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INTRODUCTION TO NANOSCIENCE AND NANOTECHNOLOGY

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 Introduction to
Nanoscience and Nanotechnology

K.K. CHATTOPADHYAY
Thin Film and Nanoscience Laboratory
Department of Physics
Jadavpur University
Kolkata

A.N. BANERJEE
Department Aerospace Engineering Sciences
University of Colorado at Boulder
Boulder

New Delhi-110001
2009
INTRODUCTION TO NANOSCIENCE AND NANOTECHNOLOGY
K.K. Chattopadhyay and A.N. Banerjee

© 2009 by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book may be
reproduced in any form, by mimeograph or any other means, without permission in writing from the
publisher.

ISBN-978-81-203-3608-7

The export rights of this book are vested solely with the publisher.

Published by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus,
New Delhi-110001 and Printed by Rajkamal Electric Press, B-35/9, G.T. Karnal Road Industrial Area,
Delhi-110033.
 Contents

Preface vii
1. INTRODUCTION 1–5
1.1 Background of Nanoscience and Nanotechnology 1
1.2 Definition of Nanoscience and Nanotechnology 2
1.3 Possible Applications of Nanotechnology 3
1.4 Organization of the Book 4
References 5

2. CRYSTAL BONDING, STRUCTURE, GROWTH AND SYMMETRIES 6–35

2.1 Introduction 6
2.2 Crystal Bonding 6
2.3 Crystal Structure 10
2.4 Crystal Growth 20
2.5 Classification of Crystals by Symmetry 21
2.6 Some Important Crystal Structures 22
Exercises 34
References 35
3. BAND STRUCTURE AND DENSITY OF STATES AT NANOSCALE 36–47
3.1 Introduction 36
3.2 Energy Bands 36
3.3 Density of States at Low-dimensional Structures 41
Exercises 46
References 47
4. ELECTRICAL TRANSPORT IN NANOSTRUCTURE 48–71
4.1 Electrical Conduction in Metals 48
4.1.1 Classical Theory—The Drude Model 48
4.1.2 Quantum Theory—The Free Electron Model 51
iii
iv • Contents

4.2 Conduction in Insulators/Ionic Crystals 53

4.3 Electron Transport in Semiconductors 55
4.4 Various Conduction Mechanisms in 3D (Bulk), 2D (Thin Film)
and Low-dimensional Systems 60
4.4.1 Thermionic Emission 60
4.4.2 Field-enhanced Thermionic Emission (Schottky Effect) 61
4.4.3 Field-assisted Thermionic Emission from
Traps (Poole–Frenkel Effect) 63
4.4.4 Arrhenius Type Thermally Activated Conduction 65
4.4.5 Variable Range Hopping Conduction 66
4.4.6 Polaron Conduction 67
Exercises 69
References 70

5. INTRODUCTORY QUANTUM MECHANICS FOR NANOSCIENCE 72–108

5.1 Introduction 72
5.2 Size-effects in Smaller Systems: Pre-quantum 73
5.3 Quantum Behaviour of Nanometric World 76
5.3.1 Bohr’s Model of Hydrogen Atom 76
5.3.2 Wave-particle Duality: de Broglie Wavelength 79
5.3.3 Wave Function Associated with an Electron 83
5.3.4 Heisenberg Uncertainty Principle; Description of Matter Wave:
Wave Packet 84
5.3.5 Schrödinger Equation 86
5.3.6 Applications of Schrödinger Equation 88
Exercises 105
References 107

6. GROWTH TECHNIQUES OF NANOMATERIALS 109–176

6.1 Introduction 109
6.2 Top-down vs. Bottom-up Technique 109
6.3 Lithographic Process and its Limitations 110
6.4 Nonlithographic Techniques 111
6.4.1 Plasma Arc Discharge 112
6.4.2 Sputtering 113
6.4.3 Evaporation 123
6.4.4 Chemical Vapour Deposition 127
6.4.5 Pulsed Laser Deposition 134
6.4.6 Molecular Beam Epitaxy 139
6.4.7 Sol–Gel Technique 142
6.4.8 Electrodeposition 155
6.4.9 Other Processes 161
Exercises 171
References 172
 Contents • v

7. CHARACTERIZATION TOOLS OF NANOMATERIALS 177–217

7.1 Scanning Probe Microscopy (SPM) 177
7.1.1 Introduction 177
7.1.2 Basic Principles of SPM Techniques 177
7.1.3 The Details of STM 180
7.1.4 Summary of STM 188
7.2 General Concept and Defining Characteristics of AFM 188
7.2.1 Scanned-Proximity Probe Microscopes 188
7.2.2 Laser Beam Deflection 190
7.2.3 AFM Cantilevers 190
7.2.4 Piezoceramics 192
7.2.5 Feedback Loop 193
7.2.6 Alternative Imaging Modes 194
7.2.7 AFM and Biology 196
7.3 Electron Microscopy 197
7.3.1 Introduction 197
7.3.2 Resolution vs. Magnification 198
7.3.3 Scanning Electron Microscope 199
7.3.4 SEM Techniques 200
7.3.5 Electron Gun 202
7.3.6 Specimen Interactions 204
7.3.7 Environmental SEM 207
7.4 Transmission Electron Microscope 208
7.4.1 High Resolution TEM 211
7.4.2 Contrast Transfer Function 214
Exercises 215
References 216

8. SOME SPECIAL TOPICS IN NANOTECHNOLOGY 218–264

8.1 Introduction 218
8.2 The Era of New Nanostructures of Carbon 218
8.2.1 Buckminsterfullerene 219
8.2.2 Carbon Nanotube 223
8.2.3 Nanodiamond 228
8.3 BN Nanotubes 232
8.4 Nanoelectronics 235
8.4.1 Single Electron Transistor 236
8.4.2 Molecular Machine 244
8.5 Nanobiometrics 251
Exercises 260
References 261

INDEX 265–268
 Preface

The discipline of nanoscience and nanotechnology has recently become one of the most
important areas of knowledge encompassing various scientific disciplines including physics,
chemistry, biology and engineering. This tremendous interest is mainly due to two reasons.
Firstly, nanoscale materials have many prospects in various technological applications because
most of the time, they show novel functionalities. Secondly, there is tremendous scope of
creating new knowledge in explaining the size dependencies of the evolution of various physical
properties, and in explaining new and previously unnoticed features, etc. Nanostructured
materials can be utilized in fabricating novel active devices with improved functionalities. For
example, one-dimensional nanomaterials (tubes, wires, rods, etc.) are an important class of
nanostructured materials with potential applications in electronics, composite fabrications or
sensor developments. On the other hand, physical properties of the one-dimensional
nanostructures will be different from their bulk behaviours. For example, electron transport
processes will be different in the one-dimensional structures from their bulk counterpart. While
physicists are more concerned with developing the requisite theories for describing the observed
properties, technologists are interested in developing some useful devices or materials.
Synthesis of nanomaterials is another key issue. Future prospects in developing nanoscale
devices for various applications largely depend on the controlled growth of nanomaterials.
General approaches in synthesizing nanomaterials involve vapour, liquid or solid state routes or
their intelligent combinations. Substantial advancement has been achieved in terms of
understanding the growth mechanism and also in creating exotic nanostructured materials in the
last few decades. However, many other related issues are involved in developing new synthesis
routes and also in fabricating useful devices. To achieve any new advancement in any of these
related fields, it is of utmost importance to have a thorough understanding of the fundamental
issues of low-dimensional systems. Moreover, acquiring an understanding of the physical
phenomena in nanostructured materials is now a common scientific issue. In recent times,
graduate and postgraduate courses have begun to be offered in nanoscience and nanotechnology
in many universities and institutes. The students come from various backgrounds including
different branches of the basic sciences and also from various engineering disciplines. Our

vii
viii • Preface

experience during the last several years of teaching M.Tech students in nanoscience and
nanotechnology has made us realize that some common minimum platform of knowledge is
essential for the students to understand and assimilate the key issues of this emerging subject
matter. This book has originated from this specific need.
The knowledge base of the nanoscience and nanotechnology has already reached a
tremendous volume to which new ideas are being added everyday. A large number of review
articles by many leading scientists from various parts of the world and numerous research papers
are being published regularly. Several international journals are specifically dedicated to
publishing papers on nanoscience and nanotechnology. It is difficult even for a specialist to
remain up-to-date with the latest information. The field of nanoscience and nanotechnology has
become too vast, too interdisciplinary and also too dynamic to be covered exhaustively in a book
of this size. On the other hand, there are many new starters in this field in universities, institutes
and also in industries. In this book, we have tried to cover some basic issues of the nanoscience
and nanotechnology. We believe that this book will not only serve as a textbook for the
undergraduate and postgraduate students in nanoscience and nanotechnology, but also be used
as a reference book by the researchers in the field. We have tried to discuss the basic scientific
issues for imparting a thorough understanding of the fundamental aspects of nanoscience and
nanotechnology rather than merely describing some general informations.
There are many scientists, students and teachers to whom the authors are grateful for helping
them in different ways in preparing the manuscript of this book. Particularly, the authors wish
to acknowledge the scholars of the Thin Film and Nanoscience Laboratory of Jadavpur
University for many suggestions and useful discussions. The authors are extremely grateful to
Prof. M.K. Mitra, Prof. G.C. Das, Prof. S. Mukherjee of Jadavpur University, Prof. T. Endo of
Mie University, Japan, and Prof. I. An of Hanyang University, Korea, for their useful
suggestions and discussions. We also wish to thank our wives for the support which they
provided during the writing of the manuscript.
In spite of our best efforts, there may be some unintentional mistakes. Comments and
suggestions to improve the book are always welcome and we will try to incorporate those in the
future editions. Finally, we fervently hope that this book will be useful to a large spectrum of
students and researchers who wish to enter this field.

K.K. Chattopadhyay
A.N. Banerjee
 1
Introduction

1.1 BACKGROUND OF NANOSCIENCE AND NANOTECHNOLOGY

Today’s widespread activities in nanoscience and technology are actually rooted in the ideas of
some leading scientists of the last century. Among them, the foremost name was
Richard P. Feynman. He delivered a legendary talk entitled “there is plenty of room at the
bottom” in the Annual general body meeting of the American Physical society on December 29,
1959 [1] at California Institute of Technology. In that talk he discussed about the ideas of
manipulating and controlling things at the atomic scale. In this famous lecture the great scientist
uttered also these famous words “the principles of physics, as far as I can see, do not speak
against the possibility of maneuvering things atom by atom”. He also envisioned building
circuits having sizes few nanometers that can be used as elements in more powerful computers.
In that time these ideas were regarded ‘too speculative’. But nearly twenty years later from this
prophetic talk, many inventions and discoveries began to appear justifying Feynman’s time-
ahead ideas. Soon the technology advisors and predictors realized the importance of these
discoveries and declared that a new revolution is imminent namely nanotechnology, just as in
the past we experienced industrial revolution and information revolution. Drexler expanded
Feynman’s ideas and definition in a stimulating and lateral thinking way in his book, ‘Engines
of Creation, the Coming Age of Nanotechnology’ [2]. We can quote Drexler to have some ideas
about nanotechnology: “Nanotechnology is the principle of manipulation atom by atom, through
control of the structure of matter at the molecular level. It entails the ability to build molecular
systems with atom-by-atom precision, yielding a variety of nanomachines.”
In recognition with this reality National Science and Technology Council (NSTC) of USA
created an integrating working group on nanoscience, engineering and technology in 1998. Then
in the year 2001 they announced the National Nanotechnology Initiative (NNI) programme with
a large amount of fund in the budgetary provisions [3]. The major objective of this initiative was
to create a common platform for the academia, industries and also private sector for working on
this new technology. Following this example, most of the advanced countries in the world and
many developing countries including China and India invested heavily on research and
development in this new field of science and technology.
1
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