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G;Z: Applications
Synthesis, Properties
NANOSTRUCTURES
& NANOMATERIALS
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& Applications
Synthesis, Properties
University of Washington, USA

NANOSTRUCTURES
& NANOMATERIALS
Guozhong Cao

Imperial College Press

 Published by
Imperial College Press
57 Shelton Street
Covent Garden
London WC2H 9HE

Distributed by
World Scientific Publishing Co. Pte. Ltd.
5 Toh Tuck Link, Singapore 596224
USA once: 27 Warren Street, Suite 401-402, Hackensack, NJ 07601
UK @ice: 57 Shelton Street, Covent Garden, London WC2H 9HE
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British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

NANOSTRUCTURES AND NANOMATERIALS

Synthesis, Properties, and Applications
Copyright 0 2004 by Imperial College Press
All rights reserved. This book, or parts thereof, muy not be reproduced in any form or by any means,
electronic or mechanical, including photocopying, recording or any information storage and retrieval
system now known or to be invented, without written permission from the Publisher.

For photocopying of material in this volume, please pay a copying fee through the Copyright
Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to
photocopy is not required from the publisher.

ISBN 1-86094-4159
ISBN 1-86094-480-9 (pbk)

Printed in Singapore by World Scientific Printers (S)Pte Ltd

 Preface
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Nanotechnology is design, fabrication and application of nanostructures

or nanomaterials, and the fundamental understanding of the relationships
between physical properties or phenomena and material dimensions.
Nanotechnology deals with materials or structures in nanometer scales,
typically ranging from subnanometers to several hundred nanometers.
One nanometer is 10-3 micrometer or meter. Nanotechnology is a
new field or a new scientific domain. Similar to quantum mechanics, on
nanometer scale, materials or structures may possess new physical prop-
erties or exhibit new physical phenomena. Some of these properties are
already known. For example, band gaps of semiconductors can be tuned
by varying material dimension. There may be many more unique physical
properties not known to us yet. These new physical properties or phe-
nomena will not only satisfy everlasting human curiosity, but also prom-
ise new advancement in technology. For example, ultra-strong ultra-light
multifunctional materials may be made from hierarchical nanostructures.
Nanotechnology also promises the possibility of creating nanostructures
of metastable phases with non-conventional properties including super-
conductivity and magnetism. Yet another very important aspect of nan-
otechnology is the miniaturization of current and new instruments,
sensors and machines that will greatly impact the world we live in.
Examples of possible miniaturization are: computers with infinitely great
power that compute algorithms to mimic human brains, biosensors that
warn us at the early stage of the onset of disease and preferably at the
molecular level and target specific drugs that automatically attack the dis-
eased cells on site, nanorobots that can repair internal damage and remove

V
 vi Preface

chemical toxins in human bodies, and nanoscaled electronics that con-

stantly monitor our local environment.
Nanotechnology has an extremely broad range of potential applications
from nanoscale electronics and optics, to nanobiological systems and
nanomedicine, to new materials, and therefore it requires formation of and
contribution from multidisciplinary teams of physicists, chemists, materi-
als scientists, engineers, molecular biologists, pharmacologists and others
to work together on (i) synthesis and processing of nanomaterials and
nanostructures, (ii) understanding the physical properties related to the
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nanometer scale, (iii) design and fabrication of nano-devices or devices

with nanomaterials as building blocks, and (iv) design and construction of
novel tools for characterization of nanostructures and nanomaterials.
Synthesis and processing of nanomaterials and nanostructures are the
essential aspect of nanotechnology. Studies on new physical properties and
applications of nanomaterials and nanostructures are possible only when
nanostructured materials are made available with desired size, morphology,
crystal and microstructure and chemical composition. Work on the fabri-
cation and processing of nanomaterials and nanostructures started long
time ago, far earlier than nanotechnology emerged as a new scientific field.
Such research has been drastically intensified in the last decade, resulting
in overwhelming literatures in many journals across different disciplines.
The research on nanotechnology is evolving and expanding very rapidly.
That makes it impossible for a book of this volume to cover all the aspects
of the field. The readers will readily find that this book has been focused
primarily on inorganic materials. However, efforts were made to include
the relevant organic materials such as self-assembled monolayers and
Langmuir-Blodgett films. Of course, in the synthesis and processing of
nanomaterials, organic materials often play an indispensable role, such as
surfactants in the synthesis of ordered mesoporous materials, and capping
polymers in the synthesis of monodispersed nanoparticles. The aim of this
book is to summarize the fundamentals and established techniques of syn-
thesis and processing of nanomaterials and nanostructures so as to provide
readers a systematic and coherent picture about synthesis and processing
of nanomaterials. In addition, the last two chapters of the book have been
devoted to characterization, properties and applications of nanomaterials
and nanostructures. This book would serve as a general introduction to
people just entering the field, and also for experts seeking for information
in other subfields. This is not a handbook with quick recipes for synthesis
and processing of nanomaterials; it has been the intention of the author that
this book is to be a tutorial and not a comprehensive review. Therefore, this
 Preface vii

book is well suited as a textbook for upper-level undergraduate, graduate

and professional short courses.
The contents benefit greatly from the interaction between the author
and colleagues or students. Most of the subjects covered in this book have
been taught as a short course in 2002 SPIE annual meeting and a regular
graduate course at the University of Washington. The precious feedback
from the students who attended the classes have been incorporated into
this book. I am grateful in particular to Mary Shang who took care of the
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figures and went through all the details to clarify many points in the pres-
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entation. I am also indebted to Ying Wang and Steven Limmer who got all
the copyright permission and helped in preparing some of the figures. Our
department chair, Prof. Raj Bordia, is acknowledged for having graciously
reduced my department committee work. Editors, Mr. Stanford Chong and
Ms. Lakshmi Narayanan at World Scientific Publishing and Imperial
College Press are acknowledged for initiating and editing the book,
respectively. The writing of this book started coincidently with the birth of
my son, Doran, and finished when he turned a year old. It has been excit-
ing to see both the little boy and the manuscript grow at the same time.
This book would not have been possible without the dedication of my
mother-in-law, who left Hong Kong to come to the States to take care of
our son. My wife, Yuk Lan Li, deserves special thanks for her support and
understanding.

Guozhong Cao
Seattle, WA
August 2003
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 Contents
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Preface V

1. Introduction 1
1.1. Introduction 1
1.2. Emergence of Nanotechnology 4
1.3. Bottom-Up and Top-Down Approaches 7
1.4. Challenges in Nanotechnology 10
1.5. Scope of the Book 11
References 14

2. Physical Chemistry of Solid Surfaces 15

2.1. Introduction 15
2.2. Surface Energy 17
2.3. Chemical Potential as a Function of Surface Curvature 26
2.4. Electrostatic Stabilization 32
2.4.1. Surface charge density 32
2.4.2. Electric potential at the proximity of solid surface 33
2.4.3. Van der Waals attraction potential 36
2.4.4. Interactions between two particles: DLVO theory 38
2.5. Steric Stabilization 42
2.5.1. Solvent and polymer 43
2.5.2. Interactions between polymer layers 45
2.5.3. Mixed steric and electric interactions 47
2.6. Summary 48
References 48

ix
 X Contents

3. Zero-Dimensional Nanostructures: Nanoparticles 51

3.1, Introduction 51
3.2. Nanoparticles through Homogeneous Nucleation 53
3.2.1. Fundamentals of homogeneous nucleation 53
3.2.2. Subsequent growth of nuclei 58
3.2.2.1. Growth controlled by diffusion 59
3.2.2.2. Growth controlled by surface process 59
3.2.3. Synthesis of metallic nanoparticles 63
3.2.3.1. Influences of reduction reagents 67
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3.2.3.2. Influences by other factors 69

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3.2.3.3. Influences of polymer stabilizer 72

3.2.4. Synthesis of semiconductor nanoparticles 74
3.2.5. Synthesis of oxide nanoparticles 81
3.2.5.1. Introduction to sol-gel processing 82
3.2.5.2. Forced hydrolysis 85
3.2.5.3. Controlled release of ions 87
3.2.6. Vapor phase reactions 88
3.2.7. Solid state phase segregation 89
3.3. Nanoparticles through Heterogeneous Nucleation 93
3.3.1. Fundamentals of heterogeneous nucleation 93
3.3.2. Synthesis of nanoparticles 95
3.4. Kinetically Confined Synthesis of Nanoparticles 96
3.4.1. Synthesis inside micelles or using microemulsions 96
3.4.2. Aerosol synthesis 98
3.4.3. Growth termination 99
3.4.4. Spray pyrolysis 100
3.4.5. Template-based synthesis 101
3.5. Epitaxial Core-Shell Nanoparticles 101
3.6. Summary 104
References 105

4. One-Dimensional Nanostructures: Nanowires 110

and Nanorods
4.1. Introduction 110
4.2. Spontaneous Growth 111
4.2. I. Evaporation (dissolution)-condensation growth 112
4.2.1.1. Fundamentals of evaporation
(dissolution)-condensation growth 112
4.2.1.2. Evaporation-condensation growth 119
4.2. I .3. Dissolution-condensation growth 123
 Contents xi

4.2.2. Vapor (or solution)-liquid-solid

(VLS or SLS) growth 127
4.2.2.1. Fundamental aspects of VLS and
SLS growth 127
4.2.2.2. VLS growth of various nanowires 131
4.2.2.3. Control of the size of nanowires 134
4.2.2.4. Precursors and catalysts 138
4.2.2.5. SLS growth 140
4.2.3. Stress-induced recrystallization 142
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4.3. Template-Based Synthesis 143

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4.3.1. Electrochemical deposition 144

4.3.2. Electrophoretic deposition 151
4.3.3. Template filling 157
4.3.3.1. Colloidal dispersion filling 158
4.3.3.2. Melt and solution filling 160
4.3.3.3. Chemical vapor deposition 161
4.3.3.4. Deposition by centrifugation 161
4.3.4. Converting through chemical reactions 162
4.4. Electrospinning 164
4.5. Lithography 165
4.6. Summary 168
References 168

5. Two-Dimensional Nanostructures: Thin Films 173

5.1. Introduction 173
5.2. Fundamentals of Film Growth 174
5.3. Vacuum Science 178
5.4. Physical Vapor Deposition (PVD) 182
5.4.1. Evaporation 183
5.4.2. Molecular beam epitaxy (MBE) 185
5.4.3. Sputtering 186
5.4.4. Comparison of evaporation and sputtering 188
5.5. Chemical Vapor Deposition (CVD) 189
5.5.1. Typical chemical reactions 189
5.5.2. Reaction kinetics 190
5.5.3. Transport phenomena 191
5.5.4. CVD methods 194
5.5.5. Diamond films by CVD 197
5.6. Atomic Layer Deposition (ALD) 199
5.7. Superlattices 204
5.8. Self-Assembly 205
 xii Contents

5.8.1. Monolayers of organosilicon or

alkylsilane derivatives 208
5.8.2. Monolayers of alkanethiols and sulfides 2 10
5.8.3. Monolayers of carboxylic acids, amines
and alcohols 212
5.9. Langmuir-Blodgett Films 213
5.10. Electrochemical Deposition 218
5.1 1. Sol-Gel Films 219
5.12. Summary 223
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References 224
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6. Special Nanomaterials 229

6.1. Introduction 229
6.2. Carbon Fullerenes and Nanotubes 230
6.2.1. Carbon fullerenes 230
6.2.2. Fullerene-derived crystals 232
6.2.3. Carbon nanotubes 232
6.3. Micro and Mesoporous Materials 238
6.3.1. Ordered mesoporous structures 239
6.3.2. Random mesoporous structures 245
6.3.3. Crystalline microporous materials: zeolites 249
6.4. Core-Shell Structures 257
6.4.1. Metal-oxide structures 257
6.4.2. Metal-polymer structures 260
6.4.3. Oxide-polymer structures 26 1
6.5. Organic-Inorganic Hybrids 263
6.5.1. Class I hybrids 263
6.5.2. Class I1 hybrids 264
6.6. Intercalation Compounds 266
6.7. Nanocomposites and Nanograined Materials 267
6.8. Summary 268
References 269

7. Nanostructures Fabricated by Physical Techniques 277

7.1. Introduction 277
7.2. Lithography 278
7.2.1. Photolithography 279
7.2.2. Phase-shifting photolithography 283
7.2.3. Electron beam lithography 284
7.2.4. X-ray lithography 287
7.2.5. Focused ion beam (FIB) lithography 288
 ...
Contents Xlll

7.2.6. Neutral atomic beam lithography 290

7.3. Nanomanipulation and Nanolithography 29 1
7.3.1. Scanning tunneling microscopy (STM) 292
7.3.2. Atomic force microscopy (AFM) 294
7.3.3. Near-field scanning optical microscopy (NSOM) 296
7.3 -4. Nanomanipulation 298
7.3.5. Nanolithography 303
7.4. Soft Lithography 308
7.4.1. Microcontact printing 308
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7.4.2. Molding 310

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7.4.3. Nanoimprint 310

7.4.4. Dip-pen nanolithography 313
7.5. Assembly of Nanoparticles and Nanowires 3 14
7.5.1. Capillary forces 315
7.5.2. Dispersion interactions 316
7.5.3. Shear force assisted assembly 318
7.5.4. Electric-field assisted assembly 318
7.5.5. Covalently linked assembly 319
7.5.6. Gravitational field assisted assembly 319
7.5.7. Template-assisted assembly 319
7.6. Other Methods for Microfabrication 32 1
7.7. Summary 32 1
References 322

8. Characterization and Properties of Nanomaterials 329

8.1. Introduction 329
8.2. Structural Characterization 330
8.2.1. X-ray diffraction (XRD) 33 1
8.2.2. Small angle X-ray scattering (SAXS) 333
8.2.3. Scanning electron microscopy (SEM) 336
8.2.4. Transmission electron microscopy (TEM) 338
8.2.5. Scanning probe microscopy (SPM) 340
8.2.6. Gas adsorption 343
8.3. Chemical Characterization 344
8.3.1. Optical spectroscopy 345
8.3.2. Electron spectroscopy 349
8.3.3. Ionic spectrometry 350
8.4. Physical Properties of Nanomaterials 352
8.4.1. Melting points and lattice constants 353
8.4.2. Mechanical properties 357
8.4.3. Optical properties 362
 xiv Contents

8.4.3.1. Surface plasmon resonance 362

8.4.3.2. Quantum size effects 367
8.4.4. Electrical conductivity 37 1
8.4.4.1. Surface scattering 371
8.4.4.2. Change of electronic structure 374
8.4.4.3. Quantum transport 375
8.4.4.4. Effect of microstructure 379
8.4.5. Ferroelectrics and dielectrics 380
8.4.6. Superparamagnetism 382
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8.5. Summary 384

References 384

9. Applications of Nanomaterials 391

9.1. Introduction 391
9.2. Molecular Electronics and Nanoelectronics 392
9.3. Nanobots 394
9.4. Biological Applications of Nanoparticles 396
9.5. Catalysis by Gold Nanoparticles 397
9.6. Band Gap Engineered Quantum Devices 399
9.6.1. Quantum well devices 399
9.6.2. Quantum dot devices 40 1
9.7. Nanomechanics 402
9.8. Carbon Nanotube Emitters 404
9.9. Photoelectrochemical Cells 406
9.10. Photonic Crystals and Plasmon Waveguides 409
9.10.1. Photonic crystals 409
9.10.2. Plasmon waveguides 41 1
9.1 1. Summary 41 1
References 412

Appendix
1. Periodic Table of the Elements 419
2. The International System of Units 420
3. List of Fundamental Physical Constants 42 1
4. The 14 Three-Dimensional Lattice Types 422
5. The Electromagnetic Spectrum 423
6. The Greek Alphabet 424

Index 42 5