, 401, 402, 403, 416, 417
strong interaction, 38, 314, 562
strontium, 352, 361, 368, 370
structural changes, 226, 574
structural dimension, 422
structural relaxation, 403
structure formation, 38
students, 291
styrene, 38, 310, 324, 326
substances, 276
substitutes, 500
substitution, 498
substrates, ix, xiv, 5, 7, 8, 9, 13, 14, 15, 18, 23, 25,
26, 27, 28, 39, 71, 72, 77, 84, 105, 134, 135, 136,
137, 138, 139, 168, 241, 243, 246, 247, 249, 250,
252, 266, 269, 276, 310, 320, 358, 436, 447, 459,
488, 526, 551
sulfur, 611, 612
sulfuric acid, 12
sulphate, 140
sulphur, 38
superconducting, 152, 153, 154, 158, 167, 170, 224,
527, 542
superconducting materials, 153, 170
superconductivity, 27, 153, 236, 278
superconductor, x, 151, 152, 163, 170
superconductors, 152, 153, 158, 159, 161, 170, 224,
291
supercritical, 291
superhard, xv, 411, 509, 510, 513, 514, 515, 516,
517, 518, 519, 520, 521, 522, 523
superimpose, 258
superlattice, 346
superlattices, 5
superposition, 386, 581
supply, 21, 53, 110, 156, 374, 394, 511
suppression, ix, 72, 73, 89, 97, 99, 101, 396
supramolecular, xvi, 559, 560, 561, 578, 590, 591,
593, 594, 595
surface area, 13, 23, 30, 31, 38, 64, 311, 549, 617
surface chemistry, 145
Index

641
surface diffusion, 242, 437
surface diffusivity, 438
surface energy, 144, 240, 245, 251, 269, 315, 450
surface layer, 9, 90, 261, 263, 376, 379
surface modification, 13, 117
surface properties, 109, 114, 132, 250, 312
surface region, 401, 414, 526
surface roughness, 20, 175
surface structure, 4, 470
surface tension, 52, 56, 437
surface-initiated atom transfer radical polymerization,
xii, 309, 310, 328
surfactant, 121, 128, 129, 130, 482
surfactants, 40, 410
surgery, ix, 107
Surgery, 107
surgical, 108
surging, 52
susceptibility, xv, 125, 287, 288, 289, 525, 526
suspensions, 134, 357, 431
switching, xv, 318, 351, 366, 525, 526
SWNTs, 34, 315, 323
symbols, 577
symmetry, 25, 184, 238, 255, 414, 470, 498, 499,
500, 561, 574, 590
synchronous, 141
synchrotron, xiv, 18, 436, 451
synchrotron radiation, xiv, 436, 451
Synchrotron radiation, 452
synthetic polymers, 310
T
tactics, 247
targets, 111, 113, 118, 148, 149, 511, 512
Taxol, 142
technology, vii, xiii, xvi, 3, 17, 18, 72, 108, 276, 277,
291, 295, 297, 300, 303, 310, 319, 360, 363, 372,
374, 392, 404, 409, 410, 453, 456, 526, 615
tellurium, 5
temperature annealing, 505, 526
temperature dependence, 77, 283, 342
temperature gradient, 158, 159, 162, 438
tensile, 90, 169, 184, 400, 403, 404, 442
tensile strength, 403, 404
tensile stress, 90, 184, 403, 442
tension, 228, 398, 402
terraces, 448
Tesla, 125, 127
testicular cancer, 133
textile, 615, 616, 619, 620
textiles, xvi, 52, 615, 617, 618, 619
thallium, 11
theory, 179, 190, 191, 223, 255, 256, 265, 268, 302,
394, 397, 404, 547, 563, 564, 565, 566, 584, 588
therapeutic agents, 115, 120, 127, 140
therapeutics, 109, 123, 128, 142, 148, 149
therapy, x, 107, 120, 123, 124, 141, 142, 143, 144,
145, 146, 149, 560
thermal activation, 352
thermal analysis, 282, 339, 492
thermal decomposition, 489
thermal energy, 123, 239, 389, 506
thermal evaporation, 79
thermal expansion, 165, 167, 175, 228, 335
thermal mechanical analysis, 340
thermal plasma, 456
thermal properties, 480
thermal stability, 344, 348, 364, 500
thermal treatment, 158, 159, 162, 345, 537, 538
thermodynamic, 152, 251, 278, 397, 411, 561, 578
thermodynamic method, 278
thermodynamic parameters, 561
thermodynamic stability, 251, 411
thermodynamics, 247, 411, 493
thermogravimetry, 282
thermolysis, 323
thin film, vii, 3, 4, 5, 7, 24, 29, 40, 56, 57, 95, 159,
171, 181, 184, 207, 276, 277, 280, 300, 455, 456,
481, 488, 489, 523, 581
Thomson, 3
three-dimensional, viii, xiii, 17, 20, 51, 52, 410
threshold, 11, 186, 187, 248, 373, 384, 526, 569
thresholds, 186
thymocytes, 147
thyroid, 133
time consuming, 332
time resolution, 376
TiO
2
, viii, xiv, xvi, 4, 27, 29, 30, 31, 336, 337, 338,
339, 349, 350, 351, 353, 363, 414, 479, 480, 481,
482, 483, 484, 488, 489, 490, 491, 492, 493, 494,
495, 496, 497, 498, 500, 501, 502, 503, 504, 505,
506, 525, 527, 530, 538, 544, 545, 606
tissue engineering, 52, 149, 619
titania, 24, 137, 480, 481, 482, 484, 489, 490, 491,
618, 619
titanium, xv, 29, 30, 31, 108, 134, 135, 136, 137, 138,
139, 243, 310, 480, 505, 509, 522, 618
Titanium, xv, 29, 134, 135, 509, 511, 513, 515, 517,
519, 521, 523
titanium dioxide, 29, 618
tolerance, 128, 175
toluene, 36, 37, 326
top-down, vii, viii, xi, 3, 4, 23, 42, 293, 300
topographic, 73, 74, 87, 88, 373, 385
topological, 354, 372, 403
topology, 372, 376
toughness, x, 151, 161, 170, 172, 173, 174, 184, 185,
186, 194, 195, 196, 197, 199, 204, 205, 215, 216,
217, 224, 228, 455, 514
toxic, 109, 120, 121, 128, 133, 134, 138
toxic metals, 121
toxicity, 121, 127, 135, 148
TPA, 442
trajectory, 383
transducer, 370
transfer, vii, xi, xvi, 3, 11, 17, 27, 35, 38, 39, 115,
141, 275, 277, 278, 279, 282, 300, 302, 303, 309,
Index

642
310, 316, 324, 367, 447, 480, 484, 489, 491, 499,
505, 559, 560, 561, 562
transferrin, 149
transformation, xii, 91, 156, 159, 167, 228, 229, 318,
335, 339, 342, 371, 429, 453
transformation matrix, 91
transformations, 373
transforming growth factor, 110
transistors, 24, 29, 72, 101, 276, 299, 526
transition metal, 282, 315
transition metal ions, 315
transition temperature, 152, 335, 368, 461
transitions, xiv, 263, 264, 467, 479, 482, 486, 489,
490, 498, 500, 501, 502
translational, 562, 572, 574, 575, 578, 583
transmission, xi, xiv, xv, 32, 75, 77, 84, 91, 92, 114,
167, 237, 321, 373, 375, 412, 459, 479, 509, 512,
526, 527, 533, 535, 592, 605, 606, 617, 618
transmission electron microscopy, xi, xiv, xv, 114,
237, 321, 412, 459, 526, 527, 535, 605, 606
transparent, 28, 29, 30, 239, 265, 342, 436, 461, 489,
618
transport, x, 7, 14, 23, 30, 41, 111, 114, 144, 152,
170, 238, 294, 372, 404, 410, 414, 429, 454
transpose, 90
travel, 278, 377, 400
travel time, 377, 400
treatment methods, ix, 107, 111
trend, 56, 137, 210, 276, 398, 514, 519
TRF, 326
trifluoroacetic acid, 32
Tsunami, 493
tubular, 42, 578
tumor, ix, 107, 108, 110, 111, 112, 113, 114, 115,
116, 118, 119, 120, 124, 125, 126, 127, 128, 141,
143, 144, 145, 146, 147, 150
tumor cells, ix, 107, 108, 110, 112, 113, 114, 120,
126, 146
tumor growth, 116
tumor progression, 143
tumors, 108, 109, 110, 111, 112, 115, 116, 119, 122,
124, 125, 127, 128, 142, 143, 145
tungsten, 20, 173, 333, 334, 335, 338, 339, 343, 353,
361, 392, 456, 538
tungsten carbide, 173, 333, 334, 335, 338, 339, 343,
361
tunneling, 11, 41, 265, 374
twins, 165, 166, 224, 225, 416, 456, 555
two-dimensional (2D), viii, xiii, 9, 51, 156, 239, 240,
245, 409, 410, 560
U
Ukraine, 371
ultra-fine, 52, 343
ultrasound, 115, 127
ultraviolet, 102, 121, 239, 248, 269, 282, 482, 546,
615
Ultraviolet, 82, 618
uncertainty, 175, 179, 257, 389
underreported, 108
uniform, ix, xiii, 9, 17, 22, 23, 25, 32, 36, 37, 58, 63,
71, 73, 87, 131, 238, 252, 253, 299, 311, 345, 358,
359, 374, 394, 409, 410, 420, 431, 450, 517, 520,
521, 606, 612
unions, 301
urethane, 144
urokinase, 110
UV, ix, 40, 72, 73, 121, 239, 240, 248, 258, 259, 260,
261, 264, 282, 283, 284, 287, 290, 294, 295, 297,
300, 303, 484, 532, 538, 539, 546, 551, 615, 616,
617
UV absorption, 532, 539
UV exposure, 121
UV irradiation, 283, 284, 290
UV light, ix, 72, 258, 282, 283, 284, 300, 303
UV radiation, 121, 616, 617
V
vacancies, 161, 258, 302, 403, 427, 503, 540, 541,
549, 551
vacuum, xv, 53, 65, 73, 93, 266, 276, 350, 374, 380,
396, 399, 410, 509, 511, 522, 527, 546
valence, 263, 265, 282, 301, 349
validation, 148
validity, 376, 397
van der Waals, 410, 560, 570
van der Waals forces, 570
vapor, 239, 241, 242, 243, 245, 247, 250, 266, 269,
277, 376, 392, 454, 455, 456, 457, 527, 546, 606,
611
vapor phase deposition, 247
vapor-liquid-solid, 238, 241, 611
variable, 4, 6, 341, 392, 399
variables, 335
variation, ix, 27, 28, 52, 71, 72, 80, 95, 97, 100, 175,
191, 351, 353, 395, 473, 494, 514, 544, 554
vascular endothelial growth factor, 110, 111
vascular endothelial growth factor (VEGF), 111
vascularization, 110, 111
vasculature, 112, 142
vector, 90, 120, 226, 468, 564, 572
VEGF, 111
velocity, 168, 253, 265, 351, 437, 438
versatility, 15, 109, 128
vessels, 110, 111, 118, 144, 147
vibration, 74, 75, 80, 84, 87, 175, 255, 334
vibrational modes, 76, 84, 416
Vickers hardness, 510
vinblastine, 133
viscosity, 52, 53, 57, 66, 164, 168
visible, 29, 41, 73, 103, 117, 121, 250, 258, 261, 265,
282, 420, 426, 489, 504, 515, 523, 538, 539, 540,
546, 562, 588, 596
vision, 149
visualization, 184
VLS, 238, 241, 242, 243, 611
Index

643
voiding, 5
voids, 36, 37, 414, 417, 421, 422, 534, 549
volatility, 332
vortex, 561, 590
vortices, 158
W
waste products, 110
water, 10, 11, 14, 17, 41, 53, 117, 125, 128, 129, 246,
249, 252, 282, 317, 318, 319, 328, 414, 420, 421,
460, 461, 485, 486, 492, 493, 560, 564, 565, 566,
571, 575, 579, 591, 615, 616
water evaporation, 414
water-soluble, 114
wave vector, 257, 468, 572
wavelengths, 82, 83, 117, 118, 282, 300, 486, 592
wealth, 10
wear, 186, 510, 512, 515, 516
Weibull, 213
weight loss, 493
weight ratio, 335, 341, 351
wettability, 319, 429
WG, 144
wide band gap, 539, 546
windows, 453
wires, xii, 9, 10, 17, 24, 40, 371, 372, 381, 388, 394,
396, 397, 401, 402, 403, 578
X
xenograft, 116, 146, 150
xenon, 493, 497, 498
XPS, 135, 136, 261, 262, 263, 282, 283, 412, 526,
527, 528, 529, 530, 531, 534, 539, 540, 541
X-ray absorption, 282
X-ray analysis, 412
X-ray diffraction, xi, xv, 194, 237, 412, 413, 439,
447, 479, 526, 527, 531, 532
X-ray diffraction (XRD), xiv, 249, 250, 251, 252,
253, 254, 287, 288, 290, 336, 337, 338, 339, 341,
343, 344, 346, 350, 412, 413, 439, 442, 446, 450,
479, 485, 487, 488, 492, 493, 494, 495, 496, 505,
512, 516, 518, 519, 520, 521, 523, 526, 527, 531,
532, 533, 534, 539, 606, 607, 609, 611
X-ray photoelectron spectroscopy (XPS), 526
Y
Y-axis, 587
YBCO, x, 151, 152, 153, 154, 156, 158, 159, 160,
162, 164, 165, 167, 168, 170, 171, 184, 194, 195,
196, 197, 198, 199, 200, 201, 202, 206, 207, 208,
209, 210, 211, 212, 213, 214, 215, 216, 217, 218,
219, 221, 222, 223, 224, 225, 226, 228, 229, 230
yeast, 133
yield, x, xv, 8, 9, 31, 151, 158, 172, 174, 175, 178,
182, 188, 191, 192, 211, 218, 221, 222, 224, 243,
245, 355, 374, 410, 480, 605, 606, 607, 612
YSZ, xvi, 525, 527, 529, 530, 534, 535, 536, 539,
540, 544, 551, 552, 553
yttria-stabilized zirconia, 527
yttrium, 156, 157
Z
zinc (Zn), viii, 27, 51, 53, 67, 242, 244, 245, 246,
247, 248, 250, 252, 255, 258, 269, 294, 310, 343,
362, 366, 546
zirconia, 364, 527
ZnO nanorods, 245, 246, 248, 249, 256, 261, 263
ZnO nanostructures, 240, 245, 253, 255