CHAPTER 1

GENERAL INTRODUCTION

1.1 Introduction

A nanometer (nm) is one thousand millionth of a meter. For comparison, a red

blood cell is approximately 7,000 nm wide and a water molecule is almost 0.3nm across.
People are interested in the nanoscale (which we define to be from 100 nm down to the
size of atoms (approximately 0.2nm)) because it is at this scale that the properties of
materials can be very different from those at a larger scale. We define nanoscience as the
study of phenomena and manipulation of materials at atomic, molecular and
macromolecular scales, where properties differ significantly from those at a larger scale;
and nanotechnology as the design, characterization, production and application of
structures, devices and systems by controlling shape and size at the nanometer scale. In
some senses, nanoscience and nanotechnology is not new. Chemists have been making
polymers, which are large molecules made up of nanoscale subunits, for many decades
and nanotechnologies have been used to create the tiny features on computer chips for the
past 20 years. However, advances in the tools that now allow atoms and molecules to be
examined and probed with great precision have enabled the expansion and development
of nanoscience and nanotechnologies. Some 30–40 years later, the vision proposed by
Richard Feynman in the famous speech ‘There is plenty of room at the bottom’ (Feynman
1960) has now become reality.1 Already at that time, Feynman noted that nanoscale
science and engineering would require the development of new experimental techniques
and of specific instrumentation that could visualize the nanoworld, and possibly even
intervene directly to modify it.

The bulk properties of materials often change dramatically with nano ingredients.
Composites made from particles of nano-size ceramics or metals smaller than 100
nanometers can suddenly become much stronger than predicted by existing materials-

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science models. For example, metals with a so-called grain size of around 10 nanometers
are as much as seven times harder and tougher than their ordinary counterparts with grain
sizes in the hundreds of nanometers. The causes of these drastic changes stem from the
weird world of quantum physics. The bulk properties of any material are merely the
average of all the quantum forces affecting all the atoms. As we make things smaller and
smaller, you eventually reach a point where the averaging no longer works.

1.2 Nanomaterials – Definition

Although a broad definition, we categorize nanomaterials as those which have

structured components with at least one dimension less than 100 nm. Materials that have
one dimension in the nanoscale (and are extended in the other two dimensions) are layers,
such as a thin films or surface coatings. Some of the features on computer chips come in
this category. Materials that are nanoscale in two dimensions (and extended in one
dimension) include nanowires and nanotubes. Materials that are nanoscale in three
dimensions are particles, for example precipitates, colloids and quantum dots (tiny
particles of semiconductor materials). Nanocrystalline materials, made up of nanometer-
sized grains, also fall into this category. Some of these materials have been available for
some time; others are genuinely new. The aim of this chapter is to give an overview of
the properties, and the significant foreseeable applications of some key nanomaterials.

Two principal factors cause the properties of nanomaterials to differ significantly

from other materials: increased relative surface area, and quantum effects. These factors
can change or enhance properties such as reactivity, strength and electrical characteristics.
As a particle decreases in size, a greater proportion of atoms are found at the surface
compared to those inside. For example, a particle of size 30 nm has 5% of its atoms on its
surface, at 10 nm 20% of its atoms, and at 3 nm 50% of its atoms. Thus nanoparticles
have a much greater surface area per unit mass compared with larger particles. As growth
and catalytic chemical reactions occur at surfaces, this means that a given mass of
material in nanoparticulate form will be much more reactive than the same mass of
material made up of larger particles.

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 The quantum effects can begin to dominate the properties of matter as size is
reduced to nanoscale. These can affect the optical, electrical and magnetic behaviour of
materials particularly as the particle size approaches the smaller end of the nanoscale
which is due to the confinement of electrons within particles of dimension smaller than
the bulk electron delocalization length, this process is being termed as quantum
confinement .2

For other materials such as crystalline solids, as the size of their structural
components decreases, there is much greater interface area within the material; this can
greatly affect both mechanical and electrical properties. For example, most metals are
made up of small crystalline grains; the boundaries between the grain slow down or arrest
the propagation of defects when the material is stressed, thus giving it strength. If these
grains can be made very small, or even nanoscale in size, the interface area within the
material greatly increases, which enhances its strength. For example, nanocrystalline
nickel is as strong as hardened steel. Understanding surfaces and interfaces is a key
challenge for those working on nanomaterials, and one where new imaging and analysis
instruments are vital.

1.3 Nanomaterial Science

Nanomaterials are not simply another step in the miniaturization of materials.

They often require very different production approaches. There are several processes to
create nanomaterials, classified as ‘top-down’ and ‘bottom-up’. Although many
nanomaterials are currently at the laboratory stage of manufacture, a few of them are
being commercialized.

Below we outline some examples of nanomaterials and the range of nanoscience

that is aimed at understanding their properties. As will be seen, the behaviour of some
nanomaterials is well understood, whereas others present greater challenges.

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1.3.1 Nanoscale in One Dimension

Thin films, layers and surfaces

One-dimensional nanomaterials, such as thin films and engineered surfaces, have

been developed and used for decades in fields such as electronic device manufacture,
chemistry and engineering. In the silicon integrated-circuit industry, for example, many
devices rely on thin films for their operation, and control of film thicknesses approaching
the atomic level is routine. Monolayers (layers that are one atom or molecule deep) are
also routinely made and used in chemistry. The formation and properties of these layers
are reasonably well understood from the atomic level upwards, even in quite complex
layers (such as lubricants). Advances are being made in the control of the composition
and smoothness of surfaces, and the growth of films.

Engineered surfaces with tailored properties such as large surface area or specific
reactivity are used routinely in a range of applications such as in fuel cells and catalysts.
The large surface area provided by nanoparticles, together with their ability to self
assemble on a support surface, could be of use in all of these applications. Although they
represent incremental developments, surfaces with enhanced properties should find
applications throughout the chemicals and energy sectors. The benefits could surpass the
obvious economic and resource savings achieved by higher activity and greater
selectivity in reactors and separation processes, to enabling small-scale distributed
processing (making chemicals as close as possible to the point of use). There is already a
move in the chemical industry towards this. Another use could be the small-scale, on-site
production of high value chemicals such as pharmaceuticals.

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1.3.2 Nanoscale in Two Dimensions

Two dimensional nanomaterials such as tubes and wires have generated

considerable interest among the scientific community in recent years. In particular, their
novel electrical and mechanical properties are the subject of intense research.

a) Carbon Nanotubes

Carbon nanotubes (CNTs) were first observed by Sumio Iijima in 1991. CNTs are
extended tubes of rolled graphene sheets. There are two types of CNT: single-walled (one
tube) or multi-walled (several concentric tubes). Both of these are typically a few
nanometres in diameter and several micrometers to centimeters long. CNTs have assumed
an important role in the context of nanomaterials, because of their novel chemical and
physical properties. They are mechanically very strong (their Young’s modulus is over 1
terapascal, making CNTs as stiff as diamond), flexible (about their axis), and can conduct
electricity extremely well (the helicity of the graphene sheet determines whether the CNT
is a semiconductor or metallic). All of these remarkable properties give CNTs a range of
potential applications: for example, in reinforced composites, sensors, nanoelectronics
and display devices

CNTs are now available commercially in limited quantities. They can be grown by
several techniques. However, the selective and uniform production of CNTs with specific
dimensions and physical properties is yet to be achieved. The potential similarity in size
and shape between CNTs and asbestos fibers has led to concerns about their safety.

b) Inorganic Nanotubes

Inorganic nanotubes and inorganic fullerene-like materials based on layered

compounds such as molybdenum disulphide were discovered shortly after CNTs. They
have excellent tribological (lubricating) properties, resistance to shockwave impact,
catalytic reactivity, and high capacity for hydrogen and lithium storage, which suggest a

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range of promising applications. Oxide-based nanotubes (such as titanium dioxide) are
being explored for their applications in catalysis, photo-catalysis and energy storage.

c) Nanowires

Nanowires are ultra fine wires or linear arrays of dots, formed by self-assembly.
They can be made from a wide range of materials. Semiconductor nanowires made of
silicon, gallium nitride and indium phosphides have demonstrated remarkable optical,
electronic and magnetic characteristics (for example, silica nanowires can bend light
around very tight corners). Nanowires have potential applications in high-density data
storage; either as magnetic read heads or as patterned storage media, and electronic and
opto-electronic nanodevices, for metallic interconnects of quantum devices and
nanodevices. The preparation of these nanowires relies on sophisticated growth
techniques, which include self assembly processes, where atoms arrange themselves
naturally on stepped surfaces, chemical vapour deposition (CVD) onto patterned
substrates, electroplating or molecular beam epitaxy (MBE). The ‘molecular beams’ are
typically from thermally evaporated elemental sources.

1.3.3 Nanoscale in Three Dimensions

a) Nanoparticles

Nanoparticles are often defined as particles of less than 100 nm in diameter. We

classify nanoparticles to be particles less than 100 nm in diameter that exhibit new or
enhanced size-dependent properties compared with larger particles of the same material.
Nanoparticles exist widely in the natural world: for example as the products of
photochemical and volcanic activity, and created by plants and algae. They have also
been created for thousands of years as products of combustion and food cooking, and
more recently from vehicle exhausts. Deliberately manufactured nanoparticles, such as
metal oxides, are by comparison in the minority.

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 Nanoparticles are of interest because of the new properties (such as chemical
reactivity and optical behaviour) that they exhibit compared with larger particles of the
same materials. For example, titanium dioxide and zinc oxide become transparent at the
nanoscale, however are able to absorb and reflect UV light, and have found application in
sunscreens. Nanoparticles have a range of potential applications: in the short-term in new
cosmetics, textiles and paints; in the longer term, in methods of targeted drug delivery
where they could be to used deliver drugs to a specific site in the body. Nanoparticles can
also be arranged into layers on surfaces, providing a large surface area and hence
enhanced activity, relevant to a range of potential applications such as catalysts.

b) Quantum Dots

Nanoparticles of semiconductors (quantum dots) were theorized in the 1970s and

initially created in the early 1980s. If semiconductor particles are made small enough,
quantum effects come into play, which limit the energies at which electrons and holes
(the absence of an electron) can exist in the particles. As energy is related to wavelength
(or colour), this means that the optical properties of the particle can be finely tuned
depending on its size. Thus, particles can be made to emit or absorb specific wavelengths
(colours) of light, merely by controlling their size. Recently, quantum dots have found
applications in composites, solar cells (Gratzel cells) and fluorescent biological labels
(for example to trace a biological molecule) which use both the small particle size and
tuneable energy levels. Recent advances in chemistry have resulted in the preparation of
monolayer-protected, high-quality, monodispersed, crystalline quantum dots as small as
2nm in diameter, which can be conveniently treated and processed as a typical chemical
reagent.

1.4 Processing of Nanostructured Materials

A number of processes are used for producing nanomaterials in bulk powders,

coatings, thin films, laminates and composites. The most commonly employed techniques
for synthesizing nanostructured materials include inert gas condensation, mechanical

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alloying, severe plastic deformation, sol-gel technique, thermal spraying,
electrodeposition, jet vapour deposition, sputtering, vacuum thermal
evaporation,chemical vapour deposition, controlled chemical precipitation etc. A brief
description of some of the important techniques used for the synthesis of nanostructured
films is presented in this section.

Nanostructured coatings have primarly been deposited via thermal spraying.

Processes used to fabricate laminates include RF sputtering, DC magnetron sputtering,
chemical vapour deposition, electroplating and physical vapor deposition.

Thermal Spraying:

Thermal spraying is a process capable of producing nanostructured materials and

nanostructured coatings. Control over the composition and structure of the final material
is very important when producing nanostructured materials.

Electrodeposition :

Electrodeposition has traditionally been used as a coating process, although

recently it has also been used to form bulk nanocrystalline materials. The process is
capable of producing nanocrystalline materials with grain size down to 5 nm. The factors
affecting the resulting grain sizes include temperature and current density. The process
can be carried out at room temperature. Compared to other deposition processes,
electrodeposition is capable of rapid deposition. Moreover, electrodeposition is a less
expensive process that can be used to large scale production .

Sputtering:

Sputtering is a well known and widely used technique for producing thin films. It
is a vacuum method capable of producing nanostructured materials.In this technique,
plasma which is generated by energizing a low pressure gas such as argon strikes a target

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transferring its momentum which causes the target material to be ejected and
subsequently deposited on to a substrate. The main disadvantage of the sputtering method
is that it is difficult to control. DC magnetron sputtering and RF diode sputtering have
been used to prepare nanolaminate materials. These methods are capable of depositing
layers of a material with a thickness below 100 nm.3

Vacuum Thermal Evaporation Technique:

The vacuum thermal evaporation deposition technique consists in heating a

material until evaporation of the material takes place. The vapours of the material finally
condense in form of thin film on the cold substrate surface and on the vacuum chamber
walls. Usually low pressures are used, about 10-6 or 10-5 Torr, to avoid reaction between
the vapor and atmosphere. At these low pressures, the mean free path of vapor atoms is
the same order as the vacuum chamber dimensions, so these particles travel in straight
lines from the evaporation source towards the substrate. This originates 'shadowing'
phenomena with 3D objects, especially in those regions not directly accessible from the
evaporation source (crucible). Besides, in thermal evaporation techniques the average
energy of vapor atoms reaching the substrate surface is generally low (order of kT, i.e.
tenths of eV). This affects seriously the morphology of the films, often resulting in a
porous and little adherent material.4

In thermal evaporation techniques, different methods can be applied to heat the

material. The equipments available in the laboratory use either resistance heating (Joule
effect) or bombardment with a high energy electron beam, usually several KeV, from an
electron beam gun (electron beam heating).

Chemical Vapor Deposition:

The process of chemical vapor deposition involves a gas-phase chemical reaction

which forms a solid material on a substrate. Nanostructured ceramics and composites are
the most common types of nanomaterials produced by CVD. Vapors of the precursor
materials are transported by a carrier gas to a heated substrate where they are deposited
and subsequently react with the substrate to form a solid material. Although it is a

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relatively slow process, chemical vapor deposition offers good control over the chemical
composition and is capable of deposition over a large area.

1.5 Applications of Nanomaterials

Below list some key current and potential shorthand long-term applications of
nanomaterials. Most current applications represent evolutionary developments of existing
technologies: for example, the reduction in size of electronics devices.5

Current Applications

a) Sunscreens and Cosmetics

Nanosized titanium dioxide and zinc oxide are currently used in some sunscreens,
as they absorb and reflect ultraviolet (UV) rays and yet are transparent to visible light and
so are more appealing to the consumer. Nanosized iron oxide is present in some lipsticks
as a pigment but it is our understanding that it is not used by the European cosmetics
sector. The use of nanoparticles in cosmetics has raised a number of concerns about
consumer safety.

b) Composites

An important use of nanoparticles and nanotubes is in composites, materials that

combine one or more separate components and which are designed to exhibit overall the
best properties of each component. This multi-functionality applies not only to
mechanical properties, but extends to optical, electrical and magnetic ones. Currently,
carbon fibers and bundles of multi-walled CNTs are used in polymers to control or
enhance conductivity, with applications such as antistatic packaging. The use of
individual CNTs in composites is a potential long-term application. A particular type of
nanocomposite is where nanoparticles act as fillers in a matrix; for example, carbon black
used as a filler to reinforce car tyres. However, particles of carbon black can range from

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tens to hundreds of nanometers in size, so not all carbon black falls within our definition
of nanoparticles.

c) Coatings and Surfaces

Coatings with thickness controlled at the nano- or atomic scale have been in
routine production for some time, for example in molecular beam epitaxy or metal oxide
deposition for optoelectonic devices, or in catalytically active and chemically
functionalized surfaces. Recently developed applications include the self-cleaning
window, which is coated in highly activated titanium dioxide, engineered to be highly
hydrophobic (water repellent) and antibacterial, and coatings based on nanoparticulate
oxides that catalytically destroy chemical agents. Wear and scratch-resistant hard coatings
are significantly improved by nanoscale intermediate layers (or multilayers) between the
hard outer layer and the substrate material. The intermediate layers give good bonding
and graded matching of elastic and thermal properties, thus improving adhesion. A range
of enhanced textiles, such as breathable, waterproof and stain resistant fabrics, have been
enabled by the improved control of porosity at the nanoscale and surface roughness in a
variety of polymers and inorganics.

d) Tougher and Harder Cutting Tools

Cutting tools made of nanocrystalline materials, such as tungsten carbide,

tantalum carbide and titanium carbide, are more wear and erosion-resistant, and last
longer than their conventional (large-grained) counterparts. They are finding applications
in the drills used to bore holes in circuit boards.

Short-term Applications (next 5 years)

a) Paints

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 Incorporating nanoparticles in paints could improve their performance, for
example by making them lighter and giving them different properties. Thinner paint
coatings (‘light weighting’), used for example on aircraft, would reduce their weight,
which could be beneficial to the environment. However, the whole life cycle of the
aircraft needs to be considered before overall benefits can be claimed. It may also be
possible to substantially reduce solvent content of paints, with resulting environmental
benefits. New types of fouling resistant marine paint could be developed and are urgently
needed as alternatives to tributyl tin (TBT), now that the ecological impacts of TBT have
been recognized. Anti-fouling surface treatment is also valuable in process applications
such as heat exchange, where it could lead to energy savings. If they can be produced at
sufficiently low cost, fouling-resistant coatings could be used in routine duties such as
piping for domestic and industrial water systems. It remains speculation whether very
effective anti-fouling coatings could reduce the use of biocides, including chlorine. Other
novel, and more long-term, applications for nanoparticles might lie in paints that change
color in response to change in temperature or chemical environment, or paints that have
reduced infra-red absorptivity and so reduce heat loss.
Concerns about the health and environmental impacts of nanoparticles may require the
need for the durability and abrasion behaviour of nano-engineered paints and coatings to
be addressed, so that abrasion products take the form of coarse or microscopic
agglomerates rather than individual nanoparticles.

b) Remediation

The potential of nanoparticles to react with pollutants in soil and groundwater and
transform them into harmless compounds is being researched. In one pilot study the large
surface area and high surface reactivity of iron nanoparticles were exploited to transform
chlorinated hydrocarbons (some of which are believed to be carcinogens) into less
harmful end products in groundwater. It is also hoped that they could be used to
transform heavy metals such as lead and mercury from bioavailable forms into insoluble
forms. Serious concerns have been raised over the uncontrolled release of nanoparticles
into the environment.

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c) Fuel Cells

Engineered surfaces are essential in fuel cells, where the external surface properties
and the pore structure affect performance. The hydrogen used as the immediate fuel in
fuel cells may be generated from hydrocarbons by catalytic reforming, usually in a
reactor module associated directly with the fuel cell. The potential use of nano-
engineered membranes to intensify catalytic processes could enable higher-efficiency,
small-scale fuel cells. These could act as distributed sources of electrical power. It may
eventually be possible to produce hydrogen locally from sources other than
hydrocarbons, which are the feed stocks of current attention.

d) Displays

The huge market for large area, high brightness, flat-panel displays, as used in
television screens and computer monitors, is driving the development of some
nanomaterials. Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and lead
telluride synthesized by sol–gel techniques (a process for making ceramic and glass
materials, involving the transition from a liquid ‘sol’ phase to a solid ‘gel’ phase) are
candidates for the next generation of light-emitting phosphors. CNTs are being
investigated for low voltage field-emission displays; their strength, sharpness,
conductivity and inertness make them potentially very efficient and long-lasting emitters.

e) Batteries

With the growth in portable electronic equipment (mobile phones, navigation devices,
laptop computers, remote sensors), there is great demand for lightweight, high-energy
density batteries. Nanocrystalline materials synthesized by sol–gel techniques are
candidates for separator plates in batteries because of their foam-like (aerogel) structure,
which can hold considerably more energy than conventional ones. Nickel–metal hydride

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batteries made of nanocrystalline nickel and metal hydrides are envisioned to require less
frequent recharging and to last longer because of their large grain boundary (surface)
area.

f) Fuel Additives

Research is underway into the addition of nanoparticulate ceria (cerium oxide) to

diesel fuel to improve fuel economy by reducing the degradation of fuel consumption
over time.

g) Catalysts

In general, nanoparticles have a high surface area, and hence provide higher catalytic
activity. Nanotechnologies are enabling changes in the degree of control in the production
of nanoparticles, and the support structure on which they reside. It is possible to
synthesize metal nanoparticles in solution in the presence of a surfactant to form highly
ordered monodisperse films of the catalyst nanoparticles on a surface. This allows more
uniformity in the size and chemical structure of the catalyst, which in turn leads to greater
catalytic activity and the production of fewer byproducts. It may also be possible to
engineer specific or selective activity. These more active and durable catalysts could find
early application in cleaning up waste streams. This will be particularly beneficial if it
reduces the demand for platinum-group metals, whose use in standard catalytic units is
starting to emerge as a problem, given the limited availability of these metals.

Longer-term Applications (next 5-15 years)

a) Carbon Nanotube Composites

CNTs have exceptional mechanical properties, particularly high tensile strength and
light weight. An obvious area of application would be in nanotube reinforced composites,
with performance beyond current carbon-fiber composites. One current limit to the

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introduction of CNTs in composites is the problem of structuring the tangle of nanotubes
in a well-ordered manner so that use can be made of their strength. Another challenge is
generating strong bonding between CNTs and the matrix, to give good overall composite
performance and retention during wear or erosion of composites. The surfaces of CNTs
are smooth and relatively unreactive, and so tend to slip through the matrix when it is
stressed. One approach that is being explored to prevent this slippage is the attachment of
chemical side-groups to CNTs, effectively to form ‘anchors’. Another limiting factor is
the cost of production of CNTs. However, the potential benefits of such light, high
strength material in numerous applications for transportation are such that significant
further research is likely.

b) Lubricants

Nanospheres of inorganic materials could be used as lubricants, in essence by

acting as nanosized ‘ball bearings’. The controlled shape is claimed to make them more
durable than conventional solid lubricants and wear additives. Whether the increased
financial and resource cost of producing them is offset by the longer service life of
lubricants and parts remains to be investigated. It is also claimed that these nanoparticles
reduce friction between metal surfaces, particularly at high normal loads. If so, they
should find their first applications in high-performance engines and drivers; this could
include the energy sector as well as transport. There is a further claim that this type of
lubricant is effective even if the metal surfaces are not highly smooth. Again, the benefits
of reduced cost and resource input for machining must be compared against production of
nanolubricants. In all these applications, the particles would be dispersed in a
conventional liquid lubricant; design of the lubricant system must therefore include
measures to contain and manage waste.

c) Magnetic Materials

It has been shown that magnets made of nanocrystalline yttrium–samarium–cobalt

grains possess unusual magnetic properties due to their extremely large grain interface

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area (high coercivity can be obtained because magnetization flips cannot easily propagate
past the grain boundaries). This could lead to applications in motors, analytical
instruments like magnetic resonance imaging (MRI), used widely in hospitals, and micro
sensors. Overall magnetization, however, is currently limited by the ability to align the
grains’ direction of magnetization.

Nanoscale-fabricated magnetic materials also have applications in data storage.

Devices such as computer hard disks depend on the ability to magnetize small areas of a
spinning disk to record information. If the area required to record one piece of
information can be shrunk in the nanoscale (and can be written and read reliably), the
storage capacity of the disk can be improved dramatically. In the future, the devices on
computer chips which currently operate using flows of electrons could use the magnetic
properties of these electrons, called spin, with numerous advantages. Recent advances in
novel magnetic materials and their nanofabrication are encouraging in this respect.

d) Medical Implants

Current medical implants, such as orthopaedic implants and heart valves, are made of
titanium and stainless steel alloys, primarily because they are biocompatible.
Unfortunately, in some cases these metal alloys may wear out within the lifetime of the
patient. Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant, bio-corrosion
resistant and bio-compatible. It therefore presents an attractive alternative material for
implants. It and other nanoceramics can also be made as strong, light aerogels by sol–gel
techniques. Nanocrystalline silicon carbide is a candidate material for artificial heart
valves primarily because of its low weight, high strength and inertness.

e) Machinable Ceramics

Ceramics are hard, brittle and difficult to machine. However, with a reduction in grain
size to the nanoscale, ceramic ductility can be increased. Zirconia, normally a hard, brittle
ceramic, has even been rendered superplastic (for example, able to be deformed up to

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300% of its original length). Nanocrystalline ceramics, such as silicon nitride and silicon
carbide, have been used in such automotive applications as high-strength springs, ball
bearings and valve lifters, because they can be easily formed and machined, as well as
exhibiting excellent chemical and high-temperature properties. They are also used as
components in high-temperature furnaces. Nanocrystalline ceramics can be pressed into
complex net shapes and sintered at significantly lower temperatures than conventional
ceramics.

f) Water Purification

Nano-engineered membranes could potentially lead to more energy-efficient water

purification processes, notably in desalination by reverse osmosis. Again, these
applications would represent incremental improvements in technologies that are already
available. They would use fixed nanoparticles, and are therefore distinct from
applications that propose to use free nanoparticles.

g) Military Battle Suits

Enhanced nanomaterials form the basis of a state-of- the-art ‘battle suit’ that is being
developed by the Institute of Soldier Nanotechnologies at MIT. A short-term
development is likely to be energy-absorbing materials that will withstand blast waves;
longer-term are those that incorporate sensors to detect or respond to chemical and
biological weapons (for example, responsive nanopores that ‘close’ upon detection of a
biological agent). There is speculation that developments could include materials which
monitor physiology while a soldier is still on the battlefield, and uniforms with potential
medical applications, such as splints for broken bones.

1.6 Present work

Nanostructured films with morphological features in the nanometer range and

structured assemblies of nanometer sized particles are remarkable sets of nanomaterials

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with enormous technological potential. In the present work nanostructured copper oxide
films were prepared by the oxidation of thin films of copper deposited on glass substrates
through thermal evaporation. Thermal oxidations of the samples were done in a furnace
at 350oC for different time intervals viz 45 minutes, 1hr 15 minutes and 1 hr 45 minutes.
Structural characterizations of the samples were done by powder X-ray diffraction, and
morphological characterization was done with AFM. UV-Visible and photoluminescence
spectroscopic studies were employed for optical characterization. DC electrical
measurements of the sample oxidized at 350 oC for different time intervals were carried
out in a home made evacuable conductivity cell. DC electrical resistance of the sample
was measured using a KEITHLEY source meter model 2400.

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References:

1 Federico Rosei, J . Phys. Condens. Matter. 16, 373 (2004).

2 L. E. Brus, J. Chem. Phys. 80, 4403(1984).
3 C Suryanarayana, Bull.Mater.Sci.17, 307 (1994).
4 “http:// en Wikipedia.org/wiki/evaporation.
5 www.nanowerk.com or www.fluigent.com.

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 CHAPTER 2

PREPARATION AND CHARACTERIZATION OF

NANOSTRUCTURED CUPRIC OXIDE THIN FILMS

2.1 Introduction

Physical properties of nanomaterials have been a subject of intense scrutiny over

the past two decades because of the scientific and technological interest on the grain size
dependence of these properties.1 Nanostructured semiconductors have been of special
interest to scientific community due to the immense possibilities the phenomenon of
quantum confinement of charge carriers has opened up for tuning their electrical and
optical properties. Several semiconductors have been synthesized in the form of quantum
dots and also in the form of thin films, and the various properties exhibited by them have
been studied in comparison with those of their bulk counterparts.2 Nanostructured films
with morphological features in the nanometer range and structured assemblies of
nanometer sized particles are remarkable sets of nanomaterials with enormous
technological potential. Much attention has been focused on the synthesis and
characterization of nanostructured semiconductor systems because of the potential
research application of semiconductor nanoparticles in various fields like chemical
sensors, microelectronics, imaging science etc.3 The shape, crystalline structure, and size
of semiconductors are important elements in determining their physical and chemical
properties.4 Thus, rational control over these elements has become a hot topic in recent
material research fields.5 Specifically, for the past few years, various efforts have been
developed to control the architecture and spatial patterning of metal oxide semiconductor
particles.
Copper forms two well known oxides: cuprite (Cu2O) and tenorite (CuO)
(Richthofen et al 1997). A metastable copper oxide, paramelaconite (Cu4O3), which is an
intermediate compound between the previous two, has also been reported (Li et al 1991).
While Cu2O forms a cubic structure with a lattice parameter of 4.27 Å, the Cu4O3 bears a

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tetragonal structure having lattice parameters: a = 5.837 Å and c = 0.9932 Å. In CuO,
units of CuO2 are chained and Cu forms four coplanar bonds with oxygen (Ohya et al
2000). Amongst the mono oxides of 3d transition series elements, CuO is unique as it has
a square planar coordination of copper by oxygen in the monoclinic structure. The lattice
parameters of CuO are a = 4.684 Å, b = 3.425 Å, c = 5.129 Å and b = 99.28° (Lanke and
Vedawyas1999). The crystal structure of Cu2O is cubic and mostly exhibits p-type
semiconductor characteristics since it has a band gap of 2.0 eV.6
CuO has a monoclinic crystal structure and presents p-type semiconductor
behavior.7 CuO is an interesting candidate in the applications of solar energy converting
devices, gas sensors and superconducting devices.8 CuO is attractive as a selective solar
absorber since it has high solar absorbency and a low thermal emittance (Yoon et al
2000). Furthermore, it is a promising semiconductor for solar cell fabrication due to its
suitable optical properties (Oral et al 2004). It also possesses an incommensurate
antiferromagnetic structure below the Neel temperature of 230 K, which is quite unusual
(Eliseev et al 2000). In some recent reports, CuO has shown high temperature
superconductivity as well, where the specific coordination between Cu and O atoms play
a crucial role (Ray et al 2001). Due to the existence of copper vacancies in the structure,
CuO exhibits native p-type conductivity (Jeong and Choi 1996). Its band gap is reported
to be between 1.3 and 1.7 eV with a black colour and a partial transparency in the visible
range (Ohya et al 2000). Its valence band is reported to lie at 5.42 eV below the vacuum
level and is made up mainly from Cu2+–3d wave functions. Similarly the conduction band
reportedly lies at 4.07 eV below vacuum level. An Oxygen –2P type band is also present
at 7.33 eV below vacuum level (Koffyberg and Benko 1982). CuO is readily available
and nontoxic and this makes it even more attractive for different applications (Oral et al
2004).9 The tentative energy band diagram of CuO is shown in figure 1.9

21
FIG 2.1 Energy band diagram of CuO.

2.2 Experimental details

2.2.1 Preparation of nanostructured cupric oxide thin films

Copper oxide can be prepared by many techniques. These are listed as the thermal
oxidation method, reactive magnetron sputtering, reactive evaporation, sol-gel method
and chemical depositions. The deposition conditions and techniques play a major role in
the physical properties of copper oxide thin films.6 In the present work nanostructured
copper oxide films were prepared by the oxidation of grainy thin films of copper
deposited on soda lime glass substrates through thermal evaporation. Glass substrates
were cleaned with detergent, etched for 5 minutes in dilute nitric acid, degreased with
methanol, and ultrasonically cleaned with acetone before deposition. Thin films of copper
were deposited on the substrate by thermal evaporation technique. Deposition of the films
were carried out not at high vacuum but at an appreciably high pressure of 3×10‾² Pa to
ensure that the copper films deposited were of granular morphology and there by the final
copper oxide films were truly nanostructured having fine grain size. Thermal oxidations

22
of these samples were done in a furnace at 350oC for different time intervals viz 45
minute, 1 hr 15 min, 1 hr 45 min.
XRD patterns of the copper oxide films were recorded using X’Pert software in the
2θ range of 10-70o. The thickness of the sample was measured using Veeco Dektak
thickness profilometer. The average thickness of the film samples was estimated to be
110 nm. UV-Visible transmission spectra were recorded using JASCO V-650
spectrophotometer and photoluminescence spectra using HITACHI F-7000 fluorescence
spectrophotometer.

2.2.2 X-ray diffraction

X-rays are electromagnetic radiation with typical photon energies in the range of
100 eV - 100 keV. For diffraction applications, only short wavelength x-rays (hard x-
rays) of wavelength in the range of a few angstroms to 0.1 angstrom (1 keV - 120 keV)
are used. Because the wavelength of x-rays is comparable to the size of atoms, they are
ideally suited for probing the structural arrangement of atoms and molecules in a wide
range of materials. The energetic x-rays can penetrate deep into the materials and provide
information about the bulk structure. X-rays are produced generally by either x-ray tubes
or synchrotron radiation. In a x-ray tube, which is the primary x-ray source used in
laboratory x-ray instruments, x-rays are generated when a focused electron beam
accelerated across a high voltage field bombards a stationary or rotating solid target. As
electrons collide with atoms in the target and slow down, a continuous spectrum of x-rays
are emitted, which are termed Bremsstrahlung radiation. The high energy electrons also
eject inner shell electrons in atoms through the ionization process. When a free electron
fills the shell, an x-ray photon with energy characteristic of the target material is emitted.
Common targets used in x-ray tubes include Cu and Mo, which emits 8 keV and 14 keV
x-rays with corresponding wavelengths of 1.54 Å and 0.8 Å, respectively.

X-ray analysis is widely used for structure characterization of nanostructured

materials synthesized through various methods. This powerful tool of material
characterization yields statistically averaged information on a number of parameters such

23
as grain size, micro distortion, texture, static and dynamic displacements, and lattice
parameters and so on.
X-ray diffraction is the most versatile tool for the investigation of the crystal
structure of materials and for the study of phase equilibrium and for measurement of
particle size.10

For a perfect crystal the condition for diffraction is given by Bragg’s law, ie

2dsinθ = nλ

where d is the interplanar spacing , θ is the angle of diffraction and λ is the wavelength of
x-ray radiation used.

The broadening of x-ray diffraction line is primarily a measure of the departure from
the single crystal perfection and regularity in the specimen. Thus, inaddition to the small
size, lattice strain, dislocations, impurities and other defects lead to the line broadening.
Neverthless as the only method , which gives the size of primary crystallites irrespective
of how they are aggregated or sintered. X-ray diffraction broadening is of great value
with nanocrystalline materials.

The grain size of the sample can be found out from x-ray diffraction pattern using
Scherrer equation.10 Scherrer equation is

D = 0.9λ/βCosθ

where D is the crystallite size, λ is the wavelength of x-ray used, β is the full width at half
maximum and θ is the diffraction angle.

24
2.2.3 Atomic force microscopy

Typically, when we think of microscopes, we think of optical or electron

microscopes. Such microscopes create a magnified image of an object by focusing
electromagnetic radiation, such as photons or electrons, on its surface. Optical and
electron microscopes can easily generate two-dimensional magnified images of an
object’s surface, with a magnification as great as 1000X for an optical microscope, and as
large as 100,000X for an electron microscope. Although these are powerful tools, the
images obtained are typically in the plane horizontal to the surface of the object. Such
microscopes do not readily supply the vertical dimensions of an object’s surface, the
height and depth of the surface features.

Unlike traditional microscopes, the AFM does not rely on electromagnetic

radiation such as photon or electron beams to create an image. An AFM is a mechanical
imaging instrument that measures the three dimensional topography as well as physical
properties of a surface with a sharpened probe.

FIG 2.2 In the AFM, a sharp probe is scanned across a surface, left, and by
monitoring the motion of the probe from each pass across the surface, a 2-D
line profile is generated. Then the line profiles are combined to create a three
dimensional image of the surface, right.

25
 The sharpened probe is positioned close enough to the surface such that it can
interact with the force fields associated with the surface. Then the probe is scanned across
the surface such that the forces between the probe remain constant. An image of the
surface is then reconstructed by monitoring the precise motion of the probe as it is
scanned over the surface. Typically the probe is scanned in a raster like pattern.

In an AFM the probe is very sharp, typically less than 50 nanometers in diameter
and the areas scanned by the probe are less than 100 μm. In practice the heights of
surface features scanned with an AFM are less than 20 um. Scan times can range from a
fraction of a second to many 10’s of minutes depending on the size of the scan and the
height of the topographic features on a surface. Magnifications of the AFM may be
between 100 X and 100,000,000 X in the horizontal(x-y) and vertical axis. Figure 1-2
illustrates the block diagram of an atomic force microscope. In the microscope, the force
between a nanoscopic needle and the surface is measured with a force sensor, the output
of the force sensor is then sent to a feedback controller that then drives a Z motion
generator. The feedback controller uses the force sensor output to maintain a fixed
distance between the probe and the sample. X-Y motion generators then move the probe
over the surface in the X and Y axis. The motion of the probe is monitored and used to
create an image of the surface.

26
 FIG 2.3 Basic block diagram of an AFM

The force sensor in an atomic force microscope is typically constructed from a

light lever, In the light lever, the output from a laser is focused on the backside of a
cantilever and reflected into a photo-detector with two sections. The output of each of the
photo-detector sections is compared in a differential amplifier. When the probe at the end
of the cantilever interacts with the surface, the cantilever bends, and the light path
changes causing the amount of light in the two photo-detector sections to change. Thus
the electronic output of the light lever force sensor, So, is proportional to the force
between the probe and sample.

Although the AFM is capable of extreme magnification, it is not a large

instrument. An AFM that is capable of resolving features as small as a few nanometers
can be easily installed in a laboratory on a desk top. The greatest deterrent to high
magnification with the AFM is often environmental vibrations that cause the probe to
have unwanted vibrations.
Although the AFM is an amazing instrument for visualizing and measuring
nanometer scale features, it has several characteristics that make it unique. They are:

a) Built-in, Atomic-scale Sensitivity - Most measuring instruments become larger when

greater sensitivity is required. With an AFM the sensitivity is built-in at the nanometer or
atomic scale. Thus to make the instrument more sensitive, there is no need to make it
larger.
b) Fabrication Technology – An AFM may be used for rapidly making changes in surface
structures at the nanometer scale. Such changes can be made for the fraction of the
amount it would cost with traditional technologies such as e-beam or photolithography. c)
c) Motion Control – Precise motion control technology is required to accurately scan and
position the probe in an AFM at the nanometer scale. Such accurate motion control
technology allows cost effective motion control at a level not achievable with other
methods. These three unique characteristics may be applied to other technological and
scientific areas such as data storage, genetic engineering and nanorobotics.

27
2.2.4 UV-Visible spectroscopy

UV-Visible spectroscopy is widely used for understanding the quantum

confinement effect in nanostructured materials. UV absorption spectra can also be used
for calculating the optical band gap of semiconductor nanostructured materials.
As the wave function of electrons and holes in crystals are confined to nanometric
dimensions, the structure of their electronic levels and the resultant optical and electrical
properties are greatly modified. Upon reducing the size of a semiconductor to
nanometers, a characteristic blue shift of the band gap appears as a result of the quantum
size effect in these quantum structures .The most striking effect in semiconductor
nanoparticles is the widening of the band gap Eg between the highest occupied electronic
states and the lowest unoccupied states.
The most direct method for probing the band structure of semiconductor is to
measure the absorption spectrum. In the absorption process, a photon of known energy
excites an electron from a lower to a higher energy state. By studying the absorption
spectra, we can have all the possible transitions an electron can make and learn much
about the distribution of energy states. The possible transitions of electrons in a crystal
are band to band, between sub bands, between impurities and band and excitonic
transitions. The fundamental absorption refers to the transition of electrons between band
to band and excitonic transitions. The fundamental absorption which manifests itself by a
rapid rise in the absorption spectra can be used to determine the energy gap of the
semiconductors.
The relation between absorption coefficient (α) and incident energy (hν) can be
written as
αhν = A(hν-Eg)ⁿ

28
 The above relation is called Taue relation in which A is a constant, Eg is the band gap
of the material. The value of the exponent ‘n’ depends on the type of transition .If the
transition is allowed direct n=1/2, for allowed indirect n=2, for forbidden direct n=3/2
and for forbidden indirect n=3.

After calculating absorption coefficient α ,the nature of the transition can be

determined by plotting d{ln(αhν)}/dhν verses hν. It will give a divergence at an energy
value equal to E1 where the transition take place. The slope of the plot ln(αhν) verses (hν-
Eg) will give the value of n1.The exact value of the band gap can be determined by
plotting (αhν)1/n verses hν graph and extrapolating the straight line portion of the graph to
hν axis.

The optical band gap of the films has been determined on the basis of UV-Visible
transmission measurements. The optical absorption coefficient (α) in the fundamental
absorption region was evaluated using the equation6:

α = (ln1/T)/t;

where ‘t’ is the film thickness and T is the transmittance.

The optical band gap of the film sample was determined based on the equations
reported by Pankove. For Cu2O which has a direct band gap, α is given by

α = A(hν-Eg)½;

On the other hand, for indirect transitions of CuO, α is given by

α = A(hν-Eg±Ep)²

Here A is a constant, Eg is the optical band gap and Ep is the energy of the absorbed (+)
or emitted (-) phonons. The value of Ep is neglected for the present calculations.

29
2.2.5 Photoluminescence spectroscopy

In order to understand the concept of a gap in energy, first consider that some of the
electrons in a solid are not firmly attached to the atoms, as they are for single atoms, but
can hop from one atom to another. These loosely attached electrons are bound in the solid
by differing amounts and thus have much different energy. Electrons having energies
above a certain value are referred to as conduction electrons, while electrons having
energies below a certain value are referred to as valence electrons. This is shown in the
diagram where they are labeled as conduction and valence bands. The word band is used
because the electrons have a multiplicity of energies in either band. Furthermore, there is
an energy gap between the conduction and valence electron states. Under normal
conditions electrons are forbidden to have energies between the valence and conduction
bands.

FIG 2.4 Process of luminescence

30
 If a light particle (photon) has energy greater than the band gap energy, then it can
be absorbed and thereby raise an electron from the valence band up to the conduction
band across the forbidden energy gap. In this process of photo excitation, the electron
generally has excess energy which it loses before coming to rest at the lowest energy in
the conduction band. At this point the electron eventually falls back down to the valence
band. As it falls down, the energy it loses is converted back into a luminescent photon
which is emitted from the material. Thus the energy of the emitted photon is a direct
measure of the band gap energy, Eg. The process of photon excitation followed by photon
emission is called photoluminescence. PL-experiments provide relatively direct
information about recombination and relaxation processes. In general, these experiments
are useful for the investigation of the electronic properties of the excited state and offer
several advantages over other optical techniques.

The technique of photoluminescence (PL) has become a standard one for obtaining
information on the nature of nanostructures such as quantum dots, nanowires, quantum
wells etc. This characterization method has been used to study many properties of
nanomaterials such as optical band gap behavior, quantum confinement effects,
impurities, strain etc. As the size of the nanoparticle is decreased so that it becomes
smaller than bulk exciton radius, quantum confinement effects sets in, and the band gap is
increased. This results in an increase in the PL peak energy with in the quantum confined
nanoparticles. The smaller the effective mass of charge carriers, the larger the quantum
confinement effects .The shift in the PL peak energy as a function of particle size can be
analysed using an effective mass approximation model just like for optical absorption
peak.

Photoluminescence is directly related to the electronic structure and transition of

charge carriers. Difference in behaviour between bulk and low dimensional
semiconductors arises due to the difference in electro density of states, g(E). For eg g(E)
of bulk semiconductor has continuous dependence of energy E as g(E) ~ E ½, where as in
two dimensional semiconductors it has a step like dependence on energy.11 In 1D
semiconductor structures it diverges as E‾½ and for zero dimensional semiconductors it is

31
a delta function of energy. In semiconductors, the electrons in the valence band absorb
photons and are lifted into the conduction band, leaving holes in the valence band .In a
bulk sample ,the excitation of valence electrons occurs provided ћωi ≥ Eg, where Eg is
the band gap of the semiconductor and ωi is the frequency of the incident photon. Some
of these excited electrons lose their energy by non radiative transition process. Usually
the lowest levels are seen in the photoluminescence spectrum and the emitted
photoluminescence frequency ωPL satisfies ωPL < ωi. Thus the frequency of
photoluminescence peak (ωo) of a bulk semiconductor corresponds to its band gap.
Because of the quantization of energy levels in the conduction band and valence band in
the low dimensional systems, the frequency of photoluminescence emission, ωPL
corresponds to the transition of excited electrons from the lowest state in the conduction
band to the lowest state in the valence band. Because ωPL < ω0, the photoluminescence
peak in low dimensional systems blue shift from that in the corresponding bulk material.
The change of band gap with decrease in size of the nanostructures can be studied from
the blue shift in the photoluminescence peak position. PL is useful in the study of
quantum confinement of electrons in low dimensional materials. Due to the change in
band gap some nanomaterials can have tunable light emission, where the tuning depends
on the size of the system. PL spectroscopy also yields information on the surface state
density from the intensity variations and the width of emission peaks in the PL spectrum.
Surface states are caused by the interruption of the periodic arrangement of the atoms and
by deposition of impurities at the surface. Because of the large surface to volume ratio of
nanoparticles, these effects are more pronounced in nanoparticles. Thus PL spectroscopy
offers a tool for improving our understanding of semiconductor surfaces.

32
2.3 Results and discussion

2.3.1 X-ray analysis

180

160
(200)
intensity (arb.units)

140
(-111)

120

100

80

60

40

20

30 40 50 60 70

2θ (degrees)

FIG 2.5 XRD pattern of the sample annealed at 350oC for 45 min

33
 140

120

intensity (arb.units)
100

80

60

(200)
(-111)

40

20

30 40 50 60 70

2θ (degrees)

FIG 2.6 XRD pattern of the sample annealed at 350oC for 1 hr 15 min

140

120
intensity (arb.units)

100

80
(-111)

60
(200)

40

20

30 40 50 60 70
2θ (degrees)

FIG 2.7 XRD pattern of the sample annealed at 350oC for 1hr 45 min

34
 XRD patterns of the copper oxide films annealed at 350 oC for different time
intervals are shown in fig (2.5 -2.7). The patterns in fig (2.5 – 2.7) show only one or two
diffraction lines while the powder diffraction files corresponding to CuO phases of
copper oxide contain data for a number of lines. For CuO sample oxidized at 350 oC for
45 min, the peak observed at 2θ =35.566 and 38.753 corresponding to the reflections
from (-111) and (200) planes respectively of CuO phase.
In the XRD pattern of the sample annealed at 350 oC for 45 min, only the two peaks
associated with CuO phase are present. This showed that the film oxidized at 350oC is of
pure CuO phase. The average crystallite size was determined employing the Scherrer
equation 10 and was found from the (200) peak of CuO phase to be 15.9 nm. Similarly in
the XRD pattern of the sample annealed at 350oC for 1 hour 15 minutes the peak
observed at 2θ = 35.354 and 38.541 corresponding to the reflections from (-111) and
(200) planes respectively of CuO phase. In the figure the (200) peak is more intense than
the (-111) peak, while the (-111) is the strongest peak in the ICDD file for CuO phase.
And for CuO sample annealed at 350oC for 1 hour 15 minutes, the average crystallite size
found from the (200) peak of CuO phase was 18.15 nm. The XRD pattern of the sample
oxidized at 350oC for 1hour 45minutes shows less intense peaks at 2θ = 35.242 and
37.966 corresponding to the reflections from (-111) and (200) planes respectively of CuO
phase .
Grain growth occurs in polycrystalline materials to decrease the interfacial energy.
Since nanocrystalline materials have a highly disordered large interfacial component (and
hence they have a high surface free energy), the driving force for grain growth is high.
However, contrary to the expectations, experimental observations suggest that the grain
growth in nanocrystalline materials, prepared by almost any method, is very negligible up
to a reasonably high temperature.12

Grain growth studies in nanocrystalline materials were conducted by observing the

grain size as a function of time at different temperatures, using direct microscopic
observations (Hofler and Averback 1990; Boylan et al 1991; Ganapathi et al 1991), or
estimated from X-ray diffraction peak broadening values.12 In the present study a very
small amount of grain growth was observed in CuO upon annealing at 350oC for 1hour

35
15minutes. It is in agreement with the results reported by J.W Mayer et al that CuO phase
nucleates randomly and rapidly in both Cu2O and Cu4O3 matrices. The small grain growth
rate of CuO suggests that nucleation rather than grain growth is the predominant event
during oxidation.13

2.3.2 AFM analysis

FIG 2.8 AFM image of the sample oxidized at 350oC for 45 min

36
FIG 2.9 AFM image of the sample oxidized at 350oC for 1 hr 15 min

37
FIG 2.10 AFM image of the sample oxidized at 350oC for 1 hr 45 min

Fig (2.8 – 2.10) shows the 1 μm×1 μm AFM image of the sample oxidized at 350 oC for
different time intervals. Figure shows that the surface of the samples were composed of
agglomerated grains. Also a grain size distribution was observed from the AFM images.
With increasing oxidation time, an increase in the number of grains was observed rather
than agglomeration of grains. The AFM images also shows pores of dimensions of the
order of nanometer indicating that the films are nanoporous.

2.3.3 UV-Visible analysis

UV-Visible transmission spectra of the samples oxidized at 350 oC for different time
intervals are shown in fig. In the case of CuO a linear fit is obtained by plotting (αhν)½
verses hν.14 The value of Eg was determined from the intercept of the line to the linear
portion of the curve with the abscissa. The observed value of Eg for the film samples
composed mainly of CuO phase is shown in fig2.12, fig 2.14 and fig 2.16.

38
 Sample Band gap (eV)

Annealed for 45 min 2.6

Annealed for 1 hr 15 min 2.5

Annealed for 1 hr 45 min 2.48

From UV-Visible transmission measurement a decrease in the band gap energy was
observed. Compared to the bulk band gap values of CuO (1.3-2.1 eV)15, the band gap of
the film sample in the present study show considerable blue shift even though they have
large grain size. Noack and Eychmuller have reported a blue shift of the absorption edge
of ZnO thin films consisting of particles of size 10 nm while the Bohr exciton radius of
ZnO is about 1 nm. They have explained this contradiction by the assumption that the
real volume accessible for the exciton is smaller than the actual geometric size of the
crystallites.

39
 80

70
Transmittance (%)
60

50

40

30

20

10

-10
200 300 400 500 600 700 800 900 1000

wavelength (nm)

FIG 2.11 Transmittance spectra of the sample annealed at 350oC for 45 min

40
 20000000

(eV/cm )
-1/2 10000000

-10000000
1/2
(α hν )

-20000000

-30000000

-40000000
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

hν (eV)

FIG 2.12 (αhν)½ verses photon energy (hν) for the sample oxidized at 350oC for 45 min

41
 70

60
Transmittance (%)
50

40

30

20

10

200 300 400 500 600 700 800 900 1000

wavelength (nm)

FIG 2.13 Transmittance spectra of the sample annealed at 350oC for 1 hr 15 min

42
 8.00E+007

(eV/cm ) 6.00E+007
-1/2

4.00E+007
1/2

2.00E+007
(α hν)

0.00E+000

-2.00E+007

-4.00E+007
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

hν (eV)

FIG 2.14 (αhν)½ verses photon energy (hν) for the sample oxidized at 350oC for 1 hr 15
min

43
 70

Transmittance (%) 60

50

40

30

20

10

-10
200 300 400 500 600 700 800 900 1000

wavelength (nm)

FIG 2.15 Transmittance spectra of the sample annealed at 350oC for 1 hr 45 min

44
 8.00E+007

(eV/cm )
-1/2 6.00E+007

4.00E+007

2.00E+007
1/2
(αhν)

0.00E+000

-2.00E+007

-4.00E+007
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4

hν (eV)

FIG 2.16 (αhν)½ verses photon energy (hν) for the sample oxidized at 350oC for 1 hr 45
min
2.3.4 PL analysis

The PL spectra of samples annealed at 350oC for different time intervals are shown
in figure (2.17 – 2.19). For all the three samples the peak positions are same. All the PL
spectra in the visible region composed of two major components. For excitation
wavelength 400 nm, the peak observed in the visible region at around 485 nm and 514
nm is associated with the near band emission, while a broad band with luminescence
peaks in the red region is related to different active trapping centers. Rohana Garuthara et
al 15 reported that the defect state emission is due to the dominant intrinsic defect ie due to
the copper vacancies. The copper vacancies creates a donor energy level below the
bottom of the conduction band. As a result, this donor level act as a center for PL
emission.

45
 From the PL spectra, there were some changes in the intensities of the peaks were
observed. It was observed that the change in intensity is not regular with annealimg
treatment. In the present study the intensity was found highest for the sample annealed at
350oC for 1 hr 15 min. The irregularity of the change of PL intensity with increasing
grain size is reported in the case of TiO2.16 It is known that annealing treatments can cause
the reduction of surface states due to the increase of grain size. Accordingly the PL
intensity should decrease upon annealing. However, the defect inside the grains can
migrate into the grain surface regions during annealing. This would increase the number
of surface states thus leading to PL enhancement to some extent. Therefore the PL
intensity can be affected by both grain sizes and annealing treatments. Taking these two
effects into account it is possible for the PL intensity to change irregularly with annealing
treatment.16

46
 700

600

500
intensity (arb.units)

400
485
514
300

200 603

100

0
450 500 550 600 650 700

wavelength (nm)

FIG 2.17: PL spectra of the sample annealed at 350oC for 45 min for excitation
wavelength 400 nm

47
 700

485
intensity (arb.units) 600 514

500

400
603

300

200

100

0
450 500 550 600 650 700
wavelength (nm)

FIG 2.18: PL spectra of the sample annealed at 350oC for 1 hr 15 min for excitation
wavelength 400 nm

48
 500

450

400
485
intensity (arb.units)

350 514
300

250
603
200

150

100

50

0
450 500 550 600 650 700
wavelength (nm)

FIG 2.19 PL spectra of the sample annealed at 350oC for 1 hr 45 min for excitation
wavelength 400 nm

49
2.4 Conclusion
In the present work nanostructured copper oxide films were prepared by the
oxidation of grainy thin films of copper deposited on soda lime glass substrates through
thermal evaporation. Characterisations of the samples were done using powder X-ray
diffraction, Atomic force microscopy, UV–Visible and photoluminescence
spectroscopies.

50
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51
 CHAPTER 3
ELECTRICAL PROPERTIES OF NANOSTRUCTURED
CUPRIC OXIDE THIN FILMS

3.1 Introduction

Nanocrystalline materials with particle size smaller than 100 nm exhibit many
special characteristics not found in conventional bulk materials, because of their small
particle size and large specific surface area.1 In tandem with surface area effects, quantum
effects can begin to dominate the properties of matter as the size is reduced to the
nanoscale. These can affect the optical, electrical and magnetic behaviour of materials,
particularly as the particle size approaches the smaller end of the nanoscale. The
electrical properties of consolidated nanoparticles of semiconductors show large
deviation from those of their single crystalline or bulk polycrystalline counterparts. These
variations in the electrical properties are a result of the band structure modification,
quantum confinement of charge carriers and dominant contribution from the largely
defective and strained grain boundaries in nanostructured materials. The electronic
properties of polycrystalline semiconductor films have been studied for many years
because of the increasing applicability of these materials in integrated circuits and low
cost solar cells.2 It is well known that the electrical properties of a polycrystalline
semiconductor differ from those of the bulk material because of grain boundaries.
Extensive work in the past ( Kamins 1971, Seto 1975, Anderson 1976, Baccarani 1978 )
has established that the boundaries between grain play an important role in determining
the conductivity of polycrystalline films. According to the grain boundary trapping theory
( Seto 1975 ), free carriers are trapped by trapping states at the boundary.2 Therefore the
grain region next to the boundary becomes depleted and because of the space charge, an

52
energy barrier exists between adjacent grains. The electrical conduction is limited by the
barriers if the voltage drop in the bulk grain is negligible compared with the voltage drop
in the barrier, in this case the film conductivity is

σ = LJ/V;

L being the grain size, J the current density and V the voltage drop in the barrier.

Furthermore, if thermionic emission of carriers over the barrier is the predominant

transport mechanism, theory predicts an Arrhenius behaviour of conductivity since

J = V qA*T/k exp (-φB – EF/kT)

A* being effective Richardson constant, k the Boltzmann constant,φB the energy barrier
height and EF the Fermi level.

This model has been used to explain most of the transport properties of
polycrystalline semiconductors. Among the various polycrystalline semiconductor films
of technological importance, CdS has been widely investigated in the literature. It has
been found experimentally that in heavily indium – doped CdS films tunneling transport
of carriers through the potential barriers may become predominant at low temperatures
(T< 170 K), while in lightly doped films conduction is mainly due to thermionic emission
over the intergrain barriers.

Although the material of CuO is a typical and common semiconductor, we have

poor knowledge about this material than one expects. With the progress of studies on the
high -TC copper oxides in recent years, however, CuO has attracted attention as one of the
simplest and most fundamental host material. Recently it has been indicated that CuO has
strong electron correlation effects on the basis of the results of the energy band structure
calculations. Thus CuO has been observed with keener interest than ever. Neverthless
there has been only a few reports available on the electrical conductivity, except in the

53
vicinity of room temperature. It is reported that CuO is a p–type semiconductor and its
activation energy changes in the vicinity of the Neel temperature. Because of difficulties
in conductivity measurement owing to its high impedance, no detailed report is available
on the electrical conductivity of CuO at lower temperature.3

Gas sensors are important due to the stringent air pollution regulations and
requirement of the industry. The most popular sensor is the metal oxide semiconductor
(MOS) type because of their low response time. The traditional MOS sensors are made of
thin films.1 The metal oxide semiconductor based gas sensors can detect various gases
and the gas sensing property can be studied by using the conductivity changes of their
surfaces due to the adsorption and desorption of gases.4 Gas sensors interact with a gas to
initiate the measurement of its concentration. The gas sensor then provides an output to
the gas sensing instrument to display the measurements. Common gases measured by gas
sensors include ammonia, arsine, bromine, carbon dioxide, carbon monoxide, chlorine,
fluorine, halocarbons or refrigerants, hydrocarbons, hydrogen, hydrogen chloride,
hydrogen cyanide, hydrogen fluoride, hydrogen selenide, hydrogen sulfide, mercury
vapor, nitrogen oxides, oxygen, ozone, sulfur dioxide, water vapor etc.

Important measurement specifications to consider when looking for gas sensors

include the response time, the distance, and the flow rate. The response time is the
amount of time required from the initial contact with the gas to the sensors processing of
the signal. Distance is the maximum distance from the leak or gas source that the sensor
can detect gases. The flow rate is the necessary flow rate of air or gas across the gas
sensor to produce a signal.

In the present work nanostructured copper oxide films were prepared by the
oxidation of grainy thin films of copper deposited on soda lime glass substrates through
thermal evaporation. Glass substrates were cleaned with detergent, etched for 5 minutes
in dilute nitric acid, degreased with methanol, and ultrasonically cleaned with acetone
before deposition. Thin films of copper were deposited on the substrate by thermal
evaporation technique. Deposition of the films were carried out not at high vacuum but at

54
an appreciably high pressure of 3×10‾² Pa to ensure that the copper films deposited were
of granular morphology and there by the final copper oxide films were truly
nanostructured having fine grain size. Thermal oxidations of these samples were done in
a furnace at 350oC for different time intervals viz 45 minute, 1 hr 15 min, 1 hr 45 min.

3.2 Experimental Details

. For electrical measurements, the cupric oxide samples were coated with
silver paint, for electroding purpose. The electrode separation was about 1 mm. The
sample is heated at 100oC for 10 minutes for electrode curing.

The DC electrical measurements were carried out in a home made evacuable

conductivity cell. Before taking the actual measurement each sample was subjected to a
thermal run between 50oC and 200oC. Before measuring the DC electrical measurement
of the sample the V-I measurements were performed to check the electrical contents in
the sample were of ohmic. The DC electrical resistance, R, of the sample was measured
using a KEITHLEY source meter model 2400 by applying a constant source voltage. The
resistance of the sample was measured at different temperatures between 50oC and 200oC
keeping each temperature constant within ± 1K. Measurement of electrical resistance was
carried out for the three samples heat treated at 350oC for different time intervals namely
45 minutes, 75 minutes and 105 minutes. Measurement of electrical resistance of the
samples annealed at 350oC for 45 minute and 1 hour 45 minute was carried out in both air
and vacuum. Resistance, R of the sample was calculated using the equation R = V/I.

Sheet resistance ρ of the film sample = Rbt/l;

where b is the breadth, t the thickness and l length of the film sample.

The electrical conductivity of the sample can be given as the reciprocal of the
measured resistivity of the copper oxide sample.ie,

55
 σ = 1/ρ;

where σ is the conductivity of the film sample.

A graph was plotted between logσ verses 1000/T. This plot is known as the Arrehnius
plot. Variation of logσ with 1/T ‾¼ (Mott’s relation) 5 is also plotted.

3.3 Results and discussion

The electrical conductivity of the film was determined by the two probe method
in the temperature range 323 – 473K. A constant voltage was applied between the two
probes on the film. Fig 3.1-3.3 shows the I-V plot to determine if the electrical contact
with the sample was ohmic oxidized at 350 oC for different time intervals viz 45 min, 75
min respectively. A voltage corresponding to the linear part of the I-V plot was used as
the source voltage for the measurement of resistance of the samples. A source voltage of
12V was used for measurement of resistance of the samples oxidized at 350 oC for 45 min
and 75 min. Similarly a voltage of 8V was used for measurement of resistance of the
samples oxidized at 350 oC for 105 min.

56
 0.30

0.25

0.20
current(µA)

0.15

0.10

0.05

0.00

0 5 10 15 20

voltage(V)

FIG 3.1 V-I characteristics of the sample oxidized at 350oC for 45 min

57
 0.25

0.20
current(µA)

0.15

0.10

0.05

0.00

0 5 10 15 20

voltage(V)

FIG 3.2 V-I characteristics of the sample oxidized at 350oC for 1 hr 15 min

58
 0.8

0.6
current(µA)

0.4

0.2

0.0

0 5 10 15 20
voltage(V)

FIG 3.3 V-I characteristics of the sample oxidized at 350oC for 1 hr 45 min

59
TABLE 3.1 Resistance at different temperature of nanostructured cupric oxide thin films
annealed for 45 min at 350oC (carried out in vacuum)

TABLE 3.2 Resistance at different temperature of nanostructured cupric oxide thin films
annealed for 1 hr 45 min at 350oC (carried out in vacuum)

60
TABLE 3.3 Resistance at different temperature of nanostructured cupric oxide thin films
annealed for 45 min at 350oC (carried out in air)

61
TABLE 3.4 Resistance at different temperature of nanostructured cupric oxide thin films
annealed for1 hr 15min at 350oC (carried out in air)

TABLE 3.5 Resistance at different temperature of nanostructured cupric oxide thin films
annealed for1 hr 45 min at 350oC (carried out in air)

Values of different parameters obtained from the conductivity measurements are shown in
table 3.1- 3.5. Fig 3.4 – 3.8 shows the plots of logσ vs 1000/T. The variation of electrical
conductivity σ with temperature indicated (fig 3.4-3.8) typical Arrhenius type of
activation. At certain temperatures some kinks were found in the logσ vs 1000/T plot.It
corresponds to the changes in the slopes.

62
 1.5

1.0

0.5

0.0
logσ

-0.5

-1.0

-1.5

2.0 2.2 2.4 2.6 2.8 3.0 3.2

1000/T

FIG 3.4 Variation of electrical conductivity with reciprocal temperature for CuO film
oxidized at 350oC for 45 min (Conductivity measurement carried out in vacuum)

63
 1.5

1.0

0.5
logσ

0.0

-0.5

2.0 2.2 2.4 2.6 2.8 3.0 3.2

1000/T

FIG 3.5 Variation of electrical conductivity with reciprocal temperature for CuO film
oxidized at 350oC for 1 hr 45 min (Conductivity measurement carried out in vacuum)

64
 1.4

1.2

1.0

0.8
logσ

0.6

0.4

0.2

0.0
2.0 2.2 2.4 2.6 2.8 3.0 3.2

1000/T

FIG 3.6 Variation of electrical conductivity with reciprocal temperature for CuO film
oxidized at 350oC for 45 min (Conductivity measurement carried out in air)

65
 1.4

1.2

1.0

0.8
logσ

0.6

0.4

0.2

0.0
2.0 2.2 2.4 2.6 2.8 3.0 3.2

1000/T

FIG 3.7 Variation of electrical conductivity with reciprocal temperature for CuO film
oxidized at 350oC for 1 hr 15 min
(Conductivity measurement carried out in air)

66
 2.0

1.8

1.6

1.4

1.2
logσ

1.0

0.8

0.6

0.4
2.0 2.2 2.4 2.6 2.8 3.0 3.2

1000/T

FIG 3.8 Variation of electrical conductivity with reciprocal temperature for CuO film
oxidized at 350oC for 1 hr 45 min
(Conductivity measurement carried out in air)

67
Fig 3.4 - 3.5 show the variation of electrical conductivity with reciprocal temperature
(Arrhenius plot) for CuO thin films oxidized at 350oC for 45 min and 1 hr 45 min whose
conductivity measurement was carried out in vacuum. logσ vs 1000/T plot of CuO thin
films oxidized at 350oC for 45 min is linear. Also the logσ vs 1000/T plot of CuO thin
films oxidized at 350oC for 1 hr 45 min shows linear behaviour in the high temperature
region and low temperature region. But the curve shows a deviation from the linear
behaviour at the intermediate temperature. Fig 3.6 – 3.8 shows the variation of electrical
conductivity with reciprocal temperature for CuO thin films oxidized at 350oC for 45
min, 1 hr 15 min and 1 hr 45 min whose conductivity measurement was carried out in
air. CuO thin films oxidized at 350oC for 45 min shows linear behaviour in the high
temperature region. CuO thin films oxidized at 350oC for 1 hr 15 min and 1 hr 45 min
shows a linear behaviour at almost all temperatures. Reported studies show that if the
conductivity of a material exhibits Arrhenius behaviour, thermionic emission is the
prominent electrical transport mechanism.6

The conductivity, σ = σo exp(-Ea/kT), where Ea is the activation energy. Activation

eergy was determined by linear fitting of the plots shown in fig 3.4 – 3.8. The activation
energy values obtained from the slopes by best fitting are shown in table 3.6 and 3.7

TABLE 3.6: Activation energy values for samples whose conductivity was measured in
vacuum

Sample Activation energy (eV)

oxidized at 350oC for 45 min 2.47
oxidized at 350oC for 1 hr 45 min 1.89

68
 TABLE 3.7: Activation energy values for samples whose conductivity was measured in
air

Sample Activation energy (eV)

oxidized at 350oC for 45 min 1.07331

oxidized at 350oC for 1 hr 15 min 1.03118

oxidized at 350oC for 1 hr 45 min 1.37341

It was found that the activation energy values were less than the actual band gap. Serin et
al reported that the activation energies of CuO were less than the actual band gap. 7 The
present results are in agreement with the reported results.

Mott’s relation ie variation of logσ with T ‾¼ is also plotted. The Mott’s relation is widely
accepted after the works of Ambagaokar et al (1971) and Pollak (1972). 5 Fig 3. 9-3.11
shows the logσ vs T ‾¼ plot of various samples. It was found that variation of logσ with
T‾¼ is not strictly linear showing that Mott’s hopping mechanism is not fully satisfied in
the case of nanostructured CuO films.

69
 1.5

1.0

0.5

0.0
logσ

-0.5

-1.0

-1.5

0.215 0.220 0.225 0.230 0.235 0.240

-1/4 -1/4
T (K )

FIG 3.9 Variation of logσ with T ‾¼ for CuO film oxidized at 350oC for 45 min
(Conductivity measurement carried out in vacuum)

70
 1.5

1.0
logσ

0.5

0.0

-0.5

0.215 0.220 0.225 0.230 0.235 0.240

-1/4 -1/4
T (K )

FIG 3.10 Variation of logσ with T ‾¼ for CuO film oxidized at 350oC for 1 hr 45 min
(Conductivity measurement carried out in vacuum)

71
 1.4

1.2

1.0

0.8
logσ

0.6

0.4

0.2

0.0
0.215 0.220 0.225 0.230 0.235 0.240
-1/4 -1/4
T (K )

FIG 3.11 Variation of logσ with T ‾¼ for CuO film oxidized at 350oC for 45 min
(Conductivity measurement carried out in air)

72
 1.4

1.2

1.0

0.8
logσ

0.6

0.4

0.2

0.0
0.215 0.220 0.225 0.230 0.235 0.240
-1/4 -1/4
T (K )

FIG 3.12 Variation of logσ with T ‾¼ for CuO film oxidized at 350oC for 1 hr 15 min
(Conductivity measurement carried out in air)

73
 2.0

1.8

1.6

1.4
logσ

1.2

1.0

0.8

0.6

0.4
0.215 0.220 0.225 0.230 0.235 0.240
-1/4 -1/4
T (K )

FIG 3.13 Variation of logσ with T ‾¼ for CuO film oxidized at 350oC for 1 hr 45 min
(Conductivity measurement carried out in air)

74
For the samples annealed at 350oC for 45 min and 105 min the conductivity measurement
was carried out both in vacuum and air. In vacuum a drastic increase in resistance was
observed. This predicts the gas sensing property of the material. In the present case the
resistance of the sample measured in vacuum increased very much compared to that in
air. From this it can be inferred that CuO is a p-type MOS sensor.

The conductivity of the CuO sample oxidized at 350oC for 75 min was found to be
slightly higher than that of the sample oxidized at 350oC for 45 min. The conductivity
was found to be highest for the sample oxidized at 350oC for 105 min. The sample
oxidized at 350oC for 45 min showed highly gas sensing behaviour compared to the
sample heat treated at 350oC for 105 min.

3.4 Conclusion

From the electrical conductivity measurement it was found that the resistance of
the CuO sample decreased with increase in temperature, showing semiconducting
behaviour. A drastic increase in resistance was observed when the measurement was
carried out in vacuum. This indicated the gas sensing behaviour of the material. The
increase in resistance in vacuum indicates that CuO is a p-type metal oxide
semiconductor sensor.

75
References

1 Hong-Ming Lin, Shah-Jye Tzeng, Peng- Jan Hsiau and Wen- Li Tsai, Nanostuctured
Materials, 10, 465 (1998).
2 M. V. Garcia – Cuenca and J. L. Morenza, J.Appl.phys, 56, 1738 (1984).
3 Takayuki Ito, Hiroyuki Yamaguchi, Katsuya Okabe, Taizo, Masumi, J.Mater.Sci, 33,
3555 (1998).
4 Wan-Young Chung and Duk-Dong Lee, Thin Solid Films, 200, 329 (1991).
5 A. K. Pal Bull.Mater. Sci, 22, 341 (1999).
6 Y. W. John Setto, J.Appl.Phys,46, 5247 (1975).
7 N Serin, T Serin, Seyda Horzum and Yasemin Celik Semicond.Sci.Technol. 20,398
(2005).

76