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Product Details
| ISBN-13: | 9780471079354 |
|---|---|
| Publisher: | Wiley |
| Publication date: | 05/30/2003 |
| Pages: | 400 |
| Product dimensions: | 6.50(w) x 9.50(h) x 0.90(d) |
About the Author
FRANK J. OWENS, PhD, is a senior research scientist of the U.S. Army's Armament Research, Development, and Engineering Center, and a professor of physics in the graduate school of Hunter College of the City University of New York.
Both authors are Fellows of the American Physical Society.
Read an Excerpt
Introduction to Nanotechnology
By Charles P. Poole, Jr. Frank J. Owens
John Wiley & Sons
Copyright © 2003 John Wiley & Sons, Inc.All right reserved.
ISBN: 0-471-07935-9
Chapter One
INTRODUCTIONThe prefix nano in the word nanotechnology means a billionth (1 x [10.sup.-9]). Nanotechnology deals with various structures of matter having dimensions of the order of a billionth of a meter. While the word nanotechnology is relatively new, the existence of functional devices and structures of nanometer dimensions is not new, and in fact such structures have existed on Earth as long as life itself. The abalone, a mollusk, constructs very strong shells having iridescent inner surfaces by organizing calcium carbonate into strong nanostructured bricks held together by a glue made of a carbohydrate-protein mix. Cracks initiated on the outside are unable to move through the shell because of the nanostructured bricks. The shells represent a natural demonstration that a structure fabricated from nanoparticles can be much stronger. We will discuss how and why nanostructuring leads to stronger materials in Chapter 6.
It is not clear when humans first began to take advantage of nanosized materials. It is known that in the fourth-century A.D. Roman glassmakers were fabricating glasses containing nanosized metals. An artifact from this period called the Lycurgus cup resides in the British Museum inLondon. The cup, which depicts the death of King Lycurgus, is made from soda lime glass containing sliver and gold nanoparticles. The color of the cup changes from green to a deep red when a light source is placed inside it. The great varieties of beautiful colors of the windows of medieval cathedrals are due to the presence of metal nanoparticles in the glass.
The potential importance of clusters was recognized by the Irish-born chemist Robert Boyle in his Sceptical Chymist published in 1661. In it Boyle criticizes Aristotle's belief that matter is composed of four elements: earth, fire, water, and air. Instead, he suggests that tiny particles of matter combine in various ways to form what he calls corpuscles. He refers to "minute masses or clusters that were not easily dissipable into such particles that composed them."
Photography is an advanced and mature technology, developed in the eighteenth and nineteenth centuries, which depends on production of silver nanoparticles sensitive to light. Photographic film is an emulsion, a thin layer of gelatin containing silver halides, such as silver bromide, and a base of transparent cellulose acetate. The light decomposes the silver halides, producing nanoparticles of silver, which are the pixels of the image. In the late eighteenth century the British scientists Thomas Wedgewood and Sir Humprey Davy were able to produce images using silver nitrate and chloride, but their images were not permanent. A number of French and British researchers worked on the problem in the nineteenth century. Such names as Daguerre, Niecpce, Talbot, Archer, and Kennet were involved. Interestingly James Clark Maxwell, whose major contributions were to electromagnetic theory, produced the first color photograph in 1861. Around 1883 the American inventor George Eastman, who would later found the Kodak Corporation, produced a film consisting of a long paper strip coated with an emulsion containing silver halides. He later developed this into a flexible film that could be rolled, which made photography accessible to many. So technology based on nanosized materials is really not that new.
In 1857 Michael Faraday published a paper in the Philosophical Transactions of the Royal Society, which attempted to explain how metal particles affect the color of church windows. Gustav Mie was the first to provide an explanation of the dependence of the color of the glasses on metal size and kind. His paper was published in the German Journal Annalen der Physik (Leipzig) in 1908.
Richard Feynman was awarded the Nobel Prize in physics in 1965 for his contributions to quantum electrodynamics, a subject far removed from nanotechnology. Feynman was also a very gifted and flamboyant teacher and lecturer on science, and is regarded as one of the great theoretical physicists of his time. He had a wide range of interests beyond science from playing bongo drums to attempting to interpret Mayan hieroglyphics. The range of his interests and wit can be appreciated by reading his lighthearted autobiographical book Surely You're Joking, Mr. Feynman. In 1960 he presented a visionary and prophetic lecture at a meeting of the American Physical Society, entitled "There is Plenty of Room at the Bottom," where he speculated on the possibility and potential of nanosized materials. He envisioned etching lines a few atoms wide with beams of electrons, effectively predicting the existence of electron-beam lithography, which is used today to make silicon chips. He proposed manipulating individual atoms to make new small structures having very different properties. Indeed, this has now been accomplished using a scanning tunneling microscope, discussed in Chapter 3. He envisioned building circuits on the scale of nanometers that can be used as elements in more powerful computers. Like many of present-day nanotechnology researchers, he recognized the existence of nanostructures in biological systems. Many of Feynman's speculations have become reality. However, his thinking did not resonate with scientists at the time. Perhaps because of his reputation for wit, the reaction of many in the audience could best be described by the title of his later book Surely You're Joking, Mr. Feynman. Of course, the lecture is now legendary among present-day nanotechnology researchers, but as one scientist has commented, "it was so visionary that it did not connect with people until the technology caught up with it."
There were other visionaries. Ralph Landauer, a theoretical physicist working for IBM in 1957, had ideas on nanoscale electronics and realized the importance that quantum-mechanical effects would play in such devices.
Although Feynman presented his visionary lecture in 1960, there was experimental activity in the 1950s and 1960s on small metal particles. It was not called nanotechnology at that time, and there was not much of it. Uhlir reported the first observation of porous silicon in 1956, but it was not until 1990 when room-temperature fluorescence was observed in this material that interest grew. The properties of porous silicon are discussed in Chapter 6. Other work in this era involved making alkali metal nanoparticles by vaporizing sodium or potassium metal and then condensing them on cooler materials called substrates. Magnetic fluids called ferrofluids were developed in the 1960s. They consist of nanosized magnetic particles dispersed in liquids. The particles were made by ballmilling in the presence of a surface-active agent (surfactant) and liquid carrier. They have a number of interesting properties and applications, which are discussed in Chapter 7. Another area of activity in the 1960s involved electron paramagnetic resonance (EPR) of conduction electrons in metal particles of nanodimensions referred to as colloids in those days. The particles were produced by thermal decomposition and irradiation of solids having positive metal ions, and negative molecular ions such as sodium and potassium azide. In fact, decomposing these kinds of solids by heat is one way to make nanometal particles, and we discuss this subject in Chapter 4. Structural features of metal nanoparticles such as the existence of magic numbers were revealed in the 1970s using mass spectroscopic studies of sodium metal beams. Herman and co-workers measured the ionization potential of sodium clusters in 1978 and observed that it depended on the size of the cluster, which led to the development of the jellium model of clusters discussed in Chapter 4.
Groups at Bell Laboratories and IBM fabricated the first two-dimensional quantum wells in the early 1970s. They were made by thin-film (epitaxial) growth techniques that build a semiconductor layer one atom at a time. The work was the beginning of the development of the zero-dimensional quantum dot, which is now one of the more mature nanotechnologies with commercial applications. The quantum dot and its applications are discussed in Chapter 9.
However, it was not until the 1980s with the emergence of appropriate methods of fabrication of nanostructures that a notable increase in research activity occurred, and a number of significant developments resulted. In 1981, a method was developed to make metal clusters using a high-powered focused laser to vaporize metals into a hot plasma. This is discussed in Chapter 4. A gust of helium cools the vapor, condensing the metal atoms into clusters of various sizes. In 1985, this method was used to synthesize the fullerene ([C.sub.60]). In 1982, two Russian scientists, Ekimov and Omushchenko, reported the first observation of quantum confinement, which is discussed in Chapter 9. The scanning tunneling microscope was developed during this decade by G. K. Binnig and H. Roher of the IBM Research Laboratory in Zürich, and they were awarded the Nobel Prize in 1986 for this. The invention of the scanning tunneling microscope (STM) and the atomic force microscope (AFM), which are described in Chapter 3, provided new important tools for viewing, characterizing, and atomic manipulation of nanostructures. In 1987, B. J. van Wees and H. van Houten of the Netherlands observed steps in the current-voltage curves of small point contacts. Similar steps were observed by D. Wharam and M. Pepper of Cambridge University. This represented the first observation of the quantization of conductance. At the same time T. A. Fulton and G. J. Dolan of Bell Laboratories made a single-electron transistor and observed the Coulomb blockade, which is explained in Chapter 9. This period was marked by development of methods of fabrication such as electron-beam lithography, which are capable of producing 10-nm structures. Also in this decade layered alternating metal magnetic and nonmagnetic materials, which displayed the fascinating property of giant magnetoresistance, were fabricated. The layers were a nanometer thick, and the materials have an important application in magnetic storage devices in computers. This subject is discussed in Chapter 7.
Although the concept of photonic crystals was theoretically formulated in the late 1980s, the first three-dimensional periodic photonic crystal possessing a complete bandgap was fabricated by Yablonovitch in 1991. Photonic crystals are discussed in Chapter 6. In the 1990s, Iijima made carbon nanotubes, and superconductivity and ferromagnetism were found in [C.sub.60] structures. Efforts also began to make molecular switches and measure the electrical conductivity of molecules. A field-effect transistor based on carbon nanotubes was demonstrated. All of these subjects are discussed in this book. The study of self-assembly of molecules on metal surfaces intensified. Self-assembly refers to the spontaneous bonding of molecules to metal surfaces, forming an organized array of molecules on the surface. Self-assembly of thiol and disulfide compounds on gold has been most widely studied, and the work is presented in Chapter 10.
In 1996, a number of government agencies led by the National Science Foundation commissioned a study to assess the current worldwide status of trends, research, and development in nanoscience and nanotechnology. The detailed recommendations led to a commitment by the government to provide major funding and establish a national nanotechnology initiative. Figure 1.1 shows the growth of U.S. government funding for nanotechnology and the projected increase due to the national nanotechnology initiative. Two general findings emerged from the study.
The first observation was that materials have been and can be nanostructured for new properties and novel performance. The underlying basis for this, which we discuss in more detail in later chapters, is that every property of a material has a characteristic or critical length associated with it. For example, the resistance of a material that results from the conduction electrons being scattered out of the direction of flow by collisions with vibrating atoms and impurities, can be characterized by a length called the scattering length. This length is the average distance an electron travels before being deflected. The fundamental physics and chemistry changes when the dimensions of a solid become comparable to one or more of these characteristic lengths, many of which are in the nanometer range. One of the most important examples of this is what happens when the size of a semiconducting material is in the order of the wavelength of the electrons or holes that carry current. As we discuss in Chapter 9, the electronic structure of the system completely changes. This is the basis of the quantum dot, which is a relatively mature application of nanotechnology resulting in the quantum-dot laser presently used to read compact disks (CDs). However, as we shall see in Chapter 9, the electron structure is strongly influenced by the number of dimensions that are nanosized.
If only one length of a three-dimensional nanostructure is of a nanodimension, the structure is known as a quantum well, and the electronic structure is quite different from the arrangement where two sides are of nanometer length, constituting what is referred to as a quantum wire. A quantum dot has all three dimensions in the nanorange. Chapter 9 discusses in detail the effect of dimension on the electronic properties of nanostructures. The changes in electronic properties with size result in major changes in the optical properties of nanosized materials, which is discussed in Chapter 8, along with the effects of reduced size on the vibrational properties of materials.
(Continues...)
Excerpted from Introduction to Nanotechnology by Charles P. Poole, Jr. Frank J. Owens Copyright © 2003 by John Wiley & Sons, Inc.. Excerpted by permission.
All rights reserved. No part of this excerpt may be reproduced or reprinted without permission in writing from the publisher.
Excerpts are provided by Dial-A-Book Inc. solely for the personal use of visitors to this web site.
Table of Contents
Preface xi1 Introduction 1
2 Introduction to Physics of the Solid State 8
2.1 Structure 8
2.1.1 Size Dependence of Properties 8
2.1.2 Crystal Structures 9
2.1.3 Face-Centered Cubic Nanoparticles 12
2.1.4 Tetrahedrally Bonded Semiconductor Structures 15
2.1.5 Lattice Vibrations 18
2.2 Energy Bands 20
2.2.1 Insulators, Semiconductors, and Conductors 20
2.2.2 Reciprocal Space 22
2.2.3 Energy Bonds and Gaps of Semiconductors 23
2.2.4 Effective Masses 28
2.2.5 Fermi Surfaces 29
2.3 Localized Particles 30
2.3.1 Donors, Acceptors, and Deep Traps 30
2.3.2 Mobility 31
2.3.3 Excitons 32
3 Methods of Measuring Properties 35
3.1 Introduction 35
3.2 Structure 36
3.2.1 Atomic Structures 36
3.2.2 Crystallography 37
3.2.3 Particle Size Determination 42
3.2.4 Surface Structure 45
3.3 Microscopy 46
3.3.1 Transmission Electron Microscopy 46
3.3.2 Field Ion Microscopy 51
3.3.3 Scanning Microscopy 51
3.4 Spectroscopy 58
3.4.1 Infrared and Raman Spectroscopy 58
3.4.2 Photoemission and X-Ray Spectroscopy 62
3.4.3 Magnetic Resonance 68
4 Properties of Individual Nanoparticles 72
4.1 Introduction 72
4.2 Metal Nanoclusters 74
4.2.1 Magic Numbers 74
4.2.2 Theoretical Modeling of Nanoparticles 75
4.2.3 Geometric Structure 78
4.2.4 Electronic Structure 81
4.2.5 Reactivity 83
4.2.6 Fluctuations 86
4.2.7 Magnetic Clusters 86
4.2.8 Bulk to Nanotransition 88
4.3 Semiconducting Nanoparticles 90
4.3.1 Optical Properties 90
4.3.2 Photofragmentation 92
4.3.3 Coulombic Explosion 93
4.4 Rare Gas and Molecular Clusters 94
4.4.1 Inert-Gas Clusters 94
4.4.2 Superfluid Clusters 95
4.4.3 Molecular Clusters 96
4.5 Methods of Synthesis 97
4.5.1 RF Plasma 97
4.5.2 Chemical Methods 98
4.5.3 Thermolysis 99
4.5.4 Pulsed Laser Methods 100
4.6 Conclusion 101
5 Carbon Nanostructures 103
5.1 Introduction 103
5.2 Carbon Molecules 103
5.2.1 Nature of the Carbon Bond 103
5.2.2 New Carbon Structures 105
5.3 Carbon Clusters 106
5.3.1 Small Carbon Clusters 106
5.3.2 Discovery of C60 107
5.3.3 Structure of C60 and Its Crystal 110
5.3.4 Alkali-Doped C60 110
5.3.5 Superconductivity in C60 112
5.3.6 Larger and Smaller Fullerenes 113
5.3.7 Other Buckyballs 113
5.4 Carbon Nanotubes 114
5.4.1 Fabrication 114
5.4.2 Structure 117
5.4.3 Electrical Properties 118
5.4.4 Vibrational Properties 122
5.4.5 Mechanical Properties 123
5.5 Applications of Carbon Nanotubes 125
5.5.1 Field Emission and Shielding 125
5.5.2 Computers 126
5.5.3 Fuel Cells 127
5.5.4 Chemical Sensors 128
5.5.5 Catalysis 129
5.5.6 Mechanical Reinforcement 130
6 Bulk Nanostructured Materials 133
6.1 Solid Disordered Nanostructures 133
6.1.1 Methods of Synthesis 133
6.1.2 Failure Mechanisms of Conventional Grain-Sized Materials 137
6.1.3 Mechanical Properties 139
6.1.4 Nanostructured Multilayers 141
6.1.5 Electrical Properties 142
6.1.6 Other Properties 147
6.1.7 Metal Nanocluster Composite Glasses 148
6.1.8 Porous Silicon 150
6.2 Nanostructured Crystals 153
6.2.1 Natural Nanocrystals 153
6.2.2 Computational Prediction of Cluster Lattices 153
6.2.3 Arrays of Nanoparticles in Zeolites 154
6.2.4 Crystals of Metal Nanoparticles 157
6.2.5 Nanoparticle Lattices in Colloidal Suspensions 158
6.2.6 Photonic Crystals 159
7 Nanostructured Ferromagnetism 165
7.1 Basics of Ferromagnetism 165
7.2 Effect of Bulk Nanostructuring of Magnetic Properties 170
7.3 Dynamics of Nanomagnets 172
7.4 Nanopore Containment of Magnetic Particles 176
7.5 Nanocarbon Ferromagnets 177
7.6 Giant and Colossal Magnetoresistance 181
7.7 Ferrofluids 186
8 Optical and Vibrational Spectroscopy 194
8.1 Introduction 194
8.2 Infrared Frequency Range 196
8.2.1 Spectroscopy of Semiconductors; Excitons 196
8.2.2 Infrared Surface Spectroscopy 198
8.2.3 Raman Spectroscopy 203
8.2.4 Brillouin Spectroscopy 210
8.3 Luminescence 213
8.3.1 Photoluminescence 213
8.3.2 Surface States 215
8.3.3 Thermoluminescence 221
8.4 Nanostructures in Zeolite Cages 222
9 Quantum Wells, Wires, and Dots 226
9.1 Introduction 226
9.2 Preparation of Quantum Nanostructures 227
9.3 Size and Dimensionality Effects 231
9.3.1 Size Effects 231
9.3.2 Conduction Electrons and Dimensionality 233
9.3.3 Fermi Gas and Density of States 234
9.3.4 Potential Wells 236
9.3.5 Partial Confinement 241
9.3.6 Properties Dependent on Density of States 242
9.4 Excitons 244
9.5 Single-Electron Tunneling 245
9.6 Applications 248
9.6.1 Infrared Detectors 248
9.6.2 Quantum Dot Lasers 251
9.7 Superconductivity 253
10 Self-Assembly and Catalysis 257
10.1 Self-Assembly 257
10.1.1 Process of Self-Assembly 257
10.1.2 Semiconductor Islands 258
10.1.3 Monolayers 260
10.2 Catalysis 264
10.2.1 Nature of Catalysis 264
10.2.2 Surface Area of Nanoparticles 264
10.2.3 Porous Materials 268
10.2.4 Pillared Clays 273
10.2.5 Colloids 277
11 Organic Compounds and Polymers 281
11.1 Introduction 281
11.2 Forming and Characterizing Polymers 283
11.2.1 Polymerization 283
11.2.2 Sizes of Polymers 284
11.3 Nanocrystals 285
11.3.1 Condensed Ring Types 285
11.3.2 Polydiacetylene Types 289
11.4 Polymers 292
11.4.1 Conductive Polymers 292
11.4.2 Block Copolymers 293
11.5 Supramolecular Structures 295
11.5.1 Transition-Metal-Mediated Types 295
11.5.2 Dendritic Molecules 296
11.5.3 Supramolecular Dendrimers 302
11.5.4 Micelles 305
12 Biological Materials 310
12.1 Introduction 310
12.2 Biological Building Blocks 311
12.2.1 Sizes of Building Blocks and Nanostructures 311
12.2.2 Polypeptide Nanowire and Protein Nanoparticle 314
12.3 Nucleic Acids 316
12.3.1 DNA Double Nanowire 316
12.3.2 Genetic Code and Protein Synthesis 322
12.4 Biological Nanostructures 324
12.4.1 Examples of Proteins 324
12.4.2 Micelles and Vesicles 326
12.4.3 Multilayer Films 329
13 Nanomachines and Nanodevices 332
13.1 Microelectromechanical Systems (MEMSs) 332
13.2 Nanoelectromechanical Systems (NEMSs) 335
13.2.1 Fabrication 335
13.2.2 Nanodevices and Nanomachines 339
13.3 Molecular and Supramolecular Switches 345
A Formulas for Dimensionality 357
A.1 Introduction 357
A.2 Delocalization 357
A.3 Partial Confinement 358
B Tabulations of Semiconducting Material Properties 361
Index 371