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physical Properties of Carbon Nanotubes
Rysical Properties of Carbon Nanotubes
GDRESSELElAUS & M S DRBSELMUS
MZT
Imperial College Press
1060 Main Street. This book or parts thereof. MA 01923. rm PHYSICAL PROPERTIES OF CARBON NANOTWES Copyright 0 1998 by Imperial College Press All rig& reserved. Pte.Ltd. Singapore912805 USA oflce: Suite lB. recording or any information storage and retrieval system ROW known or fo be invented. London WC2H 9HE! British Library C a ~ o g ~ ~ ~Data ~ b ~ ~ ~ o n A catalogue record for this book is available f o the British Library. N 07661 J WK oflce: 57 Shelton Street. Inc.Published by Imperial College Press 203 Electrical Engineering Building Imprial College London SW7 2BT Distributed by World Scientific Publishing Co. rm ISBN 1860940935 This book is printed on acidfree paper. 222 Rosewood Drive. elecironic or mechanical. including photocopying. Danvers. P 0 Box 128. please pay a copying fee through the Copyright Clearance Center. Covent Garden. In this case permission to photocopy is not required f o the publisher.. Printed in Singapore by UtePrint . USA. withmf writfen~ e ~ i s s i o n ~ o m the Publishm For photocopying of material in this volume. Farrer Road. m y not be reproduced in anyform or by any means. River Edge.
Thus. which the reader can follow with a pen and paper. by varying the nanotube diameter. The diameter of a carbon nanotube is of nanometer size and the length of the nanotube can be more than l p m . This is actually the V . and does not requiring any doping. depending on its diameter and chirality. the energy gap of semiconducting carbon nanotubes can be varied continuously from 1 eV to 0 eV. and is unique to solid state physics. The purpose of this book is t o define the structure of carbon nanotubes as clearly as possible. Further. From our definition of the structure of carbon nanotubes. and experimental results are used primarily t o provide evidence for the validity of the theory. Thus the contents of the book are rather theoretically oriented. the electronic structure of a singlewall carbon nanotube is either metallic or semiconducting. The nanotube diameter is much smaller in size than the most advanced semiconductor devices obtained so far. carbon nanotubes provide a family of structures with different diameters and chiralities.Preface A carbon nanotube is a honeycomb lattice rolled into a cylinder. this volume provides background information about the structure and properties of graphite and related carbon materials. it may be possible to specify the desired semiconducting properties using only carbon atoms with a specified geometric structure. Specifically. starting from basic physics and chemistry. One of the most significant physical properties of carbon nanotubes is their electronic structure which depends only on their geometry. we can explain the electronic structure and phonon dispersion relations based on simple physical models. Thus the availability of carbon nanotubes may have a large impact on semiconductor physics because of its very small size and the special electronic properties that are unique to carbon nanotubes. Because of the large variety of possible helical geometries known as chirality. in principle. Since the uniqueness in the electronic structure comes directly from the uniqueness of the electronic structure of graphite. Thus we can imagine that the smallest possible semiconductor devices are likely to be based on carbon nanotubes.
In order to expand this field into the future. Thus future progress is beyond our imagination. with many active research groups worldwide working independently or in collaborative research projects. electronic and phonon structures. Thus the physical properties of carbon nanotubes provide a new dimension for solid state physics. The direct evidence provided by electron microscopy for the existence of carbon nanotubes was sensational to many physicists and chemists. Another unique property of a carbon nanotube is its st. So please enjoy the book and please communicate to the authors any comments you might have about this book. since obtaining sufficient quantities of pure carbon nanotubes has been difficult in practice. and because of this fascination. When this book was started three years ago.vi PREFACE way that the field of carbon nanotubes developed. based on the great variety of possible geometries that are available for carbon nanotubes. many researchers in different fields of science should contribute to this field.rn). The authors hope that readers from any field of science can read this book without any special background requirements. At an early stage. The authors would like to acknowledge many carbon nanotube researchers who have contributed t o the contents of the book. m) consists of a set of integers which specify each carbon nanotube uniquely. corresponding to the upper limit of the best carbon fibers. In this book. the book focuses on the basic principles behind the physical properties. the physical properties are discussed in the terminology of carbon nanotubes. we will find many new friends in this field. which are commonly used as a strong lightweight material. Since quantum effects are prominent in nanotube physics. The special properties of carbon nanotubes are explained in the various chapters in this book. The authors also thank the New Energy Development Organization (NEDO) of the Japanese Ministry for . This book is not intended to be a collection of all activities on carbon nanotubes worldwide because this field is already so extensive. the magnetic and transport quantum effects are very significant. and is moving forward so rapidly at the present time. Although progress in the field is still at an early stage. The chiral index (n.iffness. which are characterized by the chiral index (n. We hope that through this book. the theory stimulated experiments in carbon nanotube physics. The early experiments were made through electron microscope observation. the present status of the field could not have been anticipated. using basic ideas of the lattice. the field of carbon nanotubes has grown explosively.
Saito. Japan Society for the Promotion of Science (JSPS).S. Cambridge. Dresselhaus. Junko Yamamoto and Ms.” R. Massachusetts . and their generous support for international collaboration which made the writing of this book possible. Massachusetts G.PREFA CE vii International Trade and Industry (MITI). Cambridge. Finally the authors wish to say to readers: “Welcome to Carbon Nanotube Physics. Laura Doughty for their help in preparing the indexes and figures of the book. Tokyo M . The authors especially thank Ms. Dresselhaus.
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. . . . . . . . . . . . .5 Unit Cells and Brillouin Zones . . . . . . . . . . . . . . 3. . . . . . . . . . . . . . . . . . . . .1 x Bands of TwoDimensional Graphite .1 Secular Equation . . . . . . . 7 1. . . . . 8 1. . . . .3. . . . 2. . . . .1. . . . . (CH4) .. . . 11 1. . .1. . . ..4 Symmetry Vector: R . . .1 Classification of carbon nanotubes . . . . . . . . 3. . .1 History . 3. . . . . . . . . . . . 5 1. . . . . . . . . . 3. . . . . 2. . . . .2 Chiral Vector: C h . . . .6 Carbynes .7 Experimental evidence for nanotube structure . . . . . . . . . 13 1. . . . TwoDimensional Graphite . . Electronic Structure of Polyacetylene . . . . . . . .2. . . . . . . . . 2. .. . . .3. . . . . . . . . . . . . . . . . . . . .6 Group Theory of Carbon Nanotubes . .2 2. . . . . . .2. . . . . . . . 2. . .2 Procedure for obtaining the energy dispersion . . . . .2 sp2 Hybridization: Polyacetylene. . . . . . .2. . . . (HC=CH). . . . . . . . . . 4 1. . . . . . . . . . . . . . . .3 Translational Vector: T . . . . . . . 1 1. .. . . . . . . . . . . . .7 Vapor Grown Fibers . . . . . . . . .1 Tight Binding Method for a Crystalline Solid . . . 9 1. . . . . . . . . . . . . . . . . . . . . . .. 2.2.2. . . . . . . . . . . ix . . . . . . . . . . . . .. . . . . . . .1 sp Hybridization: Acetylene. . .2 B Bands of TwoDimensional Graphite . . . . 14 2 Tight Binding Calculation of Molecules and Solids 2. . . HCECH . . . . . . . . . . . . .2.2 Hybridization in A Carbon Atom . . . . . . . . . . . . . . . . . . . .Contents 1 Carbon Materials 1 1. . .2. . 3. .3 . . . . . . . . . . . . . . . . 17 17 17 21 22 25 26 29 35 35 37 39 41 45 48 53 3 Structure of a SingleWall Carbon Nanotube 3. . .5 Isomers of Carbon . .3 sp3 Hybridization: Methane. . . . . . . . . . . .4 Carbon Is Core Orbitals . . 3. .
. .1 Vapor Growth Method . 4. . . . . .6. . 6. . . . . . 5. . . . . . . . . . . . . .4 Landau Energy Bands . . . . 6. . .. . . . .6 Landau Energy Bands: QuantumOscillation . . . . . . . . . . . . 5. . .6. . . 6. . . . ..1 Net Diagrams of a Junction . . 73 73 74 77 79 80 82 83 84 84 85 85 86 86 87 89 95 95 98 100 104 108 111 7 Connecting Carbon Nanotubes 7. . . . . 6. . . . 5 synthesis of Carbon Nanotubes 5. . .2 Nanotube Wetting . . . .9 Growth Mechanisms . . . . . .X CONTENTS 59 59 59 61 65 66 70 4 Electronic Structure of SingleWall Nanotubes 4. . . . . . . . . . . . . . . . . Wetting. . 7. 5. . . . .6 Nanotube Opening. . . . .. . .. . .3 Dispersion of chiral nanotubes . . . . . . . . . . . . .6. . 4. . . . .4. . . . . . . .. . . . . . .. . . .4. . . .. . . 4. . .. . . . . . . . . 4. 5. . . . . . .6. . . . . . . . . . . . . . . . . .8 Temperature Regimes for Carbonization and Graphitization . .2 The Rule for Connecting Two Nanotubes . 5. . .. . . . . .2 Laser Vaporization Synthesis Method .7 Nanotube Doping. . . . . . . . Energy gap . .1 Oneelectron dispersion relations . . . . .1 Free Electron in a Magnetic Field . .2 Other Synthesis Methods . .3 Effects of Peierls distortion and nanotube curvature . . . . . .. . . 6 Landau Energy Bands of Carbon Nanotubes 6. . . . . 5. . . . . . . . . . . .1. . . . . . .. . . . 5. 5. . .1 Nanotube Opening . 4. . . . . 5. .1 SingleWall Nanotube Synthesis . . . . .1 ZoneFolding of Energy Dispersion Relations .2 Density of States. and BN/C Composites . 5. . . . . . . . . 115 115 119 . . . . . . . . . .5 Purification . . . . . . . . . . . . . . . . ... . . .1. . . ..3 Arc Method of Synthesizing Carbon Nanotubes . .2 Energy Dispersion of Armchair and Zigzag Nanotubes . . . . . . . . 5. .. . . . . . . 5. . . . . . . .3 Nanotube Filling . . . . . . . . . . .. .. Filling and Alignment . . . . . . . . . . . . . . ... . . . . . . . . . . .3 Cosine Band in a Magnetic Field . .2 Tight Binding in a Magnetic Field .. . . . .4 Alignment of Nanotubes . . 6. . . 5. . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . Intercalation. . .5 Landau Energy Bands: AharonovBohm . . . . . . . .. 5.4 Vapor Growth and Other Synthesis Methods . . .. . . . . . . . . . . . . .. . . . . . . . .. .
. .5 Coiled Carbon Nanotubes . . . .1. . .. . . .. .1 Zone folding method ..1 Quantum transport in a onedimensional wire . . . . .5 Negative Magnetoresistance . . 152 153 8. . . . . . . . 158 8. . . . . .1. . . . . . .2. .. . . . .. . . . . .3.2... . . . . . . . . . . . . . . .4 Universal Conductance Fluctuations . . . ... . . . .3 An Individual Rope of SingleWall Nanotubes . . . . . .2 Raman experiments on singlewall nanotubes . . 151 8. . . 8. . . . 196 10. 171 9. . . . . . . . . . . . . . 159 9 Phonon Modes of Carbon Nanotubes 163 9. . . .4. . . . . . . . .3 Localization.. .4 Raman Spectra of Nanotubes with Random Orientations . . . . . .. . . . . . .3. . . . 171 9. . . .3. . . . . . . . . . .4.1 A ballistic conductor ( L << L. .. . . .1. . . 145 8. . . . .1. 203 . . . . . ) . . . . . .. . . . . .. . . .2 Phonon dispersion relations for twodimensional graphite . . . . . . . . 7.4 Tunneling Conductance of a Junction . .1. . . . . .3 Shape of a Junction . .1 Lower Frequency Raman Spectra .2.. .... . . .. . . xi . 142 8. . . .4. . . . . . . . . .2 Force constant tensor of a carbon nanotube . . .4 MagnetoTransport in MultiWall Nanotubes . . << L. . .CONTENTS 7. . . . . . . . 173 9.. . . . 144 8. . .2. . . 201 10.. . . 154 8. . . . . . 198 10. . .3 Bond Polarizability Theory of Raman Intensity for Carbon Nanotubes .. .5 Sample Orientation Dependence . . . . L . 187 10. . .. . . . . . . .. ( L . . .3 Force constant corrections due to curvature of 1D nanotubesl78 183 10 Raman Spectra of Carbon Nanotubes 10. . . . . . . .2 Classic transport. . . .1 Attaching Contacts . . . . .. . . 7. . . . . . . . . . . . . .. . . . 120 123 130 8 Transport Properties of Carbon Nanotubes 137 8. . .. . . .2 An Individual SingleWall Nanotube . .2 Higher Frequency Raman Modes . . . . . . . << L .. . .3 Phonon dispersion relations for nanotubes .1 Dynamical matrix for phonon dispersion relations .1 Raman or infrared active modes of carbon nanotubes . 148 8.2 Tkansport experiments on carbon nanotubes . ... . 195 10. . 165 9. . 183 10. . . . . . << L . . . . . L . . . . . .. . . . 192 10. . . . . . . . . 163 9. . . 137 8. .. . . << L ) . .3 Medium Frequency Raman Modes . . .
. . .3. . . References Index 239 253 ..xii 1 Elastic Properties of Carbon Nanotubes 1 11. ... ... . . . . . . .. . 207 .2 Strain Energy of Carbon Nanotubes . .. 213 217 221 11. .3 The Peierls Instability of Nanotubes . .. . .4 Properties of MultiWall Nanotubes .. . . . . .. . .3. . ... CONTENTS 207 .1 Overview of Elastic Properties of Carbon Nanotubes 11.. .. . . .. . . .1 Bond Alternation . ... . ... 210 11. . .. . . . .. ..2 Peierls Distortion of graphite and carbon nanotubes 11. 213 11.. .... . .
and carbon nanotubes. diamond. further research on carbon filaments proceeded more slowly. and others. through the work of Schutzenberger and Schiitzenberger (1890) [2]. The reason why carbon assumes many structural forms is that a carbon atom can form several distinct types of valence bonds. both in the l g t h century and more recently after World War 11.1 History We provide here a brief review of the history of carbon fibers. The first carbon fiber was prepared by Thomas A . which are the macroscopic analog of carbon nanotubes. since carbon filaments were soon replaced by a more sturdy tungsten filament in the electric light bulb. Pelabon [3]. 1.CHAPTER 1. Following this initial pioneering work by Edison. Edison to provide a filament for an early model of an electric light bulb. carbon fibers. Specially selected Japanese Kyoto bamboo filaments were used to wind a spiral coil that was then pyrolyzed to produce a coiled carbon resistor. which could be heated ohmically t o provide a satisfactory filament for use in an early model of an incandescent light bulb [l]. Nevertheless research on carbon fibers and filaments proceeded steadily over a long time frame. where the chemical bonds refer t o the hybridization of orbitals by physicists. Their efforts were mostly directed toward the study of vapor grown carbon filaments. The early history of carbon fibers was stimulated by needs for materia. Carbon Materials Carbon materials are found in variety forms such as graphite. The second applicationsdriven stimulus t o carbon fiber research came in 1 .ls with special properties. This chapter introduces the history of carbon materials and describes the atomic nature of carbon. showing filament growth from the thermal decomposition of hydrocarbons. fullerenes.
it was soon realized that long term effort would be needed to reduce fiber defects and to enhance structures resistive to crack propagation. synthesis of carbon fibers by a catalytic chemical vapor deposition (CVD) process proceeded. Because of the desire to synthesize more crystalline filamentous carbons under more controlled conditions. This stimulation also led to the growth of a carbon whisker [4]. Concurrently. and HOPG has since been used as one of the benchmarks for the characterization of carbon fibers. including rayon. Parallel efforts to develop new bulk synthetic carbon materials with properties approaching single crystal graphite led to the development of highly oriented pyrolytic graphite (HOPG) in 1962 by Ubbelohde and coworkers [7. This stimulation led to great advances in the preparation of continuous carbon fibers based on polymer precursors. The late 1950’s and 1960’s was a period of intense activity at the Union Carbide Corporation. and in developing graphitizable carbons for ultrahigh modulus fibers. CARBON MATERIALS the 1950’s from the needs of the space and aircraft industry for strong. which has become a benchmark for the discussion of the mechanical and elastic properties of carbon fibers.[9] In parallel to these scientific studies.8]. the Aerospace Corporation and many other laboratories worldwide. other research studies focused on control of the process for the synthesis of vapor grown carbon fibers. laying the scientific basis for the mechanism and thermodynamics for the vapor phase growth of carbon fibers in the 1960’s and early 197O’s. stiff lightweight fibers that could be used for building lightweight composite materials with superior mechanical properties.[l0][13] leading to current commercialization of vapor grown carbon fibers in the 1990’s for various applications. nonmetals such as Si.2 CHAPTER 1. showing superior mechanical properties for whisker structures [6]. and by theoretical studies [5]. polyacrylonitrile (PAN) and later mesophase pitch. while decreasing costs . fibers with special characteristics. polymerbased carbon fiber research has continued worldwide. and oxides such as Alz03. with emphasis on greater control of processing steps to achieve carbon fibers with everincreasing modulus and strength. While intense effort continued toward perfecting synthetic filamentary carbon materials] and great progress was indeed made in the early ~ O ’ S . The growth of carbon whiskers was also inspired by the successful growth of single crystal whisker filaments at that time for many metals such as iron. New research directions were introduced because of the difficulty in improving the structure and microstructure of polymerbased carbon fibers for high strength and high modulus applications. mostly in industry.
1.1 [14171. As research on vapor grown carbon fibers on the micrometer scale proceeded. HISTORY 3 . Early work [14. papers were given on the status of fullerene research by Smalley [21].15]. was occasionally observed and reported [14. 1. Discussions at the workshop stimulated Smalley to speculate about the existence of carbon nanotubes of dimensions comparable to (360.S. Dresselhaus [23].. the growth of the initial hollow tube and the subsequent thickening process were reported. These conjectures were later followed . and a review of carbon fiber research by M.17] An example of a very thin vapor grown tubules (< 100 A) is shown in the bright field TEM image of Fig.1. such as shown in Fig. the discovery of a new synthesis method for the efficient production of fullerenes by Huffman [22]. of the commercial products.1: High resolution TEM micrograph showing carbon nanotubes with diameters less than 10 nm [14171. Whereas the outermost layers of the fiber have properties associated with vapor grown carbon fibers.. there may be a continuum of behavior of the tree rings as a function of diameter. Reports of such thin filaments inspired Kubo [18] to ask whether there was a minimum dimension for such filaments. with the innermost tree rings perhaps behaving like carbon nanotubes.[l6. 1. but no detailed systematic studies of such thin filaments were carried out. Direct stimulus to study carbon filaments of very small diameters more systematically [19] came from the discovery of fullerenes by Kroto and Smalley [20]. . In studies of filamentous carbon fibers. Fig. the growth of very small diameter filaments. showed very sharp lattice fringe images for the innermost cylinders corresponding to a vapor grown carbon fiber (diameter < 100 A).1.15] on vapor grown carbon fibers. .1. obtained by thickening filaments such as the fiber denoted by VGCF (vapor grown carbon fiber) in Fig.1. 1. In December 1990 at a carboncarbon composites workshop.
and molecules are unique in many ways. d0=55A. CARBON MATERIALS Fig. In this section we introduce the hybridization in a carbon atom and consider the family of carbon materials. and (c) N = 7 . di=23A. du=65k [19]. It w a s this work which bridged the gap between experimental observation and the theoretical framework of carbon nanotuhes in relation to fullerenes and as theoretical examples of 1 systems.2: The observation by TEM of multiwall coaxial nanotubes with various inner and outer diameters. with suggestions on how zone folding could be used t o examine the electron and phonon dispersion relations of such structures. 1.2) [19). which is known as the hybridization of atomic orbitals. However. clusters. 1. (b) N = 2. the real breakthrou~h carbon nanotube research came with on Iijima’s report of experimental observation of carbon nanotubes using transmission electron microscopy (see Fig. du=67A.4 CHAPTER I . and numbers of cylindrical shells N : reported by Iijima using TEM: (a) N = 5 . D Since the pioneering work of Iijima [19]. the study of carbon nanotubes has progressed rapidly. 12 . Hybridization in A Carbon Atom Carbonbased materials. up in August 1991 by an oral presentation at a fullerene workshop in Philadelphia by Dresselhaus [24] on the symmetry proposed for carbon nanotubes capped at either end by fullerene hemispheres. dj and d o . Carbon is the sixth element of the periodic table and is listed at the top . One distinction relates to the many possible configurations of the electronic states of a carbon atom.
and they are called core electrons. This mixing of 2s and 2 p atomic orbitals is called hybridization. In the crystalline phase the valence electrons give rise to 2 s . 2 s 2 . and the absence of nearby inner orbitals facilitates hybridizations involving only valence s and p orbitals for carbon. Carbon differs from Si and Ge insofar as carbon does not have inner atomic orbitals except for the spherical Is orbitals. is formed. thereby changing the occupation of the 2 s and three 2 p atomic orbitals so as to enhance the binding energy of the C atom with its neighboring atoms. three possibIe hybridizations occur: s p .2. respectively. 232p3 which is denoted by 5S i s 4. Four electrons occupy the 2s22p2 orbitals. the excited state. Ge exhibit primarily sp3 hybridization. denoted by ] s p a ) and Ispa). tIn the free carbon atom. The lack of s p and sp2 hybridization in Si and Ge might be related to the absence of “organic materials” made of Sis and Ge.+ the electronic wave functions for these four electrons can readily mix with each other. In carbon. sp2 and sp3. Since the energy difference between the upper 2 p energy levels and the lower 2 s level in carbon is small compared with the binding energy of the chemical bonds.2. L = 1) using the general notation for a twoelectron mdtiplet. are expressed by the linear combination of 12s) and 12p. Each carbon atom has six electrons which occupy 1s2. other group IV elements such as Si. and these more weakly bound electrons are called valence electrons. 2p. 2p. From the twoelectron orbitals of a carbon atom.1 sp H ~ ~ A c e ~ ~ ~He G C Hi ~ ~~ e .) wavefunctions of the *The ground state of a free carbon atom is 3P (S = 1.. for example 2ps. a linear combination of the 2s orbital and one of the 2 p orbitals of a carbon atom. and 2p2 atomic orbitals. $Because of the electronhole duality. 3 t 2 p electrons is called spn hybridization PI.18 eV above the ground state. 1. 2 .. ~ ~ ~ ~ ~ ~ In s p hybridization. §It should be mentioned that the “organic chemistry” for Si is becoming an active field today.’ The ls2 orbital contains two strongly bound electrons.1. n = 4 and 5 are identical to IZ = 2 and 1. . and 2pz orbitals which are important in forming covalent bonds in carbon materials. two hybridized s p orbitals. ~ Y ~ ~ ~ ~ IN A CARBON ATOM ~ Z A T ~ O N 5 of column IV. whereas the mixing of a single 2 s electron with n = 1 .
we obtain the relationship between the coefficients Ci : c c + 2 4= 1 3 c c c ” c4” 3+ 0. Using the orthonormality conditions (spa(spa) = 0. c.+c. where Ci are coefficients. The shading denotes the posihive amditude of the wavefunction.1 / d so that In Fig.)+Cy)2py)+C.12p.) is elongated in the positive direction of (upper panel).3) is desired for forming a chemical bond that a mixing of 2p orbitals with 2s orbitals occurs. (1. and 2pz orbitals behave like a vector. is unity. 2p. and (SpbISpb) = 1.2) is C1 = C2 = C. the wavefunction shows a directed valence in the direction of y axis. = 1/. i C i + C.) is elongated in the positive direction of 2 .)2pt).). 1.Isp. since the 2p. CARBON MATERIALS + 12s> 3 12px> + + IsPo> 12s>  12px> bpb> Fig.z+c:= 1. = 1.6 CHAPTER 1./2 and C = 4 . A wavefunction C.. 12s) + (2p. is the 2p where C + + .12p. which gives rise to a higher binding energy. (sp. It is only when an asymmetric shape of the wavefunction (see Fig. 1.2) The last equation is given by the fact that the sum of 12s) components in Ispa) and Ispb). The solution of (1.) = 1. The mixing of only 2p orbitals with each other gives rise to the rotation of 2p orbitals. while that of (2s). the overlap of Ispa) with the wavefunction at x > 0 becomes large compared with the original (2p. If we select 12py) for 12p. The shading denotes a positive amplitude of the wavefunction.) is elongated in the negative direction of x. y.3 we show a schematic view of the directed valence of the Ispa) (upper panel) and Jspb) (lower panel) orbitals. 1. 1. Thus when nearestneighbor atoms are in the direction of x axis. while that of 12s) .3: sp hybridization.) is elongated in the negative direction of 2 (lower panel). ( 2 .) function. z ) .= c.(2p. The wavefunction of 12s) 12p.” = 1.
C.O. HC=CH. A simple carbonbased material showing s p hybridization is acetylene.2. ( f i / 2 . wavefunction whose direction of positive amplitude is the direction (Csl C. wavefunctions form relatively weak bonds called T bonds with those of the other carbon atom. All u bonds shown in the figure are in a (xy) plane. The acetylene molecule HCzCH is a linear molecule with each atom having its equilibrium position along a single axis and with each carbon atom exhibiting s p hybridization. In sp2 hybridization.2 sp2 Hybr2~z~ation: o ~ y a c e ~ y ~(HC=CH)n F e~e.) Cy. through sp2 hybridization. and 2% wavefunctions of each carbon atom are perpendicular to the u bond. called a u bond. (HC=CH)as is shown in Fig.l . All u bonds shown in the figure are in the plane..2.. 3 ) correspond to (C. and in addition..4 are ( 0 . 1. one u bond and two T bonds yields the triple bond of HCzCH.C.l. 1 / 2 . and 2 q . where carbon atoms form a zigzag chain with an angle of 120O.f i / 2 . O .l. where 5 is used by chemists to denote a triple bond between two carbon atoms. 0 ) . The 2p wavefunctions of Eq. respectively.1. the corresponding sp2 hybridized . the 2s orbital and two 2p orbitals. a T orbital for each carbon atom exists perpendicular to the plane. 0 ) . Since the directions of the three u bonds of the central carbon atom in Fig.C. and ( . in addition.) = ( l .. and. An example of sp2 hybridization is polyacetylene. Thus. are hybridized. and 2p. O ) . 1.4: transpolyacetylene. and the 2p. HYBRIDIZATION IN A CARBON ATOM 7 'i' I \ C /"\ C /"\/ C I I I H H H yL x H Fig. for example 2p.O).4. The hybridized Ispa) orbital of one of the carbon atoms in HCrCH forms a covalent bond with the ISPb) orbital of the other carbon atom. (HC=C€I)nl the carbon atoms form a zigzag chain with an angle of 120' . one T orbital per carbon atom exists p e r p e n d ~ c u to the l~ plane. C z ) . ( 1 . The 2p. 1 / 2 .)= (1. O ) and (C.
l ). . l ) . .4) are positive. we obtain three equations for determining the coefficients. The four directions of tetrahedral bonds from the carbon atom can be selected as (l . ..8 CHAPTER 1 . the 2s orbital and three 2 p orbitals are mixed with each other..G T 12py) We now determine the coefficients C1.. and 2py orbitals as follows: ISP3 = C112S) . . In order to make elongated wavefunctions to these direction. .J1.5) given by C1 = C = l / f i and C. 1.J1.l . c ) are made from 2s. as shown in Fig.c2 2 ClC3+ . 1. 1.5) JCZj =o = 0..4.l / f i . 2p. and orthonormal atomic +  1 (1. 1. and these threedirected orbitals are denoted by trigonal bonding. the coefficients of the )2py)terms in Eq. (1. (i = 1. = c. l).3 sp3 Hybridization: Methane. (1. forming an sp3 hybridization. (CH4) The carbon atom in methane. Ci (i = 1. but are changed to .C2. and Cs. (1. = . 12p.l). CARBON MATERIALS orbitals Isp:) (i = a .1. denoting different directions for the nearestneighbor hydrogen atoms.+c.4). 2 The sp2 orbitals thus obtained have a large amplitude in the direction of the three nearestneighbor atoms. b .4) but with the four unknown coefficients. There are two kinds of carbon atoms in polyacetylene.4. ( . F'rom the orthonormal requirements of the Ispi) and 12s). 3 ) : c. (1. Ci. 1 .1 .2. (1. . .1 2 ~ ~ ) the lower carbon atoms for in the figure. (CH4).) orbitals.+c. For the upper carbon atoms in Fig. Using equations similar to Eq. yielding the solution of Eq.. 1. provides a simple example of sp3 hybridization through its tetragonal bonding to four nearest neighbor hydrogen atoms which have the maximum spatial separation from each other.
while the remaining fourth direction is determined by orthonormal conditions imposed on the 2p orbitals.1. However the covaient bonding energy for u orbitals is larger (3 4 eV per bond) than the 2s2p energy separation.( n 1) electrons are in ?r orbital. . the energy of the Is core level is measured relative to the position of the *This notation denotes an admixture of sp2 and sp3 hybridization. Because of the small overlap between the Is orbitals on adjacent atomic sites in the solid.4 Carbon Is Core Orbitals Carbon Is core orbitals do not generally affect the solid state properties of carbon materials. n 1 electrons belong to the carbon atom occupied in the hybridized u orbital and 4 . f f Y ~ R X ~ X Z A T A 0 ~ IN ~ CARBON ATOM 9 wavefunctions. the four valence electrons occupy 2s' and 2p3 states as u bonding states. Using Xray photoelectron spectroscopy (XPS). It is important to note that the directions of the three wavefunctions in the sp3 hybridization are freely determined. The excitation of 2s' and 2p3 in the solid phase from the 2sa2p2 atomic ground state requires an energy approximately equal to the energy difference between the 2s and 2 p (4 eV) Levels. In the case of sp3 hybridization. This fact gives rise to possible sp2 hybridization of a planar pentagonal (or heptagonal) carbon ring and sp2+q (0 < q < I) hybridization* which is found in fullerenes. A general sp2+q hybridization is expected to have a higher excitation energy than that of the symmetric sp2 hybridization discussed here because of the electronelectron repulsion which occurs in the hybridized orbital. + +  1. since the energy position of the 1s core levels is far from the Fermi energy compared with the valence levels.2. we obtain the sp3 hybridized orbitals in these four directions: In general for spn hybridization. the energy spectrum of the 1s core levels in carbon materials is sharp and the core level energies lie close to that of an isolated carbon atom.2.
The XPS data are shown on two energy sales to emphasize features near EF (upper spectrum) and features farther away in energy (lower spectrum) "&]. XPS spectra have been obtained for the unoccupied orbitals for a variety of fullerenes. narrow main line (peak #1 in Fig.5) identified with the emission of a photoexcited electron from the carbon 1s state. which has a binding energy of 285. 1.65 eV at halfmaximum intensity [25]. we can see welldefined peaks which show an in6 tense. XPS refers to the photoelectron spectroscopy (PES) process when the excitation photon is in the xray range and the electron excitation is from a core level. c Is 1. For example. The sharp fea6 ture 1 is the fundamental XPS line. while the downshifted features 210 refer t o c 0 excita6 tions (see text). 1.10 CHAPTER 1. Specifically. CARBON MATERIALS c. the 1s core level shifts in energy relative to the vacuum level by an amount depending on the interaction with nearestneighbor atoms. In this spectrum..9 eV hv= 1486. vacuum level.0 eV and a very small linewidth of 0. and this effect is known as the chemical shift of XPS. 1. . Fig. Furthermore. and this energy difference is especially sensitive to the transfer of electric charge between carbon atoms.5 shows the XPS spectrum for c0 [25].6 eV I 10 5 0 l I 1 I l L I I 1 1 I I 1 I I J 60 45 30 15 0 Relalive Binding Energy (eV) Fig.5: Xray photoelectron spectra (XPS) for the carbon 1sderived satellite structures for c 0 films [25].
Plasma excitations are also prominently featured in core level electron energy loss spectra (EELS). A threedimensional solid is formed by gathering these carbyne chains. It is interesting that sp2 hybridization which forms a planar structure in twodimensiona1 graphite also forms a planar local structure in + .9eV semiconductor 0D 11 Dimension isomer hybridization density [g/cm31 Bond Length electronic properties carbon 2.40(C=C) 1.22. (n 1) u bonds per carbon atom are formed.1. four D bonds defining a regular tetrahedron are sufficient to form a threedimensional structure known as the diamond structure. In s p hybridization.13 1.54(CC) insulating E.5 Isomers of Carbon The sp" hybridization discussed in the previous section is essential for determining the dimensionality of not only carbonbased molecules. while features 6 and 10 represent intramolecul~ plasmon collective oscillations of the T and cr charge distributions.1: Isomers made of 1D CEO nanotube fullerene carbyne sp2 SP2 (SP) 1.44(C=C) semimetal 3. these cr bonds making a skeleton for the local structure of the ndimensional structure. 1.47eV The sharpest sideband feature in the downshifted XPS spectrum (labeled 2) is identified with an onsite molecular excitation across the HOMOLUMO gap at 1. Carbon is the only element in the periodic table that has isomers from 0 dimensions (OD) to 3 dimensions (3D).683.2.72 1.1.44(C=C) 1.0 2. In sp3 hybridization.42(C=C) 1.9 eV [ZS].515 23 1. as is shown in Table 1. 4 and 5 are the photoemission counterparts of electric dipole excitations seen in optical absorption. which is known as a 'carbyne'.46(CC) semiconductor metal or E. HYBRIDIZATION IN A CARBON ATOM Table 1. Features 3.D graphite fiber SP2 3D diamond amorphous SP3 tJ4l 2. In sp" hybridization.2. = 1.26 N2 1. but also carbonbased solids. Here we introducepossible structures of carbon materials in the solid phase. = 5. which are closely related t o the sp" hybridization. two c bonds make only a onedimensional chain structure.
LllUlD 400 OUMONO ’ the closed polyhedra (0dimensional) of the fullerene family and in the cylinders (1dimensional) called carbon nanotubes. be related to carbynes. as indicated by the phase diagram of Fig. randomly. which consists mainly of sp2 hybridization. 1. is a graphite with random stacking of graphitic layer segments. the graphite phase with strong inplane trigonal bonding is the stable phase. and an unexplored high pressure phase. which has not been studied in much detail and may. CARBON MATERIALS Fig.12 CHAPTER 1 . 1400 OlPUOND \. A carbon fiber. Other phases shown in the diagram include hexagonal diamond and a high temperaturehigh pressure phase. which has been studied at low pressures and high temperatures. consists of many graphitic planes and microscopically exhibits electronic properties that are predominantly twodimensional.6: One version of the phase diagram of carbon suggested by Bundy [26]. threedimensional material in which sp2 and sp3 hybridization are both present. Under ambient conditions and in bulk form. Under the application of high pressure and high temperature (both of which are somewhat reduced when catalyst particles like iron or nickel . meteorites and shockquench. thereby forming a solid lubricant. Closely related to carbon nanotubes are carbon fibers which are macroscopic onedimensional materials. because of their characteristic high length to diameter ratio. 1. which may be metallic. Liquid carbon. amorphous graphite can behave like a twodimensional material. are also indicated on the figure. The diamond (Di) and graphite (Gr) phases are emphasized in this figure. Because of the weak interplanar interaction between two graphitic planes. in part. these planes can move easily relative to each other.6 [26281. . Amorphous graphite. Amorphous carbon is a disordered. In this sense. denoted in the diagram by du Pont. however. .
as the subject of the following chapters. near the surface of the solidified droplets formed upon solidification [32]. in principle. * C=C. which are related to nanotubes.” This carbon structure is stable at high temperature and pressure as indicated phases. ion micromass analysis. ~ Y ~ ~ I ~ ~ Z A T IC A NB O N T O ~ IN A O ~ A 13 are used). transformation to the diamond structure takes place.2. Carbynes are silverin the phase diagram of Fig.I .31]. and spectroscopic measurements which show some characteristic features that identify carbynes in general and specific carbyne polymorphs in particular. which is graphite.24 A. The crystal structure of carbynes has been studied by xray diffraction through identification of the Bragg peaks with those of synthetic carbynes produced from the sublimation of pyrolytic graphite [33.68 A [31]. * Itp for la > 10 has been reported in rapidly quenched carbons and is referred to as “carbynes. it will very slowly transform back to the thermodynamically stable form of solid carbon.37].6 as shockq~enched white in color and are found in meteoritic carbon deposits. A polymeric form of carbon consisting of chains [. carbynes and carbon fibers. It has been reported that carbynes are formed during very rapid solidification of liquid carbon. Application of pressure converts the  . Some researchers [31351 have reported evidence that these linearly bonded carbon phases are stable at temperatures in the range 2700 < T < 4500 K. where the carbynes are mixed with graphite particles. Carbynes were first identified in sampfes found in the Ries crater in Bavaria [36] and were later synthesized by the dehydrogenation of acetylene I31. Synthetic carbynes have also been prepared by sublimation of pyrolytic graphite [30. 1. Hereafter we introduce the ‘onedimensional’ isomers.94 A. When exposed to various perturbations. Once the pressure is released.. cp = 7. In fact. both being hexagonal and with lattice constants a. diamond remains essentially stable under ambient conditions although. scanning electron microscopy (TEM) .2. diamond will quickly transform back t o the equilibrium graphite phase.6 Carbynes Linear chains of carbon which have s p bonding have been the subject of research for many years [29]. ca = 15. a@= 8. such as irradiation and heat.36 A. 1. The carbynes have been characterized by xray diffraction. two poIymorphs of carbynes (labeled Q and /3) have been identified. = 8.37].
Vaporgrown carbon fibers with micrometer diameters and lengths of 30 cm provide a close analogy t o carbon nanotubes with diameters of nanometer dimensions and similar length to diameter ratios (see Chapter 5).13 g/cm3 for the p phase [38]. The preparation of these fibers is based on the growth of a thin hollow tube of about 1000 A diameter from a transition metal catalytic particle (100 di diameter) which has been supersaturated with carbon from a hydrocarbon gas present during fiber growth at 1050OC. Because of the difficulty in isolating carbynes in general.7 Vapor Grown Fibers Vaporgrown carbon fibers can be prepared over a wide range of diameters (from less than 1000 A to more than 100 prn) and these fibers have hollow cores [9].68 g/cm3 for the a phase and 72 and 3. In fact vaporgrown fibers with diameters less than lOOA were reported many years ago [41431. respectively.7(b)]. 1. In the solid form. and after heat treatment to about 30OO0C.44]. 1. The numbers of atoms per unit cell and the densities are. these carbynes have a hardness intermediate between diamond and graphite. Despite the many precursors that can be used to synthesize carbon fibers. These densities determined from xray data [31] are in rough agreement with prior estimates [39. Asprepared vaporgrown fibers have an “onion skin” or “tree ring” morphology [Fig. The thickening of the vaporgrown carbon fiber occurs through an epitaxial growth process whereby the hydrocarbon gas is dehydrogenated and sticks to the surface of the growing fiber. they form facets [Fig. the preferred orientation of the graphene planes is parallel t o the fiber axis for all types of carbon fibers.40]. 144 and 2. CARBON MATERIALS a phase into the . thereby accounting for the high mechanical strength and high modulus of carbon fibers [9].14 CHAPTER 1. and specific carbyne polymorphs in particular . It is expected that other less prevalent carbyne polymorphs should also exist.7(a)]. 1. these faceted fibers are closest to crystalline graphite in both crystal structure and properties.f3 phase. little is known about their detailed physical properties.2. Subsequent heat treatment to w25OO0C results in carbon fibers with a tree ring concentric cylinder morphology [44]. Carbon fibers represent an important class of graphiterelated materials from both a scientific and commercial viewpoint. The commercial pitch and PAN fibers with other . each having different crosssectional morphologies [9. Of all carbon fibers [9].
7: Sketch illustrating the morphology of vaporgrown carbon fibers (VGCF): (a) asdeposited at llOO°C [9]. Typical diameters for these individual commercial carbon fibers are 10 pm. These fibers are woven into bundles called tows and are then wound up as a continuous yarn on a spool. are exploited for their extremely high bulk modulus and high thermal conductivity.2. while the commercial PAN (polyacrylonitrile) fibers with circumferential texture are widely used for their high strength [9]. 1. HYBRIDIZATION IN A CARBON ATOM 15 a b Fig.44].1. The high modulus of the mesophase pitch fibers is related to the high degree of caxis orientation of adjacent graphene layers.  . morphologies (not shown). which inhibit the slippage of adjacent planes relative to each other. and since the fibers are produced in a continuous process. (b) after heat treatment to 30OO0C [9]. while the high strength of the PAN fibers is related to defects in the structure. The remarkable high strength and modulus of carbon fibers are responsible for most of the commercial interest in these fibers [9. they can be considered to be infinite in length.
.
CHAPTER 2.46]. lattice vectors. There are many possible functional forms of 9 which satisfy Eq. the 7r electrons are valence electrons which are relevant for the transport and other solid state properties. (2) the numerical accuracy only depends on the number of the plane waves used. However. 2. Tight Binding Calculation of Molecules and Solids In carbon materials except for diamond. + 3). The reason why plane waves are commonly used is that: (1) the integration of the plane wave wavefunction is easy and can be done analytically. The most commonly used form for Q is a linear combination of plane waves. any wave function of the lattice. and is the wave vector[45. Tight Binding Method for a Crystalline Solid In this section we explain the tight binding method for a crystalline solid. In the following sections.1). we show some examples of energy bands for carbon materials discussed in the Chapter 1.1. 21 . (2. a'i. the plane wave method also has limitations: (1) the scale of the a 17 . should satisfy Bloch's theorem where Tai is a translational operation along the lattice vector 4. (i = 1.1 Secdur ~ q ~ u ~ ~ o n Because of the translational symmetry of the unit cells in the direction of the . A tight binding calculation for the 7r electrons is simple but provides important insights for understanding the electronic structure of the 7~ energy levels or bands for graphite and graphiterelated materials. $.
the 'pj's in the N (. the phase factor appearing in Eq. ) The merits of using atomic orbitals in Bloch functions are as follows: (1) the number of basis functions. From this boundary condition. Bloch function @j(z. from which the wave number lC is related by the integer *The limitations of the tight binding method are that: (1) there is no simple rule to improve the numerical accuracy and (2) atomic orbitals do not describe the interatomic region. The number of atomic wavefunctions in the unit cell is denoted by n .i direction.18 CHAPTER 2. = 1.q is given by. n . (2.q in Eq. (2. Another functional form which satisfies Eq. (2. (2.1) is based on the j. TIGHT BINDING CALCULATION computation is large.2).he periodic boundary condition for the M in each S. (2.2) to represent the Block functions. where we use t.* Hereafter we consider the tight binding functions of Eq. can be small compared with the number of plane waves. and (2) it is difficult to relate the plane wave wavefunction to the atomic orbitals in the solid. Here R' is the position of the atom and pj denotes the atomic wavefunction in state j.th atomic orbital in the unit cell (or atom).1) since z.2) satisfies Eq.loz4) unit cells are weighted by the phase factor exp(iz 2 and are then summed over the lattice vectors of the whole crystal. and we have n Bloch functions in the solid for a given To form @j(c. (2. . It is clear that Eq. and ( 2 ) we can easily derive the formulae for many physical properties using this method. N1/3 unit vectors consistent with the boundary condition imposed on the translation vector T M ~ .2) satisfies exp{ikMui} = 1. A tight binding.
n ) as a function of 5 is given by . as k. the wavevector is defined for the z.2.3 as follows: q z . q= j'=l c n Cjjl(rC'>@j. + The jth eigenvalue Ej(k) (j= 1.. (2.9) for a given value. (2.?Z).7) and making a change of subscripts. we obtain the following equation. R j j ~ ( 2 ) S j j t ( i ) are called transfer and integral matrices and overlap integral matrices. the coefficient C$ is optimized 80 as to minimize &(Z). y and z directions. TIGHT BINDING METHOD FOR A CRYSTALLINE SOLID 19 In three dimensions. .. n n C CGCijt(@jl@j.6) into Eq.*. where H is the Hamiltonian of the solid. the summation in Eq. j. j ' = l.* Bjj/(lc) { @ j p i I @ j / ) . where the ki can be considered as continuum variables.'. n).j}=l where the integrals over the Block orbitals. 3 (2. (2.q are should also satisfy Bloch's theorem.3( j = 1.) C Sjj. Sjj. (2. . The eigenfunctions in the solid @ j ( z . are expressed by a h e a r combination of Bloch functions @ji[Z.9) When we fix the values of the n x n matrices ' ? i j j t ( i ) and Sjji($) in Eq.ji=l j. respectively. . Icy and lcz. (2. * .(i)CGCij. * . Substituting Eq.1.(lc'.6) where C j j ~ ( $ ) coefficients t o be determined. Since the functions Sj(Z.6) is taken only for the Bfoch orbitals @j/(g.$) = = ((ajlay) ( j . Thus M 3 = N wave vectors exist in the first Brillouin zone. with the same value of 2.where n is the number of Bloch wavefunctions. which are defined by .
while fixing the other Ciji. and is an equation of degree + n .and Cij coefficients. (2. (2.20 CHAPTER 2. (i 'Since C. we obtain C Rjji(k)Ciji = Ei(Z)C Sjji(Z)Ciji.14) where Eq.13) Transposing the right hand side of Eq.+we obtain zero for the local minimum condition as follows. and C:. whose solution gives all n eigenvalues of Ei( i) = 1. is generally a complex variable with t w o degrees of freedom. can be varied independently.. .11) j'=l ji=l Defining a column vector. (2. CGl. Thus the eigenfunction is given only when the inverse matrix does not exist.8) into the second term of Eq. determined for each $.E i ( z ) S ] exists.Ei(i)S]' to obtain Ci = 0 (where 0 denotes the null vector).13) to the left. . N N (2.. (2. + N N (2.10) N When we multiply both sides of Eq. c = i Eq. (2.. (2.ES] = 0.14) is called the secular equation. When we take a partial derivative for Ci. TIGHT BINDING CALCULATION It is noted that the coefficient C j is also a function of iand therefore Czj is T .10). a real and a complex part. (2.10) by Sjji(~)C~Cij~ and substitute j. both C.12) G N xci = E j ( i ) S C i .jl=l the expression for E i ( i ) of Eq. (2. we obtain ['H E i ( i ) S ] C i = 0. we multiply both sides by [X. n ) for a given k.11) is expressed by (c:)l (2. consistent with the condition given by det[X . which means that no wavefunction is obtained. . If the inverse of the matrix ['Id .
(2. from which the updated electron occupation is determined using. and points along the high symmetry axes. Specify the Bril~ouin zone and the reciprocal lattice vectors.* 4. The eigenvalues Ei(g) are a periodic function in the reciprocal lattice. &. Tightbinding calculations are not selfconsistent calculations in which the occupation of an electron in an energy band would be determined selfconsistently. the oneelectron energy eigenvalues E . the eigenvalues are said to have been obtained selfconsistently. (2. ' . then the SlaterKoster extrapolationscheme results. calculate the transfer and the overlap matrix element. which can be described within the first Brillouin zone. When the input and the output of occupation of the electron are equal to each other within the desired accuracy. Eq. it is difficult t o show the energy dispersion relations over the whole range of k values. Specify the unit cell and the unit vectors.14). *Whenonly the transfer matrix is calculatedand the overlap matrix is taken as the unit matrix.14).7) and (2.1. In a two or three dimensional solid. Select the high symmetry directions in the Brillouin zone. The actual procedure of the tight binding calculation is as follows: # 1.. 2. solve the secular equation Eq. (2. and thus we plot Ei($) along the high symmetry directions in the Brillouin zone.Using the expression for Ei(2) in Eqs.2 Procedure for obtaining the energy dispersion In the tight binding method. the coefficients Ci as a function of $ are determined. (2. n ) and the coefficients Cij($). ( l ) are obtained by solving the secular equation Eq. For the selected $ points. For the selected $ points. for example. Specify the coordinates of the atoms in the unit cell and select n atomic orbitals which are considered in the calculation. .11). . of high symmetry i 2. for a number points. 3. 4. That is. the potential of the Hamiltonian is calculated. In order to obtain the energy dispersion relations we (or energy bands) E{($)). Mulliken's gross population analysis [47]. solve the secular equation. for given electron occupation. 3cij and Sij.14) and obtain the eigenvalues Ei(2) (i = 1.
.2. The Bloch orbitals consisting of A and B atoms are given by 4 (2. in the unit cell. for the A or B .. C I Fig.... louin zone is the line segment a/n < b < a / a . In Fig... and showing two inequivalent carbon atoms. In applying these calculational approaches t o real systems.2 Electronic Structure of Polyacetylene A simple example of nenergy bands for a onedimensional carbon chain is polyacetylene (see Sect. As discussed in Sect.*.2)... 1.1 we show.. 2. within the box defined by the dotted lines... The lattice unit vector and the reciprocal lattice vector of this onedimensional molecule are given by a'l = (a.. 2.O) and b l = ( a / 2 ~ .. iH i I \ dp/\ ci c i 1 : H i / H .15) where the summation is taken over the atom site coordinate R. H i I ... thus giving rise to two nenergy bands called bonding and antibonding nbands in the first Brillouin zone....1: The unit cell of iranspolyacetylene bounded by a box defined by the dotted lines... 0 . in the unit cell.2.. the symmetry of the problem is considered in detail on the basis of a tightbinding approach and the transfer and the overlap matrix elements are often treated as parameters selected to reproduce the band structure of the solid obtained either experimentally or from first principles calculations. TIGHT BINDING CALCULATION . 1..which contains two inequivalent carbon atoms. A and B.2.22 CHAPTER 2. 0.. A and B... there is one 7relectron per carbon atom. Both extrapolation methods such as 5 perturbation theory or interpolation methods using the SlaterKoster approach are commonly employed for carbonrelated systems such as a 2D graphene sheet or 3D graphite [9]. the unit cell for transpolyacetylene (CH). 2. The Bril. 0 )respectively..
In the real (CH).16) the maximum contribution to the matrix element RAAcomes from R = R'. (2.17) and denoted byt. (2. simplicity. 'Note that czP is not simply the atomic energy value for the free atom. and the two atomic integrations in Eq. (2. The matrix element X E A ( T ) obtained is from X A B ( Y ) through the Hermitian conjugation relation 3 .. In Eq. See details in Sect. t = ('PA(TR)lXIPB(rRf a/2))* (2. (2. bond alternation occurs. compound.3A bonds.17) me not equal. +(terms equal to or more distant than R = R' & 2a) = €a.. in which the bond energy alternates between 1. 11. we obtain X B A = FLAB.5A bonds).18) It is stressed that t has a negative value..The next order * contribution t o X A A comes from terms in R = R ' f a .3.The largest contribution to X A B ( P ) arises when atoms A and B are nearest neighbors. The ( 2 x 2) matrix Hamiltonian. ELECTRONIC STRUCTURE OF POLYACETYLENE 23 carbon atoms in the solid.15) into Eq.1 . Thus.l = X. p . ( o . and thus the lattice becomes deformed by a process called the Peierls instability. we only consider the cases R' = R f a/2 and neglect more distant terms to obtain = 2t cos(lca/2) where the transfer integral 1 is the integral appearing in Eq. P = A .2. tHere we have assumed that all the T bonding orbitals are equal (1.9). and this gives the orbital energy of the 2p level.7A and 1. + (terms equal to or more distant than R = R' f a). ~ 2 ~ . B ) is obtained by substituting Eq. in the summation over R'.2. the electronic energy always decreases more than the lattice energy in a onedimensional material. (2. but since ~ ~ X A B is real. Although the distortion of the lattice lowers the energy.d = A. Next let us consider the matrix element X A B ( T ) . When o = . X . Similarly. which will be neglected for also gives cZp for the same order of approximation. because the Hamiltonian contains a crystal potential.
2.4(t . 1. . (2.s E ) cos2(ka/2) ~ = 0. The levels E+ and E. Curves E+(L)and E(k)are called bonding a and antibonding a* energy bands. TIGHT BINDING CALCULATION L J 2.R k a/2)). respectively.are degenerate at La = &T.] is given by 2(t .5 0.2.19) S = ( ‘ P A ( r . 2.sE) COS(LQ/~) ~2~ . except that the intraatomic integral yields the energy for the crystal Hamiltonian Xij. .s E ) CoS(ka/2) E 2(t . where we use values for the parameters.20) = (cap . The overlap matrix Sij can be calculated by a similar method as used for Xij. each with a different + . ~2~ = 0.0 0.( k ) are called bonding a and antibonding a* energy bands.21) with values for the parameters t = .5 1. given by Eq.1 and s = 0.24 CHAPTER 2.0 ka/n 0. .0 Fig.E)’.2. t = 1. Since there are two a electrons per unit cell.R)l(oB(r .sign defines the other branch.< L < ) 1 f 2s cos(ka/2) ’ Q Q (2. and s = 0. respectively. if we assume that the atomic wavefunction is normalized. where s is the overlap integral between the nearest A and B atoms. 2.].20) given by E*(i) = EZp f 2t cos(Ica/2) a a (. and the plot is given in units of Itl. as shown in Fig. .2: Th: energy dispersion relation E*(L) for polyacetylene [(CH). The secular equation for the 2pz orbital of [(CH).21) in which the sign defines one branch and the . (2.0 I . (2. but the overlap matrix rather yields unity for the case of Saj. SAA = SBB = 1 and SAB = S B A = 2scos(ba/2). yielding the eigenvalues of the energy dispersion relations of Eq. E + ( k ) and E .E 62p (2.
. the real space unit vectors 21 and a'z of the hexagonal lattice are expressed as 4  (2... ....428L. Fig. Thus the electronic structure of 2D graphite is a first approximation of that for 3D graphite... which makes the total energy lower than &zp. respectively.. TWODIMENSIONAL GRAPHITE 25 (b) g$vq@ . acc=1. spin orientation..y coordinates shown in the Fig.46A is the lattice ~ ~ n s t a of t two21 n dimensional graphite. respectively. are unit vectors in real space.K < * "L ~ g@$@ M . 23 . respectively..3..22) where Q = 11 = 1221 = 1. forms a twodimensional (2D) material. 2... .. ( i = l . A single layer of graphite. . r. . called 2D graphite or a graphene layer. Even in 3D graphite. In the s... &$.3 we show (a) the unit cell and (b) the Brillouin zone of twodimensional graphite as a dotted rhombus and shaded hexagon..3... I< and M . and b1 and bz are reciprocal lattice vectors.. Correspondingly the unit vectors & and & of the recip . 2. the interaction between two adjacent layers is small compared with intralayer interactions. 2. In Fig. TwoDimensional Graphite Graphite is a threedimensional (3D) layered hexagonal lattice of carbon atoms. .3: (a) The unit cell and (b) Brillouin zone of twodimensional graphite are shown as the dotted rhombus and the shade_d hexagon..42 x & = 2... Energy dispersion relations are obtained along the perimeter of the dotted triangle connecting the high symmetry points.35A is much larger than nearestneighbor distance between two carbon atoms..2. i34. where 21 and Za.. 2 ) are unit vectors and reciprocal lattice vectors. both electrons occupy the bonding ?r energy band. and bi. since the layerlayer separation of 3...
Here we define the three high symmetry points. In Sect. When we consider only nearestneighbor interactions. provide the basis functions for 2D graphite. and thus X A A = X B B = c a p .22.3(b). makes 7r covalent bonds. r. 2.24) . By selecting the first Brillouin zone as the shaded hexagon shown in Fig. respectively. the corner.3(b). while. We then consider the contribution t o as follows: Eq. 2. which are denoted by the vectors l?1.3. which is perpendicular to the graphene plane.3.1 T Bands of TwoDimensional Graphate Two Bloch functions. as shown in Fig. constructed from atomic orbitals for the two inequivalent carbon atoms at A and B in Fig. then there is only an integration over a single atom in X A A and X B B . The direction of the unit vectors & and of the reciprocal hexagonal lattice are rotated by 90' from the unit vectors a'l and 2 2 of the hexagonal lattice in real space.&. TIGHT BINDING CALCULATION (2. and I&. 2.26 rocal lattice are given by: CHAPTER 2.3. (2. As discussed in Sect. and the other 2p. The energy dispersion relations are calculated for the triangle I'Mli' shown by the dotted lines in Fig. 2. 2.17) from 21.16). because we know that the x energy bands are covalent and are the most important for determining the solid state properties of graphite. and (2. orbital.23) corresponding to a lattice constant of 47rlfia in reciprocal space. (2. three u bonds for 2D graphite hybridize in a sp2 configuration. and the center of the edge.3.2. K and M as the center.9. as is shown in Eq. we must consider the three nearestneighbor B atoms relative to an A atom. 2.1 we consider only x energy bands for 2D graphite. 2. For the offdiagonal matrix element X A B . the highest symmetry is obtained for the Brillouin zone of 2D graphite.
3. and the H a ~ l t o n i a n forms a Hermitian matrix. ing Eq. Here we use the parameters ezp = 0.48]. 2. 5f(k)* 5 ~ ( ~ ) ) (2. and ky: k. we write %!BA = %> in which * denotes the complex conjugate. Us!.signs. (2. (2.033eVl and s = 0. and SAB = s f ( k ) = SSA. (2.3(b). and the Iower half is the renergy bonding band. The upper R* band and the lower T band are degenerate at the K points through which *We often use the symbol 70 for the nearest neighbor transfer integral.25). (2.y coordinates of Fig.26) 1  . 3).2. which give the antibonding x* band. Here s has the same definition as in Eq. so that the explicit forms for %! and S can be written as: 3c= (E2P tfW* E2p Solving the secular equation det(% ES) = 0 and using ‘ and S as given in E Eq.t = 3. Using the 2. the overlap integral matrix is given by SAA= SBB = 1.18)* and f ( k ) is a function of the sum of the phase factors of esE’Aj (j= 1. +yo is defined by a positive value.19).27) where the + signs in the numerator and denominator go together giving the bonding x energy band.a) I _ (2. and likewise for the . f(k) is given by: 1 f(k) = eik=a/&f Since f ( k ) is a complex function. The upper half of the energy dispersion curves describes the R*energy antibonding band. .129 in order to reproduce the first principles calculation of the graphite energy bands [9. (2. TWODIMENSIONAL GRAPHITE 27 where t is given by Eq. the energy dispersion relations of twodimensiona~ shown throughout the Brillouin zone and the inset shows the energy dispersion relations along the high symmetry axes along the perimeter of the triangle shown in Fig. while the function w [ c ) is given by: graphite are In Fig. the eigenvalues E(Z) are obtained as a function w($).4.26). 2. + + 2eiksa/2flcos (k.25) * ~ f ( ~ )S= ( 1 ). 2.3(a).
Since a detailed calculation of the density of states shows that the density of states at the Fermi level is zero. the site energy ~2~ would be different for B and N . The existence of a zero gap at the K points comes from the symmetry requirement that the two carbon sites A and B in the hexagonal lattice are equivalent to each 0ther. as shown in Chapter 3. Since there are two ?r electrons per unit cell. and therefore the calculated energy dispersion would show an energy gap between the n and T * bands.28 CHAPTER 2. 2. in the SlaterKoster scheme) are commonly lased as a simple approximation for the electronic structure of a graphene layer: tIf the A and B sites had different atoms such as B and N. The energy dispersion relations in the case of s = 0 (i.4: The energy dispersion relations for 2D graphite are shown throughout the whole region of the Brillouin zone. (2. twodimensional graphite is a zerogap semiconductor. the Fermi energy passes.. The inset shows the energy dispersion along the high symmetry directions of the triangle I'MK shown in Fig. the A and ?r* bands become symmetrical around E = cap which can be understood from Eq.3(b) (see text). When the overlap integral s becomes zero. these two A electrons fully occupy the lower T band.e. . 2. TIGHT BINDING CALCULATION Fig.t The existence of a zero gap at the A points gives rise to quantum effects in the electronic structure ' of carbon nanotubes.27).
at the high symmetry points. f t and 0.5. (2.”. TWODIMENSIONAL GRAPHITE 29 In this case. s A A = ( i 0 :0) 1 i . and 2p. r. The calculation of the Hamiltonian and overlap matrix is performed analytically. 2. We will calculate these six u bands using a 6 x 6 Hamiltonian and overlap matrix. 2s. which is consistent with the three connected n bonds. three of the six c bands are bonding u bands which appear below the Fermi energy.16) and e2s is the orbital energy of the 2s levels. respectively.3.2 u Bands of TwoDimensional Graphiie Finally let us consider the IT bands of twodimensional graphite. The matrix element for the Bloch orbitals between the A and B atoms can be obtained by taking the components of 2p. 2p:.bes. the 0 and 7r energy bands can be solved separately.3.30) where ezp is defined by Eq. Then the matrix elements coupling the same atoms (for example A and A ) can be expressed by a 3 x 3 small matrix which is a subblock of the 6 x 6 matrix. .1. using a small number of parameters. because matrix elements of different symmetry types do not couple in the Hamiltonian. 2. 2 p t . Thus the band width gives I6t1. yielding six u bands. upon mirror reflection about the zy plane. 2px and 2py. we show how to rotate the 2px atomic orbital and how t o obtain the u and n components for the rightmost ‘Since the planar geometry of graphite satisfies the even symmetry of the Hamiltonian li and of 23. the energies have the values of f3t. and the other three u bands are antibonding u* bands above the Fermi energy. and the odd symmetry of 2pz. the small Hamiltonian and overlap matrices are diagonal matrices as follows. For the eigenvalues thus obtained. 2sA. (2.2 to obtain a simple approximation for the electronic dispersion relations for carbon nanotu. and 2py in the directions parallel or perpendicdar to the u bond.2. 2pp. The simple approximation given by Eq.16). 4. M and I< in the Brillouin zone. and we will then solve the secular equation* for each point.29) is used in Sect. % A A = ( S 0: 2 p : s 0 E2p ). Zp. In Fig. Within the nearest neighbor site approximation given by Eq. 2pf. 2sB. We thus have six Bloch orbitals in the 2 atom unit cell. (2. Hereafter we arrange the matrix elements in accordance with their atomic identity for the free atom. (2. There are three atomic orbitals of sp2 covalent bonding per carbon atom.
1 . and this . 2. respectively.30 CHAPTER 2. 6 : The band parameters for u bands. where shaded and notshaded regions denote positive and negative amplitudes of the wavefunctions... orbitals in the directions parallel and perpendicular to the desired bonds. which is discussed in Sect.. < .y.6 correspond to nonvanishing matrix elements and the remaining four cases from (5) t o (8) correspond t o matrix elements which vanish because of symmetry. 6 .7(a) and (b) we show examples of the matrix elements of ( 2 s A I ' H [ 2 p f ) and (2p$ 171(2pf). In the case of Fig. respectively. This procedure is also useful for fullerenes and carbon nanotubes. 2 .. 2 .7 (a).) is decomposed into its and T components as follows: This type of decomposition can be used t o describe a bond in any general direction. orbital.5: The rotation of 2p. 2 . 2. In Figs.s:. By rotating the 2 p . 2. This method is valid only for p orbitals. there is only one nonvanishing contribution. and 2p. In Fig. bond of this figure. 2. when we consider the curvature of their surfaces. The four cases from (1) to (4) in Fig. the matrix elements appear in only 8 patterns it9 shown in Fig. The four cases from (1) to (4)correspond to matrix elements having nonvanishing values and the remaining four cases from (5) to (8) correspond to vanishing matrix elements.5 the wavefunction of ]2p. The corresponding parameters for both the Hamiltonian and the overlap matrix elements are shown in Fig. 2.6. x . 2. 2P # 2 2~ a Fig. The figure shows how t o project the u and T components along the indicated bond starting with the 2p. obtained by the methods described above. Fig. TIGHT BINDING CALCULATION \&=+\ .
lfn)eik=a/26eikva/2. For given points we then calculate the energy dispersion of the r bands from the secular equation of Eq. (2.+(xu + 3tT)..1. the 6 x 6 Hamiltonian matrix is obtained as a function of t . respectively.6 ( 2 ) . 2. we get the matrix elements in Eq.7: Examples of the Hamiltonian matrix elements of r orbitals.(eiksa/fi + eik=a/2fiCOs Y . comes from Fig.2.3. and k. yielding a fit of the functional form of the energy bands imposed by symmetry to the energy values obtained for the first principles band calculations at the high symmetry points [48].AlWP. TWODIMENSIONAL GRAPHITE 31 (2sJ I#I 2pXJ) (~P~AI#~ZP. .J) Fig.33) The resulting matrix element in Eq. (2P. (2. 2. we get the following result: ( 2 s ~ l z 1 2 p : )= x.33). (2. in the case of Fig.32) and Eq. the nonzero matrix elements correspond to the cases of Fig.32) ):' Similarly. The other pertinent cases of Fig. 2. By rotating the 2p orbitals.6 ( 3 ) and (4). The results thus obtained for the calculated u and ?r energy bands are shown in Fig. .14). However. the calculated results for the energy eigenvalues give real values.7 (b). (a) (2sA17iF1(2pf)and (b) ( 2 p t ( N ( 2 p f ) . (2. (2.B) = + ( X u + '. 2. Here we have used the parameters listed in Table 2. When all the matrix elements of the 6 x 6 Hamiltonian and overlap matrices are calculated in a similar way. 2.8.33) is a pure imaginary. Multiplying the phase factors for the three nearest neighbor B atoms with the matrix elements. 2.5iksa/2fieikva/2 = q(7iu +xFl.6 (5) or ( 6 ) give matrix elements that vanish by symmetry.)eikXa/2asin&$!* (2.
32 Fig.769 S. have different symmetries).868 (")The value for ~2~ is given relative to setting czp = 0. The relative positions of these crossings are known to be important for: (1) phototransitions from u to ?r* bands and .129 8.146 H Zt '.8. 2.42A. As is shown in Fig. E s 0.037 s . value (eV) S value %a 6. the formu~ation be used to describe the sp3 diamond system and can s p carbyne materials.3. Table 2. 0. 0.033 S . % 5. the 7r and the two u bands cross each other (i.8: The energy dispersion relations for u and r bands of twodimensional graphite. 3.580 Ssp 0.212 5..102 31.1: Values for the coupling parameters for carbon atoms in the Hamiltonian for T and cr bands in 2D graphite. However. because of the different group theoretical symmetries between u and r bands.1. In the absence of more detailed experimental or theoretical information.e. 2. 1. as do the T* and the two cr* bands. Here we used the parameters listed in Table 2. no band separation occurs at the crossing points.. 31. if the parameters are only slightly changed. these parameters can be used as a first approximation in describing the matrix elements for most sp2 carbon materials for which the carboncarbon distance is close to that of graphite. Further.
respectively. we next discuss the structure and electronic properties of singlewall carbon nanotubes in Chapters 3 and 4.3. Using the basic concepts of twodimensional graphite presented in Chapter 2. and (2) charge transfer from alkali metal ions to graphene sheets in graphite intercalation compounds. TWODIMENSIONAL GRAPHITE 33 from ?r to c* bands.2. . which satisfy the selection rule for electric dipole transitions.
.
1. Structure of a SingleWal! Carbon Nanotube A singlewall carbon nanotube can be described as a graphene sheet rolled into a cylindrical shape so that the structure is onedimensional with axial symmetry. we define several important vectors. without any distortion of the hexagons except for the distortion due to the curvature of the carbon nanotube. length/diameter which can be as large as 104105). From this figure.CHAPTER 3. The chirality. which are derived from the chiral vector. it can be seen that the direction of the sixmembered ring in the honeycomb lattice can be taken almost arbitrarily.* though most of the observed singlewall nanotubes have diameters <2 nm. even though the basic *Many carbon nanotubes that are observed experimentally are multiwall structures which are discussed in Chapter 11.1 Classification of carbon nanotubes A singlewall nanotube is defined by a cylindrical graphene sheet with a diameter of about 0. An interesting and essential fact about the structure of a carbon nanotube is the orientation of the sixmembered carbon ring (hereafter called a hexagon) in the honeycomb lattice relative to the axis of the nanotube. as defined in this chapter.10. This fact provides many possible structures for carbon nanotubes. called chirality. The synthesis of singlewall carbon nanotubes is discussed in Chapter 5. and in general exhibiting a spiral conformation.e. 35 . 3. Three examples of singlewall carbon nanotubes ( SWCN’s) are shown in Fig. 3. To specify the structure of carbon nanotubes. is given by a single vector called the chiral vector..0 nm. If we neglect the two ends of a carbon nanotube and focus on the large aspect ratio of the cylinder (i. these nanotubes can be considered as onedimensional nanostructures.7 .
The primary symmetry classification of a carbon nanotube is as either being achiral (symmorphic) or chiral (nonsymmorphic). and (c) chiral nanotubes. Chiral nanotubes exhibit a spiral symmetry whose mirror image cannot be superposed on to the original one. since such structures are called axially chiral in the chemical nomenclature. 3. Each cap contains six pentagons and an appropriate number and placement of hexagons that are selected to fit perfectly to the long cylindrical section.1 (a) and (b). The names of armchair and zigzag arise from the shape of the crosssectional ring.6. From the figure it can be seen that the orientat~onof the sixmembered ring in the honeycomb lattice relative to the axis of the nanotube can be taken dmost arbitrarily. An achiral carbon nanotube is defined by a carbon nanotube whose mirror image has an identical structure to the original one.1 we show the terminations of each of the three nanotubes. A classification of carbon nanotubes is given in Table 3. 3. We have thus a variety of geometries in carbon nanotubes which can change diameter. 3.36 CHAPTER 3. armchair and zigzag nanotubes. The terminations are often called caps or end caps and consist of a “hemisphere” of a fullerene. Axial chirality is commonly discussed in connection with optical activity.1 and is further discussed in Sect. . 3. chirality and cap structures.2 and Sect. There are only two cases of achiral nanotubes. respectively. as is shown at the edge of the nanotubes in Fig. as are shown in Fig. shape of the carbon nanotube wall is a cylinder. In Fig.1 (a) and (b). respectively. In this chapter we focus on the periodic structure along the nanotube axis. SINGLEWALL CARBON NANOTUBE bon nanotubes: (a) armchair. (b) zigzag. 3. We call this tube a chiral nanotube.
00) Ci) Shape of cross section 30' ( n . and by rolling the honeycomb sheet so that points 0 and A coincide (and points B and B' coincide).* The vectors translational vector T of a carbon nanotube.2) which corresponds to a section of the nanotube perpendicular to the nanotube axis (hereafter we call this section the equator of the nanotube). 3. (3.O) and (c) (10. 3. in which O B is the direction of the nanotube axis. (3.2) of the hexagonal lattice defined in Eq. respectively.m ) chiral vectors correspond to chiral nanotubes. In + Fig. respectively. m are integers n # m.m are integers. n ) . (2. and B'. (a) (5. (XI). Because of the hexagonal symmetry of the honeycomb lattice. 3.2 and then construct a paper model of a carbon nanotube. . that is C h = ( n . and the direction of O A corresponds to the equator.3. as further explained below.netryc) Dn 8 Ci Dn CZI Ci c 8 CNfd d ') The chiral angle 0 is defined by Eq.2. where n . All other ( n . or c h = ( n .1: Classification of carbon nanotubes. and a zigzag nanotube corresponds to the case of m = 0. 3. 3. 5). B .22): Ch = no1 62 + ma2 ( n . *The authors recommend that the readers copy Fig.m ) . m )for chiral nanotubes. This construction exercise is very useful for understanding the nanotube structure. The chiral vector is defined by Eq. (b) (9. By considering the crystallographically equivalent sites 0. n ) cistype O0 ( n .1.5). The group theory of carbon nanotubes is discussed in Sect. CHIRAL VECTOR: CH 37 Type armchair zigzag chiral a) b. The chiral vector C can be expressed by the real space unit vectors a1 h and a2 (see Fig. 3.2 is ( 4 . an armchair nanotube corresponds to the case of n = m.2 Chiral Vector: Ch * The structure of a singlewall carbon nanotube is specified by the vector ( O A in Fig.4). 3.0) transtype 0' < 101 < 30' ( n . As is shown in Table 3. and the chiral vector shown in Fig. we need to consider only 0 < Iml < n in c h = ( n .2.1 are.0). 0 5 Iml I n). 3. a paper model of a carbon nanotube can be and 6%define the chiral vector C h and the constructed.6.m) mixture of cis and trans + Syml. 2 ) . Table 3. the unrolled honeycomb lattice of the nanotube is shown.1) The specific chiral vectors c h shown in Fig. A . ( n .
42A. d l .5). is tThe CC bond length of graphite is l. (34 It is noted here that a and a are not orthogonal to each other and that the 1 2 inner products between a and a2 yield: 1 where the lattice constant a = 1.38 CHAPTER 3. and B and B'.22). dt = 6. 3. The figure corresponds to c h = (4. .1). ! ' The diameter of the carbon nanotube. a nanotube can be 4 + constructed. 3. whose end cap is a hemisphere of the fullerene CSO. the diameter of the armchair nanotube (5.44A x f i = 2. N = 28. The vector R denotes a symmetry vector (see Sect. When we connect sites 0 and A .WALL CARBON NANOTUBE Fig. O A and O B define the chiral vector C h and the translational vector T of the nanotube. d = dR = 2. In the case of carbon nanotubes. respectively.49A of the honeycomb lattice is given in Eq. ! = (4. (2. 5). L = l c h l = d== adn2 + m2 + nm. The rectangle OAB'B defines the unit cell for the nanotube. the CC bond length is known to be slightly larger than graphite: 1.t For example. in which L is the circumferential length of the carbon nanotube: dt = L I T .44A.4). R = (1. is given by L I T .8SA. SINGLE.2).2: The unrolled honeycomb lattice of a nanotube.
2 can be expressed in terms of the basis vectors a1 and a 2 as: T = t l a l +tzaz (tI. Using C h . 33 .5) The translation vector T corresponds to the first lattice point of the 2D graphene + sheet through which the vector O B (normal to the chiral vector C h ) passes. and (3. The lattice vector T * shown as O B in Fig. (3. then d~ can be + + .3. respectively.2. Also.2) is defined as the angle between the vectors C and a1 . and the angle 0 specifies the spiral symmetry. (3. The chiral angle 0 denotes the tilt angle of the hexagons with respect to the direction of the nanotube axis.3). with values of 0 in the range 0 5 101 5 30°. by introducing d as the greatest common divisor of n and m. because of the hexagonal h symmetry of the honeycomb lattice. 3. t2= 2n+m dR where d R is the greatest common divisor (gcd) of (2m n ) and (273 m). 3.t2 areintegers). TRANSLATIONAL VECTOR: T 39 The chiral angle 0 (see Fig. The chiral angle 0 is defined by taking the inner product of C h and a1 .t2).3. to yield an expression for cos 6 : (3. we obtain expressions for tl and t2 given by: tl = 2nz ~ dR +n. it is clear that t l and t2 do not have a common divisor except for unity. (3.m) defined in Eq.1).4) thus relating 0 to the integers ( n . (wheretl. zigzag and armchair nanotubes correspond to 0 = 0’ and 0 = 30°.1). From this fact. In particular. 3. (3. The vector T is parallel to the nanotube axis and is normal to the chiral vector C h in the unrolled honeycomb lattice in Fig. Translational Vector: T The translation vector T is defined t o be the unit vector of a 1D carbon nanotube.5). T = 0 and Eqs.
m ) = gCd(3m.O)zigzag nanotube we have dR = d = 9.respectively. . we have dR = 3d = 15. y .2(m2 n2 I x a21 dR + + nm) .2). When we denote the greatest common divisor as y = gcd(a. Thus there are 2 N carbon atoms (or 2pZ orbitals) in each unit cell of the carbon nanotube.2~~ a2dR ' (3. 12 .rn is a multiple of 3 d . the number of hexagons per unit cell N is obtained as a function of n and m in Eq. 7 ) . SINGLEWALL CARBON NANOTUBE related to d by* dR= { d if n . The area .m) is a multiple of 3d. ( 3 . 2) [Fig. 7Z .1) [Fig.m ) = gCd(3d. T = (1. 3.1(a)]. m ) have a common divisor or when ( n . The length of the translation vector. while the vectors a1 and a2 define the area of the unit cell of 2D graphite.7).9) where L and dR are given by Eqs.m ) . since the vector products of the unit vectors are: a x a =a 1 1 2 x a2 =o and J ux~ 2 1 = 6 a 2 / 2 a where (a1x a 2 1 corresponds to the area of the rhombus generated by of the rhombus is equal to that of the hexagon. then y is also the common divisor of (a p ) and p (Euclid's law).while for the c h = (9.l(b)]. TI is given by: where the circumferential nanotube length L is given by Eq. ( 3 . When the area of the nanotube unit cell ( c h x T (where the symbol x denotes the vector product operator) is divided I by the area of a hexagon (la1 x azl). (3. a and 1 a2.5) armchair nanotube. ?Z which gives Eq.m is not a multiple of 3d 3d if n . the calculation using the vector product is easier than using the inner product.40 CHAPTER 3. We note that the length T is greatly reduced when ( n .2. have a common divisor.7) In the case of Fig.2). we get  dR = gCd(2m + 12. and we note that each hexagon contains two carbon atoms.P). 3. 2 ) . and T = (1. 'This relation is obtained by repeated use of the fact that when two integers. we have d = dR = 2 . The unit cell of the 1D carbon nanotube is the rectangle OAB'B defined by the vectors c h and T (see Fig.5). T = (4. 3. (3. In fact. where c h = (4.27Z + m ) = gCd(2m + 12. 1 ) as:t N= Ich l1 a x T . ( 3 . 3. a and p (a> p). for the c h = (5. 2 ) and ( 3 . tFor nonorthogonal unit vectors.
in Fig.2) having the smallest component in the direction of c h . S Y M M E T R Y VECTOR: R 41 Fig.. which follow from Eqs. T Or T*R T  IChXRI L ’ where L and T are given by Eqs. respectively.q ) ..17. R = )$1(.11) *If p and q were to have a common divisor. When i R goes out of the unit cell..16.. L  IRxTI.. that is.. Note that N $ = 2~ and N r = M T . is proportional to the value of T x R given by:t T x R = (tiq . tHereafter we frequently use the relation between the inner product and vector product of a vector R with the two orthogonal vectors and TIto obtain: c h .. q are integers) (3. and 3.R Ch...10) where p and q do not have a common divisor except for unity... Here we assume that between C h and T. where i is an integer (i = 1 .. or c h . 3.t z p ) (a1 x az). in which $ denotes the angle of rotation around the nanotube axis and T is the translation in the direction of T as specified by the symmetry vector R in Eq.* The C h component of R.. 5Ch 2n 3..3. (3. 3. The vector R is used for generating the coordinates of carbon atoms in the nanotube.. 3. . and R is expressed in terms of a1 and a as: 2  R =pal + qa2 ( p .18. R. R/r would have a smaller component in the direction of Ch than does R... we shift it to lie within the unit cell through translation by an integral number of c h or T vectors.. using periodic boundary conditions.. It is convenient to express the R vector in terms of its projections on the orthogonal vectors c h and T of the nanotube unit cell.. rl then..3.2) and (3....4 Symmetry Vector: R We denote the carbon atom site vectors within the 1D nanotube unit cell by i times the vector R ..16). (3.3: Space group symmetry operation.3. ( p . The symmetry vector R is then defined as the site vector (shown by O R in Fig.. 3. iR.. 3... 3..8). N ) . as shown in Fig. as R lies .4.. (3.
t z p ) becomes N . as explained below. d g . (3.t z p ) on the right hand side of Eq. Here we use the notation possible value of Q corresponds to the for the symmetry vector R defined in Eq. (3. The definition of NR . (3. arises from the fact that R exists within the 1D nanotube unit cell. (3.15) Since the first condition of Eq. to Further. (3.. §It is noted that the definition of R is different from that by Jishi et al. Eq. SINGLEWALL CARBON NANOTUBE where ( t l q . and (3. (i = 1 .L .13) (3. .2).( = L .14) and from Eq.12) satisfies Eq.11 is an integer.nq _< N ) . Similarly.9).42 CHAPTER 3. using Eqs. Therefore iR. [49]. then ( N / d ) R would become a site equivalent to 0. 0 <tlq tap 5 N. we get the condition.(i = 1 N ) . such that t l q .t z p ) = i for each i. and will thus have different values for their projections along the direction of C h . If Q and N would have a common divisor.6) and (3.8) and (3.12).N J Rx T f i a 2 d R .9). 3. (0 < mp. (3. (3. (3.n q < N . We select p and q of R to form the smallest site vector (i = l). (3.  + . L T dRa2 2 f i L where w e made use of Eqs.5) do not have a common divisor except for unity.2L2 . LT N using Eqs.nq (3. uniquely generates N different atom sites in the unit cell of the nan0tube. (3. The largest defined by Jishi et al. N ) of the nanotube unit cell.t 2 p = 1. (3.9). (3. The second condition in Eq.x RJ.14). (3.s I . (3. C h This fact can be shown as follows: R given here is independent of whether or not d = 1. (1 5 Q 5 N ) where the integers Q and N do not have a common divisor except for unity. 0 < mp . [49]. it is not necessary to add this condition to the definition of R.mp. and note that the maximum value of i ( t 1 q .14).12) for p and q is uniquely determined if t l and t z of Eq.8). Using the factt that the C h component of N R is always equal to IC. so that 1. we use the expression i ( t l q .12). we obtain another necessary condition arising from R being within the 1D unit cell: RT O < F = JC. To determine all N site location vectors iR. the vectors iR define N inequivalent sites in the nanotube unit cell.12) The solution of Eq.12) can be generalized t l q t z p = 9 .
where ( $ 1 ~ ) ~= E is the identity operation.)( acts on an atom at (O.9).8). 3.4. where N is the number of hexagons in the 1D unit cell of the nanotube given by Eq. and reflects the basic space group symmetry operation of a chiral nanotube. ($1~)(0~0) ( p . i. the symmetry operator ( $ 1 ~ ) ~brings the lattice point 0 to an equivalent lattice point C as shown in Fig.3.18) is an integer which denotes the number of T vectors that are necessary for reaching the distance from 0 to N R .2).O).4. the rotation angle $ becomes 2 n f N . while the projection of R on T gives the translation T of the basic symmetry operation of the 1D space group of the carbon nanotube. ( $ 1 ~ ) ~ ~ are all distinct symmetry operations of an Abelian group denoted by CN. Referring t o Fig.e.. 3. The physical significance of the vector R is that the projection of R on the chiral vector c h gives the angle $I scaled by L / d t [see Eq. Taking the indicated vector products R X h and R x T and using Eqs. denoted by R = ($17) and shown in Fig. (3.16) and using these definitions. 3. the vector €2 consists of a rotation around the nanotube axis by an angle $ combined with a translation T in the direction of T .3. we obtain the expressions for the length of T and the rotation angle $. SYMMETRY VECTOR: R 43 From a physical standpoint. where and where Msmpnq (3.3. (3. (3.9).12). q ) . The integers ( p . (3. If = ( $ 1 ~ ) is a symmetry operation for the nanotube. then ( $ 1 ~ ) ~ IT)^. . c (3.q ) denote the coordinates reached when the symmetry operation $1. as follows: # . and (3. (3. .2)].
~) a) C h 182 62 194 20 2n 2n (1. t z ) . C h d d~ dt (A) L/a 1 ' Tla N R M (4.4. In Table 3. 3.47 7. the greatest common divisor of n and m.C given by Eq. M = m p . the number N of hexagons per unit cell of the 1D nanotube.including d. In the figure we show the case C h = (4.O) (6.15 6. the translation vector T .2) (5.56 &na/?r na/?r I/% 9 (4.9).8) in u n i t s of a = 4 a c . SINGLEWALL CARBON NANOTUBE Fig.5) (9. but separated from 0 by the vector MT. is given by Eq.55 7. m ) .4: The vector N R = cal surface.O) (1.19) (1. Table 3.l) (1.22).2) (16.nq indicates how many T translations are necessary for going from 0 to N R in Fig. Also listed in Table 3.4) (873) 2 5 9 1 1 2 15 9 1 3 4.c for a 2D graphene sheet).78 7. R = ( p .5) fi (l. which is given by Eq.44 CHAPTER 3.1) (1. = ( n .l) fi 6 5 9 a &in n 1 10 n n 1 30 3n n a 1 & 1 (10. m ) is given by Eq.0) fi n (1.72 13.5) whose length T is given by Eq.2) 1 28 10 18 (l.1) n (3. ( $ 1 ~ ) ~is shown on the cylindri 3. the symmetry vector R .lO) (n. (3. T = ( t l . and the related quantity dR which is given by Eq.05 7.2) where M = 6. d is the greatest common divisor of n and m.2). After rotating by 27r around the tube. (3. respectively. (3.n) (n. (2. which are given by Eq. d t and L = I c h l are the diameter and equatorial length of a carbon nanotube.2 are the nanotube diameters dt in units of A.O) (l.l) (1. (3. (3.2: Values for characterization parametersa) for selected carbon nanotubes labeled by the chiral vector c h = ( n . q ) is the symmetry vector defined in Eq.1) (1. (3.7). the lengths of the chiral vector L and of the translation repeat distance T of the 1D lattice (both in units of the lattice constant a = f i a c . N is the number of hexagons in the 1D unit cell of the carbon nanotube.1) (1.6) (14.4) 11 11 41 10 (1.17) (5.1).10). The translational vector.m).1) (3. the vector N R reaches a lattice point C equivalent to point 0.2 we list the characteristic parameters of carbon nanotubes specified by ( n .5) (7.
N = 18. As a final example. L = m a . and M = 5. The basic symmetry operation R = $1. but since n . the lattice vectors in real and reciprocal *Since nanotubes are onedimensional materials. we will have N pairs of bonding A and antibonding A* electronic energy bands.m ) values. For this nanotube.5 Unit Cells and Brillouin Zones The unit cell for a carbon nanotube in real space is given by the rectangle generated by the chiral vector Ch and the translational vector T. we have dR = 3 x 5 = 15. of the chiral vectors c h . the highest common divisor is 5 . N = 62. which has half a C60 fullerene t o form its end caps. Thus we obtain L = f l u . we give the smallest observed zigzag nanotube (9. Similarly the phonon dispersion relations will consist of 6 N branches resulting from a vector displacement of each carbon atom in the unit cell. K 2 is a reciprocal lattice vector. so d = 1 . there are no common divisors. In Appendix we show programs which generate the parameters and the coordinates for given ( n . we have dR = 3. respectively.3.2. For the armchair nanotube (5. 1c. t z ) and R = ( p .4. n and m. we consider the case of the nanotube c h = (7.16) and values for T = ( t l . Kj = 2n&j. q ) . yielding N = 10.5. 3. 5). which has T = (4. and for this nanotube.2. K 1 . Eq. and M = 9. The values of all the parameters listed here depend on the two integers. d = dR = 2 . . T = m u . and M = 11 translations of the vector T.m = 3 [49.2. we have d = dR = 9. r = 6T/28 and M = 6 translations of the vector T to reach the point C in Fig.3. 3. and since n . where R. z Expressions for the reciprocal lattice vectors K along the nanotube axis and Kl in the circumferential direction* are obtained from the relation R. R = (1. 3. r = T / 2 . and Kj are. as is shown in OAB’B in Fig.m = 0.O)also having end caps consisting of c 6 0 hemispheres. As a second example. T = m a .2) nanotube shown in Fig.)( can be obtained from Table 3. l).5). Since there are 2N carbon atoms in this unit cell.4) which is a chiral nanotube for which n .2 we refer to the c h = (4. UNIT CELLS A N D BRILLOUIN ZONES 45 and the integer M . . To illustrate use of Table 3. only gives discrete k values in the direction of c h . 3. (3. All parameters defined in this section are summarized in Table 3. = 2 ~ 1 1 0 r = T/2. N = 28.m = 3.)I = 2x118.50].
m) gcd(2n +:.($. 4 ) = l b ) N) in radians ~~ In this table n. m.2m tn)b) T T translational vector T = tlai + t 2 a 2 ( t i .a2 1 bi.a) symbol a name length of unit vector unit vectors reciprocal lattice vectors chiral vector length of C h diameter chiral angle formula a = 4 3 a c . t z . m ) denotes the greatest common divisor o the two integers n and m. symmetry vector pitch of I1 = T & = 2(n2+dJ3 n m ) m + dR dR dR R R $ rotation angle of number of ~~ M a) T in NR.m gcd(ti I t 2 ) I*) length of T N R 7 Number of hexagons in the nanotube unit cell. q are integers and d. d R N and M are integer functions of these integers.MT 7 = . 2dn3 + m2 + nm 2Jn2 dR = A m 0 I I4 I 6 fim 2n m ?r tane= + gcd(n. e d dR sin0 = + m2 + nm 272 + m case = . SINGLEWALL CARBON NANOTUBE Table 3.46 CHAPTER 3. ~~ R = pai t q a 2 3 9) t l q .+MT ~ ~~ gcd(p.y coordinate 1) a' C'h = nai + maz G ( n . *) gcd(n. p. t 2 ) 2m+n 2n+m tl = . value a C .nq)T .49 A.t 2 = . b2 c h L dt x .nq S ( m p .c = 2. f . (TI.44 A a .I) 2" x.3: Parameters for Carbon Nanotubes.m )) is not multiple3dof 3 d n. ( 0 I Iml 5 n ) L = l C h l = a J n 2 + m2 + nm dr = L / n . y coordinate (y. 11.. (0 < mp .N N 2% 4J=y NR=C.) & (2 ?. T= if is multiple of { 3d d if (( n .t z p = 1.) I a & l a . m ) .c = 1.
3.5. UNIT CELLS A N D BRILLOUIN ZONES
47
Fig. 3.5: The Brillouin zone of a carbon nanotube is represented by the line segment WW’ which is parallel to Kz. The vectors K1 and K2 are reciprocal lattice vectors corresponding to c h and T , respectively. The figure corresponds to C h = ( 4 , 2 ) , T = (4,5), N = 28, K1 = (5bl 462)/28, K2 = (4bl  2b2)/28. space. Then, using Eqs. ( 3 . 6 ) ,(3.9), and the relations
Ch.K1 = 2 C h . K2 = 0,
+
~ , T.Ki=O, T K2 = 2 ~ ,
(3.19)
we get expressions for K1 and K2:
 nbz), (3.20) N where 61 and b2 are the reciprocal lattice vectors of twodimensional graphite given by Eq. (2.23). In Fig. 3.5, we show the reciprocal lattice vectors, K1 and K z , for a C h = ( 4 , 2 ) chiral nanotube. The first Brillouin zone of this onedimensional material is the line segment WW’. Since N K 1 =  t 2 b l + tlb2 corresponds to a reciprocal lattice vector of twedimensional graphite, two wave vectors which differ by N K 1 are equivalent. Since t l and t 2 do not have a common divisor except for unity (see Sect. 3.3), none of the N  1 vectors p K l (where , = 1, . ,N  1) are reciprocal lattice vectors of twodimensional u graphite. Thus the N wave vectors p K 1 ( p = 0 , . . . , N1) give rise to N discrete Ic vectors, as indicated by the N = 28 parallel line segments in Fig. 3.5,which arise from the quantized wave vectors associated with the periodic boundary conditions on c h . The length of all the parallel lines in Fig. 3.5 is 2 n / T which is the length of the onedimensional first Brillouin zone. For the N discrete values of the k vectors, N onedimensional energy bands will appear (see Chapter 4 ) . Because of the translational symmetry of T , we have continuous wave vectors in the direction of K2 for a carbon nanotube of infinite length. However, for a nanotube of finite length L t , the spacing between wave vectors is 2 n l L t ; this spacing between wave vectors has been observed experimentally [51].
K2 =  ( d l
1 K1 = T (  t z b l
+ tlba),
1

48
CHAPTER 3. SINGLEWALL CARBON NANOTUBE
Fig. 3.6: Symmetry of armchair (a,b) and zigzag (c,d) nanotubes with odd (a,c) and even (b,d) numbers of unit cells around the circumferential direction: (a) (5,5) armchair, (b) (6,6) armchair (c) (9,O) zigzag and (d) (10,O) zigzag nanotubes. Here we show the inversion centers i. Dot circles show carbon atoms in part of the neighboring unit cell.
3.6
Group Theory of Carbon Nanotubes
Here we discuss of the symmetry of carbon nanotubes which are classified in Sect. 3.1. The symmetry of the carbon nanotubes is used in the interpretation of the Raman spectra in Chapter lo.* Here we only consider the point group of the unit cell and we do not discuss the space group of the lattice. Since many of the the physical properties of solids depend on the dispersion relations near k = 0, the symmetry of the unit cell gives sufficient information for the interpretation of many physical properties. Hereafter we define the horizontal or vertical directions as those that are perpendicular or parallel to the nanotube axis, respectively. In the achiral nanotubes, armchair ( n ,n) and zigzag (n, 0) nanotubes (see Fig. 3.1 and Table 3.1) have (1) a vertical, nfold rotational axis, C,, and (2) n horizontal, %fold axes, nCz. Each horizontal C2 axis intersects the center of a CC bond or the center of a hexagon which are located at opposite sides of the nanotube from each other.+ Thus the achiral nanotubes belong to the point group D,. The D, group has a different group structure, depending on whether n is even ( n = 2j) or odd (n = 2 j l ) , as can be seen in the character tables, shown in Tables 3.4 and 3.5, respectively. The horizontal nC2 operations are either divided into the two
+
‘The reader who is not familiar with group theory may skip this section, which is necessary, however, to understand the group theory for the Raman spectra observed in singlewall carbon nanotubes. tSince we now have ‘up’ and ‘down’ directions in a nanotube, the center of the hexagon has only 2fold symmetry.
3.6. GROUP THEORY OF CARBON NANOTUBES
49
classes for groups with n = 2 j , or are in a single class in the case of n = 2 j + 1. In the case of n = 2 j , a Cz operation in one class bisects the angle between two adjacent C2 axes in the other class. Table 3.4: Character Table for Group D(zj)
A2 B1
B 2 El E z
1 1 1 2 2
1 1 1 2 2
1
1 1
2 cos q5j 2 cos 245
2cos(j
1 1 1 2~0~245 2cos4q$
...
... ...
. . I
...
1 1 1 2cos(j1)4, 2c0s2(jl)$~
1 1 1 0 0
.
*
1 1 1 0 0
.
E3i 2 (1)3'2
O)

2cos2(j

... 2cos(j  1)24, o
.
0
.
.
Where
d3 = 2 ~ / ( 2 j ) .
Table 3.5: Character table for point group D ( z j + l ) . R E 2C; a) 2 c $ , ... 2C$ (2j+i)C;
A1 1 1 1 A2 1 1 1 El 2 2cos4j 2cos24j E 2 2 2cos245j 2 ~ 0 ~ 4 4 ,
... ... ...
. * .
. ..
.. .
1 1 2cosj4j 2cos2j4j
1 1
0
0
a)
E, 2 2cosjdj 2cos2j$j Where 4j = Z?r/(Zj + 1).
... 2cosj2$j
0
Further it is clear from Fig. 3.6 that for both zigzag and armchair nanotubes, there is an inversion center for both even and odd number n achiral nanotubes. In Fig. 3.6 (b) and (d) we show part of the nearest unit cell by dotted lines and circles. We can choose the unit cell so that the inversion operation transforms the carbon atoms in the unit cell to the other carbon atoms within the same unit cell.$ The total symmetry of an achiral nanotube is expressed by the direct product of the groups D, 8 Ci, where the group Ci consists of the identity and inversion operators, E and i. Group theory tells us that the direct product
:In the case of the (6,6) armchair nanotube, the corresponding unit cell is such that half of the carbon atoms lie on the boundary of the unit cell. For the boundary atoms, we consider the half bails for operations. In this case, a symmetry operation from an upperhalf ball to a lowerhalf ball for the same atom is different from the identity operation.
50
CHAPTER 3. SINGLEWALL CARBON NANOTUBE
D , 8 Ci depends on whether n is an even or an odd number, as follows: Dn
@
ci=
{
D,h when n = 2 j (even) Dnd when n = 2 j + 1 (odd)
(3.21)
’
If n in D , is even ( n = 2 j ) , there is a class of ?r (CZm,= Cz) rotations along Z , the principal C, axis. Since the product of the vertical C m rotation with the inversion operation gives a mirror operation on the ‘horizontal’ plane, which is perpendicular to the principal axis,
m C,, x i = b h
(3.22)
we have an element of uh in the direct product of Dn @ Ci, which corresponds to Dnh. The product of a horizontal C2 axis and the inversion center i gives a ‘vertical’ mirror plane nu,,which are the elements of Dnh. Here we take the horizontal Cz axes t o include the inversion center in the axes. If n in D , is odd (n = 2 j l), there is no C2 rotation along the principal C, axis. Thus in the direct product of D(zj+l)@ Cj = D(Zj+l)d,there is no U h , operation but there is rather a ‘diagonal’ vertical mirror plane between two horizontal C2 axes. The vertical mirror planes are given by the product of a horizontal Cz rotation and the inversion center i. These symmetry issues are clarified in Fig. 3.6. It is very confusing in the case of odd n numbers ( n = 2 j 1) that we can visually see the mirror symmetry on a horizontal plane, through the horizontal C  C bonds of the armchair tubes or through the centers of the vertical C  C bonds of the zigzag tubes. However, there is no U h operation in the D(2j+l)d group. This might raise a question about whether there might be higher symmetry in achiral carbon nanotubes. The answer to this question is no, so far as we consider the symmetry of the unit cell, since the uh operation for ( n = 2 j 1) is used only for the space group.§ Let us consider this question in the case of the armchair tube with n = 5 , ( 5 , 5 ) . There is 20 atoms in the unit cell as shown in Fig. 3.6 (a). When
+
+
+
§The following is the reason why we need these statements in the text. All horizontal lines which intersect the nanotube axis and the center of CC bond can be Cz axes, thus giving rise to 2n C axes in the unit cell for achiral (n,n) (n,O)nanotubes. We will select only n 2 or CZ axes of the 2n C axes which can be elements of the point group. The other n Cz axes are 2 operators for the space group of the lattice, because these other n Cz axes require a trmslation along the nanotube axis.
3.6. GROUP THEORY OF CARBON NANOTUBES
51
we keep the chemical bonds between two carbon atoms rigid, we have only 20 inequivalent operations that do not change the unit cell. Ten of the 20 operations are operations which change the A atom to an equivalent A atom, and the other 10 are operations which change the A atom into a B atom. Here A and B atoms denote inequivalent carbon atoms of the hexagonal network as shown in Fig. 2.3. Furthermore, 5 of the 10 A+A operations are given by proper C5 operations, and the other 5 require the inversion operation, which changes an A atom on one horizontal plane to an A atom on the other horizontal plane. When we consider the inversion center, as shown in Fig. 3.6 (a), the symmetry corresponds to the D5d point group. In D 5 d symmetry, we have 20 symmetry elements which are sufficient to describe 20 possible operations for the 20 atoms in the unit cell.
D5d
Ai, Azs El,
~2~
AiU Azu
E +1 +1 +2 +2 +1 +1
+2 +2
ZC5 r 1
+1 +1
ZC: +1
+1
5ci +1 1
0
i
2; s’
2510
5ad
( h = 20)
(2“
+1
+1
r
+1
+1 r  1 r
r
1
+1 +1
7
7
+Z
+2 1 1
2 2
r
1
7
+1 +1
+1
+1
7
+1
1
0
fY’),z’
o
41
1
0 0
1
1
r
R,
s ( z + i y , z  iy) [ ( z + i y I 2 , ( z iy12]
o
1

ElU Ez,,
71
1 1 I+ +r
1
+1
0 0
+r
17
(r+iy,z  i y )
D5h
E
Zcs
+1 +1 r 1
2c:;!
+1 +1
7
5c;
+1 1
2i
E;
t1
+1
+:,
ah +1 +1
E:
A;’ A”
+2
E! E;
+1 +1 +2
+2
r +1 +1 r 1 r
71 $1
o o
+1
+z
+Z 1
1 2
255 +1 +I
7 7
1
2s; 50, + 1 ’ i1 $1 1
7
( h = 20)
zr+y2,z2
7  1
o o o o
Rz
( z , y ) , (zz2,yz2)
(z2y2,zy) z , z3,z(z2+y2)
+1
7
1
o
o
1 1 1r
1 1
1 +1
+r
1r
71
2
+r
(~,,~~),(zz,yz) [zyz,z(z2 y2)1

Let us show that D5h is not the proper point group symmetry of the ( 5 , 5 ) armchair nanotube. D5h is given by direct product 0 5 x c h , where Ch is the point group which has only the symmetry elements E and c h . In Tables 3.6
1 (1)l €2 €*f €22 .* €r2( N .. CN1 c1 c 2 CN E A +    B 1 1 1 1 1 1 €2 €*Z €4 €14 . N ) form an Abelian group. SINGLEWALL CARBON NANOTUBE and 3.. and thus both symmetries seem to be applicable.4. d .8: The character table for the Abelian group CN for chiral nanotubes .7. Thus D 5 h is not sufficient for describing the 20 distinct operations in the unit cell. . and N / d ) denotes any one of the three Abelian groups in ... . we show the character tables of D 5 d and D 5 h l both having the same structure. When n and m in a chiral vector (n. the lattice belongs to a nonsymmorphic translational group which only has pure spiral symmetry operations. has no mirror plane.. An Abelian group is a group in which all symmetry operations commute with each other. d = 1. d in not unity. 1 1 €Nl €*(Nl) €2( N ... Table 3. ..*22 . Achiral nanotubes are the only nanotube types that have the vertical (or horizontal) mirror operation. which does not belong to either the armchair or zigzag nanotube categories. the nanotube is invariant under a pure rotation of c d around the nanotube axis. *: €2 .. As discussed in Sect..1 ) } . ..52 CHAPTER 3. The chiral nanotube..* . In this case the symmetry group of such a chiral vector is the direct product of the two Abelian gr'oUPs1 CN = c d 8CN/d (3. we either go over all N A atoms or all N B atoms in the unit cell by operating with Ri (i = 1.rn) have no common divisor except for unity.23) where C. However.. N ) on a carbon atom. in the D 5 h point group there is no operation which changes an A atom in one horizontal plane to an A atom in the other plane. . 3. .. Thus the operations Ri (i = 1... .. that are given by the symmetry vector R and repeated operations of R. ( p = N . {. c e .1 ) When the common divisor of n and m..
' ' P we show the character table for C for chiral nanotubes.7) and scanning tunneling microscopy (STM) (see Fig. this table are N t h roots of unity. 3. m > or their characteristic parameters (d. In Table 3. showing singlewall carbon nanotubes in a triangular lattice. or onedimensional A or B irreducible representations. All characters in . C2. Structura~ h a r a ~ t e r i z a t i ~ ne ~ u r e m e n t s dt and 6 are d i ~ c u to tmake c m of ~ because of the small physical size of the nanotubes. each having p elements. 3. C. with a tube diameter of 1. vibrational. 8)..7: High resolution TEM micrograph of the top view of one bundle of singlewall nanotubes from the collarette of the cathode of a carbon arc apparatus (see Sect.4 nm and an average intertube distance of 1.7 nm.8). These techniques are especially useful for the structural characterization of the nanotubes.3. 0 " and C = E . and the low atomic number 2 of carbon which gives rise to low cross sections for xrays and electrons. The irreducible representations are either twodimensional En representations.7 Experimental evidence for nanotube structure The existence of singlewall carbon nanotubes has been confirmed experimentally through high resolution transmission electron microscopy (TEM) (see Fig. E .. and other physical properties of carbon nanotubes to their geometrical structure. Eq. 5.. Each bundle in the micrograph consists of about 20 aligned singlewall nanotubes which are selforganized into a triangular lattice [52]. . the structural characterization of carbon nanotubes on which physical measurements are made is very important. 3.3). The nanotube bundle is bent in such a way that it is seen edgeon in the image plane. as described by the integers ( $ 2 . the two more commonly used conventional structural characterization probes. 3. EXPERIMENTAL EVIDENCE FOR NANOTUBE STRUCTURE 53 Fig... Because of the sensitivity of the electronic.7. 3.8 . whose characters for each operation are complex conjugates of each other.23.
The bundles typically are 520 nm in diameter and exhibit a triangular lattice with an intertube distance of 1. The singlewall nanotubes shown in Fig.7 shows the tendency for the singlewall nanotubes t o grow in bundles containing 1050 aligned nanotubes.46 ti 'L'hc lattice sites show that this nanotubc is not a zigzag nanotube. 3. The TEM micrograph of Fig. particularly using the STM and TEM techniques. held together by weak intertube interactions. so that some portions of the nanotubes are oriented parallel to the electron beam.7 nrn [52. Thc periodic packing of these nanotubes is confirmed by electron diffraction patterns obtained from an assembly of such nanotube bundles. 3. and progress has also been made with the manipulation of individual nanotubes 1531. and the nanotubes were collected from a collarette located around the cathode electrode [52]. resulting in a crosssectionlike view.8: Atomic resolution STM topographic image of a singlewall nanotube on an Au (111) substrate at 4. 3.2 at% Ni catalyst contained in the anode. showing individual singlewall nanotubes.2 K. By taking precautions to use low electron beam currents.7 were grown in an electric arc discharge apparatus using a 1at% Y and 4. it has been possible to obtain good TEM measurements of lattice . Similar arrays of nanotube bundles were first reported using the laser vaporization technique [55]. there is considerable difficulty associated with the manipulation of individual singlewall nanotubes. Since the bundles of nanotubes are frequently bent.54 CHAPTER 3. the tube ends can be imaged in a transmissio~electron microscope. SINGLEWALL CARBON NANOTUBE Fig. Some progress has been made in developing sensitive tools for the structural characterization of nanotubes. The dark spots indicate thc hexagons which are spaced by 2. In addition. indicating that it could be either an armchair (chiral angle 30') or a general chiral nanot ubc. Image size is 51 x 26 A' [54]. The very weak electron scattering from nm diameter carbon nanotubes (atomic number 2 = 6) and their high susceptibility to damage by the 100200 keV electron beam of the TEM instrument make it difficult to carry out electron diffraction studies.55].
while the V geometry can be used to determine the intertube spacing in the case of multiwall nanotubes. Referring t o Fig. However. for example. which is the angle between the nanotube axis and the nearest zigzag axis. Transmission electron microscopy has been widely used to characterize the many defect structures that have been observed in multiwall nanotubes [57. Nevertheless. we see.9: This sketch indicates how the interference pattern for the electron beam that is incident radially on the planes with the H orientation is used t o determine the chiral angle 0 .7. very small diameter nanotubes tend t o be more perfect. Whereas nanotubes with diameters > 2 nm tend to show many structural defects. with fewer structural defects.e. The interference pattern. TEM evidence has been presented to show that the walls of singlewall nanotubes have the local structure of a graphene sheet [58]. in principle.9. determines the intershell distances in the case of multiwall carbon nanotubes [19].59621. 3.3. EXPERIMENTAL EVIDENCE FOR NANOTUBE STRUCTURE 55 Electron beam Fig. chiral angle of an individual nanotube) as is. obtained when the lattice planes are in the orientation V with respect to the electron beam and the nanotube shells.. done with the LEED technique in surface science. m ) nanotube [63]. how the electron diffraction techniques can be used in the H geometry to measure the orientation (i. fringe images and electron diffraction patterns on singlewall nanotubes [56] and multiwall nanotubes [57]. The interpretation of TEM electron diffraction patterns on singlewall carbon nanotubes should be greatly aided by the use of computer simulations which give the diffraction pattern expected for an ( n . TEM experiments on singlewall (and even double wall) nanotubes remain an experimental challenge. 3. These computer simulations are based on an analysis carried out by Cochran. Crick and Vand in 1952 [64] in connection with their elucidation of the structure of the .
Measurements of the crosssectional STM profile shows direct evidence for the curved surface of the nanotube [66]....... the computer simulation [63] is not yet able to carry out the inverse process of converting an observed diffraction pattern into a real space structure ( n . .. Right: Corresponding electrondiffraction pattern in which the most intense features appear the darkest... Rather detailed information on the site location and the periodic arrangement of the carbon atoms within the nanotube is found from atomic resolution STM micrographs.. such as the diffraction pattern shown in Fig... 3. An example of an STM to~ographic pattern of a singlewall carbon nanotube ~1 nm in diameter is shown in Fig.. . SINGLEWALL CARBON NANOTUBE Fig... and such experiments can be done successfully on singlewall nanotubes. By calculating the structure factor for all the atoms in the 1D unit cell of a general singlewall nanotube. . the experimentalist would have to compare the observed patterns to available simulations... The dimensions of the diffraction pattern scale linearly with sinB.10 for a (17. Combined STM measurements to monitor dl and 4 and STS (scanning tunneling spectroscopy) t o give the 1D density of states provides a powerful technique for studying the electronic structure of carbon nanotubes [65].. .. DNA molecule from Xray diffraction experiments..3) singlewall carbon nanotube. where 28 is the scattering angle (see list of numbers) and 4 = 0 is at the center of the pattern. . ... . rn) for the atomic sites within the 1D unit cell... IJO ... .... . 299. ... 3. At present....2 K [54].3) carbon nanotube projected on a plane normal to the incident wave vector.. . . .10: Left: Atomic structure of the (17... . The tube diameter is continuously measured by the STM technique in terms ... the expected diffraction spots (and streaks) and their relative intensities are found 1631.... which was made at 4.. At present.  . .8.. The vertical direction is parallel to the nanotube axis ~31.56 CHAPTER 3. especially at low temperature. 3. a@ .
95A.68].. with a lattice constant of 16.2. and a circle radius 6.8 2. Vertical tick marks on curve b are the calculated Bragg positions..11: XRD profile of SWNT material prepared by the laser vaporization method [55].7. ... * .4 1.... ..*..6 1. 3.9A.3. while the chiral angle determination can be made from the site positions of the carbon atoms relative to the nanotube axis (see Fig. .4 0.8). . .6) nanotubes. . weakly interacting through a van der Waals interaction.0 0 (k’) ‘L _ . and showed the most stable configuration to be that of a triangular lattice with the space group PG/mcc where the nearestneighbor carbon atoms on adjacent nanotubes are oriented in the ABAB stacking arrangement of 3D graphite [67..8 1. With the STM it is also been possible to measure the nearest neighbor carbon distance and to show that its value is essentially the same as that for graphite (1. Curve c show analysis of the form factor used t o obtain the lattice constant of the triangular lattice [55].I . p0. Fig.0 0. Datafitted background (curve a) compared with a model profile (curve b) that assumes a 2D triangular lattice of uniformly charged cylinders. Recent experimental studies of the lattice structure of arrays of singlewall carbon nanot. ’:. It is further expected that carbon nanotubes will be widely used for the manipulation of nanostructures more generally because of their excellent mechanical properties (see Chapter 11).ubes [55] using Xray diffraction techniques .1..68]. .. EXPERIMENTAL EVIDENCE FOR NANOTUBE STRUCTURE 57 4 I * .42A) [66]. has been treated theoretically [67. These calculation considered the stabilization of a nanotube array of (6. It is expected that improvements in the techniques for characterizing and manipulating carbon nanotubes will be forthcoming and that these techniques will enhance our general capabilities for the characterization of carbon nanotubes. The possibility of forming arrays of singlewall carbon nanotubes. 3..0 1. of the height difference between a substrate and the maximum height of the nanotube relative t o the substrate.6 0.2 0.
58
CHAPTER 3. SINGLEWALL CARBON NANOTUBE
confirm that the 3D structure is that of a triangular lattice with alattice constant of 17A for nanotubes of 1 . 3 8 f 0 . 0 2 nm diameters and an intertube separation of 0.315 nm (see Fig. 3.11). Variation in the mean nanotube diameter and the diameter distribution can be achieved by using different catalysts and growth conditions (see Chapter 5). Many of the early quantitative experiments relevant t o singlewall nanotubes have thus far been carried out on nanotube arrays that were prepared in the same way as the material yielding the diffraction pattern of Fig. 3.11.
CHAPTER 4.
Electronic Structure of SingleWall Nanotubea
Using the definition of the structure of carbon nanotubes discussed in Chapter 3, the electronic structure of carbon nanotubes is derived by a simple tightbinding calculation for the nelectrons of carbon atoms. Of special interest is the prediction that the calculated electronic structure of a carbon nanotube can be either metallic or semiconducting, depending on its diameter and chirality. This onedimensional metal is stable under the socalled Peierls instability. Th e energy gap for a semiconductor nanotube, which is inversely proportional t o its diameters, is directly observed by scanning tunneling microscopy measurements.
4.1
Oneelectron dispersion relations
4.1.1 ZoneFolding of Energy Dispersion Relations
The electronic structure of a singlewall nanotube can be obtained simply from that of twodimensional graphite. By using periodic boundary conditions in the circumferential direction denoted by the chiral vector Ch, the wave vector associated with the Ch direction becomes quantized, while the wave vector associated with the direction of the translational vector T (or along the nanotube axis) remains continuous for a nanotube of infinite length.* Thus the energy bands consist of a set of onedimensional energy dispersion relations which are cross sections of those for twodimensional graphite (see Fig. 2.4). When the energy dispersion relations of twodimensional graphite, EgaD(k) [see Eqs. (2.27) and/or (2.29)] at line segments shifted from WW’ by pK1 ( p =
*For real carbon nanotubes, since the length of a nanotube ( L c N )is on the order of pm, discrete k vectors (Ak = 2 7 ~ / L c can be expected. In low temperature transport experiments [51], ~) this discreteness becomes important. See further details in Sect. 8.2.
59
60
CHAPTER 4. ELECTRONIC STRUCTURE OF NANOTUBES
K ‘
L
k.
Fig. 4.1: The condition for metallic energy bands: if the ratio of the length of the vector Y K to that of K1 is an integer, metallic energy bands are obtained.

, N  1) are folded so that the wave vectors parallel to Kz coincide with WW’ as shown in Fig:3.5, N pairs of 1D energy dispersion relations E,(lc) are obtained, where N is given by Eq. (3.9). These 1D energy dispersion relations are given by
O,...
corresponding to the energy dispersion relations of a singlewall carbon nanotube. The N pairs of energy dispersion curves given by Eq. (4.1) correspond to the cross sections of the twodimensional energy dispersion surface shown in Fig. 2.4, where cuts are made on the lines of lcKz/lK21 pK1. If for a particular ( n , m ) nanotube, the cutting line passes through a K point of the 2D Brillouin zone (Fig. 2.3), where the ?r and ?r* energy bands of twodimensional graphite are degenerate by symmetry, the onedimensional energy bands have a zero energy gap. Further, as will be shown in Sect. 4.2, the density of states at the Fermi level has a finite value for these carbon nanotubes, and they therefore are metallic. If, however, the cutting line does not pass through a I( point, then the carbon nanotube is expected to show semiconducting behavior, with a finite energy gap between the valence and conduction bands. The condition for obtaining a metallic energy band is that the ratio of the length of the vector Y K to that of K1 in Fig. 4.1 is an integerj Since the vector
+
t
tThere are two inequivalent K and K’ points in the Brillouin zone of graphite as is shown in Fig. 4.1 and thus the metallic condition can also be obtained in terms of A”. However, the results in that case are identical to the case specified by Y K .
4.1, ONEELECTRON DISPERSION RELATIONS
61
0 : metal 0 : semiconductor
...
Fig. 4.2: The carbon nanotubes ( n , m ) that are metallic and semiconducting, respectively, are denoted by open a.nd solid circles on the map of chiral vectors ( n ,m).
+
Y K is given by
yri=
*
2n+m 1 K 3
I
(4.2)
the condition for metallic nanotubes is that (2n 4 rn) or equivalently ( n  m) is a multiple of 3.i In particular, the armchair nanotubes denoted by (n,n)are always metallic, and the zigzag nanotubes (n,O) are only metallic when n is a multiple of 3. In Fig. 4.2, we show which carbon nanotubes are metallic and which are semiconducting, denoted by open and solid circles, respectively, From Fig. 4.2, it follows that approximately one third of the carbon nanotubes are metallic and the other two thirds are semicondu~ting.
4.1.2
Energy Dispersion of Armchair and Zigzag Nanotubes
To obtain explicit expressions for the dispersion relations, the simplest cases to
consider are the nanotubes having the highest symmetry. Referring to Fig. 4.3, we see the unit cells and Brillouin zones for the highly symmetric (achiral) nanotubes, namely for (a) an armchair nanotube and (b) a zigzag nanotube. The appropriate periodic boundary conditions used to obtain the energy n) eigenvalues for the (a, armchair nanotube define the small number of allowed wave vectors km,g in the circumferential direction
n&t,,,a
= 2xq,
(g = I,. . . , 2 n ) .
(4.3)
Substitution of the discrete allowed values for k,,, given by
!Since 3% a multiple of 3, the remainders of (2n is
Eq. (4.3) into
+ m ) / 3 and (n m ) / 3 are identical.
Fig. 4.3: Part of the unit cell and extended Brillouin zone of (a) armchair and (b) zigzag carbon nanotubes. a and bi are i unit vectors and reciprocal lattice vectors of twodim~nsiona1 graphite [see Eqs. (2.22) and (2.23) and Fig. 2.31, respectively. In the figure, the translationai vector T [Eq. (3.5)] and the eorresponding reciprocal lattice vector Kz [Eq. (3.20)] of the nanotube are shown.
Eq. (2.29) yields the energy dispersion relations E:(L) for the armchair nanotube, Ch = ( n , n ) [69],
(T
< kU < T ) ,
(4
= 1,.. .,272.)
in which the superscript a refers to armchair and k is a onedimensional vector in t the direction of the vector K2 I= (bl  bz)/Z. This direction co~responds o the I? t o K point vector in the twodimensional Brillouin zone of graphite* (see the top of Fig. 4.3). The resulting calculated 1D dispersion relations E:(E) for the (5,5) armchair nanotube are shown in Fig. 4.4(a), where we see six dispersion relations for the conduction bandst and an equal number for the valence bands. In each case, two bands are non~egenerate labeled by “a” and the four labeled by “e” are doubly degenerate, leading to 10 levels in each case, consistent with the 10 hexagons around the circumference of the (5,5) nanotube. For all armchair nanotubes, the energy bands show a farge degeneracy a t the zone boundary, where ka = T , so that Eq. (2.29) becomes
*Note that K z vector is not a reciprocal lattice vector of 2D graphite. tThe Fermi energy corresponds to Eft = 0. The upper half of Fig. 4.4 corresponds to the unoccupied conduction bands.
) for the 2D graphene sheet.5) occurs. The crossing takes place at the Fermi level and the energy bands are symmetric for fc values. (See Eqs.7). The latter case corresponds to zigzag nanotubes ( n .3(a) for the real space lattice. respectively.4(a) for the armchair n a n o t u b ~ cross at a k point that is two thirds of the distance from k = 0 to the zone boundary at k = n / a . we have dispersionless energy bands with an energy of ft. l Because of the degeneracy point between the valence and conduction bands tThe large degeneracy comes from the equienergy lines of the energy bands of 2D graphite which connect the two nearest M points (See Fig. 5 ) . depending on whether there are even or odd numbers of bands n at the I? point ( k = 0). (b) zigzag (9. 4.4: Onedimensional energy dispersion relations for (a) armchair ( 5 . The abands are nondegenerate and the ebands are doubly degenerate at a general kpoint [70]. When Kz is parallel to the equienergy line. which causes a degeneracy of the energy bands at the boundary of the Brillouin zone. The valence and conduction bands in Fig. independent of zone folding and independent of a. and (c) zigzag (l0. the two carbon atoms on the same sublattice of a graphene sheet are symmetrically equivalent. (4.0).O) carbon nanotubes labeled by the irreducible representations of the point group Dnd or Dnh.* Although there are four carbon atoms in the unit cell of Fig. 4.4). 4.63 3 3 2 2 1 2 1 I 0 1 0 1 1 2 3 2 . 2. When is perpendicular to the equienergy line. a large degeneracy of Eq.3 2 3 k k k Fig.4) and (4. O ) with an even number of n. x z . X points for armchair and zigzag nanotubes correspond t o k = f n / a and k = f n / f i a . (4.
whereas the (10.) are used to distinguish energy bands with the same symmetry from one another.O) nanotube indeed shows an energy gap. the f signs refer to the corresponding signs in Eq. (2. because only infinitesimal excitations are needed to excite carriers into the conduction band.a t the band crossing.29).O) nanotube at k = 0.4) with 2n conduction and 2n valence bands. (4.6) to yield the 10 dispersion relations for the 4n states for the (n. All ( n . 4. (4. and of these 2n bands. 2 . which gives E ( n / a ) = ft. . when n is not . Dispersionless energy bands occur at q / n = 112 in Eq. all armchair nanotubes are expected to exhibit metallic conduction. The symbols u and g in Fig. Thus. which gives a singular density of states at that energy.O) zigzag nanotube (denoted by the superscript z ) The resulting calculated 1D dispersion relations Eg((1)for the (9. there is a dispersionless energy band a t E / t = f l .a = 2nq. where the bands cross the Fermi level.. .O) zigzag nanotubes are shown in Figs. when n is a multiple of 3.41.3).2n). two are nondegenerate and ( n . .4(b) and (c). The energy bands for the C h = ( a .71761.. n ) armchair nanotubes have a band degeneracy between the highest valence band and the lowest conduction band at L = f2a/(3a). as: nk.O) and (10.O) nanotube.4).. Especially in the case of the (10. (2. For a general (n. show that dl ( n . 4. and (4. (4.1) are doubly degenerate. (4.. (q = 1. respectively. . as given by Eqs.O) zigzag nanotube. however. (4. 5 ) armchair nanotube is thus a zerogap semiconductor which will exhibit metallic conduction a t finite temperatures.4) and the integers ( 1 .n ) armchair nanotubes yield 4n energy subbands analogoiis to Eq.. There is no energy gap for the (9.4(a) indicate the even and odd behavior of these states regarding inversion symmetry. similar to the behavior of 2D graphene sheets [69.29) by writing the periodic boundary condition on L. Similar calculations.0) zigzag nanotube Eq(L)can be obtained likewise from Eq. the ( 5 . the energy gap at k = 0 becomes zero.
(4. As is pointed out in Sect. the crossing of the four energy bands a t k = 0 in the case of the (9. respectively. The situation of metal1 in Table 4. since d~ = d. the nanotubes can be classified into three general categories [77. we show dispersion relations for the (9. when n is an even number. (3. The cl~sification this table can in be understood in terms of the length rY shown in Fig. different symmetries. Further. 4 5 is an accidental degeneracy.4) chiral nanotubes. 3. 4. the Y point becomes the I point since is ' the K2vector becomes a reciprocal lattice vector in this case. A more detailed analysis of the E ( k ) relations for chiral nanotubes which is generally given by Eq.m).7) and m is one of the integers of the chiral vector. (4.6.a multiple of 3. the band degeneracy at the Fermi level . Further when m / d ~ an integer. occur for odd and even numbers of n.1. and (2) whether or not nm is multiple of 3 4 whenever n. an energy gap opens at k = 0.6.5 and 4. dispersionless energy bands appear.5 and 4. respectively. Since the metallic condition Eq.6) nanotube in Fig. 4. 4. Dnd and D n h . In Figs.1. In this case. and d is the highest common divisor of n and m.3 Dispersion of chiral ~ a ~ o ~ ~ b ~ s It should be noted that the L values for the band degeneracies for metallic nanotubes are L = &2n/3T or Ic = 0 for armchair or zigzag nanotubes. respectively. 4.1. Further. the L values a t the Fermi level band crossings are at k = 0 and f2n/3T for Figs. 4. Since the highest degeneracy of irreducible representations of the group of the wave vector at k = 0 is two.2) is satisfied in these cases. respectively. depending on: (1) whether or not n . Since 91 .1 corresponds to this case. these two chiral nanotubes are metallic.1) shows that.m is a multiple of 3. d R is given by Eq.m is a multiple of 3.1 is folded into the Y point. Here d is the highest common divisor of n and m in Ch = ( n . m ) .78].l is along the nanotube axis.6) and (7. The same k values also denote the positions of the energy gaps (incfuding zero energy gaps) for the general case of chiral tubes. The three cases are summarized in Table 4. the point K in Fig.m is a multiple of 3 in the both cases. Ch = ( n .6. and that these kvalues are also the locations of the band gaps for the semiconducting zigzag nanotubes. but not in the case when n is an odd number. which is given by where IK.
Metallic zigzag nanotubes.13 eV. 0).* ~ *While the value of yo for 3D graphite is 3. 4 at k = O . then m / d R is not an integer. ELECTRONIC STRUCTURE OF NANOTUBES Table 4. denoted by ( 3 q .80] must be considered for the case of orbitally degenerate bands. and this 2D value has been found to yield good agreement with first principles calculations [Sl]. Armchair nanotubes (n. (v is an integer). as discussed above. are n) in the category metal2.2 Density of States. (3.1:Classification of solid state properties of nanotubes. (') Degeneracy at the Fermi energy. ('1 d R is given by Eq. gcd denotes the greatest common divisor. a value of It1 = 2.7 eV has been estimated by the Delft group . Properties Semiconductor Metal. (a) occurs at k = 0 and involves a 4fold accidental band degeneracy.3 ) ( a ) 1 3 3 dg) d C h = (n. 4. Energy gap For all metallic nanotubes. it follows that the density of states per unit length along the nanotube axis is a constant given by where u is the lattice constant of the graphene layer and It1 is the nearestneighbor CC tight binding overlap energy usually denoted by yo in the graphite literature [78].7).1 Metal2 gcd(n . When the spin of the electron is included. This corresponds t o the case of metal2 and the degeneracy occurs at k = f2n/3T.66 CHAPTER 4.5 eV is obtained for this overlap energy in the 2D case when the asymmetry in the bonding and antibonding states is averaged out. independent of their diameter and chirality.Experimentally the value It1 = 2. the & signs occur in both cases for the dispersion relations near k = f2n/3T. always fall into the category of metal1. ( d ) 2 at k = rt2n/3T. When dR = 3d.rn. Since the inequivalent K and Ii" points are folded into different points in the Brillouin zone.m)  d 3d Degeneracy(") 0 (Energy gap oc l/dt). Since group theory allows only one and twodimensional irreducible representations. the fourfold degeneracy is accidental. but rather m / d R = vf 113. the effect of spinorbit interaction in carbon [79.
4.allic 1D chiral nanotube ( n . The general behavior of the two band degeneracies at Ic 2 f(2/3)(n/T) is typical of the case where dR = 3d (Metal 2)[77]. and the value of d R is d R = 3. The values of d and d~ are d = 1 and d R = 3.5 10 .4.rn) = (9.G) is d = 3. DENSITY OF STATES. m ) = (7. Fig.5 0.o 1. [SZ] in fitting S T M density of states data.5 00 .5 1.5: Plot of the energy bands E ( k ) for the metallic 1D nanotube ( n . The largest common divisor of (9.4) for values of the energy between t and t in dimensionle~units E(k)/ltf. 0. The Fermi level is at E = 0.o 0.0 kT/rc 0. G ) for values of the energy between t and t . in dimensionless units E(k)/til. The general behavior of the four energy bands intersecting at k = 0 is typical of the case where d R = d (Metal 1) [77]. T h i s S T M value may be about the best experjment~ .6: Plot of the tight binding energy bands E( k) for the met. 4.2. kT/n Fig. ENERGY GAP 1. respectively.0 0.
0 3.5 % 5 cn r . Another important result.68 CHAPTER 4.8 the 1D density of states for a (10.0 2.7: Electronic 1 D density of states per unit cell of a 2D graphene sheet for two ( n . 2.0 0. 4.0 3. We also show in Fig. The comparison between the 1D density of states for the nanotubes and the 2D density of states for a graphene layer is included in the figure.0 1. i .0 1.0 1 i l .lO) nanotube. Of particular interest is the density of states near the Fermi level EF located a t E = 0. pertaining to semiconducting nanotubes. 4. but is nonzero (and small) for metallic nanotubes.0 2. % '. l .7 which compares the density of states for metallic (9. . (b) the (10. . as shown in Fig.= 0. This density of states has a value of zero for semiconducting nanotubes. Also shown in the figure is the density of states for the 2D graphene sheet [76]. shows value we have €or Jtl 80 far. . 4. l . 80'04.0) zigzag n a n ~ t u b ~ : the (9.0 1.0 0 Energy40 7 T  r 3. Of particular interest has been the energy dependence of the nanotube density of states.0 P 0.0 5 m C .= L 1.0 1.0 2. Of equal interest are the singularities in the 1D density of states corresponding to extrema in the E ( k ) relations. . which is within 15% of the 3D value.O) (a) nanotube which has metallic behavior.O) nanotube which has semiconducting behavior. J .0 EnergYlYo Fig.O) and semiconducting (l0.O) zigzag nanotubes. ELECTRONIC STRUCTURE OF NANOTUBES .0 3. these data have been extensively used for the analysis of various experimental data. .
10) ~ndependent the chiral angle of the semiconducting nanotube. i. 4. as given by the local density functional calculation [Sl]. (4.8: Electronic density of states (DOS) calculated in a tight binding model for (V).10) and (11111) armchair nanotubes.10) suggests that the band gap exceeds thermal energy at room temperature for nanotube diameters dt 5 140 A.. Using a value of It1 = 2. because this result allows measurements to be made on individual semiconducting nanotubes.13 eV. The results in Fig. ENERGY GAP 69 2 0 2 Energy [eV] Fig. which are characte~izedonly with regard to nanotube diameter without regard to their chiral angles. and the nonconducting constituents will play almost no role. (4. 4.9 are important for testing the 1D model for the electronic structure of carbon nanotubes. since about one third of the cylinders of a multiwall nanotube are conducting. A plot of Es vs. by the contributions from the conducting constituents.9 for the graphite overlap integral taken as It1 = 3. by Density of states m e ~ u r e m e n t s scanning tunneling spectroscopy (STS) provide a powerful tool for probing the electronic structure of carbon nanotubes . (10. l / d t is shown in Fig. Eq.e.DENSITY OF STATES.(9191. 2tl + c1 and v2 t c2 as indicted for the case of the (8. The energies (in eV) for various optical transitions are indicated on the figure [83]. such as the electrical ~ o ~ d u c t i v of tn a n o t u ~ e will be d o ~ i n a t e d ~ y ~. 4.8) nanotube. where acc = of a/& is the nearestneighbor CC distance on a graphene sheet.5 eV. Wavevector conserving optical transitions can occur between mirror image spikes. certain electronic proper tie^. Furthermore. that their energy gap depends upon the reciprocal nanotube diameter dr.
4. However. ' ' " t Fig.7) have been observed on metallic and semiconducting nanotubes whose diameters and chiral angIes were determined by operating the instrument in the scanning tunneling microscopy (STM) mode 1821.ll.0' ' ' t . 0 0 9 & 0. The STS results confirm the theoretical model that the energy between the lowestlying resonance in the conduction band and the highestlying resonance in the valence band is smaller for semiconducting nanotubes and larger for metallic nanotubes. As the nanotube diameter increases.70 0. Such measurements confirm that some nanotubes (about 113) are conducting. 4.3. and some (about 213) are semiconducting (see Fig.82]. Thus if we consider finite temperatures or fluctuation effects. 4.6 04 . Thus the main 1D q u a n t u ~ features predicted theoreticalIy for carbon nanotubes have now been observed experimentally. 1 t CHAPTER 4 .9) [G5. M e ~ u r e m e n t s on semiconducting nanotubes confirm that the band gap is proportional to I/& (see Fig.2 dfw 80 ' 0. 4. and . Resonances in the density of states (see Fig. chiral carbon nanotube EW a function of 100 Ah.3 Effects of Peierls distortion and nanotube curvature ~ e t ~ l1Dc i energy bands are generally unstable under a Peierls distortion.5 eV is taken for the transfer integral.ldt. Detailed discussion is presented in Sect. so that the Peierls gap quickly approaches the zeroenergy gap of 2D graphite [G9.2). I . the Peierls energy gap obtained for the metallic nanotubes is found to be greatly suppressed by increasing the nanotube diameter. i ' i .82]. 4.71]. the nanotubes become more twodimensional.9: The energy gap Eg scaled by It[ for a semiconducting. ELECTRONIC STRUCTURE OF NANOTUBES . and that the density of states at the Fermi level is nonzero for metallic nanotubes. but zero for semiconducting nanotubes [82]. where dt is the nanotube diameter in and a value of It1 = 2. more wave vectors become allowed for the circumferential direction. It is noted that the relationship be [G5. it is believed that such a small Peierls gap can be neglected. b .
3 P ~ ~ I S T ~ ~ ~ T CURVATURE ~ AND ~ O ~ S ~ 71 as illustrated in Fig. The inclusion of curvature effects complicates the calculation considerably. the degeneracy o the conduction and f taking account of the hybridi~tion valence bands is not affected by the hybridization. this symmetry holds. by introducing four tight binding parameters. VJpa = 4. The dependence of Eg on d t l is obtained analytically from k: . which has been used to describe carbon nanotubes when their curvature is neglected.. the range that has been observed experimentally. The effect of curvature of the carbon nanotubes has been considered within the tight binding approximation [81].4. and VpPD = 4. with values given by VppT = 2. This degeneracy comes from the symmetry that A and 3 atoms are equivalent to each other in the unit cell of graphite.9. the band crossings at EF are between energy bands of different symmetry.76 eV. the semiconducting band gap decreases. except for armchair nanotubes. that one third of the nanotubes are metallic and two thirds are semiconducting. .7 nm).37 eV [85..) Thus no interaction or band splitting would be expected at E F . resulting in a small energy gap (on the order of meV) for nanotubes with small diameters.77 eV. has a symmetry basis which is discussed in *When we see unfolded energy bands of carbon nanotubes in the t w ~ ~ m e n s i o n ~ Brillouin ' zone of graphite. It should be mentioned that for both the armchair and zigzag nanotubes.87891. yielding results in substantial agreement with the simple tight binding results which are described in this section. (Even when na. V. = 4.86]. Some first principles calculations for the electronic structure have been carried out for carbon nanotubes [72. since the shift of the k vector at the Fermi energy by the curvature effect is along the onedimensional Brillouin zone.p theory near the IC point [84]. Tightbinding calculations which consider 2s electrons 1731 and other local density approximation (LDA) calculations [87. In armchair nanotubes. since the hybridieation effect does not change the equivalence between the A and B atoms. the degenerate point at the K point moves away from the A point by effect. 4. we get a metallic condition for armchair nanotubes even when curvature effects are taken into account. The simple tight binding result for singlewall nanotubes which considers only x orbitals.90] show that the large curvature of small singlewall carbon nanotubes leads to a hybridization of u* and 7r* orbitals.* The effect of this hybridization is large for nanotubes of diameter less than that of CSO is not but so great for nanotubes in the range (dt > 0. From the figure we clearly see that the energy gap is inversely proportional to the diameter. However. Thus.33 eV.5 eV. instead of the single tight binding parameter Vppr= 2.81.notube curvature is considered the bands that cross will have different symmetries.
Electron energy loss spectroscopy studies on individual nanotubes confirmed the BN stoichiometry [92. .91]. and the band gap of crystalline BN is of about the same magnitude throughout the Brillouin zone. with inner diameters of 13 nm and lengths up to 200 nm. and the results suggest that BN nanotubes should be stable and should have a band gap of 5. ELECTRONIC STRUCTURE OF NANOTUBES Sect. These calculations for the electronic structure of BN nanotubes stimulated experimental work. Thus no quantum effects as are observed in carbon nanotubes are expected for B N nanotubes. so that BN nanotubes on either the inside or outside of carbon nanotubes can be used to provide insulation to carbon nanotubes.93]. 4. hence suggesting that all very smalldiameter nanotubes should be metallic. LDAbased calculations have also been carried out for BN nanotubes. A first principles LDA calculation [go] has determined that for very smalldiameter nanotubes the curvature of the graphene sheet results in band shifts which move their band edges into the semiconducting energy gap. There are several physical processes that tend to modify these simple considerations. compared with carbon nanotubes. a relatively large energy gap is expected.1.72 CHAPTER 4 . However. The B N nanotubes are produced in a carbonfree plasma discharge between a BNpacked tungsten rod and a cooled copper electrode.1. A contrary conclusion could be reached if a Peierls distortion of the 1D conductor produced an energy gap at the Fermi level. independent of diameter [90.5 eV. leading to the successful synthesis of pure BN multiwall nanotubes [92].
Two relatively efficient methods to synthesize singlewall carbon nanotubes have been identified: laser vaporization and carbon arc synthesis. For these reasons most of the experimental studies continued to be done on multiwall nanotubes. carbon nanoparticles and other carbonbased materials. only small quantities of singlewall nanotubes were available experimentally for systematic studies. at first. and the singlewall constituents contained a distribution of diameters and chiral angles. with primary emphasis on singlewall nanotubes.1 SingleWall Nanotube Synthesis The first experimental identification in 1991 of carbon nanotubes was on multiwall nanotubes[l9]. The experimental discovery of singlewall carbon nanotubes in 1993[58. the purification of carbon nanotubes. offered major new opportunities for quantitative experi73 .CHAPTER 5. as explained below. 941 further stimulated work in the field. The recent discovery in 1996 of a much more efficient synthesis route. though. 5.1). involving laser vaporization of graphite [55] t o prepare arrays or “ropes” of ordered singlewall nanotubes. Synthesis of Carbon Nanotubes This chapter describes synthesis methods for carbon nanotubes. Also discussed in this chapter are the synthesis of multiwall carbon nanotubes. the insertion of metals into the hollow core of carbon nanotubes. This report stimulated a large number of theoretical works on the structure and properties of the simpler and more fundamental singlewall carbon nanotubes. 3. Other techniques such as vapor growth are also reviewed. one atomic layer in thickness in the radial direction (see Fig. These singlewall nanotubes were generally found along with very much larger concentrations of amorphous carbon. and both methods depend on the use of catalysts. and the doping of carbon nanotubes with alkali metals.
filling and alignment (Sect.8).2 Laser Vaporization Synthesis Method An efficient route for the synthesis of bundles of singlewall carbon nanotubes with a narrow diameter distribution employs the laser vaporization of a graphite target.6). 5. high yields with >70%90% conversion of graphite to singlewall nanotubes were reported in the condensing vapor of the heated flow tube (operating at 12OOOC). temperature regimes for carbonization and graphitization (Sect.9). Therefore we can expect extensive research to be carried out on the growth mechanism and on the development of new growth techniques that provide more controlled growth of nanotubes. and this may perhaps be accomplished by vapor growth methods discussed in Sect. consisting of 1.CHAPTER 5. The remaining sections of the chapter briefly deal with the purification of nanotube samples (Sect. nanotube doping (Sect.8 atom ' %) [55]. and growth mechanics (Sect. 5. By making the singlewall nanotubes available to many research groups worldwide. catalyst species are necessary for the growth of the singlewall nanotubes. nanotube opening. 5. another synthesis route was found for the synthesis of gram quantities of singlewall carbon nanotubes.2 atom 3% CoNi alloy with equal amounts of Co and Ni added to the graphite (98. Whereas multiwall nanotubes require no catalyst for their growth. The detailed mechanisms responsible for the growth of these nanotubes are not yet well understood.51. A CoNi/graphite composite laser vaporization target was used.Two sequenced laser pulses were used to evaporate a target containing carbon mixed with a small amount of transition metal from the target (see .synthesis of singlewall carbon nanotube ropes. SYNTHESIS OF CARBON NANOTUBES mental studies of carbon nanotubes. In the early reports of the laser synthesis technique [55]. 5. wetting. Soon after the publication of the laser vaporization method for the .7). progress was made for the first time in quantitative measurements of the physical properties of singlewall carbon nanotubes. 5. Because of the potential interest of carbon nanotubes for practical applications. 5. using the carbon arc method [52]. 5. and more than one catalytic species seem t o be necessary t o grow ropes of singlewall nanotubes.4. there is also interest in developing continuous synthesis methods more appropriate for scaleup and low cost.
5. each rope is found to consist primarily of a bundle of singlewall carbon nanotubes aligned along a common axis. just outside the furnace [55 961. Xray diffraction (which views many ropes at once) and transmission electron microscopy experiments (which view a single rope) show I551 that the diameters of the singlewall nanotubes have a strongly peaked distribution at 1.1: Singlewalled nanotubes produced in a quartz tube heated to 1200°C by the laser vaporization method.1).38ir0.2(b)]. LASER VAPORIZATION SYNTHESIS METHOD furnace at 1. very close to . 5. 5.2.200’ Celsius 75 \ LL watercooled copper collector argon neodymiumyttfiumalumlnumgarnet laser 1 graphite target Fig. Fig. The material thus produced appears in a scanning electron microscope (SEM) image as a mat of “ropes” 1020 nm in diameter and up to 100 pm or more in length [see Fig.02 nm.2(a)]. Under transmission electron microscope (TEM) examination [see Fig. Flowing argon gas sweeps the entrained nanotubes from the high temperature zone to the watercooled Cu collector downstream. using a graphite target and a cooled collector for nanotubes [95]. 5. 5.
7 nm.rn) are mainly (10.8) to ( 1 1 .9) (20%). presumably using different growth conditions. while others.4 nm.2.3O [56. (9. (b) At higher magnification. 5. arranged in a triangular lattice (with lattice constant 1. Thus for nanotube diameters ranging from that for the (8.315 nm at closest approach within a rope [55].lO) nanotube which is defined in Eq. 3. By varying the growth temperature. The ropes are 1020 nm thick and 100 p m long.lO) (44%). and some (12. l l ) armchair nanotubes. the TEM image shows that each rope contains a bundle of singlewall nanotubes with diameters of 1.8) [97]. A detailed transmission electron microscopy study of carbon nanotubes prepared by the laser vaporization method [55] has shown that the carbon nanotube chiral indices (n. there are only 17 possible nanotubes [97].7 nm). and an intertube separation of 0. Such an image is seen when the rope bends through the image plane of the microscope [55I* the diameter of an ideal (10. The singlewall nanotubes are held together by weak van der Waals internanotube bonds to form a twodimensional triangular lattice with a lattice constant of 1.2: (a) Ropes of singlewall carbon nanotubes observed by scanning electron microscopy (SEM). have reported chiral angles in the range A0 = 7.98]. SYNTHESIS OF CARBON NANOTUBES Fig. the catalyst .76 CHAPTER 5.
The growth of carbon nanotubes appears to be unfavorable under the conditions that are optimized t o synthesize fullerene molecules. the length of the positive electrode (anode) decreases (see Fig. a carbon deposit forms on the negative electrode. no catalyst need be used and the nanotubes are found in bundles in the inner region of the cathode deposit where the temperature is a maximum (25003000°C). For the multiwall carbon nanotube synthesis. Surrounding the nanotubes is a hard grey shell consisting of nanoparticles. It is found that the spread in nanotube diameters within a single rope is smaller than between ropes grown at the same time and under the same nominal growth conditions. n . and ropes of singlewall nanotubes [52]. Once the arc is in operation. Ni. the average nanotube diameter and diameter distribution can be varied [99].3) [ l o l l1041. The nanotube bundles are roughly aligned in the direction of the electric current flow (see Fig. 'During arc synthesis fullerenes are predominantly found in the soot produced by the arc and removed by the helium gas flow. 5. Catalysts used t o prepare isolated singlewall carbon nanotubes include transition metals such as Co. Arc Method of Synthesizing Carbon Nanotubes The carbon arc provides a simple and traditional tool for generating the high temperatures needed for the vaporization of carbon atoms into a plasma (>3O0O0C) [loo1021. 5. Although the details of the diameter (and chirality) distribution of the singlewall carbon nanotubes depend on the synthesis conditions.3). ARC METHOD OF SYNTHESIZING CARBON NANOTUBES 77 composition and other growth parameters. Co/Ni and Co/Pt have been used to synthesize ropes of singlewall nanotubes.' Adequate cooling of the growth chamber is necessary to maximize the nanotube yield in the arc growth process. Fe and rare earths such as Y and Gd. 53 .3. The arc is typically operated in 500 torr He with a flow rate of 515ml/s for cooling purposes. As the carbon nanotubes form. while the nanotubes are contained i a deposit on the cathode. while mixed catalysts such as Fe/Ni. This technique has been used for the synthesis of singlewall and multiwall carbon nanotubes.5. Typical conditions for operating a carbon arc for the synthesis of carbon nanotubes include the use of carbon rod electrodes of 520 mm diameter separated by 1 mm with a voltage of 2025 V across the electrodes and a dc electric current of 50120 A flowing between the electrodes. fullerenes and amorphous carbon [1051071.
5. corresponding to the diameter of c60. the smallest fullerene to obey the isolated pentagon rule [108]. and the growth rate of a 1 pm carbon nanotube is estimated to be less than 0. Since the length of a carbon nanotube is typically on the order of 1 pm. temperature of the arc and the catalyst that is used. the average nanotube diameter is usually small (51. the time for the growth of a single circumferential carbon ring is second.7 nm.78 CHAPTER 5. as illustrated in Fig.3: Crosssectional view of a carbon arc generator that can be used t o synthesize carbon nanotubes [103]. with ~ 2 0 % the consumed carbon being converted into singlewall of carbon nanotubes in the collarette. This time scale is much shorter than the time needed for the direct obser .4.1 second. SYNTHESIS OF CARBON NANOTUBES to Pump Gas Inlet Window Fig. An efficient method for the synthesis of gram quantities of bundles of singlewall carbon nanotubes using the carbon arc technique has been achieved [52]. The greatest mass of singlewall carbon nanotubes is found in a collarette around the cathode. It is interesting t o note that the minimum nanotube diameter that has been observed for singlewall carbon nanotubes is 0.5 nm) and the diameter distribution is usually narrow. 5.
t Carbon nanocapsules consist of multiwall polyhedra of graphene sheets with interlayer separations of 0. When certain transition metals (Fe.1 1. in which hydrocarbons (e. Mo. W. Go. singlewall nanotubes are observed at the surface of the deposit and nanocapsules are observed in other regions.). Thus the growth of carbon nanotubes occurs under stable conditions but over a limited range of He (or Ar) pressure.17. CH4. or their oxides are packed into a hole in the central region of the positive electrode. Co. vation of the carbon arc electrodes by transmission electron microscopy (TEM) but is much longer than the phonon frequency 1015 Hz.4 Vapor Growth and Other Synthesis Methods Fe. Nil Cu and Au) or metal carbides M.g. Co. GdTm. C6H6) and Hz gases are reacted in the presence of Fe. ..4 1.8 0. Co.7 0. Co. Thus purification is necessary to separate out a pure singlewall nanotube sample.. and Ni.94]. Pb.44].9 1..C (M = transition metal such as LazC (La = rare earth metal). and Ni particles are known to be catalysts for vapor grown carbon fiber synthesis [9. tIn the case of Fe. or Ni particles in a reaction tube at llOO°C. electric current and arc voltage.0 1.2 1. rareearth metals (LaNd. Ni. catalysts.VAPOR GROWTH AND O T H E R SYNTHESIS METHODS 79 0. Cu. 5. Au. . Lu). 5. a well as metal clusters encapsulated s within graphene layers [58. carbon nanocapsules are often obtained in the deposit on the negative electrode [109].6 Nanolube diameters (nm) Fig.4: Diameter distribution of isolated singlewall carbon nanotubes prepared by the arc method using a Fe catalyst [581.34 nm inside which are contained metals (Fe.3 1.5 1. The iron or cobalt catalyst in the arc process forms both singlewall carbon nanotubes and nanometersize carbide particles surrounded by graphene layers.
catalysts and catalyst supports have been used successfully by various groups worldwide to synthesize carbon nanotubes. with the furnace temperature held at llOO°C and using Fe catalyst particles. A variety of other hydrocarbons. SYNTHESIS OF CARBON NANOTUBES Fig. cut in liquid nitrogen and showing (white arrow) a carbon nanotube emerging from the center of the fiber. (b) HRTEM image showing the broken part of a very thin vapor grown carbon fiber.4. Growth of carbon nanotubes from the vapor phase has also been demonstrated [59].1 Vapor Growth Method The synthesis of carbon nanotubes from the vapor phase utilizes equipment similar to that used for the preparation of vaporgrown carbon fibers [17. 5.5: Carbon nanotubes appear after breakage of the vaporgrown carbon fiber. The nanotube is clearly observed.110].44].80 CHAPTER 5. One big advantage of the vapor growth approach is that carbon nanotubes can be made continuously and thus if the optimum conditions for growing pure carbon nanotubes could be found. as shown in Fig. Thus the vapor growth method . indicating that thin vapor grown carbon fibers grow from a nanotube core by thickening [59]. 5.5. (a) An SEM image of a broken vapor grown carbon fiber. this could be a very good way to synthesize large quantihes of carbon nanotubes under relatively controlled conditions. 5. The innermost tubes of vapor grown carbon fibers are considered to be carbon nanotubes. but using a low benzene gas pressure [59.
5. but some singlewall nanotubes can also be present. Vaporgrown carbon nanotubes have been studied by highresolution TEM in both their asgrown form and after heat treatment. The crystallinity. a seen in highresolution TEM s studies [110]. has some advantage for scaleup and commercial production. however. Many presently identified applications of carbon nanotubes can be met with vapor grown carbon nanotubes.4. so that the exposed cap layer provides growth along the length and the epitaxial layers follow this growth while at the same time adding to the nanotube diameter. Referring to the bamboo structure seen on the inside of vapor grown carbon nanotubes (see Fig. V A P O R G R O W T H A N D O T H E R SYNTHESIS METHODS 81 Fig.7). Fracture of a thin vapor grown carbon fiber shows the presence of a nanotube at the fiber core. (b) an exposed nanotube and a nanotube that had been pyrolytically coated. 5. Endo [110] argues that the capping of an inner layer terminates its growth. . as shown in Fig.6. thereby increasing the nanotube diameter. 5. as is seen in Fig. Carbon nanotubes can grow at the same time as conventional vaporgrown carbon fibers.5.5. 5. Most of these nanotubes are multiwall. is much improved after heat treatment to 25003000°C in argon.6: Two kinds of vaporgrown carbon fibers (VGCF) observed in an asgrown sample: (a) a thick hollow fiber formed by a catalytic metal particle. The frequentlyobserved bending of the growth axis of the nanotubes is related to the introduction of a heptagonal defect at the bend location. The asgrown nanotubes generally show poor crystallinity.
SYNTHESIS OF CARBON NANOTUBES Fig. The nearly periodic structures of the conical shells appear inside the cone tips [see (a)]. Here a number of bamboolike structures are observed in the core region near the cap [110].2 Other Synthesis Methods Another method of nanotube synthesis relates to the use of carbon ion bombardment to make carbon whiskers [lll.82 CHAPTER 5. carbon is vaporized in vacuum through ion or electron irradiation [113]. and the resulting deposit containing carbon nanotubes.11 pm and several mm in length. which are attributed to overshooting growth on the basis of the open tube growth model [107]. (b) Commonly observed nanotube structure for the cap region of vaporgrown carbon nanotubes heat treated at 28OOOC in Ar. 5. 5. In the ion bombardment growth method. along with other structures is collected on a cold surface. Little is known about the optimization of the ion bombardment technique in relation to the preparation of nanotubes. Carbon whiskers are known as a graphite material with high crystallinity [4]whose diameter is 0.7: (a) Transmission electron micrograph of a cone containing only single conical shells.4.1121. The use of solar energy for the synthesis of singlewall carbon nanotubes has .
(b) TEM picture of gas phase purified nanotubes [116]. and centrifugation) have been tried. but not found to be effective in removing the .5 Purification In many of the synthesis methods that have been reported. A mixture of Ni and Y catalysts is used in an argon atmosphere (pressure of 450 mbar).5.5.8: (a) Transmission electron micrograph of a web of singleshell nanotubes formed in the catalytic carbon arc method. such as amorphous carbon and carbon nanoparticles (see Fig.115]. liquid phase. increase the yield of ropes of singlewall nanotubes. PURIFICATION 83 Fig. using an experimental chamber where solar energy is focussed on the crucible t o achieve a temperature of 3000 K on a clear day. The separation of nanotubes according to diameter (and chirality) is not considered under the topic of purification. 5. 5. and t o characterize the carbon nanotubes that are produced. been reported [114. and is not thought to be practical at this time. The classical chemical techniques for purification (such as filtering. Three basic methods have been used with limited success for the purification of the nanotubes: gas phase. carbon nanotubes are found along with other materials.8). Further research is needed to optimize and control the synthesis process. and intercalation methods [116]. Purification generally refers to the isolation of carbon nanotubes from other entities. minimize the concentration of carbon nanoparticles and amorphous carbon produced. chromatography. 5.
Wetting. the intercalation of unpurified nanotube samples with CuC12KCl results in intercalation of the nanoparticles and other carbon species.8 [116]. fullerenes and other contaminants has also been reported [83. 5.118]. Filling and Alignment Nanotube Opening 5. A method for the purification of samples containing singlewall nanotube ropes in the presence of carbon nanoparticles. The carbon nanotubes obtained by gas phase purification are generally multiwall nanotubes with diameters in the range 202OOw and 10 nmlpm in length [104].117. Thus subsequent chemical removal of the intercalated species can be carried out [120].6 Nanotube Opening. Liquid phase removal of nanoparticles and other unwanted carbons has been carried out with some success using a potassium permanganate KMn04 treatment method which tends to give higher yields than the gas phase method. Heating could thus be useful for purification. except that it results in an increase in nanotube diameter due to the accretion of epitaxial carbon layers from the carbon in the vapor phase resulting from heating. Heating preferentially decreases the amount of disordered carbon relative to carbon nanotubes.1211231. The gas phase purification process also tends to burn off many of the nanotubes. Finally. but not the nanotubes which have closed cage structures. since the smaller diameter tubes tend to be oxidized with the nanoparticles.6. amorphous carbon and other unwanted species shown in Fig. Much slower layerbylayer removal of the cylindrical layers of multiwall nanotubes occurs because of the greater stability of a perfect graphene layer to oxygen than disordered or amorphous carbon or material with pentagonal defects [117. The gas phase method removes nanoparticles and amorphous carbon in the presence of nanotubes by an oxidation or oxygenburning process [104.118]. 5.1 Experimental studies show that the cap of a nanotube is more reactive than the cylindrical part because of the presence of pentagons and hence the greater . This method was in fact first used to synthesize a singlewall carbon nanotube. The oxidation reaction for carbon nanotubes is thermally activated with an energy barrier of 225 kJ/mol in air [118].119]. SYNTHESIS OF CARBON NANOTUBES carbon nanoparticles. but results in nanotubes of shorter length [116.CHAPTER 5.
The material that is sucked up the nanotube. the hollow core of the nanotube will be wet by a fluid if where 0 is the contact angle of a liquid on a surface. Rb. then pressures exceeding 2y/r are needed for tube filling. Tube opening can occur at quite low temperatures (4OO0C). however. S. such as with HNOs [116. where the contact angle 0 exceeds n/2. Ni. the cap region is burned off first. Thus in a vapor phase oxidation process. 5. a lead metal catalyst in air [125].3 Nanotube Filling Three methods have been used to fill the hollow core of carbon nanotubes: capillarity. with some reports of long continuous nanowires [127. y s v .6.6. N A N O T U B E OPENING.5. where r is the inner radius of the nanotube. and solvent carrier methods [126].6. In this work sulfur was shown t o catalyze nanotube filling with many metal species. for example. 5. Examples of liquids which 2 wet carbon nanotubes are HNO3. is an oxide of lead [104]. as discussed in Sect. If a liquid does not wet the nanotube. The presence of the pentagons in the cap region also promote tube opening by various chemical reactions. the solidvapor. respectively. solidliquid. Se. using.2. On the basis of classical theories for wetting. though in some cases whole compartments have been filled [124]. Another method that has been successful for introducing high surface tension materials such as Co. W E T T I N G . thereby providing one method for tube opening. 5.6. Fe is the use of a solution using H N 0 3 that performs both wetting and tube opening. Wetting occurs when 0 > ~ / or ysv > ysr. water. The capillarity method exploits removal of the cap (or the opening of the tube) followed by wetting. pressure.126]. In many cases only partial filling of a nanotube compartment has been achieved. and at the same time .2 Nanotube Wetting A number of liquids have been found to wet the hollow core of carbon nanotubes and others do not show wetting behavior [126].128]. various organic solvents and various oxides such as P b and BiaO:! [124. and and liquidvapor interfacial surface tensions.124]. FILLING A N D ALIGNMENT 85 curvature and reactivity of the caps. Cs.ysl and Tiv are.
most of the experimental activity on the doping of nanotubes has been with the alkali metals [131. Therefore the alkali metal ions enter into the carbon nanotubes near structural defects. These alkali metal layers donate electrons to the graphite layers.132]. on the cathode deposit.86 CHAPTER 5. nor is there enough space for these ions between adjacent shells of a multiwall nanotube.7 Nanotube Doping. Subsequent chemistry is used to remove the carrier solvent [129]. their large size rips open the nanotube wall. thus greatly increasing the electrical conductivity. Selfaligned bundles of multiwall and singlewall carbon nanotubes are found on the copper collector in the laser vaporization method. while at the same time greatly expanding the sample size along the direction normal to the lattice planes. If a sample contains an assembly of randomly oriented nanotubes. which do not act as substitutional dopants.6. 5. the relatively large alkali metal ions cannot find easy entry into perfect nanotubes. SYNTHESIS OF CARBON NANOTUBES contains a solute which is to be deposited within the nanotube. Although some experimental work has been done on the substitutional doping of carbon nanotubes with B and N. . alignment can be achieved by rubbing in one direction or by cutting a material such as paraffin which contains embedded nanotubes. This effect can be seen by microscopic probe studies on carbon nanotubes that have been attacked by alkali metals [131. Once the ions penetrate the outer surface of the nanotube. and BN/C Composites The substitutional doping of carbon nanotubes with B and N dopants to make the nanotubes ptype and ntype has been discussed [130].132]. Because of the closed cylindrical structure of carbon nanotubes. and in the collarette for the case of growth by the arc method. Alkali metals readily intercalate into graphite as sheets of alkali metal which are located between graphene sheets in the crystal lattice. but are predicted to lead to enhanced metallic conductivity [133]. the most common source for the alignment of nanotubes is by a selfalignment growth process. Nevertheless. 5.4 Alignment of Nanotubes For a variety of experiments and applications it is desirable t o align the carbon nanotubes parallel to each other. Intercalation.
5.5. Transport measurements confirm that the intercalant uptake by the nanotube results in a dramatic increase in the electrical conductivity both for the case of Br:! and K [136]. we summarize in the following some of the important temperature regimes for carbon materials. consistent with the transfer to electrons from the nanotubes to the halogen [135].136]..8. In addition to the melting (4450 K ) and vaporization (4700 K) temperatures for carbon. consistent with electrons donated by the alkali metals t o the nanotubes. Typical temperatures that were used in the twezone furnace for the alkali metals were 120OC for the nanotubes were 160OC.9. with 3 carbon shells at the interior followed by 6 BN shells in the central region. The carbonization temperature is the temperature at which the volatile species are driven off from precursors for carbon materials. . and 5 carbon shells on the outside. while the Brz intercalation leads to an upshifted mode frequency. The graphitization temperature (23OO0C) is the temperature at which interplanar site correlation is established and the ABAB stacking . A composite multiwall nanotube 12 nm in diameter. vibrational mode at 1593 cm' in the undoped nanotubes are down shifted by Rb and K intercalation. as shown in Fig.8 Temperature Regimes for Carbonization and Graphitization Because of the importance of temperature as a growth parameter for carbon nanotubes. The large uptake of the alkali metals Rb and K is consistent with a decoration of the carbon atoms on the nanotube surface by a (2 x 2) superlattice of alkali metal species. a twozone furnace was utilized similar to that previously used for similar intercalations into crystalline graphite 11341. 87 For the intercalation of alkali metals and halogens into ropes of single wall carbon nanotubes. BN nanotubes have also been prepared by packing a tungsten rod with BN [87]. has been synthesized by the arc discharge method using an HfBz electrode and a carbon electrode in a Nz atmosphere [137]. as well as uptake of alkali metal in the interstitial spaces between the nanotubes in the triangular lattice [135. two other temperatures are of importance: the carbonization temperature (650750OC) and the graphitization temperature (2300 K). The A . 5. TEMPERATURE REGIMES FOR CARBONIZATION AND . leaving behind the basic structural units on the order 1 nm in thickness. The structure and composition was obtained by a scanning EELS probe across the diameter of the nanotube.
the state of amorphous carbon is metastable below the carbonization temperature. Oxygen or hydrogen atoms are removed above about 7OOOC in the form of HzO. The carbonization temperature is closely related to the desorption temperature of oxygen or hydrogen that is chemically bonded at the edge of graphitic nanocrystals. are broken in the . C0. Between the carbonization and graphitization temperatures. and CN. bonds. carbon cannot change its sp2 covalent bonding configuration. 5. CO2 at temperatures in the 80O0C12OO0C range where the oxidation process occurs. carbon can transform from an amorphous carbon to a stable graphite planar structure at ambient pressure by cutting and reconnecting sp2 covalent bonds. which are related to CH.88 CHAPTER 5. Chemical reactions also occur in the presence of 0 2 . etc. Dangling carbon bonds. Below the carbonization temperature. H 2 0 .9: Various steps of the graphitization process as a function of heat treatment temperature THT[138]. CO:!. molecules by cutting carboncarbon bonds. with only a small stability region for the liquid phase of carbon. this phase is always the most stable state. The melting and vaporization temperatures for carbon are both extremal values for the condensed phases of matter. Thus if the solid state is formed by a rapid quenching process t o amorphous carbon. CO. SYNTHESIS OF CARBON NANOTUBES Fig. If the solid state is single crystal graphite. arrangement of the 3D graphite structure is formed. and CH.
< <   5. the columnar structures increase in length with a lesser degree of misorientation of the basic structural units as shown in Fig. much higher THTvalues (28003000°C) are generally used to obtain 3D graphite crystals by the heat treatment approach. The various steps leading to graphitization have been studied by heating amorphous carbons to various temperature THT(see Fig. The second school [107. 5. For 1500 THT 1900°C. 5. most of the inplane structural defects have been eliminated so that a rapid increase in La can occur due t o the disappearance of tilt and twist boundaries. The purification temperature for carbon nanotubes corresponds to the temperature for CO and COz formation. One school of thought [141. and CC bonds are reformed at somewhat higher temperatures. By 21OO0C. For 800 5 THT 5 1500°C. start to pile up and form distorted columnar structures.142] assumes that the nanotubes are always capped and that the growth mechanism involves a Cz absorption process that is assisted by the pentagonal defects on the caps.143] assumes that the nanotubes are open during the growth process and that carbon atoms are added at the open ends of the nanotubes. individual misoriented basic structural units become aligned and the crystallite size along the caxis L . both the inplane and caxis crystallite sizes La and L .9 Growth Mechanisms The growth mechanism for cylindrical fullerene nanotubes is especially interesting and has been hotly debated. In this step. the basic structural units. For THT5 800°C. Although the graphitization temperature is usually given as 23OO0C. interlayer distance decreases. interlayer site correlation between layers starts to develop.9. the columnar structure disappears as wavy ribbons or wrinkled layers are formed by hooking the adjacent columns together. GROWTH MECHANISMS 89 carbonization process. the At higher T'T.140]. As the graphitic structure develops further with increasing THT.5. and in this range of THT. mostly in gaseous form.9. as impurity atoms are released. increases gradually. Since the experimental conditions for forming carbon nanotubes vary . consisting of a short length (% 10k)of about three parallel layers. with L a values higher than 200 A at THT 20OO0C. By THT 17OO0C. increase rapidly.the wavy planar structure begins to disappear and a turbostratic planar stacking arrangement starts to appear.108.9) and then observing the TEM micrographs [139.
SYNTHESIS OF CARBON NANOTUBES Fig. indicated by open circles between 2 and 3 .10 and 5. 5. 5. as necessary for the execution of each C2 absorption. and if the new bonds denoted by dotted lines form.10.llOO°C) and assumes that growth is nucleated at active sites of a vaporgrown carbon fiber of about 1000 A diameter. Referring to the basic model for Cz absorption in Figs.11.90 CHAPTER 5.5) nanotube which have six pentagons denoted by numbers from 1 to 6.5) nanotube. 5. more than one mechanism may be operative in producing carbon nanotube growth.10: Cz addition t o a cap of (6.[144] significantly according to growth method.10(a) we show a hemisphere cap of (6. The first school of thought focuses on nanotube growth at relatively low temperatures (. 5. (a) Numbers from 1 to 6 indicate the position of the six pentagons on the hemispherical cap. we see that sequential addition of Cz dimers results in the addition of a row of hexagons to the carbon nanotube. In Fig. When we introduce . it is usually necessary to use the StoneWales mechanism to bring the pentagons into their canonical positions. If we add one Cz molecule. it is seen that the shape of the cap is the same for (a) and (b). we get a new hexagon denoted in (b) by dark shading. To apply the Cz absorption mechanism. the growth of the carbon nanotube is thought to be associated with the absorption of a Cz dimer near a pentagon in the cap of the nanotube. (b) Through rotation by 7 2 O . in accordance with Fig. Although the parent vaporgrown carbon fiber is itself nucleated by a catalytic transition metal particle [44].
and growth of the nanotube by the open end process will be terminated.10(b). it has been proposed that the nanotubes grow at their open ends[143. The introduction of heptagonpentagon pairs can produce a variety of nanotube shapes. If carbon atoms should be added out of sequence. 5. 511). In the case of an armchair edge. which requires only a C1 monomer. the open end of the nanotube will likely form a cap. Referring to Fig. initiation of growth requires one trimer C3 (see Fig. 5. Thus the sequential addition of C2 dimers will result in continuous growth of the chiral nanotube. we return to Fig. Iijima argues that the inner tubes are capped first with the capping providing a method for relieving strain in the cap region. The introduction of pentagons leads to positive curvature. If the nanotube has chirality (see Fig. here again a single C2 dimer will add a hexagon. which could lead to capping of the nanotube. In Fig. While the tubes grow along the length. they also grow in diameter by an epitaxial growth process. 5.7. it will form a pentagon.11). we see that the shape of the cap is the same for Fig. a C2 dimer is initially bonded at a zigzag edge. 5. 5. while capping with heptagons lead to changes in nanotube size [see Fig.12. except for the last hexagon in the row. as shown in Fig. For the case of a zigzag edge. while the addition of a C3 trimer out of sequence merely adds a hexagon. A schematic diagram for the open tube growth method is shown in Fig.7(b)] and orientation.10(a) but with the addition of one more ring of carbon hexagons around the nanotube.145]. Multiple additions of Cz dimers lead to multiple additions of hexagons to the armchair edge. 5. Because of the curvature that is introduced by the pentagon. 5. 5. At present the growth model for carbon nanotubes remains incomplete with . we get a new hexagon denoted by dark shading in Fig. For the growth of carbon nanotubes by the arc discharge method. The large aspect ratio of the nanotubes implies that growth along the tube axis is more likely than growth along the nanotube diameter. 5.[110.10(a) and (b). it is easily seen that the absorption of a single C2 dimer at the active dangling bond edge site will add one hexagon to the open end.5. which then provides the necessary edge site to complete one row of growth for the nanotube through the addition of C2 dimers.10(b) by 72'. then addition of a C2 dimer would result in the addition of a pentagon.144] Repeating this process five times. 5.10(a) we consider new chemical bonds denoted by dotted lines. When we rotate Fig. however. If.12 [107]. GROWTH MECHANISMS 91 C2 molecule between the pentagons 2 and 3.9.
so that all the coaxial nanotubes grow at once at these elevated temperatures [141]. is the containment of a smalldiameter carbon nanotube inside a largerdiameter nanotube.92 CHAPTER 5. for the arc discharge synthesis method. At these high temperatures. In this lower temperature regime. the growth of the nanotube core and the thickening process occur separately. . the temperature where nanotube growth occurs has been estimated to be about 340OOC [146].11: Proposed growth mechanism of carbon nanotubes at an open end by the absorption of CZ (dimers) and C3 (trimers). SYNTHESIS OF CARBON NANOTUBES Fig. Such a feature seems to require growth by an open tube mechanism. any dangling bonds that might participate in the open nanotube growth mechanism would be unstable. In contrast. Since the vapor phase growth occurs at only llOO°C. and the open nanotube growth may be favored. reported by several groups [106. regard to the role of temperature and helium gas. 5.107. so that the closed tube approach would be favored. where the inner nanotube has no access to a carbon source. Absorption of a C3 trimer at the open end of a zigzag carbon nanotube and subsequent Cz dimer absorption. nanotube growth and the graphitization of the thickening deposits occur simultaneously. One interesting growth feature.147].
the capping of the longest open end.9. and the initiation of new nanotubes. G R O W T H MECHANISMS 93 Fig. owing to the helical tube structure. .5. (a) Some shells are terminated at the positions indicated by arrowheads as illustrated in the circle. The figure shows the addition of carbon atoms to the open ends. 5. (c) Similar termination of the shells near the top of the tip. (b) Terminated shells carry lefthanded or righthanded kink sites. forming steps. as indicated by the arrowheads [107].12: Schematic diagram for open tube growth of nanotubes from a carbon supply. one atom in height.
.
= v/w.t where A is the vector potential (V x A = B ) . R H . Quantum confinement of electrons in onedimensional carbon nanotubes and confinement through application of a magnetic field show interesting phenomena as a function of the chirality of the carbon nanotubes and of the direction and strength of the magnetic field. 6. an electron with velocity v experiences a Lorentz force eu x B. but RH = l/nec.e A becomes p . such as the Landau gauge. This is. where po is the permeability of free space and H is the magnetic field in free space. however. In quantum mechanics. the motion of an electron is described by the transformation p t o p . In CGS units. so that the transformation of p . A gauge for A . not the case for the Hall coefficient.for which SI units give RH = l/ne. we obtain the socalled cyclotron motion of the electron in a magnetic field with a cyclotron frequency we eB =m and a cyclotron radius of r .1 Free Electron in a Magnetic Field In a uniform static magnetic field. in CGS units.CHAPTER 6. is used to relate A *We here simply call the magnetic field.* B . B = p o H .. By solving the equations of motion. In this chapter we show how to calculate the Landau energy bands of carbon nanotubes using the tightbinding method.eA in the Hamiltonian. which is perpendicular to both B and v. 95 .e A / c in CGS units. we simply replace e by e/c. tWe use MKS (SI) units here. Strictly B should be called the density of magnetic flux on a unit surface. Landau Energy Bands of Carbon Nanotubes Itinerant electrons in a magnetic field give rise to Landau quantization of the energy bands.
4) for the N t h magnetic energy subband and harmonic oscillator center X is.y) motion of the free electron is quantized by the Landau index N .. [ X . z ) = ei(hvY+k. B ) . the form has qx.y. and this commutator relation does not depend on the gauge.6) Thus the twodimensional ( x . the Hamiltonian and the operator X commute.Y ] i A / e B . @(. When we use the solution to Schrodinger’s equation for a onedimensional harmonic oscillator Hamiltonian. The Hamiltonian for a free electron (V = 0 ) in the Landau gauge becomes (6. 1 . is not a constant but is an operator which does not commute with the positmion Thus a general uncertainty y.6).O). A = (O. (6.~).Z) 9 (D(xc) 7 (6. (6. the energy levels EN are given by E ~ ( k z= huc(N ) + 5)+ 2 2 h k z . the center of the harmonic motion. and the threedimensional energy bands in zero magnetic field are divided into onedimensional energy bands IabeIed by N as in Eq. and a’H/dz = 0).O.).96 CHAPTER 6. 2./eB. = . (6.(z. LANDAU ENERGY BANDS OF CARBON NANOTUBES explicitly to the magnetic field B = (O. ) and X = hlc. relation applies to the two operators X and Y for the centers of the harmonic motion in a magnetic field. X = A k y / e B .. so that the quantum number associated with X is a good quantum num.ber* describing the wavefunction and its degeneracy. The corresponding wave function p(x) in Eq. we can assume that the wavefunction. ( N = 0 ..4) in which ~ ( xsatisfies the harmonic oscillator Hamiltonian. tFor a crystalline solid. Further. (6’H/ay = 0..2) Since the Hamiltonian does not depend on y and z .Bx.
the wave number ky is quantized as k . (My = 0 . Even in this case it is found that most energy bands show Landau quantization in a uniform magnetic field. When B = lT. in which the energy bands do not show explicit Landau levels. L . When we consider Landau quantization of the aenergy bands. Hi(()= 2<.. a 2 / 2 d 2 degenerate statesf in the area L. The Landau radius is thus a quantum variable which is clearly different from the classical. Thus. However. we have one degenerate state (Landau level) per area 2a12 for a given Landau index.66 nm. f . N . VOrthogonality between two harmonic oscillator wavefunctions comes from the orthogonality of the plane waves in the y direction. . and H z ( ( ) = 4t2 . since the magnetic field that is applied t o the curved surface of a carbon nanotube is not uniform. The overall picture for the energy bands in a magnetic field can be obtained using the tight binding approximation. and since the net magnetic flux penetrating the surface is always zero.1 ) and thus X = h k y / e B = 2 d 2 M Y / L y ais quantized. The H n ( t ) used here has the explicit expressions for n = 0 . . cyclotron radius of rc = v/w. 1 . L y a . 1 . We then have L . too. / L y a . . 2 given by Ho(E) = 1. 2 . The energy band width in this case shows new oscillations with a period that is scaled by the cross section §Different definitions of the Hermite polynomials may give rise to confusion. = 2 a M .a x L. a special situation occurs. Using a periodic boundary condition in the direction of y with period. L . we should consider the periodicity of the unit cell due to the crystal potential. in the case of carbon nanotubes.6.. but they do instead have energy dispersion for all values of the magnetic field. Thus when we consider a twodimensional electron system. FREE ELECTRON IN A MAGNETIC FIELD 97 where H N is the N t h Hermite polynomials defined here as and e is the Landau radius defined by The Landau radius represents the size of the wavefunction in a magnetic field and depends on the strength of the magnetic field.a. the ratio of 27rL2 to the area of the unit cell is an important factor for describing the energy bands in a magnetic field.2.1. which we will discuss in the following section. then e = 25. and a lattice constant a .
R ) .2 Tight Binding Approximation in a Static Magnetic Field Here we explain a formalism for the tight binding approximation in a static magnetic field.2 [69. This phase factor corresponds to the continuous modulation of the periodic boundary condition for the wave function in a periodic system.eA)2 1 (6.11) where it is noted that GR is a function of T and the integration in Eq. d( = J 0 1 (T . the Bloch functions in a static magnetic field can be expressed as (6. Because of the breakdown of the Bloch condition in the wavefunction. depending on the vector potential.R])dX. C?h.10) where R is a lattice vector and GR is the phase factor associated with the magnetic field and is expressed by [153] GR = Ji A ( ( ) .1.11) is taken along the line from R to T as shown in Fig. As is discussed in Sect.149]. When the Hamiltonian 3t for an electron in a crystal potential V ( T ) and in a magnetic field. depending only on the symmetry of the tube. A simple result of this formalism shows that in describing the magnetic field dependence of the wave function. . we need only consider a phase factor.71. 6.A ( R + X[T . which have a twodimensional surface. 4. 6. LANDAU ENERGY BANDS OF CARBON NANOTUBES of the unit cell of the nanotube.1.3).75.98 CHAPTER 6 .12) 2m + v. the electronic structure is especially unusual in the sense that carbon nanotubes can be either metallic or semiconducting. (6.152] experiments on carbon n an0t u b es .148. in Fig.73. An interesting feature of the electronic structure of carbon nanotubes in a magnetic field is the dependence of the solid state properties on the chiral vector of the nanotube. as specified by its chiral vector. The magnetic response of the electronic structure for such onedimensional materials. (6. is especially interesting. which in turn is specified by the symmetry of the nanotube (see Sect. 31 = . the size of the unit cell changes as a function of magnetic field. 3. Within the tight binding scheme. and is relevant to recent magnetoresistance [150] and magnetic susceptibility [151. 3.( p .
(6. we obtain Fig.1: The vector RR' shows the integration path of A(<)in calculating GR . and (2) P(T .13).13) the operator which acts on the wavefunction is the Hamiltonian in zero magnetic field. Eq. cPo(r) is the flux that penetrates the triangle defined by the three points. It is important to note that in the last line of Eq. 6.13).14).13) is independent of the value of the magnetic field B and the functional form of A [153]. Using Eq.2. Thus the Hamiltonian matrix element in a magnetic field can be obtained through multiplication of the Hamiltonian matrix element in zero field by a phase factor. Except for the phase factor. It is noted here that we will have a term in exp((ie/h)(GR .GR. (6. (6. we can calculate the matrix elements of 71 between two Bloch functions and solve the matrix Hamiltonian to obtain the eigenvalues.T ) . R' and r . In obtaining the last line of Eq. in Eq.R ) is localized at T = R . R .R ) .6. TIGHT BINDING IN A MAGNETIC FIELD 99 R r operates on Q ( k . we use the fact that: (1) the magnetic field is slowly changing with distance compared with the spatial change of P(T . (6.G R ~ ) ) the matrix in . (6.
a fractal behavior has been found theoretically in the energy band spectra in a magnetic field of magnitude B .14) where @ O ( T ) is the flux that penetrates the triangle defined by the three points.GR' = IRR' A([)& + @O(T)i (6. R.* In a twodimensional cosine band with lattice constant u . . 6.we only observe Landau levels.GRt)l. The 'We hereafter neglect the effect of the magnetic field on the overlap integral matrix. Thus the integration on r of the Hamiltonian matrix element gives the zero field matrix element multiplied by the phase factor. LANDAU ENERGY BANDS OF CARBON NANOTUBES elements. h / 2 e . This in approximation is valid when the magnetic field changes slowly as a function of the lattice constant.3 TwoDimensional Cosine Band in a Magnetic Field A simple example of a twedimensional electron system is a square lattice.105T)for presently available laboratory magnetic fields. The difference between the two definitions comes from the different charge of a carrier compared to a Cooper pair. $J~ = . All of the energy dispersion relations are periodic functions of integer values of Bu2/q50. B . where 40 is the flux quantumt defined by. For simplicity we neglect the phase factor coming from @o(r) the integrals over the atomic matrix element. which is perpendicular to the twedimensional surface. except for the Landau subbands near E = 0 in the case of a 2D cosine band. However. In relatively weak fields ( w 102T). since the wave functions near E = 0 are for extended orbits [156]. R' and T as shown in Fig.15) and a is the lattice constant of a graphene sheet [155]. the magnetic field necessary to observe this fractal behavior explicitly is too large (. 6.100 CHAPTER 6. exp[(ie/h)(GR . Thus the matrix S is always taken to be the unit matrix.1. This approximation is consistent with the assumptions that we made above [154]. S . whose energy dispersion is known to be that of a twodimensional cosine band. Let us start from the simple case of a twodimensional square lattice in a magnetic field. depending on whether Bu2/q50 is a rational or irrational number. tThe flux quantum in a superconductor is half of this definition.1356 x 1Ol5[T/m2] e h (6. which is explicitly dependent on r as GR .= 4.
21) . (k . because the vector potential A in Eq. From Eq. Further.R) = ( 0 .GR' = 1 1 (R' . ( R.20) Using R . the vector potential A . only the two cases of (R' .R ) = (0. GR .R])dX.16) Using a Bloch wave function in a magnetic field.iR. (6. (6. which is only a function of x.16).R') and the fact that we can sum ' ' ' Eq.R and A . s + eik.R ) * A ( R .GR' = 1 + 1 (ka)BxdA= f B a x . B z ) .a 1 (6.13).3.16) has only y components.X[R' .i k y a+ e2ui B a x l +o+i k.(lck') ( e i k .18) The phase factor difference GR .19) In the inner product between R' . h a ) among the four nearest neighbor sites have nonzero values. we can define 'HRR' as the following Hamiltonian matrix element in zero magnetic field.X[R' . (6.12) between states k and k is given by ' in which R and R' are taken as lattice vectors to nearestneighbor sites.R ] ) = (0. (6. (6.6. (6. has the same value of A ( R .V ) k . COSINE BAND IN A MAGNETIC FIELD 101 vector potential A in the Landau gauge is given by A = (0. the matrix element of the Hamiltonian in Eq.a + e 2 u i B a x / + ~ . then x k k ' is given by %!kk'  =t R . (6.17) over R'.19) gives GR .k R = R . (6.GR' is calculated by using Eqs. (6. B z ) along the entire integration path from R to R'. since the integration path in the case of (R' . where x is the t component of R (or R'). (6. Thus Eq. h a ) is in the y direction.11) and (6.
n 40 E Bn r = n. m. q 5 L are integers. . y ) . s are integers whose largest common denominator is unity). p . (6. k.e.26) where L' = L / s . y) (6. + 2 A k . Here we consider periodic boundary conditions for the area of a square La x La in real space.23). i.25) in which B = Ba2/q50 is the magnetic field per the unit cell measured in units of flux quanta. LANDAU ENERGY BANDS OF CARBON NANOTUBES where t is the transfer integral.21) as follows (6. S (6. k. Then we can carry out the summation on R of Eq. the number of k. we solve the s x s Hamiltonian matrix of Eq. and R = ( x . Since s A k corresponds to the reciprocal lattice vector of the twodimensional square lattice. we can solve the Hamiltonian matrix for given k. Then the lattice vector R and the wave vector Ic are quantized as follows: R = ( 2 . From Eq. Thus.24) and Bax 40 Ba2 . A k . interact with each other. Since the wavevector k. Thus to obtain the energy dispersion relations.. (6. in a magnetic field is no longer a good quantum number and k. the states with k. values to + . (6. B = r / s . . = ( n a .22) where 1 5 n . couples with other k i separated by 2n Ak = rL' La =  2n r a s1 (6. values which interact with each other becomes a finite number ( 6 ) whenever B has a rational value. we can see that k. Here we consider only the case where B is a rational number. is still a good quantum number even in the presence of magnetic field.23)..102 CHAPTER 6.m a ) . (where r . with B as a rational value.
we will have to diagonalize the s x s Hamiltonian matrix L x L’ times. direction are plotted using the Landau gauge given by Eq. An explicit form of the Hamiltonian matrix is given by. too. a te”Ua 7f/= teikua 2t cos(k. In fact.2. Along the horizontal axis. . y coordinate system with area sa x a . ( 6 . = z q .. Furthermore. ( p = 1. 2 ) . the calculated energy states should not depend on the gauge.. L ) .. the calculated Landau energy levels of the twodimensional ( 2 D ) cosine energy band are shown for a magnetic field value for which the ratio of the unit cell t o the area per quantum flux is 1 / 6 0 . / s ..27) ( q = 1. values simultaneously as a function of k.1)Ak)a (6. the k values in the k . as is also observed in the case of the Landau quantization of the 2D free electron gas. In Fig. The above discussion makes explicit use of the gauge of the vector potential. = 0 and the energy dispersion is given as a function of k. COSINE B A N D IN A MAGNETIC FIELD 103 obtain s energy bands. . *.L’).3. 2t cos k .28) where a is the lattice constant of the 2D square lattice. 0 + Ak)a teikya 0 0 teikua teikara .. we note that the Brillouin zone is folded s times in the direction of ks to k . (6. values as 2n kx = L a p ... the unit cell in the magnetic field becomes a rectangle in the x . In this case.2 that most of the energy bands are dispersionless.. 0 ... 2n k. and Icy. It is useful to show the energy dispersion for different k. The corresponding Brillouin zone consequently becomes a rectangle in reciprocal space with area 27r/a x 2 n / s a . It is important to note th a t the calculated energy dispersion relations in a magnetic field are twodimensional and are a function of both k . + ( s .. 6. since T = 1 and s = 60. It is convenient t o express the k. teikua 2t cos(k.6. . Since we will solve the Hamiltonian matrix for given k. Thus we consider the Landau energy levels for only the value k . Near the E = 0 region. . and these oscillations may reflect the delocalized nature of the wave functions. 6. and k. some oscillations in the energy bands can be seen. we can see from Fig. .. However. .
2j 0.4 0.8 1.6 kann 0. A and B . using the Landau gauge of Eq. and (2) the directions of the nearest neighbors is not always parallel to the 2 or y axes.0 6. and we will use the formulation discussed in the previous section. The Hamiltonian matrix between A and B sites is given by. Here the ratio of the area of the unit cell to the area per quantum flux is 1/60.2 0.0 0. .2: Landau energy bands for a twodimensional cosine band in a magnetic field perpendicular to the twodimensional plane. 6.0 2. The energy is normalized to the nearest neighbor overlap energy t and the horizontal axis plots R values in the direction of y in dimensionless units. LANDAU ENERGY BANDS OF CARBON NANOTUBES p/q=1/60 4.0 4.104 CHAPTER 6.0 Next we consider the Landau energy bands for twodimensional graphite. The two differences from the previous section are that for the case of a 2D graphene sheet: (1) there are two atomic sites. 2.4 Landau Energy Bands of Graphite I 1 1 I Fig. (6. in the unit cell as discussed in Sect.0 20 .2).3. I 0.
(6. Finally. we obtain the . (6. s which have no common divisor except for unity.ik’. (6. n .k ’ ) = Zni[n(pp’)+m(qq’)]/L. ( R ’ . T .and the first term becomes i R e ( k . we have discrete values of R and k as follows: where m. (2.29) to i ( k R . the magnetic phase factor appearing in Eq. as in the previous section.24). LANDAU ENERGY BANDS 105 where t is the transfer integral between nearestneighbor sites in zero magnetic field.3) of Eg.R ) . Further.q are integers between 1 and L . Here we again assume. Using the same magnetic field derived from Eq. (j = 1. (2.2.€2’ = R j . using Eq. which is defined in Eq.n. (6.29) can be expressed as: (6.4. that t3 is a rational number which can be expressed by the ratio of two integers. we can calculate AG GR .31). and 1% in units of the reciprocal lattice vectors bl and b2. 1 5 r n . p . Then we transform the phase factor in Eq. R’) = i R + ( k k’).p. q 5 L . B = T / S .32) where B is the number of magnetic flux quanta within a hexagon of the honeycomb lattice.GRI as follows: AG=O a Bax Ba2 (6.k .6.18).30) Expressing R in unit vectors of a1 and a2.16) and the nearest neighbor direction R .
following result for a matrix element of Eq. (6.29):
(6.33)
The matrix element ((a$~Xj(a$)is ca~culated a similar way. We can then in solve the 2s x 2s matrix Hamiltonian as a function of k, and k,. In Fig, 6.3 we show the Landau energy bands of twodimensional graphite in a magnetic field perpendicular to the twGdimensiona1 plane. Here the ratio of the area of the unit cell t o the area per quantum flux unit is 1/60 and the energy is plotted in units of the nearest neighbor overlap energy t . Along the horizontal axis, fcYa/4?rvalues are plotted using the Landau gauge of Eq. (6.2). Again we can see dispersionless energy bands, except that the Landau levels near E = 0 have some dispersion. Comparing Fig. 6.3 with Fig. 6.2, we see that the level spacing between two dispersionless energy bands at k = 0 near E = 0 is not uniform in the case of twodimensional graphite, in contrast to the uniform level spacing observed for the twodimensional cosine bands. These results are identica~ with the original Landau level ca~culation twoof dimensional graphite by McClure [9,157] using k.p perturbation theory near the Fermi energy E = 0. When we use the approximation of linear energy dispersion near E = 0, the density of states is proportional t o E and thus the Landau quantization occurs a t En = &Cfi, where C is a constant and n = 0,1,2,. .. In this case it is interesting that we always have the n = 0 Landau level at E = 0 , with a density of states that increases with increasing magnetic field, causing an increase of the free energy. This is why we calculate a large diamagnetism for graphite, in agreement with experiment. The n = 0 Landau level at E = 0 arises from a wavefunction consisting of contributions from both the bonding 7~ and antibonding T * bands. The equivalence between the A and B sites in the unit cell, which is discussed in Sect. 2.3 in connection with the energy dispersion relations of twodimensiona~graphite, results in a band degeneracy at E = 0, so
6.4. LANDAU ENERGY BANDS
107
30 .
2.0
1.O
0.0
1.O
2.0
3.0 0.0 0.2 0.4
0.6 0.8
1.0
kYd&
Fig. 6.3: Landau energy bands for twodimensional graphite in a magnetic field perpendicular to the twodimensiona1 plane. Here the ratio of the area of the unit cell to the area per magnetic quantum flux is 1/60. The vertical axis expresses the energy in units of the nearest neighbor overlap energy and the horizontal axis plots the k values in the y direction using the Landau gauge of Eq. (6.2).
that the 7r and 7r* bands are not split, even in the presence of interband coupling. In a real system, the deviation from the linear k dispersion is important for understanding the level spacing between the Landau energy bands. For l example, the density of states diverges ~ogarithmicallyat E / t = f giving rise to a high density of energy bands. If we have dense energy bands folding into the first Brillouin zone in a weak magnetic field, we can expect the energy dispersion t o become flat and the predicted fi level spacing to be clearly seen. Figure 6.3, however, corresponds to a very large magnetic field, for which there
108 CHAPTER 6. LANDAU ENERGY BANDS OF CARBON NANOTUBES
is a quantum flux unit per 60 hexagons or B 103T. In this case the number of Bloch wavefunctions that are coupled to each other (s = 60) is not large enough to make completely fiat bands. Such a situation will occur for the case of a carbon nanotube for which the number of Bloch wavefunctions is limited not by the magnetic field, but rather by the periodic boundary conditions along the chiral vector.
6.5

Magnetic Energy Bands of Carbon Nanotubes for B Bohm Effect
11 z :
Aharonov
Using the method discussed in Sect. 6 . 3 , we now consider the electronic stmcture of carbon nanotubes in a uniform external magnetic field. There are two high symmetry cases for the direction of the magnetic field: one with the magnetic field parallel to the nanotube axis ( B 11 z ) and the other with the magnetic field perpendicular to the nanotube axis, ( B I z ) . Hereafter the nanotube axis is taken along the zaxis. In this section we consider the case of B 11 z . When the magnetic field is parallel t o the nanotube axis, electrons moving within the nanotube surface will feel a force perpendicular to the surface. As far as we consider only the transfer integral between two atoms within the nanotube surface, the electronic structure would appear to be unaffected by the magnetic field. This, however, is not correct. The wavefunction will change its phase factor and thus its momentum, k, will shift depending on the magnetic flux penetrating the cross section of the carbon nanotube. This phenomenon is generally known as the AharonovBohm effect, discussed often in the case of cylindrical geometry. Since the carbon nanotube can be a metal or a semiconductor, depending on whether there is an allowed wavevector k in the circumferential direction that has the value of the K . point in the twodimensional Brillouin zone (see Fig. 3.5), this AharonovBohm effect will modify the energy gap of a carbon nanotube as a function of magnetic field [84]. Here we use the twodimensional Cartesian coordinates (x,y) in thc directions of C h and T in the honeycomb lattice of Fig. 3.2 [158,159], respectively.*
*When we roll the honeycomb lattice into a cylinder, the twodimensional coordinate z = rcp (where v ,9 are cylindrical coordinates) becomes a curvilinear coordinate in three dimensions. We now take special care on making a rotation of the vector potential. However, as far as we y) use twodimensional coordinates (5, on a cylindrical surface in threedimensional space by adding a coordinate in the radial direction, T , instead of using cylindrical coordinates, ( T , cp, z ) ,
6.5. LANDAU ENERGY BANDS: AHARONOVBOHM
109
The vector potential A for BII this coordinate system is given by, in
A = ($,O)
(6.34)
where # is the magnetic flux penetrating the cross section of a carbon nanotube, and L = (Ch1.t The magnetic phase factor GR of Eq. (6.11) is given by
(6.35)
so that the phase factor difference, AGRRI= G R  GRI becomes
A G R = 2 ~ ~
Thus if we shift k, by
.x X‘ 4.
L
(6.36)
4/(L40),that is
(6.37)
in the magnetic Hamiltonian, the phase factor of the Bloch matrix element of Eq. (6.17) becomes,
(6,
+
&)
X  (k;
+ $)
X’ = (k,X
 kiX’)
 ( X XI) 4
L40
(6.38)
The second term of Eq. (6.38) cancels with the term ~ G R R I / # O (6.36) upon of Eq. substitution into Eq. (6.17). Using this fact, we can obtain the energy bands of a carbon nanotube in a magnetic field, B (1 z , by shifting the onedimensional energy bands in the direction of k, (or K in Fig. 3.5) in the twodimensional 1 reciprocal lattice of twodimensional graphite. Since the presence of an energy gap in a carbon nanotube is determined by whether or not the onedimensional energy bands cross or do not cross at the I(
no complicated situations occw due to curvilinear coordinates. In fact, the coefficients often used in vector analysis becomes unity; hl = hz = h3 = 1. tAn integration of the vector potential A in Eq. (6.34) on a circumferential loop, c , satisfies
4=
A . dr =
x
A . dS =
which is consistent with the fact that the magnetic flux, accordance with Stokes’ theorem.
4, penetrates the cross section S in
s,
B
ds,
110 CHAPTER 6. LANDAU ENERGY BANDS OF CARBON NANOTUBES
15
o'oO.O
0.5
1.0 0.0
0.5
1.0 0.0
0.5
10 .
Magnetic Flux (units 01 +J
Fig. 6.4:The energy gap in units of 4nly1/3L (y Itl) at the IC and IC' points of the Brillouin zone are plotted as a function of magnetic field in units of $0 for metallic (v = 0) and semiconducting (v = fl)nanotubes [160]. Here v is the residue of ( n  m) divided by 3.
or I ' points at the corners of the 2D Brillouin zone, a semiconducting carbon i nanotube can become metallic in a parallel magnetic field at certain values of the phase shift, and conversely a metallic nanotube can become semiconducting in a parallel magnetic field. The energy gap thus oscillates like a triangular chopped wave as shown in Fig. 6.4 [160], where the energy gap is plotted in units of 4nlt1/3L (E4aly1/3L in the figure) at the I and IC' points of the i Brillouin zone as a function of magnetic field in units of 40 for metallic (v = 0) and semiconducting (v = f l ) nanotubes. Here v is the residue of ( n  m) divided by 3. The energy gap is found to oscillate with a period of 4 0 . In the semiconducting nanotubes, the oscillations of the energy gap at the K and IC' points have different phases with respect to each other, while the oscillations have the same phase in metallic nanotubes. This can be explained by a shift in the k vector in the direction of K1. This phenomenon corresponds to the AharonovBohm (AB) effect for a carbon nanotube. The significance of the AB effect in a carbon nanotube is that the semiconducting or metallic nature of the nanotube can be altered only by applying a magnetic field parallel to the nanotube axis. This is because the distinction between a semiconducting and a metallic carbon nanotube arises from a quantum effect in which discrete wave numbers in the circumferential direction distinguish between metallic and semiconducting properties. It is noted that the onedimensional energy dispersion relations for carbon nanotubes at the top of the valence band and the bottom of the conduction band follow a linear t relation only when the carbon nanotube is metallic. When the carbon nanotube has a semiconducting energy gap, the energy dispersion is quadratic at the top of the valence band and at the bottom of the conduction band. Thus the effective mass
( L = IChI). + + . + O<x<L. the net magnetic flux penetrating the nanotube surface is always zero.40) where u is the lattice constant of the honeycomb lattice ( u = f i a c . Ch. but only 8 T for a circumference of 800 A. For a chiral vector. Since all t h e magnetic flux which comes in at one side of a nanotube goes out from the other side. in analogy to those defined in Eq. respectively. 6.39) where L is the length of the chiral vector. (6. L = adnz + m2 + nm (6. The twodimensional vector potential A for the nanotube surface is then given by A= (i: .c ) . (6. The period of the oscillatory behavior associated with the AB effect is 40 for the cross section of a given carbon nanotube. Thus the AB effect is expected to have periodicity involving a lower magnetic field for larger diameter nanotubes. 3 . Thus when we consider the phase factor due to the magnetic field. m ) .7)]. LANDAU ENERGY BANDS: QUANTUMOSCILLATION 111 of an electron contributing t o the transport properties of a carbon nanotube is a function of magnetic field. the unit cell of the nanotube is a rectangle specified by Ch and a translational vector T as shown in Fig. 3 .6.sinx .rn: integers. (3. Ch = nu1 mu2 = ( n .) 0.6 Magnetic Energy Bands of Carbon Nanotubes for B Iz : QuantumOscillations Next we consider the magnetic energy bands for a magnetic field perpendicular to the nanotube axis: B Iz . ul. the phase factor will always be zero (a rational number) for the original unit cell of the carbon nanotube in zero magnetic field. In fact. and the integer d R is the highest common divisor of ( 2 n m. 2 ) .34) (see Fig.u2: unit vectors). 2 . the magnetic field corresponding to $0 is 1400 T for a circumference of 60 A. and the coordinates 2 and y are taken along the circumferential and nanotube axis directions. 2m n ) [see Eq.( n .6.
. . N . (3. In Fig. in the graphene unit cell. Further. Since we have two inequivalent carbon sites.5 we show the calculated energy dispersion relations in a transverse magnetic field for a C h = (10. wave vector.0 (c) 2. LANDAU ENERGY BANDS OF CARBON NANOTUBES Using the vector potential Eq. (6. 6. AY). and thus the wavevector ky in the y direction remains a quantum number of translation even in the presence of a magnetic field. is X given by the definition of the symmetry vector defined in Eq. p 2n X L and N is the number of hexagons in the nanotube unit cell given by Eq. * . 2n 2n L = r ( r = 1. (3. we must solve a 2N x 2N matrix to find the energy eigenvalues for a given 6 .39).. in the 2 direction mix with each other in the presence of a magnetic field in accordance with Eq. (6. AY). we have three possible values of ( A X . (6. Because of the ..cos(X 2x L B E [o: c sX 2n L + AX)] (AX # 0) BAY sin X ( A X = 0). = L .43) ( p = 0 . A Y ) are the same for A sites or B sites.12).39). (b) 1. The wavevectors k.O) zigzag carbon nanotube as a function of the dimensionless wave vector Q = kYT/2n for several values of the dimensionless inverse magnetic length L/2nl: (a) 0. Since all carbon atoms belong to either A sites or B sites.19) is given by AG = GRGR~ = = 1 { [:I2 1 LB 2n d X A Y z sin r_(X + AAX) . the z coordinate of R. .0.0 for the magnetic field B perpendicular to nanotube axis. A G defined by Eq.1) Icp. 6. N ) . A and B . This reflects the invariance of the unit cell with respect to the magnetic field. (6.41) where R = (XIY) and A R = R' . (n < kyT 5 n). In Fig. the values of ( A X . (6. Since a carbon atom at an A (or B ) site will have three nearest neighbors. .5 we see that the energy dispersion relations for the subbands of the 1D carbon nanotubes become less dispersive with increasing magnetic field.42) = r.R = (AX.0 (d) 3. The total number of wavevectors in the x direction is N where 2n (6. L N N Since A G depends only on X I we can immediately carry out the summation on Y in Eq.29).9). (6.112 CHAPTER 6.
0 1 .0 20 . and the calculated dispersion relations approach those of 2 .o I 0.30.0 1.0. along the circumference of the carbon nanotube ( n . = 0 as a function of the dimensionless magnetic . a large magnetic field (3. (a) 3.1 0.0 (C) (d) 2.4 0. \ finite number (20) of wave vectors Ic.6: The energy at ky = 0 as a function of the dimensionless magnetic field ( L / 2 n t ) ’ / d ~ for a zigzag nanotube (a) ( n .0 1.o 2.0 1. 6. m )= (lo.5 1 1 3.o 0.6 the energy at L.0 0.0 3.0 3. (b) 2.20.2 0.0 2.20) (b).5: Energy dispersion relations of a Ch = (IO.0 (b) 3.5 rl Fig.o 1 .0 3’0 2.0.0 : .O) zigzag carbon nanotube as a function of the dimensionless wave vector 7 = kyT/27r for several values of the dimensionless inverse magnetic length L/27rE: (a) 0.1 0.0 2. and (9. In Fig.s   .00.3 0.5 11 0.o 2. 6. m ) = (20. $perturbation theory near the r point.0.40.4 0.2 0.O 0.o 1.0 1 .1 0.0 0.o 00 . 1.o 0. m ) = (20.0 2.9) .3 0.0 1.s  1.00.0 0.0 Fig. where != h/eB.5 11 0.o = .0).0 3.0 2.4 0.0 (d) 3.0 (c’ 3.2 0.6.3 0. 1.()).o 2.0 3. When the diameter (or L ) increases.0 3. LANDAU ENERGY BANDS: QUANTUMOSCILLATION (a) 113 3. (b) 2.o 0.1 0.86 x lo4 T) is required to reach L/27rE = 3.00. and two armchair nanotubes of different diameters: ( n .o 2.6. 0. The magnetic field B is perpendicular to the nanotube axis.0 2.0 1 . the magnitude of the transfer integral.0 GI 2 1 .0 30 . and the energy is plotted in units of It(. 6.0 1 . the magnetic field required to form Landau subbands becomes smaller.0 2.
Figure 6.m) = (20. 6. 6. values 0scillates periodically as a function of magnetic field.O) [Fig. The energy dispersion near the Fermi energy is especially important.6(b)] and (9.O) zigzag nanotube as a function of the dimensionless magnetic field v 2 = ( L / 2 ~ t ) ~ . LANDAU ENERGY BANDS OF CARBON NANOTUBES 00 . 6.114 CHAPTER 6.7 might be related to the oscillation of the electronic conductance of a'multilayer carbon nanotube as a function of magnetic field a t low temperature.5. 6.6(c)].7: Density of states per carbon atom at the Fermi energy for a Ch = (9.o) zigzag nanotube as a function of the dimensionless magnetic field ( L / ~ A .20) [Fig. . ( L / 2 ~ l ) ~ / dshown for a zigzag nanotube ( n . which can be scaled by the dimensionless magnetic field.0 15.6(a)].9) [Fig.0 jo. in analogy to the case of BIIdiscussed in Sect.7 the density of states at the Fermi energy is plotted for a c h = (9. In Fig.m)= (20. This phenomena can be identified with the AharonovBohm effect. 6.7 shows that when the magnetic field increases. ! ) ~ . field. a metallic Fermi surface appears and disappears in an irregular manner. is ~ . The mixing of Bloch orbitals with different k. The irregular oscillation in Fig. and for two armchair nanotubes of different diameters ( n . 6.O ( L /2nl)' Fig. 6. 5.
as it relates to rolling up a graphene honeycomb sheet of width L equal to the magnitude of the chiral vector. 7. since a semiconductormetal junction is realized by connecting a semiconductor and a metal carbon nanotube. Sect.3. 7. 71 .2. provides a useful description for considering the three dimensional structure of a single carbon nanotube.7.7.O) and (b) (12. described by different chiral vectors ( n . Coiled carbon nanotubes are reviewed in Sect. and by demonstrating the resulting junction explicitly. we show examples of (a) (12.2 and Sect.4 the transport properties of such nanotube junctions are discussed. In this section we use a net diagram t o describe a junction which connects two carbon nanotubes of different geometries [i..O)(8.1 in the literature showing the junction between two carbon nanotubes with different diameters using high resolution transmission microscopy [107]. In this chapter the general framework for joining two singlewall nanotubes of different diameters and chiralities is presented in Sect. As discussed in Fig. 3.5.2.7.m)].O) zigzag 115 . a net diagram of a carbon nanotube.e.7.O)(9.7. In Fig. In this chapter we first show how to connect two carbon nanotubes and then we calculate the electrical conductance of such a junction. Connecting Carbon Nanotubes Connecting two singlewall carbon nanotubes is an interesting problem.CHAPTER 7.2 we show that two arbitrary nanotubes can be joined in a unique way by introducing a single pentagon and heptagon pair. while in Sect.1. In Sect.7. Net Diagrams of a Junction There are many illustrations such as Fig. In this figure the larger diameter multiwall carbon nanotube AB is joined t o a smaller diameter multiwall nanotube C D through a junction section BC containing a single pentagon B and a single heptagon C.
respectively [107]. (b) A schematic representation of (a). 7. CONNECTING CARBON NANOTUBES Fig. 7. All carbon atoms in the junction have three u sp2 covalent bonds. ( r bonds due to the curvature of the tube .* Thus we can say that the pentagon and heptagon defects are topological point defects. makes the diameter of the carbon nanotube decrease in going from left to right in Fig. associated with the joining of the two nanotubes. All the other polygons in the nanotube junction region are hexagons. as is generally seen in fullerenes. showing a pentagon and heptagon at B and C . and there are no sp3 covalent bonds in the junction.2. and the negative curvature of the heptagonal ring prevents further decrease in the nanotube diameter. nanotube junctions. (c) A schematic illustration of the transition region between nanotubes of different diameters.1: (a) A high resolution TEM image of the junction between two multiwall carbon nanotubes. Thus. in which the carbon atoms of the pentagon and the heptagon rings are indicated by filled circles.116 CHAPTER 7. when the difference between the diameters of the 'Here we neglect the small s p 3 component in the and the junction. The positive curvature of the pent(agona1 ring.
2: (a) (12. . AB and C D . eight circumferential zigzag chains are shown.3 we show a net diagram of two carbon nanotubes which are given by the rectangles TABU and RCDS. For each nanotube.O)(8. the chiral vectors AB and C D correspond to the tThis situation can be easily understood when the reader copies Fig. respectively. 77r 3 (7.t Since the solid angles of a pentagon and a heptagon in the fullerene are 2 7 r . should correspond t o these angles. NET DIAGRAMS OF A JUNCTION 117 7. two carbon nanotubes becomes large. the distance between the pentagon and heptagon also becomes large. In Fig. 7.1) The threedimensional structure is obtained by connecting AT t o B U .~ / 3 and 27r+n/3.O) zigzag nanotubes are shown in which the carbon atoms of the pentagon and the heptagon are indicated by filled circles. This fact gives the angle relations: LACR+ L B D S = 57r ’ 3 and LCAT+ LDBU = . The smaller tube TABU and the larger + + tube R C D S .3 and makes a junction by cutting and connecting the edges.1.O)(9. the sum of the angles on the net diagram around the pentagon and the heptagon. are uniquely determined by the chiral vectors. indicated by shaded hexagons. AC t o BD.O) and (b) (12. Here a pentagon exists at the site C (or D)and a heptagon exists at A (or B).respectively. and C R t o DS through cylindrical surfaces. When we roll up the net + + diagram t o make a tube.7. 7.
(7. At the shaded hexagons in the figure. (b) The cone of OALB and (c) its projection are shown for understanding that the line A M B is a line of minimum length for going around the surface of the cone. a pentagon exists at the site C (or D) and a heptagon exists at A (or B). CONNECTING CARBON NANOTUBES L Fig. 7. The threedimensional structure is obtained by connecting AT to B U .5).3: (a) Net Diagram for the joint between two nanotubes. The + which is given joint region is uniquely expressed by a vector. by Eq. The relation O M IA M B satisfies both (b) and (c). CA.and CR t o DS through cylindrical surfaces. + The chiral vectors for the two nanotubes are shown by AB and + CD.118 CHAPTER 7. + circumferential directions of the tubes while the translational vectors AT and + + * C R which are perpendicular to AB and CD.respectively.AC to BD. . correspond to the directions of the nanotube axes in three dimensions.
and C A as CD= C5 = (125. AB= C7 = (127. .. = na'l+ m?lz by 7r/3 on a honeycomb lattice. First we will give a formula for rotating a vector Zn..3). we ret " 27r LACD LBDC = . and Rj = (2.2 The Rule for Connecting Two Nanotubes LFrom Eq.2) give the rule for connecting two nanotubes * as discussed below.m) Thus RCn..7. Figure 7. * + + . ms).5). T H E RULE FOR CONNECTING TWO NANOTUBES 119 7. we get ( n . c.and A C = BD. (7. + Hereafter we denote CD. j . once the two chiral vectors. will be used frequently in the following discussion. respectively. m7. is uniquely determined. A B .  'Here 5 and 7 i c and n 5 mean that the chiral vectors C5 and C7 exist on the pentagon and heptagon sides of the junction. 4 . 6 5 and 6 are given.*and CA= j = ( j l . Then the condition for j1 and j z for given 6 5 and 6 7 vectors is. . 727. respectively.. The conditions in Eq. 6). are integers. and j . we obtain the components of the joint vector 3 Thus the joint vector.4) for Rv'.1) and using the fact that we connect AC to BD in Fig. j1. t  Using Eq. 7. 4).2.3. m5. Denoting a n/3 rotation by R . is given by This formula of Eq.3 is drawn for 2 = (5. j 2 ) . which 7 5 7 gives j = (6. where 125. and 6 = (1.m7).4). (7. (74 3 + + + Then BD is given by (1) rotating AC around C by n / 3 and then (2) translating by CD. (7. (7.
AOAC E AOBD.3(b)].9' 1 (7. we have LAOB = LCOD = a/3. (7. since LAOC = LBOD. is defined as the crossing of the two lines O M and OH such that OM and OH are perpendicular bisectors of A B and C D . CO= R CD= (n5 + + + + + + (7.AO= When we define the angle of the vertex of the cone in three dimensions as 20. Since O A = O B . where the lines A M B and CHD are minimum in length for going around the nanotube surface.7) that CO .3 + + + m5. while the path A M B is a circle on the nanotube surface. The polygon. 7.Thus we conclude that AOCD is a regular triangle.n5). TABU and RCDS. 0 is given by I. 0 = sin' . the line A M B is a line of minimum length for going around the surface of the cone. while the cone and its projection. ACDB is part of a cone whose vertex is denoted by 0 in Fig. OALB. too. for the two tubes. respectively. as is shown in Fig.120 CHAPTER 7. 7. 7. this fact does not affect the angle on the tube or cone surface. The shape of the joint determines the shape and axis of the cone as shown in Figs. CONNECTING CARBON NANOTUBES Shape of a Junction 73 .3(a). the two triangles. in the net diagram of Fig. For the cone. 7. 7. are shown in Figs. AO= R AB= (727 + m7.2: 9 5 4 . Thus A O A B is a regular triangle. Thus LAC0 = LBDO. and AC = B D . However. the vertex of the cone. 727). 7.3(a) denotes the joint which connects t<hetwo nanotubes. are identical to each other. ACDB. We assume here that the lines A M B and C H D in Fig. too. respectively. Thus this assumption regarding minimum length lines seems to be reasonable.7) We can easily check from Eqs. Thus we always expect some distortion arising from the elliptical shape of the cone section relative to the circle shape of the nanotube surface. OC = O D . Similarly. since the distortion is perpendicular to the surface. 6 .3(b) and (c). It should be mentioned here that the path A M B is an ellipse on the cone surface in three dimensions [see Fig. in which OM I A M B satisfies both Figs. The + + position of 0 is given by rotating CD or A B by ~ / . This idea is valid.8) . 7. 0.3(b) and (c).3(b) and (c). Within this assumption.3(a) correspond to the minimum lines of the cone surface. which gives LACD LBDC = LOCD LODC = ~ 1 3 .3(b). 7.6) and (7.
(7. we can write the angles.7.10) Using Eq. The thick line EFGII' provides a wire frame model for representing the axes for the nanotubes and the cone.9). 7. is defined by the rotation angle around the cone axis between AOFD and A O F N . If the points 0. we use the following facts [see Fig. as shown in Figs. (7. as a function of n5.19O. m5. 7. In this case the bending angle of the nanotube axes in the net diagram.4(b)]: D N = O D * Q. since the dihedral angle of a threedimensional molecule is defined by three chemical bonds. which corresponds *To obtain Eq. and (2) the cone axis OF and an axis of the tube at the heptagon side GI<. the positions of the pentagon and the heptagon (Dand B in Fig. SHAPE O F A JUNCTION 121 The angle 8 is the angle between the axis of the tube and the axis of the cone in three dimensions. When the pentagon and heptagon are neither along the same line nor on opposite sides of the cones. the angle between the two axes of the tubes becomes zero. but when the pentagon and the heptagon are on opposite sides of the cone surface. The dihedral angle. we can define a dihedral angle.4(a) and (b). The definition of the dihedral angle provides a good analogy to chemistry. When the dihedral angle (o is n.3.* (7.3(a) as follows. = FN O D : FN = 27r :r / 3 . respectively) are opposite each other.6). n7 and m7. 7. 7. The dihedral angle (o is relevant t o the angle LBOD = @ shown in the projection map of Fig.3(a) lie on a line. @ and cp. (o. cp. between two planes as shown in Fig. and D in Fig.4. then the angle between the two axes of the tubes becomes 28 = 19.4. 7. The dihedral angle is useful for understanding the threedimensional structure of the two nanotube axes and the single cone axis joining the two carbon nanotubes. The two planes are defined by (1) the cone axis OF and an axis of the tube at the pentagon side F E . 7. In this case. * (o and . the two nanotube axes do not intersect with each other. B .
The crossing points of the cone axis with the nanotube axes.9). shown on the cone.3). sum to T . The ellipses are defined by rolling .8. respectively. D and B are the positions of the pentagon and the heptagon. Here DH I O H and O M I M B . The thick line E F G K corresponds to a wire frame model for reproducing the axes for the nanotubes and the cone. 7. 7. (7. The bond angles. and both P and Q are on the nanotube axes. which corresponds to the case discussed by Dunlap [161. CONNECTING CARBON NANOTUBES Fig. L N F D = cp is defined between the two planes A O F D and A O F N . LGFE and L F G K . O F . cp. in the joint region (see Fig. becomes n/6 (or 30°). The points P and Q are both centersof the darkshaded ellipses in Fig.162]. It is noted that points 0. The light shaded circle is the bottom surface of the cone and two dark shaded ellipses are the cross sections between the cone and each nanotube. Points P and Q are both centers of ellipses. (b) Another view of the dihedral angle. F and G . Ii' and N are in another single plane.4: (a) The dihedral angle. 7. F E and GI{ are the axes of the two nanotubes. F .122 CHAPTER 7. is on both planes.4(b). to Q in Eq. are not located on these ellipses. Here the axis of the cone. D and E are in a plane and that G . F .
3 so that DH IOH and O M IM B in Figs. we consider a system that incIudes the . the ratio of b t o a is given as a function of 8.12) using the fact that OG IGB.OG = (1651 I~~~)COS@. 127 and my. sum to T . Using all the formulae given here. we consider some specific cases and their electronic structure. It is important to point out that there is no ambiguity in the structure of the junction if we specify the two chiral vectors of the nanotubes.918 = 0.4. 7. 7. 7. 2 7 1 (7.0.8). It is clearly seen from Fig.3 and 7.4.4(b). Finally we discuss the shape of the dark shaded ellipses shown in Fig. When we denote the longer and the shorter axes of the ellipses as a and b. T U N N E L I N G C O N D U C T A N C E OF A JUNCTION 123 up A M B and C H D in Fig. In the next section.11) The length of the cone axis FG is given by FG = OF . LGFE and LFGII'. Thus the nanotube axis length on the pentagon side becomes shorter by P F in the wire frame model and the nanotube axis length on the heptagon side becomes longer by GQ.7.4 ~nnelin~ Conductance of a Junction To discuss the electronic structure and the tunneling conductance of a junction connecting two carbon nanotubes. After some calculation. (7. m5. the skeleton of the wire frame in three dimensions is well defined by only the four integers of the two chiral vectors.4(b) that P and Q are not crossing points of the nanotube axes with the cone axis. FG.2% distortion at the junction.13) where we make use of Eq. Thus the cross section of the circle at the end of the nanotube is distorted by 10. (7. where P F and GQ are given by P F = 1 3 1 8. ~~ sin2 GQ = 1 sin2 B. 125. Thus the geometrically optimized structure or electronic structure of the connected nanotubes is uniquely described by the chiral vectors of the two nanotubes.082 = 8. The bond angles. 7. 7. and the two dark shaded ellipses have the same eccentricity but have different sizes. b/a is given by (7.
Carbon atoms for the p ~ ~ t a g o n heptagon rings are and indicated in Fig.2 by filled circles. Thus zigzag nanotubes are suitable for considering a metalsemiconductor junction and armchair nanotubes are not. as discussed in Fig. Here the unit vector of each zigzag nanotube is 22 if 21 is selected in the circumferential direction.O) zigzag nanotubes. 1. and the unit cells of each carbon nanotube start from the carbon atoms of the pentagon or the heptagon that is connected to each nanotube.O)(9.O)(8.O)(8. and Gaussian broadening is used for calculating the density of states and for calculating the conductance. but all armchair nanotubes are known to be metallic. 3) and (4.O) zigzag nanotubes. A zigzag nanotube defined by (n. The threedimensional lattice structure is represented by formulae given in Sect. with eigenvalues E = 0 and eigenfunctions localized in a region about 6u ( u = Iii~l) from the nanotube end. and the junction region between them. respectively.where is an integer. the (n7. respectively.rn7) nanotube. are given by (3. In the calculation. the lengths of the carbon nanotubes at both ends are taken as 16 unit cells. has one of the smallest unit cells among carbon nanotubes. whose magnitude is known to be between 2. 41. An armchair nanotube. all electronic states are given by discrete electronic levels. the dangling covalent x bonds give rise to edge states. depending on whether or not n is a multiple of 3. The electronic structure is calculated by a simple tightbinding method in which only the nearestneighbor transfer energy. The structure of the junctions that we use for illustrative purposes is the junction between two zigzag nanotubes [69]. though only 8 unit cells are shown in Fig. 4. The total numbers of carbon atoms in the calculations are thus 735 and 720 for the (12. (n. Since only the amplitude of the wavefunction in the junction is included . In Fig.O). respectively. respectively.0)(9.13 eV [69]. n). Since we consider carbon nanotubes of finite length. 7.7.O) and (b) (12. which are used here as examples of a metalmetal junction and a meta1se~conductor junction.2. At the ends of the carbon nanotube. ( j l . also has a small unit cell.0) and (12. and the small hybridization due to the curvature of the nanotube or junction is neglected. m5) nanotube. and the electronic structure of a zigzag nanotube is either metallic or semiconducting.5 eV and 3. 7. 7. The corresponding junction vectors. for ?r orbitals is considered. All the calculated energies are in units o f t .3.2 we show the top view of the junction of two zigzag nanotubes for the cases: (a) (12.j z ) . and the dihedral angle p is always zero for zigzagzigzag carbon nanotube junctions.2.124 (n5.
5) correspond to edge states whose wavefunctions are localized not in the junction region but rather at both ends of the nanotubes. The density of states of these connected twonanotube systems can be understood primarily as the sum of the density of states of the two const~tuent carbon nanotubes. TUNNELING C O N D U C T A N C E OF A JUNCTION 125 in the conductance calculation. the density of states near the Fermi energy is smaller than that of the (12.O)(9.O)nanotubes. The energies of all eigenstates are within IE/tl 5 3.O) zigzag nanotubes.O) and (9.7. as a function of energy in units of JtJ. Otherwise. though their energy is at the Fermi energy E = 0. Were again all E = 0 states (see Fig. which gives rise to a tu ~ n e lin g probability ils a function of electron energy.O) .5) that not only the twodimensional van Hove singularities of graphite at E/t = f l but also many o n e . This situation is easily explained by the fact that the plane wave of an electron is reflected or transmitted at a positive square potential. because the junction does not correspond to an attractive potential.0~(8.4. the Bloch wavefunctions of each carbon nanotube are scattered by the pentagon. a delocalized wavefunction for the whole system is formed. and (3) edge states localized at the both ends. no localized states in the junction region. the heptagon and the junction region of the nanotubes. a delocalized wavefunction is formed only in each nanotube region. 7. the effect of these edge states is automatically excluded. The ca~culatedresults show that the eigenfunc~ionsof the energy levels consist of contributions from: (1) the delocalized wavefunction for the whole system.0) zigzag nanotubes is plotted per carbon atom per energy 1. In the case of the metalsemiconductor (12. Thus these states do not contribute to the conductance. In Fig. Since translational symmetry is broken at the junction. however.O) and (b) (12. 7.5. Even when we remove the contribution of the localized states to the density of states. the density of states for the junction of the (a) (12.~ i m e n s i o n ~ ~ 1 / f i singularities due to the onedimensional energy bands are quantized in the circumferential direction [69].O)(9.O)(8. (2) the delocalized wavefunctions for each of the carbon nanotubes. If the energies of the wavefunctions in the two carbon nanotubes are equal to each other. the resulting density of states is finite near the Fermi energy E / t = 0 which indicates that onedimensional metallic energy bands exist for both the (12. We can see in the plot of the density of states (Fig. 7. There are. which is consistent with three carbon bonds associated with each carbon atom.
Because of the Gaussian broadening that is used.O) nanotube with the same length.4. These differences can be explained a s follows. the tunneling elect. system because of the absence of a finite density of states for the (8.5(b). In this case the wavefunctions are only delocalized in the (l2. 7.O)(9. All E = 0 states correspond t o edge states whose wavefunctions are localized not in the junction region but rather at either end of the nanotubes.62.y of states than Fig.5(a). we get an energy gap of Es/ltl = 0. 7. where the structures are shown in Fig. Using the eigenfunctions for the electrons in the nanotube junction structures shown in Fig.O) and (b) (12. and also the energy width for the constant region is the larger in the case of Fig. It might be difficult to see the differences between Fig.033.5: The density of states of junctions for (a) (12. I . the energy gap is reduced to = E9/1t1 = 0.O)nanotube. By calculating the energy levels of a (8. T ~ ~ G Fig. is given by 21631 .O)(8. When a voltage V is applied to this system.5(a) and (b).O) carbon nanotube near the Fermi energy.126 ~ ~ A P T E RC O N N ~ ~ CARBON ~ A ~ ~ T U B 7. the conductance can be determined by c a ~ c u l a t i n ~ the current density. AE/1%1 0. 7+5(a)shows a larger value of the densit.4.55.O) nanotube region near the Fermi energy. 7. 7. 7. 7. However when we look carefully at the almost constant. and not in the (8.ric current. Fig. density of states region around E = 0.O) zigzag nanotubes plotted in units per single carbon atom per energy t .
in the case of f a ) for ~ e t a l ~ i c .6 are made as a function of applied voltage 0. used above far c a ~ c ~ ~ lG itj ~ n ~ a ~ etc. 7. we see that J. the ~ a v e f ~ n c t ~ o n is then over o s that obtained should be a ~ ~ r # ~ i rby a t ~ ~ n a delocalized w a v e ~ ~ n c t ~ o n T 0. scattered in the periodic region but8only in the junction region. ftetmning to Eq.o the right. and these i~~ osciliations are closely related to the universal conduc~ance ~ c t u a t i1164 re~ ~ns cently reported in carbon nanotubes [165].5 < V / t < 0 3 . the conductance ina~~i~ creases with increasing appiied voltage. at F/ : In Fig.g is t ~ o n . 7. Jij is the current operator for atomic orbitafs at sites a’ arid j given bv where (pi is ith atomic orbital. ~  ~ (7.4 (a) (12. The plots in Fig. for two different Gaussian broadening values.m e tnariotube junctions. appears when the energy of the wa~efunction to the Ieft of the junction coincides with the energy plus e l f of that t.33 (solid line) and AE/t = 0. and Ci.v a n ~ ~ h ~ n g only for 7’ and j at nearest neighbor sites. (T.0) zigzag carbon and nanotubes. This f o ~ ~ n u ~ a ~ .16) from the Eq.141. Rere we ~ S S B I Ithat it is only in ~F the junction region that we export a voltage drop.0)(9~0~ (b) (12.6.4.50 (dotted line). we show the calculated conductance I / V for the carbon nanotube junctions of Fig. a surface integral t*o a. and the integrati~n taken at the same surface is So as was used for calcu~ating current density.>. such as shown in Fig.15)~ ~ where E. are the pth eigenvatue and ith component of the pth eigenfunction. which are obtained by solving the t~ghtb~nding Hamiltonian for the junction structure. 7. Since this nanotube juiiction system is so small. and in regions where the voltage changes sig~ificant~y between sites i atid j . we consider the carbon network to be in the mesoseopic regime. When the voltage matches the ~ u ~ ~ ecoiidition for ~ o n n ~ ~ t i n ~ ~ j n g delocaliwd ~ ~ ~ v e f u ~ i c ~ ithe~whole region.0)~$. 7. The increase of the conductance with ~ n c r e ~V n ~ i comes from the fact that (1) the resonance t ~ n ~ e lpi r~og a b ~ is ~ t ~ b ~ .Here G is the imagin~ry past of the resolvent given by Gi/i(E) = P C ~ E. Turineling current. AE/t = 0. volltine integral [IG3]. The oscilfations in the con~uctance show resonances in the t u n ~ e i probability between the two nanotubes. i o Ibe valid even for delocatized w a v ~ f ~ ~ ~ c ~ the ~ s may i over i o whole region. in which electrons are iiot. By conver~~~ng (7. respectively.
and if that (2) the current operator.6(b) for a meta1se~conductor nanotube junction.~) zigzag carbon nanotube junctjon (see Fig.4 for their structures).33 (solid line) and AE/ltl = 0. using two different Gaussian broadening vdues. C ~ ~ ~ E CARBON ~ G T ~ ~ C T ~ NANOTUBES V/# Fig. Thus the amplitude of the oscillations will decrease relative to the absolute value of the tunneling conductance and the average level spacings will decrease as energy bands are formed. The results clearly show that a delocalized wavefunction is present near the Ferermi level only in the metallic (12.55ft1. as a function of voltage V in units of ltl.6: Calculated conductance I / V for (a) (12.128 C ~ A F 7. if there is a structural defect in the nanotube.6) are closer to this case compared to the A plot for smaller A E . Thus it is concluded that a semiconductormetal junction is well established even in a nanoscale.O) nanotube region.O) nanotube though there is a finite density of states near the Fermi level. The estimated energy gap for the (8. 7. J q is proportional to V .O) and (b) (12. which can be automatically excluded because their wavefunctions have no amplitude in the junction region.0~{8. 7. When the length of the nanotube increases. AE/)tl = 0. there are more states near tke Fermi level.O)(9. mesoscopic structure. the density of states is constant near the Fermi energy.O) s e ~ i c o ~ d u c tnanotube is or 0. 7. Again it is noted that there is no contribution to the conductance from the edge states. The ~alculated resu~ts with larger energy b r o a d e n i ~ ~E {dotted line in Fig. However. there is no conductance in the energy gap region for the semiconducting (8. weak ~ o c ~ ~ i z a twill make it possible to have a finite level spacing near the ion . proportional to V . 7. On the other hand.50 (dotted line). in the case of Fig.
p method in a magnetic field [168]. In Landauer's formula. we have four contributions of channels { m .K ' } . is calculated by the recursive Green's function technique [170] in which the S matrix is calculated by a tightbinding calculation [169] or by a Ic . is the transmission coefficient between the incident channel n on the left side and the outgoing channel m in the right side. we can treat the conductivity by the linearresponse theory known as Landauer's formula [166. Especially when we consider a metalmetal junction system connecting two semiinfinite metallic nanotubes. This might be a possible reason for the observation of universal conductance fluctuations in carbon nanotube systems in which the region of the voltage drop corresponds t o a disordered region [164]. R2/R1. { K ' . the conductance G is given by (7. (7.I<}. TUNNELING CONDUCTANCE OF A JUNCTION 129 junction region which gives rise to conductance fluctuations. The reason for this assumption is that we obtain three kinds of wavefunctions in the above calculation and that two of the three are localized in the constituent nanotubes. {It'. I{}. numerical calculations show that f(R2/R1) oc ( R ~ / R I ) ~ [169]. =z f e2 ($). The transmission probability tm. The conductance of a junction in a magnetic field is an important tool for monitoring the phase change of the scattered wavefunction at the junction.7. 8.I('} [168.4. the energy subbands a t the Fermi energy can be well defined over the junction and thus this assumption may be applied.167] (see Sect. In the above discussion we have assumed a voltage drop in the junction. The . if there is no voltage drop at the junction nor over the nanotubes.1). An interesting result is a scaling law for the radii of the constituent nanotubes. Thus.169]. As for the channels. expressed by a dimensionless scaling function f . This result clearly gives the power dependence of the amplitude of the wavefunctions in the junction region. However.1.18) When R2IR1 >> 2.n } = { K . and {It". we consider only energy subbands which cross the Fermi energy.17) where t . We have shown in the Chapter 4 that there are two metallic channels whose wave vector corret' sponds to the It' and I' points of the twodimensional Brillouin zone.
Numerical cal~ulations show that the ratio of the intra. which are known as intervalley scattering centers. including both arc discharge grown nanotubes [107] and carbon nanotubes prepared from pyrolytic carbon and heat treated t o 28OO0C [59].8A.7 and 7. and the other shape is a helically coiled shape. 6 which is close to the diameter of the c 0 molecule [171]. These complicated cage structures were first discussed in detail mainly by Ihara and his coworkers [171]. 7.9(a) in terms of a sock turned inside out. we show much more complicated cage structures which have many pentagonheptagon pairs. 7. These phenomena can be applied t o enhance the capabilities of nanoscale magnetic devices. We also have intravalley scattering centers where the wavefunction is scattered by defects without experiencing any change of wave vector. respectively. as shown in Figs. . The diameters of the central toroidal hole are the same for (a) and (b).9(b) shows a typical toroidal structure. Figure 7.and intervalley scattering processes can be modified by a magnetic field [168].5 Coiled Carbon Nanotubes In this section. Several observations of semitoroidal structures are described in the literature for singlewall nanotubes [54]. 7. 7. CONNECTING CARBON NANOTUBES c360 c240 Fig. and for multiwall nanotubes.130 CHAPTER 7.7: Optimized toroidal structures: (a) torus C360 and (b) torus C240: Pentagons and heptagons are shaded.8. mixing of the wavefunctions between the 'I and I' wave vectors occurs at a pair of pentagonal and heptagonal defech. One possible shape for a nanotube is a toroidal (or donut) shape. which can be readily understood using the schematic diagram in Fig. 7.
The tiling pattern of heptagons in the inner ridge line is changed upon changing the coil length.23k.7.9A and (b) coil length (a) . COILED CARBON NANOTUBES 13 1 Fig. Helicallycoiled carbon nanotubes which are obtained by using a cobalt cat . one pitch contains a torus C ~ C ~ O coil length = 12.9: (a) I l l u s t ~ a ~ i o n a semitoroidal termination of a nanof otube which is caused by six pairs of pentagonal and heptagonal rings in it hexagon network. 7. = 13. (b) A TEM micrograph of a semitoroidal termination of a nanotube which consists of' six graphene shells [lo?].8: Heli~allycoiled nanotubes: in both eases.5. 7. Fig. though the pattern of pentagons in the outer ridge is fixed.
the center.10.19) f5 .9) in which the genus g is the number of topological holes. and a pitch of about 30 nm. The number of pentagons and heptagons. This helical structure is well known in carbon fiber growth patterns [172]. fs and f 7 . and these two growth points provide the mechanism for twist. have also been observed by high resolution TEM with inner and outer diameters in the range 37 nm and 1520 nm. (that is g = l ) . CONNECTING CARBON NANUTUBES Fig.10 for the catalytic pyrolysis of acetylene might be considered to foflow the same basic crystal growth mechanism. It is estimated from TEM observations that O. alyst on a silica surface.Oll% of certain nanotube samples are crop circle tori. as shown in Fig.1 investigation of such structures [81]. Another category of torus that has been observed experimentally is formed from a long singlewall nanotube by joining the two ends in a seamless way and thus has a very large outer diameter compared to the tube diameter. and up to 30 pm in length. 7. The multiwall twisted helical carbon nanotube obtained in Fig. in which two growth points can occur at a single nanotube cap. the number of pentagons .f7 = 12(1 . This multiwall coiled carbon nanotube contains about 10 wall layers [173]. in the toroidal structures is given by the Euler theorem for polyhedra as (7. This selfassembled torus has been called a “crop circle” [174]. 7.10: A high resolution TEM image of a helixshaped structure with a radius of about 18 nm. Since a torus (or a donut) has a single hole at. Experimental observations of toroidal structures [173] have also inspired theoretica.132 CHAPTER 7. 7. respectively. growth which characterizes helical carbon nanotubes.
8)(5. and if some joint conditions concerning the twisting of the nanotube are satisfied at the ends.5. If a torus consists of such a joint with a bend angle of 2O0. when the dihedral angle defined in Eq. Thus the angle 'p defined by Fig. When the structure is periodic and f5 = f7 = n (for n = 1 . pentagons and heptagons appear in both the outside and inside of the main ring of the torus.11: A superlattice structure consisting of the periodic joining of the two armchair sections. An infinite length of carbon nanotube can be considered as a torus with an infinite toroidal radius.11. If the helical coiled carbon nanotube does not have any helical pitch.5) [175]. a toroidal carbon nanotube is formed. (8. we generally get helical coiled carbon nanotubes.. in which case we have twelve pentagons per fullerene. f5 = f7. 7.) per the unit cell. as shown in Fig. .8) is close to 20'. and the angle 28 defined by Eq. When we do not consider any heptagons a t the caps. eighteen pentagonheptagon pairs are necessary to make 360'. we get a singlewall carbon nanotube defined by a single chiral vector. we can no longer image a loop. . if the + . 3 . When f5 = f7 = 0 . Further. as in Fig. 7. the number of pentagons f5 becomes twelve for the two caps. so that g becomes zero. COILED CARBON NANOTUBES 133 Fig.7. which can be specified by n 1 sets of chiral vectors. On the other hand. giving fs .9) becomes zero.4 is about T . 2 .f7 = 12. (7.10. a onedimensional superlattice is obtained. and thus f5 = f7 here also. 7. When we consider the caps at the both ends of a nanotube. 7. In the case of a toroidal shape structure. and heptagons are equal. This case corresponds to all fullerenes. (7. Thus a general coiledshape nanotube can be considered to connect many joints. each with a pentagonheptagon pair.
The inner and outer radii. with overlapping valence and conduction bands. a small charge transfer occurs between these two bands.hole of the torus is missing at the center. 7. is fourteen for (2240 and twelve for (2360 as shown in Fig.7. The apex angle of the cone made by a pentagon is 2arcsin(5/6) = 113O. Their calcu~atedresults for the 7r orbitals within the tight binding approximation show that helical nanotubes can be either (1) a metal. Since a solid angle of 7r/6 is missing at a pentagon defect. *The corresponding angle for corannuleneis 130. and the optimized cohesive energy lies between that of c 6 0 (7. (2) a semiconductor.. or ( 3 ) a semimetal. depending on the position of the pentagon and the heptagon.4'. using a StillingerWeber model potential [171]. tubular radius. we can imagine a cone shape around a pentagon. . The actual number of pentagonheptagon pairs in the optimized structure calculated by Ihara et al. Helicallyco~~ed carbon nanotubes such as in Fig. comes from the fact that a coiled carbon nanotube consists of at least two different constituent carbon nanotube shells.9' and that for a regular truncated icosahedron is 117.10 should be defined by two chiral vectors and the length of the pitch per unit of the two nanotubes. Since each carbon atom has three CT bonds. In fact. Thus the lowest conduction bands and the highest valence bands do not always come from the same constituent shells. The semimetallic electronic structure. The optimized m depends on the shape of the torus and the value of n. as well as the pitch and twist values of the helical structure may be obtained from the chiral vectors. have also calculated the cohesive energy per carbon atom of (Cn)m by changing the order m of the rotational symmetry for a given unit of C. The electronic structure of coiled carbon nanotubes was discussed by Akagi et al. giving rise to semimetallic behavior. Ihara et al.44 eV)[171]. then twelve pentagons are sufficient to form a fullerene. 7. the effective curvature becomes large compared with an isolated pentagonheptagon pair. As a result. which is consist~nt with the above discussion.29 eV) and that of graphite (7. 11761. the most geometrically optimized calculation shows that from ten to fourteen pentagons are necessary for constructing the outer side of a torus.* That means that if adjacent pentagons are close t o one another or are arranged in three dimensions. after folding the energy bands of the constituent carbon nanotube shells in accordance with the superstructure of the coiled carbon nanotubes.. which are obtained numerically by an optimization of the calculated structure.
because the T electrons show electronhole symmetry around the Fermi energy. implies that Nc is an even number. the electronhole symmetry also holds..5. which however never occurs for a singlewall carbon nanotube without a pentagon or heptagon. COILED CARBON NANOTUBES 135 the number of carbon atoms and thus the number of x electrons in the unit cell is always an even number. in the matrix Hamiltonian. . which means there is electronhole symmetry.7. In the k * p’ approximation. respectively.$ tThis fact clearly follows from Euler’s theorem.+ Therefore. If we denote the number of carbon atoms and Q bonds by Nc and Nu. the crossing of two energy bands at the Fermi level is sufficient for semimetallic behavior. then 3Nc = 2Nu holds if there are no dangling bonds. If these matrix elements are neglected. the band widths of the condu_ction and valence bands are identical. The equation 3Nc = ZN. $The symmetry breaking between electrons and holes in tight binding results from the inclusion of the overlap matrix elements S .
.
the resistivity p and the conductivity . the resistance R[Q] given by Ohm's law. Conductance Buctuations as a function of the magnetic field.1) is the conductance G[U] which is related to the conductivity d z l/p[Urn'] by G = (T* are physical properties which do not generally depend on either the length of the wire L or the applied voltage t o the sample but only on the material. and are discussed both experimentally and theoretically. is R=p L r w2 ' w2 L CT where p [am] is the resistivity.2. Then some results on transport experiments in carbon nanotubes are summarized in Section 8.1. Transport Properties of Carbon Nanotubes At low temperature a singlewall carbon nanotiibe is a quantum wire in which the electrons in the wire move without being scattered by scattering centers. In the q~iantum regime. are found in carbon nanotubes. The inverse of R in Eq.(8. then p and (T will both depend on the length L through quantum effects. W . the electrons act like waves that show 137 In a macroscopic conductor. We review the difference between classical and quantum transport very briefly in Section 8. known as universal conductance fluctuations.CHAPTER 8. However. Quantum transport in a onedimensional wire In considering an electric current in a square wire with a width (and a depth). 81 . when the size of the wire becomes small compared with the characteristic lengths for the motion of electrons. and a length L .
where electrons occupy states from the bottom of the valence band to the Fermi energy in accordance with the Pauli exclusion principle. (2) the Fermi wavelength XF and (3) the phaserelaxation length L . The scattering by a static potential is known to be elastic. TRANSPORT PROPERTIES interference effects. The Fermi wavelength XF = 2?r/kF is the de Broglie wavelength (Xg z h/rnv) for electrons at the Fermi energy. Here 'static' means that the potential has no freedom to promote the electron to an excited state.+ a phase shift of the wavefunction can be expected after the elastic scattering event. The mean free path L . [177]. is the average length that an electron travels before it is scattered by a scattering center.100 n m which is larger than the microscopic or atomic size of around 1 . and thus the wave remains coherent. In mesoscopic systems* we consider three kinds of characteristic lengths: (1) the momentum relaxation length (or simply. Electronelectron scattering between two valence electrons does not contribute to L ..$ In this sense there *A mesoscopic system is a solid of small enough size. Thus elastic scattering does not contribute to L . tIn a n elastic scattering process an electron does not change its energy as a result of the scattering event. but also with themselves within the coherence or phase relaxation length L. but only to L.lOA and smaller than the macroscopic size which is more than lpm. It is useful to note that the effect of spin excitation can be suppressed by applying a magnetic field. However. so that the interference of electron wavefunctions can be observed. the ground state of the N electrons is no longer the Fermi sphere in the presence of electronelectron interactions. A typical size of a mesoscopic system is around 1 . and L. electronelectron interaction between any two of the N electrons does not change the electronic state under interchange of the two electrons with each other.138 CHAPTER 8. If the scattering of an electron is elastic.. mean free path) L. This infers that the phase of the electron is well defined along the propagating path of the wave.. but only to L. depending on the boundary conditions and the impurities and defects that are present in the nanotube. If the scattered wave loses energy by either exciting core electrons... spins associated with magnetic impurities or phonons. Thus the electron waves can interfere not only with other electron waves. When we take into account electronelectron in . the phase information of the wavefunction as a function of the position r is lost. when we consider N electrons on the Fermi sphere. After two electrons are scattered by their mutual Coulomb potential that is dynamic. The phaserelaxation length L .. Thus the electronelectron interaction decreases L. is the length over which an electron retains its coherence as a wave. tStrictly speaking. such inelastic scattering events contribute both t o L .
The relationship between these characteristic lengths determines the three transport regimes: ballistic. In this sense we conclude that electronelectron scattering in the valence band does not contribute to L m . t m and t . L. that the sum of the changes in momenand x . are scaled by the Fermi velocity VF as where 1 and t . and therefore we cannot say that the electron state is changed upon electronelectron scattering. and classic transport. L T . However. D. The table will be useful for finding the parameters in this chapter. for example. Classical conductance is the conductance which satisfies the Ohm's law. the phase relaxation length is much longer than the mean free path in diffusive motion. respectively.1 we show the parameters which are used in the present chapter. are called the momentum relaxation time and the phase re. in diffusive motion. the excited states of the N eiectrons are added to the variational function of N electrons which is expressed by a s u m of the linear combination of the Slater d e t e r ~ t s . but rather correspond to an average time for the many collisions which result in significant changes of momentum and phase. many elastic scattering events occur.1 we do not define yet M . since such an excitation process requires energy which could be supplied by phonons. On the other hand. These times are compared with the transit time t t during which an electron transverses the sample length L . Ballistic transport consists of single electron conduction with no phase and momentum relaxation. In accordance with the Pauli exclusion principle. However. respectively. reach hlc~ In Table 8. and t. Here a significant change means. do not imply the time of a single scattering event by the relevant scattering mechanism. .8 . Here we do not consider the excitation of the two electrons out from the Fermi sphere. QUANTUM TRANSPORT IN A ONEDIMENSIONAL WIRE: 139 is no change in the Fermi sphere before and after electronelectron scattering. In classical teractions. respectively. we cannot distinguish any two electrons in the A'electron state. tum and phase over the times t . l . laxation time. only electrons near the Fermi energy contribute. diffusive. In Table 8. so that the lengths Lm and L. which brings about the Iocalization of the wavefunction.. the wavefunction of an electron is determined over the sample by solution of Schrodinger's equation. and is known as the configuration interaction.Ro and Go which will be introduced later in this chapter. In a ballistic conductor. In transport experiments.
&/vF .28)) Time for an electron to go a distransit time tance L. L . (8.6)) G O quantized conductance Go = = 77. (8. *) We simply call L. (8.1: Parameters in transport phenomena Definition A channel is the electronic states which propagate an electron in a coherent way.4)) Length of sample in the direction Sample length of the current. diffnsion constants I) = L$/tv (see Eq. (8. momentum relaxation time”) ta = LmbF n phase relaxation time“) 1 = . Wavelength of an electron at the Fermi wavelength’) Fermi energy 2 a / k ~ ~omentum relaxation length*) Length over which an electron changes most of its original momentum. TRANSPORT PROPERTIES Table 8. (See Eq. = ML. Thermal diffusion length L$ = (See Eq.7)) s Here V F is the Feimi velocity and kp i the Fermi wave vector.140 CHAPTER 8.9064kn (see Eq. (8.4809 x lo% (see Eq. the mean free path (see further discussion in the text).= 12. Length over which an electron localization length wavefunction is extended. Symbol M Name Number of Channels [States] & . Length over which an electron phase relaxation length’) changes most of its original phase.28)) quantized resistance Ro = .18)). (8.(See Eq.
8. In Table 8.1. the concentration of ionic and magnetic impurities. In the table we list. *) The freedom for excitation of a spin can be suppressed by applying a magnetic field. N i Lrn Dec. are parmeters which can vary from sample and sample. 8.~ ~ ~ E ~ WIRE ~ A 141 S I O L Table 8.: Decreases a) Elastic means no freedom for carrier excitation by the scattering potential. local . both momentum and phase refaxation occur frequently and thus an electron can be considered as a particle. too.1. The frequency Of all scattering processes can be changed (not independently) by changing the Fermi velocity. Dec. No: no effect.2). In elastic and magnetic scattering. The excitation of phonons is suppressed at low temperature but the relaxation of an electron by emitting a phonon is determined by the e~ectronphononinteraction. No L. and the band width W of the valence band.1. classical transport (Sect. 8. The magnetic scattering can be suppressed by a magnetic field.1). The energy band width W can be chanted by pressure and by some special geometry of the crystal such as the presence of superlattices. Dec. 1 Only electronelectron interaction in the valence band is considered.B T Nc. No Dec. Dec . The electronelectron interaction is determined by the carrier concentration N . how a givenscattering mechanism changes the characteristic lengths. These conductance regimes will be introduced in the following subsections. which is implemented by applying a gate voltage to the semiconductormetal junction. ' Length w conductance.2 we list the relationship between the characteristic lengths and the scattering mechanisms. Dec. Q U A N T U M T R A N S P O R T IN A O ~ E .2: Dependence of characteristic lengths on scattering mechanism Scattering mechanism magnetic electronelastic') impurityb) Phonons electronc) Ns. Ni and N . Thus we can prepare materials for transport experiments by making the desired relationship between these parameters and the various scattering mechanisms. Dec. In the following subsections we review the characteristics of various transport regimes: ballistic transport (Sect.
. 8. respectively...11 and p 2 . Since the two electrodes have a large electron capacity. respectively....... there are several energy subbands Ej(k)which have the same k value.. only those electrons having wave vectors k > 0 (in going from the left to the right in Fig.1) and having energies in the range p2 < E < p i contribute to the net current...........1. An electron which has a velocity *The pseudoFermi energies are defined here by the highest occupied energy for k > 0 and k < 0 electrons.. The number of channels is a function of energy E... 8...5)) all of which pertain t o transpork in carbon nanotubes under appropriate conditions...... ization phenomena (Sect...... .. If there are no reflections of electrons at the electrodes.... 1 and 2 (see Fig....1. .3). there is a single Fermi energy for electrons.. (PI > p z ) ...4)...2 A ~ ~ ~ l z ~ t ~i c ~ (L << o r L p ) c o ~ c ~ A.1: A ballistic conductor with length L is connected t o two electrodes 1 and 2 whose chemical potentials are 1.. Hereafter the subbands which have k states in the energy range pz < E < 111 are called channels. In this case a voltage drop occurs at the contacts with the electrodes. .which is denoted by M(E)[states]..... 8.. 8... 8.. universal conductance fluctuations (Sect..... we can treat k > 0 and k < 0 electrons as independent electrons.. since there is no scattering between k > 0 and k < 0 electrons................... TRANSPORT PROPERTIES e L P1 ..142 CHAPTER 8. and negative magnetoresistance (Sect... The pseudoFermi energies* for the wire should be p 1 and p z for the k > 0 and k < 0 electrons... Thus the total current 1 is given by the sum of the microscopic currents for the k > 0 states of all the subbands Ej(k) which have an energy p2 < E j ( k ) < 111. 8... the electron chemical potentials for electrodes 1 and 2 are constants denoted by p1 and p 2 .1..1... P2 1 2 Fig.... Electrons going to electrode 2 are assumed to have an initial energy E at the point contact of electrode 1.... However. If there i s a thermal equilibrium state.. For baIIistic transport we consider an ideal case where we have no electron scattering on a wire of length L connected to two electrodes.. respectively.1).. Because of the quantization of electronic states in the direction perpendicular to the current.. 8.. M is the number of channels for electrons with wave vectors k > 0 t o propagating from 1 to 2....
(8.he width of a wire W is very small (less than 1 nm).2) is the Fermi distribution function with the Ferrni energy denoted by pi. (8.p2 = 1 eV. All the k states are integrated in Eq.= e / t l . G. Thus we should not count the number of k states in the direction parallel to the current to M . When we assume that the total number of conduction channels M ( E ) is constant M over p2 < E < P I . On the other hand.1). in which t l is the carrier transit time t. Go =: 2e2 .v = ~ . 8.p i ) (i = 1. In fact the dimension of M ( E ) and M is not [states/J].= 77. is called the contact resistance and h/2e2 is the quantized resistance R . = GoM. Then the total current I is given by where the sum on k is converted to the integral with a spin degeneracy of 2 and the inverse of the level spacing L/21r.9Ot54kQ2.12.4).pz)/e is the voltage between the electrodes. Since V = ( p i .5) gives the contact conductance G.p2 = 1 eV.lo6) for p1 . the resistance of the ballistic conductor is given by (8. we t obtain the last line of Eq. but is rather [states].5) where R. M becomes very large (.4809 x lO'U. O 2e2 The inverse of Eq. 2e/h in Eq.' ( a ~ / a> 0 in an unoccupied state for 113 < E < p1 contributes to k~ the microscopic current I. h . If t. which is related to the quantized conductance Go by Ro=:. if the width of a wire is on the order of 1 pm.4) is the quantized current per subband per unit energy [A/J].4). (8. and the Fermi energy is about 1 eV. f ( E . It is i m ~ o r t a n to note that M ( E ) is not a density of states. It should be noted that we have many k states even when M = 1. M = 1 even for p1. = L / u (See Table. (8.
the conductance of metallic nanotubes is 2Go. When we consider static scattering. When we consider the range of values of M for a metal nanotube of finite length L . Thus in the ballistic limit. The Landauer formula applies only if the wavefunction can spread over the whole sample.4) is applicable as a first approximation. the total transfer probability is given by . for a single channel is given in terms . the wavefunction is solved by a onedimensional Schrodinger equation. which is given by the sum of transmission probability from ith to j t h channel. a similar discussion for the contact conduc~ance can be applied. The quantized resistance and conductance can be observed in clean semiconductors at very low temperature on samples which have a small M [178].f179] When the length of a nanotube L is finite. we expect to find discrete k values spaced by 27rlL. the relation v = bEj(k)/dK in Eq. phase recombination processes are expected. scattering by a potential in one dimension. The resistance of a mesoscopic wire R.2 R = 1 .144 CHAPTER 8. Thus we cannot solve the Schrodinger equation over the entire sample since the electron wavefun~tion cannot be described by a single phase. The conductance G and the resistance R are thus given by where 7 is the transmission probability for a channel to go from electrode 1 to electrode 2. ltaj 1” Here we assume again that 7 is constant near the Fermi energy. Equation (8. of the transmission probability 7 as since the reflected wavefunction. Since the phase and amplitude of the wavefunction a t electrode 2 can be obtained from those at electrode 1. << L.6). TRANSPORT PROPERTIES Thus in a wire with no scattering the conductance is proportional t o M . When we neglect the effect of interference during a scattering event. causes a Cdnssic ~ ~ a ~ L. we expect to find two energy bands ( M = 2) for k > 0 (see Figs. which is proportional to voltage drop in the wire. (8. 4.1. 4.4. Even if the h states are discrete but still numerous. << L s ~ o ~ . 8. that is.5 and 4.7. In a macroscopic metal..8) is known as the Landauer formula.
the overall transmission probability 7 1 2 between electrodes 1 and 2.1)] in which the macroscopic resistance is proportiona~ L.10).1.12) where N is the number of scattering events and 7 is an average transmission probability for an individual scattering event over a mean free path L. We then appIy this result to the N scatterers and we get + (8. t 2 . QUANTUM TRANSPORT Iff A ONEDIMENSIONAL WIRE 145 summing over each transmission probability and of each reflection 7 2 d = 1x. The phase shift 0 corresponds to a round trip .1. . (8. (8.N). (8. (8. .9)lfor every momentum relaxation length L. << L ) When we consider the phase shift at each scattering event.n. R12 = R1 R2.11) we see that the resistance of the wires is additive. (8. When we consider the transmission coefficient t l 2 for a wavefunction between electrodes 1 and 2. (i = 1 . 71 and 1'2 is the transmission and reflection amplitudes of a wave' function. then t 1 2 is given by an equation similar to Eq. When we consider multiple reflections between i = 1 and i = 2.10) by using (8. (8. (8.11) Using the formula for the resistance given by Eq. and Eq. 8. [Lm << L. Thus the total resistance is given by a series connection of microscopic resistances [see Eq. This is nothing but Ohm's to law [see Eq. is given by (8.8.. the wavefunctions which are reflected many times between 1 and 2 are added along with their phases and the sum is then squared to obtain the transmission probability. . called the Smatrix.13) where t l .91.10) We can rewrite Eq.3 Localization.
(8.15) that involves 2R& causes an e x ~ o n e n t ~ ~ ~ divergence for R as a function of L . o + = R(L). (8. (8. (8. we consider many reflections of a coherent wave in Eq.R(L) .) . Then Eq. Rlz is not additive (that is R12 # R1 Rz. This means that the wavefunction near the Fermi energy becomes localized so that the transmission probability from one electrode to the ‘Here we assume the foliowing: R I = R(L Am).16) is ( L 3 Go).10). R ~ 1 R .) and thus Ohm’s law is not expected to be valid. From Eq. However the two equations (8. (8.It might seem that Eq. The nonadditive term in Eq. In Eq. The resistance Rlz is obtained by taking an average over 8 such that (cos 8 ) = 0. Thus the calculated T12’s in Eqs.17) Thus the resistance becomes very large in the limit of large L so that the material becomes an insulator. (8.16) The solution of Eq.14) and (8. On the other hand.15) gives the ~ifferential equation. (8. (8.13) where we add the amplitude of multiple reflections.and R2 = R ( A L ) = R(Lm)  .10).9). (8.15). (8. Thus we add the probability of multiple reflections in Eq. In the incoherent limit of Eq.10). (8.10) are not analytically connected to each other. and Ri = i ~ i 1 ~ .between electrodes 1 and 2. since the assumptions for the two equations are different as follows.14) and [8.(8.13) we obtain the probability for the transfer of an electron from electrode 1 to electrode 2 where = l. we consider that the reflected wave is incoherent to the original wave. to obtain where R1 and R2 are given by Eq.* +  dR = dL R(L + L. in the coherent case.Ro + 2R Lc Lc  (8.. when R( L ) is defined by a step of Lc L.14) should be compared to the case of the incoherent limit given by Eq.10) are generally independent.ta12. (8.
when L . In the strongly localized regime.17) occurs.17) is the effect of a random potential on the oneelectron wavefunction and this is called Anderson localization. LC Ballistic Am > L. by[l80] L . < L . the conductance arises from the thermal hopping from one localized site to another.. > L L N other is almost zero.1. (8. This second type of localization is called Mott localization. smaller. the electron cannot move.17) should be terminated at L = L. << L . = MA. < L many L. which makes L . The localization described by Eq. (8.t Localization can occur even when M is large. is larger than L. This is known as the localization phenomen0n.. then L in Eq. Q U A ~ TRANSPORT IN A O ~ U ~ N ~  ~ ~ WIRE ~ ~ ~ S ~ 147 O ~ A Table 8.3 we summarize the cunditions pertinent to the various transport regimes by listing the pertinent relations between the characteristic lengths and the coherence length of an electron.’s weak L. then the strong localization effect of Eq. L. just like cars on a highway not being able to move above a critical density. (8.18) When L . << L L. When the electronelectron repulsion is large compared with the average level spacing.. we can redefine the localization length L . In Table 8. On the other hand. The coherence length of an electron infers the existence of an upper limit for the length over which we can solve the Schrodinger equation for an electron with a single phase. the phase relaxation length L . strong L. For both strong and weak localization. the conductor is said to be in the weakly localized regime. In the case of large M . and for small L.3: Transport regimes of a conductor Regime Relationship Coherence length Classical L.. known to be in the weakly localized regime and heavilydoped semiconductors and intercalated graphite with a large fluorine uptake are known to be in the strongly localized regime [181. is required to be much larger than the mean free path L. > L.182]. (8. Localized L . Most lowdimensional metals.. < L.. is much larger than L. When the coherence tThere are two kinds of localization. . In this case. such as thin metallic are wires or carbon fibers with high THT.8. for small M . The localization becomes strong for large L.
Here we show that the fluctuations do not depend on M unless L . < L . as discussed in Sect.2. When the sample is large and thick. Here the (6G2) is defined by (SG') = (G2>.length or inelastic scattering length (. we have many scattering centers and thus many scattering processes because of the multiple scattering events for the many centers. the conductance fluctuation.15. (8. if the coherence length is close to the sample size. (8. respectively. since the transmission probability may be distributed homogeneously from 0 t o 1. in which the resistance is an additive property. << L . Let us consider M paths of conducting current for each sample.5. respectively. we can observe two interesting quantum interference effects: universal conductance fluctuations (UCF) and negative magnetoresistance (NM)."  *If M paths were independent.183]. for the weak or strong localizat~on regimes.19) d m where ( X ) denotes the ensemble average of X for the sample. or L . the interference effect can be observed as a microscopic scattering process.the fluctuation m / ( G ) for M paths would be proportional to r y 1mThe fact that the fluctuation does not depend on M is an interference effect which / . L. When M = 1. Furthermore. For the each path. is 2 e 2 / h . quantum interference occurs within the lengths of L. the conductance is given by the Landauer formula [Eq. << L v ) .(G>2.1.) is smaller than the elastic scattering length (Lm). in a ballistic conductor. but its contribution to the resistance becomes small compared with the classical resistance. When the coherence length contains many elastic scattering lengths ( L . An ensemble average means an average for many samples with different impurity distributions. classical transport occurs. the conductance will fluctuate from sample to sample because of differences in the inhomogeneous distribution of scattering centers. is close t o the sample size L .4 Universal Condsctance F~uctsutio~~ When the phase delocalization length L . In the weak localization regime ( L .4 and Sect.811 in which the number of propagating states and their probability for transmission determines the conductance. the conductance is described by a wavefunction that is defined over the entire sample.1. On the other hand. ). 8. interference effects associated with the wavefunction become important [164. If we prepare many samples of the same size. 8. . 8.
20) + (s") (Sg2) = M 2 ( 6 T 2 )= M 2 ( 6 X 2 ) . A P ( m+ n ) can be expressed. In Fig.20)... Within the phase coherence length L. . for example.. Here we consider 4 channels (M=4).8..23).1. The reflected wave function \k(n + m). (8. (8..2). There are many scattering processes in R ( l + 4) as shown below.2: A scattering process of the reflected wavefunction for the path entering 1 and exiting 4 in electrode 1 (A. fluctuations can be derived from either the fluctuation of  9MT=MM7Z.. or of (S?)..}..8) for the conductance normalized by 2 e 2 / h . 8. R denote the average on M possible paths of 7 ( r n + n ) and R(rn + n ) . by Ap(m  n ) = t ( m + m l ) e x ~ { i k n ~ L r n l } d r n ~ )e x ~ { i h n ~ L r n ~ } W (8. + + can be seen universally.L.23) . $ We start from the Landauer formula Eq.. the conductance is generally proportional to M as shown in Eq.M ( R ) and (g2) = M2(?') = M 2 . ( r n + n ) . 112 1 AP (P4) 2 Fig.2 we show a scattering process of R ( l + 4).21) Here we consider the fluctuations of the reflectivity... is given by the summation of the wavefunction A p ( m+ n ) for the pth multiple scattering processes..(1 4)). Q U A N T U M T R A N S P O R T IN A ONEDIMENSIONAL W I R E 149 M=4 111 . for the path entering n and exiting to rn in electrode 1 (see Fig. . n)exp{it. which are known to be relevant for the following discussion.... the amplitude of the scattering wavefunction is given by Eq. When we have M channels. (8. where 7. where rn and n denote specific channels. 2e2/h (8.t(m. '. Note that the fluctuations become small for samples large compared with L. (1 5 n 5 M ) for given rn.22) P where a scattering process of the reflected wave. Since ( 9 ) = M ( T ) = M . (8.2 M 2 ( z ) ( E ) 2 the conductance .. Q ( n + rn) = C A .. 8. 8.. (8..
28) 1. p l ~ + . In order to discuss the fluctuations we define the following quantity (R(pn 3 n)’} = = P.24) where we use the fact that the ensemble average of the sum of ApAil for p jt+ p’ gives zero because of the assumption of a random phase. This fluctuation can be seen by changing the length of the sample provided that the sample size is smaller than the phase relaxation length ( L c L. Here we assume that R and 7 are in order of 1. (8.23)] is changed by the vector potential eA.150 CHAPTER 8. becomes smaller than L . P (8. When the phase delocalization length L. (8. + (8. The effective distribution of impurities can be changed by applying a magnetic field since the phase of each process [see Eq.27) Thus the fluctuations in g are on the order of the quantum of conductance 2e2/h which does not depend on M {or on a particular choice of material).P’!PI’. We cannot avoid this fluctuation from sample to sample with the same impurity concentration.). the fluctuations can be smoothed out.P’. When we consider N = L / L . TRANSPORT PROPERTIES When we assume that the overall phase of A p ( m4 n) is random in @(n m).. N tThe probability of choosing channel n from M channels i s on the order of 1/M. quantum fluctuatin~ conductors in series. p~ ~It ~p t .25) = 2{R(~~TI)}Z Thus the fluctuations of the reflectivity are given by (6R(m TI)’) Since (R(m n ) ) +  (R(m n)’) . (8. .21).P“‘ P.(R(m + + l/Mt we get from Eq. Note that the conductance G is N MGo. 4 the ensemble average of the reflection probability R(m + T I ) is given by (R(mt n)) = lQ(n + m>I2= ( p lAPl2 + PfP’ ApA:t) =( 1Ap12). This power dependence can be seen by changing L. p l l ] [ ~ j ~ + (8. I ~ ~ A~ .P” IP”’ C C {ApAp/Ap//Ap/ii} ( I A . (Sg2) N = (R(m T I ) ) ’ .p . the fluctuation of the conductance become l/N3i2 L3/2 smaller than for a single conductor. p l l ~ p .
R ( m m) would give 21AI2. + mp + m . . At high temperatures such that EBT is larger than h/t. (8. . : m + ml + ml + .31) If there is no phase correlation between A and Aa. . is larger than L . QUANTUM T R A N S P O R T IN A ONEDIMENSIONAL W I R E 151 When we fix the sample length L . Actually there is no time reversal symmetry in R(m + n ) for n # m. [see Eq. since R ( m t n) and R ( n m) are different paths from each other. .23)] in which the starting and ending sites are identical. Here we show the basic idea behind the negative magnetoresistance. When we define the thermal diffusion length LT for a given diffusion constant D . and L .)I2 * * / A Aa12 = 41AI2. the Einstein relation savs that (8. so that the $ + + f m )= ((A1 + A2 + . that is R(m + m).30) 8. . and A.1. can be considered as an energy width for phasecoherent motion.28) (8. and the timereversed processes A: : m + m q . an electron can vary its energy by h / t .so that the overall phases are identical. which refers to a decrease in the resistance with increasing magnetic field. from the uncertainty relation. This means that within a lifetime t . Consider a process A. Consider the special case for A. + m2 f ml + m .kB T >h t l p h tL (8.29) Thus the universal conductance fluctuations show a temperature dependence given by m=Go { constant (2)lJ2T1/2 T<t.1.8.5 Negative Magnetoresistance An another interesting phenomena observed in the weak localization regime is negative magnetoresistance. + + . (8.24) for R(m m). Thus when we consider the reflection probability of Eq. : R(m (8. expect a we coherence between A. then N = kBT/(h/tlp) independent channels are open incoherently. the energy h / t .) + (AT + AT + .
measurements of nanotubes show different aspects depending on the sample type. and can be applied to radar systems for searching a cloud which can be treated as a random material.152 CHAPTER 8. For an armchair nanotube this wouId involve a phonon of 47r/3T where T is the Iength of the 1D translation vector. considers quantum transport in general. since the lengths of the loops are different for different Ap’s. 8. and this is discussed in Sect. thus we can no longer expect any enhanced backward scattering. Subsequently.2. (8. 8.2 Transport experiments on carbon nanotubes In this section we discuss quantum transport in carbon nanotubes. phonon with wave vectors 2n/T are effective.31) i s known as enhanced backward scattering. rather large diameter (20 nm) multiwall nanotubes were used. the phases of A and A” become different from one another. Whereas Sect. The coherence associated with Eq. . In the initial transport experiments on an individual carbon nanotube [184]. single wall nanotubes became more available and the focus of research on the transport properties of carbon nanotubes shifted emphasis to the singlewall nanotubes. a single rope (SWNT bundle). a single multiwall nanotube (MWNT) and a single MWNT bundle.1. The phase difference is proportional to the magnetic flux penetrating through a loop made from a set of Ap and A?. The most difficult experimental problem for the transport experiments on carbon nanotubes is the attachment of electrodes to the extremely thin nanotubes. whereas for zigzag nanotubes. 8. scattering processes involve taking an electron from +CF to IF or visa versa. where transport properties for an isolated singlewall nanotube are presented. This is an explanation of the origin of negative magnetoresistance under weak localization conditions. Since the Fermi surface of a 1D nanotube consists of the two points f k p . Transverse acoustic (outofplane) phonons are most effective in this scattering process through the electronphonon interaction [78]. Transport. 51s discussed in Sect. T ~ A ~ S P O R T~ O P ~ ~ T ~ E P reflection probability becomes 21A1’.2. 8. such as a singlewall nanotube (SWNT). However. thus decreasing the reflection probability.1.2. When a magnetic field is applied. since singlewall nanotubes represent a model system for studies of q ~ a n t u m transport. we start this section with a few comments about quantum transport in carbon nanotubes generally and then proceed to discuss specific experiments.
2. but has the disadvantage of a high contact resistance and of not providing four contacts . 8. 8. as seen in Fig. One is method for attaching contacts t.2. containing suspended nanotubes. 8. on a substrate on which electrodes were previously deposited. is seen in Fig. The four Leads are connected to a gold pad and the currents a. TRANSPORT EXPERIMENTS ON CARBON NANOTUBES 153 This is followed by a report in Sect. transport me* surements can be carried out [150. a single contact is made with this technique and a scanning tunneling probe is used to make the second contact as this probe moves along the wire.nd voltages are observed by a fourpoint contact measurement. This method has the advantage of perturbing the nanotube only weakly. The 80 nm wide tungsten wire contacts are deposited by focusedionbeam induced deposition using a W(CO)6 carrier gas.2.3 for four contacts attached to a multiwall nanotube in the 510 nm diameter range on an oxidized silicon surface [185]. 8.0 pm range.151]. The distance between the probing leads on the sample is in the 0. The nanotube is visualized by the focusedionbeam with a low beam current (4 PA) for imaging the nanotube.4 where the carbon nanotube is placed on top of a Si/SiOz substrate on which two P t electrodes had previously been deposited. that utilizes so of the techniques mentioned above. A third method involves the use of sophisticated semiconductor Si technology to attach 4 tungsten leads by a focused ion beam deposition technique. 8. The advantages of this method is that 4 contacts can be placed reliable on the single nanotube. The effect of strain introduced by lead attachment process is not understood.o an n a n o t u b ~ to place a liquid drop. In another version of this method.31. The deposition of the contacts is performed under computer control without any visualization.8. Another approach for making electrical contact.21 Attaching Conlacis We summarize here some of the techniques that have been used for attaching contacts t o carbon nanotubes for carrying out transport experiments [185].nce as a function of nanotube length [186]. continuously measuring the resista. Phenomena associated with weak localization and universal conductance phenomena are observed in multiwall nanotubes and are discussed in Sect.4. For those nanotubes which connect two electrodes.3 on transport in a single rope of singlewall carbon nanotubes where intertube interactions play a role.
Fig.ionbeaminduced deposition [185].2. 8.4) is placed on top of a Si/SiOz substrate with two 15 nmthick and 140 nm wide P t electrodes as shown in Fig.154 CHAPTER 8. Because . 8.Wall ~~ a ~~ I ~ % ~ ~ t ~ ~ e We now discuss experimental results from the first transport experiment on an individual isolated singlewall carbon nanotube [51]. 8. A gate voltage Vgate. p1 and pz (see Fig. In this experiment a single wail nanotube (the very thin wire in Fig. applied to the third electrode in the upperleft hand corner of Fig.1).2 APL ~ ~ z Siszgle.4 [51] and the bias voltage vbiw is measured between the two electrodes.4 is used to change the electrostatic potential seen by the nanotube. 8. 8. The bias voltage v b i a changes the chemical potentials of the two electrodes.3: An individual multiwall carbon nanotube connected to four 80 nm wide tungsten wires by focused. p1 and pz. TRANSPORT PROPERTIES Fig. while the gate voltage Vgate changes the position of the energy levels of nanotube relative to the chemical potentials. 8. 8. A schematic circuit diagram is presented at the top of this figure and is relevant to the transport experiments shown in Fig.4: AFM tappingmode image of a carbon nanotube on top of a Si/SiOz substrate with two 15 nmthick and 140 nm wide Pt electrodes. 8.5 [51].
TRANSPORT EXPERIMENTS ON CARBON NANOTUBES 155 Fig. Currentvoltage curves of a carbon nanotube at a gate voltage of 88. 8. where we use an estimate for the Fermi velocity of VF = 8. The two traces were performed under the same conditions and represent a bistability (see text) [51]. The t w ~ p o i nresistance at roomtemperature of such a single wall nanotube is t 1 Ma. 8. = e 2/2C. more I . of the finite length of the nanotube ( L =3 pm). The estimated contact resistance. The plateaus of nonzero current clearly show ballistic transport when a conducting channef is in the range of vbim = ( p l p Z ) / e . we must consider not only the level shift effect but also the Coulomb charging effect of the nanotube.1 mV (curve B) and 120. Current versus gate voltage at vbim = 3 0 p V . However. 104.0 mV (curve C).1 x 105 m/s. The position of the steps in the I vbim curves is changed by increasing the gate voltage. 8. In the inset.2 mV (curve A). the onedimensional energy band is split into energy levels whose spacing AE = h v ~ / 2 L estimated t o be AE is 0. Thus. Since the energy of the levels in a nanotube > can be modified by Vgate.2 mV (curve A).5a are the N N    .5a. the current Aow can be blocked by this energy shift when the charge from the current flow itself shifts the levels out of the bias window between p 1 and p 2 . In Fig. the nanotube is considered as a capacitor with a capacitance C. .0 mV (curve C ) at 5 mK.8. obtained from a similar nanotube on which a fourpoint contact geometry was used. of an electron k g T < E. At very low temperature. current Row in Fig. 8. whereby.vbim curves are shown with. b.6 meV. such that the thermal energy k g T is smaller than the charging energy E..V ranging from 50mV (bottom curve) to 136 mV (top curve). is 300kSZ at room temperature and 1MS2 at 4 K.5b appears only when him E.1 mV (curve B) and 120.5: a. step positions shown in the inset of Fig. 104. we show the I vbia curves at a gate voltage of 88.2.
8. 8. with the minimum bias window vbim = 1OpV. TRANSPORT PROPERTIES 0. ~ .156 CHAPTER 8. 8.02 0.6 shows the temperature dependence of the spectra of a sharp peak that is observed in Fig.00 3 2 1 0 AVgeie (mV) 1 2 3 Fig.. showing the contribution from the lowerlying levels within the bias window [51]. / 2 a k B T ) . smoothly changed by changing Vgate. as a function of the gate voltage shift AV. Right inset shows the current vs gate voltage for vbim = 0.4.6 is the ratio of AVgate to the shift of the energy levels.0. Figure 8. as shown in Fig. : where the factor a = 16 obtained from Fig. This bistability may be explained as the result of switching offset charges that shift the energy levels of the 1D carbon nanotube. which are taken under the same experimental conditions. Solid lines in Fig../a2k~T).6 m v . from the peak conductance point.6: Conductance G = I/vbi.08 5 "k P 4 P 0. 8. 8. Some double &functions are also observed in the two traces in Fig.04 8 0. the current flow appears like a delta function of Vgate. : Left inset shows a model for explaining the temperature dependence of G. The solid lines represent fits to the function G 0 ~osh~(eAV.2 and 1. vs AVgate at the bias voltage vbim for three different temperatures with the bias window vbias = 1OpV. This ratio corre .~.~ ( e A v ~ . A decrease in intensity and a broadening of the conductance peak with increasing temperature shows the relaxation of the phase and amplitude of the resonance tunneling by phonon scattering events.only when the energy levels are in the bias window between p1 and p2.. When the bias window denoted by vbjm is very narrow ( 3 0 p V ) ..1.8. 8.5b.5b.5b.6 are fitted to the function G 0 ~ o s h .
6 (110. 8. This value of a = 1 2 is in satisfactory agreement with the previous value of ~ ~ in 1 brings the system back to the first approximation. 4. Although the absolute value of conductance is ff0. value. The plateaus correspond to the entry of a state at the Fermi level (denoted by the solid line in the left inset of Fig. The temperatures in Fig. to AE. and charging effects amociated with the micro capacitances of the nanotube and the gate.6}. 8. 8. The discrepancy between the fitted and the observed temperatures is due t o the finite bias voltage (10pV = 116 K) and the residual noise in the measurement system.4 meV (see the left inset of Fig..2.6) into the bias window. If the conductance is observed with a smaller bias voltage and a larger ct. TRANSPORT ~ X P ~ R I ~ E N T CARBON ~ A ~ ~ T U ~ 157 S ON S E sponds t o the ratio of the capacitance of the gate to that of the nanotube. These results are consistent with the fact that the curves in Fig. 8.6 meV for a L =3pm nanotube. and 830 mK) are the fitted temperatures for the plotted curves. which was first predicted theoretically. When we further decrease Vgater next plateau appears the and is attributed t o conduction processes associated with the lower level below A E 0. step structures are observed.. thus providing clear evidence for quantum c o n d u c t ~ c e .1. For curves at high gate voltages (about 140mV) plateaus can be seen for different values of Vim. which is consistent with the estimated level spacing of AE 0.6. described in Figs. the conductance of Fig. since the state at the Fermi level is now located outside of the bias window.5 and 8. while the room temperature resistivity is about 10' Qcm in semiconducting nanotubes. When the gate voltage increases (see the right inset of Fig. The resistivity is about 104103 Qcm for the metallic nanotubes.61. 8. 8. while the measured temperatures are 5 . the quantum conductance 2e2fh could be obtained at a smaller bias voltage.8. A value of a = 1 2 is estimated for the data in Fig.03(2e2/~). The further decrease of Vgate a no current situation. The resistance measurements for various nanotube samples show that there are metallic and semiconducting nanotubes.4. 8. respectively. dearly show ballistic transport effects associated with the discrete levels imposed by the finite length of the onedimensional nanotube conductor. The semiconducting nanotubes exhibit a slope . The observed phenomena can be understood by steps in the quantum conductance. 8. and 600 mK. 390. 8.6 from the ratio of AV. as discussed in Sect. 240.6 wiil show saturation at 2 e 2 / h .6 with a larger bias window vbim show a signal within a larger range of   6 Vgate * The experiments.
8. the I V characteristics gives Ohmic behavior.7.2. 0 E h 20 4 0 . TRANSPORT PROPERTIES 40 20 a.4 nmdiameter [187].5 4 .158 CHAPTER 8. 8.3 eV. In the right inset shows schematic energy levels near Fermi energy which are quantized because of the finite length of tube.1 0 1 2 3 4 5 6 v (mY Fig. while the conductance is suppressed near V = 0 for T < 10K.w a l ~ carbon nanotubes. This variation has been attributed to the presence of many defects in ~ u l t i . the sample may contain a large number of defects. 8.Wall ~ ~ n o ~ ~ b e ~ al Next we show transport results from a single 12nmdiameter rope containing about 60 SWNTs of 1. At room temperature. which seriously affect the measured conductance. A similar  .10. In Fig.3 .7: I .6 . the currentvoltage characteristics are shown for the rope segment between contacts between 2 and 3 (Left inset).4nmdiameter nanotubes at different temperatures for the rope segment between contacts between 2 and 3 (Left inset). On the other hand. [l87] in a plot of logR versus 1/T.3 An I n d ~ v ~ d uRope of Single.2 . Since the nanotube sample shows a slight positive magnetoresistance. for the metallic nanotubes.V characteristics of a single 12nmdiameter rope made up about 60 1. large variations from sample to sample are observed in the absolute values of the resistance and in its temperature dependence from 4 K to 300 K. thereby indicating an energy gap in the range 0. which is consistent with the theoretical values of the energy gap for the corresponding nanotube diameters.
I1 T.8: Resistance R(T) of a bundle of muitiwall nanotubes as a function of temperature at the indicated magnetic field values. 8.7. about a €O% increase of the resistivity was reported from 50 K to 280 K [l88]. From Fig.8 we show the resistance of a bundle of multiwall nanotubes as a function of temperature at several values of the magnetic field (4 T. and 14 T) 21501.4 Magneto. The temperaturedependent resistance R(T) shows three kinds of temperature regimes (see text [150]. The reasons for these temperaturedependent trends are not explained. TRANSPORT EXPERIMENTS ON CARBON NANOTUBES €59 Fig. gap is obtained by other single ropes with different diameters and lengths [187]. 8.8.2. A negative with a dependence of pfT) was even found in the higher temperature region when a single rope has a disordered nanotube alignment. In Fig. LFrorn . we see that the resistivity decreases with increasing temperature. while a decrease in the resistivity with increasing T was found bejow 50 K.2.Transport in Mu&&Wall Nanotubes One of the early transport experiments on multiwall nanotube bundles with 50 nm diameter showed a negative magnetoresistance. 8.  ~~~~~ 8. 7 T. In another experiment on a single rope. It is believed that the transport between singlewall nanotubes in a rope makes an essential contribution to the current at low temperatures. and this is not typical metallic behavior.
the magnetoresistance becomes quite large (up to A R / R = 0.3 K and 1. thereby suggesting a conducting nature of carbon nanotube bundles.160 CHAPTER 8. which is a typical value for the magnetoresistance in the weaklylocalized regime [192]. In the higher temperature regime I. the magnetoresistance shows the same magnetic field dependence at 2. the negative magnetoresistance shows relatively large values of A R / R as shown in Fig. a relatively small negative magnetoresistance A R / R = [R(H)R(O)]/R(O) 0. The other possible reason is associated with Landau level formation at the Fermi level.4. TRANSPORT PROPERTIES the figure we can see three kinds of temperature regimes denoted I. In 1 the temperature regime 1 . In the figure. Since the interlayer interaction in the multiwall nanotube is incommensurate. which is consistent with the smaller value of A in the small diameter nanotubes. 8.The phase delocalization length L . This enhancement of the density of states at the Fermi Level contributee to an increase in the current path and thus is expected to give rise to a negative magnetoresistance. and 111. In the temperature regime 111. However below 1 K .3). and the density of states increases with increasing magnetic fieid.7 meV for the band overlap. the n = 0th Landau level in two dimension~l graphite always appears at the Fermi energy. the resistance is almost independent of temperature and has a value of loe2 to $2cm. In the very low temperature region below 1 K . a peak in the resistance is observed whose origin may relate to possible ordered states induced by lowering the symmetry. the band overlap can be expected to be much smaller. which is much smaller than A == 40 meV in 3D graphite [190].13 K. weak locatization effects are expected to occur at much lower temperatures. reflecting the degeneracy of the Landau orbits. These phenomena were accounted for using a simple twoband semimetal model [189] for the electron and hole concentrations n and p as a function of temperature T. the resistance continuously increases with decreasing temperature. There are at least two possible reasons for the observed negative magnetoresistance. One explanation is the effect of weak localization. However. By lowering the temperature. and a value of 3. As shown in Chapter 6.9 [150]. the resistance quickly decreases. Thus the negative magnetoresi~tance above 4 K may be associated with a Landaulevel effect (called the Bright model 11911). as discussed in the previous section. as discussed in Section 11.1 is observed with I normal to < ? the tube axis. increases . In the low temperature regime below 77 K. 11.
Clearly the magnetoresistance is seen to fluctuate randomly by varying the magnetic field. 8. I Q. Thus the fluctuations in the magnetoresistance are not associated with noise but rather are due to a quantum interference effect known as universal conductance fluctuations.2 .15 0. The fluctuations in resistance that are observed at the same values of magnetic field at different temperatures are known as universal conductance fluctuations [184]. However the peaks in the magnetoresistance for different temperatures appear at the same value of the magnetic field. I 12 14 18 0 2 4 6 8 10 Magnetic Field P I Fig. 8. By applying an external magnetic field. the carrier scattering . TRANSPORT EXPERIMENTS ON CARBON NANOTUBES 161 0 Q. 8.O. These data show a complete quenching of the enhanced backscattering. At the lowest temperature of 0.ao6] .8.9: Magnetoresistance A R / R as a function of magnetic field at low temperatures below 1 K. which is discussed in Sect. 8.4. It is interesting that the negative magnetoresistance phenomena occur below that temperature.1. Thus a negative magnetoresistance effect is observed in carbon nanotubes at lower magnetic fields than is usually found in graphite.10 the magnetoresistance for a 20 nm multiwall nanotube at very low temperature is presented as a function of the magnetic field.2.9 a saturation of A R / R is observed at large magnetic fields.3 Fig. 8. with decreasing temperature so that the loop of phase difference discussed in the previous section becomes large even for small magnetic fields.3 K in Fig. I I L 0 r. 8. In Fig.10: Magnetic field dependence of the magnetoresistance of a 20 n m multiwall carbon nanotube at the indicated temperatures.U 4. The data are taken on the same multiwall carbon nanotube as in Fig.8 [150].OJ 0.
10 are constant in magnitude below 0. from which we can estimate t .162 CHAPTER 8..  .7)]. showing that the multiwaI~carbon nanotube consists of N 5 serial quantum wires of length L. = 2 x sec. consistent with Eq. TRANSPORT PROPERTIES processes are changed. AG = O. The amplitudes of the two indicated fluctuations in Fig 8.lGo. The effect of variation of the magnetic field is the same as the fluctuations in the conductance that would be observed from sample t o sample. where Go = 2 e 2 / h is the quantum conductance [see Eq. thus having the same effect on the magnetoresistance as is observed in Fig 8. (8.4 K.301. The amplitude of the fluctuation is constant below 0. (8.4 K .4 K and decreases as T1I2 above 0.10.
(9. The r onefolding technique is the same as that used in treating the electronic structure of carbon nanotubes. . . The sum over j in Eq. 9..1.2. Phonon Modes of Carbon Nanotubes The phonon dispersion relations of carbon nanotubes can be understood by zone fold~ng the phonon dispersion curves for a single 2D graphene sheet.CHAPTER 9. (i = 1 . Although the model is simple. which is discussed in Sec. 9.y’. z’ coordinate system. in which interatomic forces are represented by spring constants.1 Dynamical matrix for phonon dispersion relations We start with an approach for calculating the phonon dispersion relations within a force constant model. we first explain how to calculate phonon dispersion relations in twodimensional graphite. y.N ) . In general. . In Sec.1) where Mi is the mass of the ith atom and Id”) represents the 3 x 3 force constant tensor* between the ith and the jthatoms. and obtain results for the phonon dispersion relations. where U is a unitary matrix which transforms the x . 9. . *A second rank tensor is defined by a 3 x 3 matrix whose elements ( K z s .l). we can reproduce the experimental results as closely as possible by increasing the number of the force constants.1. u = ( 2 1 . We also consider the threedimensional dynamical matrix. the equation of motion for the displacement of the ith coordinate.. Then we discuss phonon dispersion relations for carbon nanotubes in See. 163 . . KzY.zi) for N atoms in the unit cell is given by i Miiii = j IW(uj Ui). yi. 9.1 and See. (9.3. K z z ) can be transformed as Ulh’U.. taking the curvature of the nanotubes into account. 4. t coordinates into another orthogonal r’.
5) can be shifted to a site in the original unit cell. k = k’. In a periodic system we can perform a Fourier transform of the displacement of the ith atom with the wave number.Rj is the relative coordinate of the ith atom with respect to the jthatom.1) becomes i C j I<(ij) C eik’.e. Ic’. which for a 2D graphene sheet has been carried out up to 4th nearestneighbor interactions [193].. then by tlv. The vibration of the ith atom is coupled t o that of the jthatom through the Ii(ij) force constant tensor. then Eq. to obtain the normal mode displacements ui’ where the sum is taken over all ( N n ) the wave vectors k’ in the first Brillouin zone+ and Ri denotes the original position of the ith atom. (9. (9. i that is u = . in which case 6k&  has the vdue of . (9. When we assume the same eigenfrequencies w for all u . is the number of unit cells in the solid and thus Nfi * 6 k .3) by e i k . R . We note that j in Eq. .3) k’ Upon multiplying both sides of Eq.is normally taken over only a few neighbor distances relative to the ith site. differ by a lattice vector).5) where f is a 3 x 3 unit matrix and ARij = R. Here we show that all j in Eq.Rju(i) k’ (9. k / is a delta function which vanishes unless 1mNty.w 2 u j . taking a summation on Ri. When the j and j ‘ sites are equivalent to each other (i. Rj and Rj.1) can be a site in the neighboring unit cell when the iehatom is near the unit cell boundary. and using the following orthogonality condition in the continuum k spacel$ we get (9. (9..
9. and the sum over j' is taken for the equivalent sites to the jth atom.  I ) ( k ) u k = 0.+. (9.2 Phonon dispersion relations for twodimensiona~ graphite §This corresponds to the diagonal block of the dynamical matrix. .6) To obtain the eigenvalues w 2 ( k ) for P ( L ) and nontrivial eigenvectors u k # 0 .. 9. (9.5) can be formally written as follows by defining a 3N x 3N dynamical matrix 'D(k) t(ut). j = 1. 2. the last term can appear in the diagonal block of the dynamical matrix.7 is in the offdiagonal (ij) block of the dynamical matrix. Then Eq.5) for 3~ unknown variables U k u f ) . where we denote D ( k ) by {D(ij)(k)} and from Eq. The last term in Eq. (9. and the last term appears only when the jthatom is coupled to the ith atom through If(") # 0. (9. we can show that u f ) = ugi' using the definition of z l f ) in Eq."k 1. In a periodic system. ( i .2). . (9.2 PHONON DISPERSION RELATIONS FOR 2D GRAPHITE 165 considering Rj . When the ikhatom has equivalent neighbor atoms in the adjacent unit cells. that D('j)(k) is expressed as where the sum over j" is taken for all neighbor sites from the ith atom with K(dj")# 0.5) it follows . and vice versa.7) have nonvanishing values only when i = j. in which the superscript t denotes the transpose of a row vector into a column vector.5) contains the variables u:) within the original unit cell. Thus Eq. the dynamical matrix elements are given by the product of the force constant tensor IC('j) and the phase difference factor e i k ' A R i j . It is convenient t o divide the dynamical matrix D ( k ) into small 3 x 3 matrices ID(ij)(&). The first two terms5 of Eq.Thus we obtain simultaneous equations in Eq.R j l .1). This situation is similar to the case of the tight binding calculation for the electronic structure where the matrix element is given by the product of the atomic matrix element and the phase difference factor (see Sec.9.N). (9. (9. The contributions of I d @ ' )in which the j' sites are equivalent to the j sites. . we solve the secular equation detD(k) = 0 for a given k: vector. are added to I<(ij)with a phase factor eik'ARiJ1. (W for a given Iz vector.
(see Fig. in the unit cell. A and B . (9. and B3 whose contributions to 21 are contained in D A B . and open hexagons (4"). and the coupling between them When we consider an A atom.1 for the electronic energy bands for the t~ and ?r electrons of graphite. The phonon dispersion relations for a single graphite plane (or a twodimension3 graphene sheet) are calculated by following the procedure used in Sec. B2.* In twodimensional graphite.3). 2.open squares (3rd).The dynamic^ matrix V for twodimensiona~graphite is written in terms of the 3 x 3 matrices D A A D A B .D B A . we must consider six coordinates u k (or 6 degrees of freedom) in Eq. the three nearestneighbor atoms (see Figs. solid squares (2nd). a direct correspondence to the phonon dispersion curves. we plot open circles (lst neighbor). . Circles connecting the same neighbor atoms are for guides t o the eye. within the unit cell.166 CHAPTER 9. 9.6). *From a symmetry s t ~ d p o i n tonly the electronic bands related to the carbon p electrons have . From the lst to the 4th neighbor atoms. respectively.1.1: Neighbor atoms of a graphitic plane up to 4th nearest neighbors for (a) an A atom and (b) a B atom at the center denoted by solid circles.and DEB for the A and E atoms . since there are two carbon atoms. The secular equation to be solved is thus a 6 x 6 dynamical matrix V .1 and 9. 9. 4. PHONON MODES OF CARBON NANOTUBES Fig.2) are 3 1 .
Vol LI s. with contributions to D that are contained in DAAand so on. PHONON DISPERSIOX RELATIONS FOR 2D GRAPHITE 167 82 2 ~~~~ Fig. respectively. .*. 9. Johnson and G.9... Quantum Chem. 2.9) where $!"I. The remaining problem is how to construct the force constant tensor I d i j ) . Here #. and $$:' represent the force constant parameters in the radial (bondstretching). the determinant should be invariant under any operation of the point group for the unit cell. and $to represent forces for the nearestneighbor atoms in the radial (bondstretc~ing). 9. J. B 2 equivalent are BI. #$I.'.. and L...3 (a)]. In Fig. Rev. while the six nextnearestneighbor atoms denoted by solid squares in Fig. G. Dresselhaus and M. It is important to note that the A and B sites do not always appear alternately for the nth neighbors. whose force constant tensors are obtained by appropriately rotating the tensor €or A and B1.. 333 (1968) for silicon and germanium.l(a) are all A atoms.. inplane and outofplane tangential (bondbend in^) directSince the determinant of the dynamical matrix is a scalar variable.2.t First we consider the force constant between an A atom and a nearestneighbor B1 atom on the 2 axis as shown in Fig. .. Further details are given in the references: G. or . which gives blockdiagonalization in accordance with the irreducible representations of the symmetry group of periodic structures. S. 2275 (1973) for graphite.2 [see also Fig. The force constant tensor is given by (9.. we show neighbor atoms up to 4th nearest neighbors for the A and B atoms. Thus the proper combina~io~ of terms in the product of the force constant tensor h(j '') and the phase difference factor e'k'aRdj is determined by group theory. Phys.. Dresselhaus.. 9. $ti. Int. B7. Here we show a simple way to obtain K('j). .2: Force constants between the A and B1 atoms on a graphene sheet.... 63 A B1 X nearest neighbors and B3 to respectively.inplane and outofplane tangential (bondbending) directions.. In fact the third and the fourth neighbor atoms belong to equivalent atoms.. 9. Dresselhaus. __I' .1 (a>and (b). .
’ I{(A*B2) =  4 l i &((Pi. (fA1) + 34:. Here the graphene plane is the xy plane. COS%.% Urn = ~ 0 ~ 8sin6. if we consider a virtual atom on the 5 axis. The matrix for the rotation of the axes is the transpose matrix of the matrix for the rotation of atoms. and the corresponding phase factor. 4 . we introduce two parameters to describe the inplane (y) and outofplane ( z ) tangential modes. e i k ’ A R i j I becomes exp(ik.a/2].3) (9. (9. B2 and I33 are obtained by rotating the matrix in Eq.§ To $The formulation should be in terms of the rotation of the axes connecting an atom A to its various equivalent neighbors. (9.)(6.I ( F P) ) 461:) . R ~ P ~ O ~~ O O~ OF CARBON ~ A ~ O T ~ ~ E ~ S E tions of the nth nearest neighbors.10) the rotation of atoms.). 3 . (9. we show next the force constant matrix for the B2 atom at [a/(26).168 C ~ A P T 9.O). a/2.a/fi) for the B1 atom at (a/&. and if we then rotate the matrix.”)) O &(& 0 3 4 y + #.9) according to the rules for a secondrank tensor: &A. respectively.10) where the unitary matrix U. 9. 0 . However. B ~ ) u m i I ( m = 2. However. the interaction between two nearestneighbor atoms is not sufficient to reproduce the experimental results.. such as from the nth neighbor atoms. This happens at 4th neighbor atoms in graphite. In that case it does not seem that we can build an initial force constant matrix as given by Eq. + . 0 ( 0 0 1 (9. is here defined by a rotation matrix around the z axis in Fig.2) corresponds to the direction of the (7 bonds (dotted lines). 2 . 9. sin%. we can get the force constant matrix without any difficulty. we present in Eq. ..ll) To make the method explicit. and we generally need to consider contributions from longdistance forces. (9. for easy understanding. Since graphite is an anisotropic material. taking the B 1 atom into the Brn atom.2. and Vz is evaluated assuming 6 2 = 2 ~ / 3 . and the two tangential directions (y and z ) are taken to be perpendicular to the radial direction. a/(2&) ik.12) and the corresponding phase factor is given by exp[ik.Bm) = u m I { ( A . ( n = 1 . the radial direction (z in the case of Fig. In the case of the phonon dispersion relations calculation for 2D graphite. these atoms are not always located on the 5 (or y) axis. §When we consider the force constant matrix of the nrhneighbor atoms. The force constant matrices for the two other nearestneighbor atoms.0].9). 0.
and to refer to radial. Table 9.’ $1.3. denoted by solid lines.4(a) reproduce the experiment^ points o b t ~ n e d by electron energy loss spectroscopy very well [194. 9.29 #it)= = 0. Here the subscripts T. transverse inplane and transverse outofplane.2. are shown using the set of force constants in Table 9.195]..) 4::’ 4$3) = 4. Radial Tangential 4. in which the outer two atoms vibrate around the bond of the two inner atoms as shown in Fig.3: In order to describe the twisted motion of four atoms.2. See Figs..92 (4) 3. it is necessary to consider up to at least fourthnearestneighbor interactions. In Fig. The numbers shown in the figure denote the nth nearestneighbor atoms from the leftmost oth atom. 9..25 &’ = 2.00 4::) = 5. respectively.50 = 24.82 #. The calculated phonon dispersion curves of Fig. as for example from i n e l ~ t i c neutron scatter in^ or electron energy loss spectroscopy measurements along the I’ M direction [194.9. Thus the inclusion of fourthneighbor interactions is sufficient for reproducing the phonon dispersion relations of 2D graphite.4(b) the corresponding density of states is plotted per C atom per cml.1) are obtained by fitting the 2D phonon dispersion relations over the Brillouin zone as determined experimentally. Values for the force constants [193] (see Table 9.40 sf. t i . 9. = 1. PHONON DISPERSION RELATIONS FOR &D GRAPHITE 169 (4) Fig. 9. contributions up to a t least the fourth nearestneighbor interactions are necessary [194].58 graphene In Fig. where the energy is in units of crnl. which originate from the .4(a) the phonon ~ispersion curves of a t w ~ ~ i m e n s i o n a ~ sheet.(2) = 8. 9. The three phonon dispersion curves (or branches). describe the twisted motion of four atoms.1 and 9.195].1: Force constant parameters for 2D graphite in units of 104dyn/cm 11931.) I : 3.15 0.23 I #$) = 0.’) = 36. 9.50 = 9.80 4.1.
components and a 1 x 1 matrix of y z components. The remaining three branches correspond to optical modes: one outofp~ane mode and two i n . an inplane tangential (bondbending) mode and an inplane radial (bondstretching) mode. 00 .4: (a) The phonon dispersion curves. . PHONON MODES OF CARBON NANOTUBES 1600 1200 800 400 r M U r . (b) The corresponding density of states vs phonon energy for phonon modes in units of states/lCatom/cml x ' point of the Brillouin zone [see Fig. It is noted that the outofp~a~e transverse) acoustic branch shows a h2 energy dispersion relation around the I point. using the set of force constants in Table 9. respectively.170 CHAPTER 9. 1. . .10) that all rotations U are within the z . as is normally seen for acoustic modes. plotted along high symmetry directions. listed in order of increasing energy.4(a)]. 9. It is clear in Eq. x lo9 statellCatom/cm' Fig. One reason why we get a k2 dependence for the outofplane mode is simply because this branch corresponds to a twodimensional phonon mode and because graphite has threefold rotational symmetry. . while the other two inplane acoustic branches show a linear k depen' dence.p ~ a n ~ modes. 9. (9. y plane in the case of twodimensional graphite.1 [193]. Thus the force constant matrix can be decomposed into a 2 x 2 matrix of z. for a 2D graphene sheet. The 1 x 1 force constant tensor I<!:') for the nth neighbor atoms . correspond to acoustic modes: I an outofplane mode.
(k 0). which wi~s discussed in f 9. axis.5). 6 N phonon + + %n general. such as ak. except that the zonefolding is applied to the 2D phonon dispersion relations. (with constant values for a.9) and (3. no linear combination of k.865 cml at the r point) shows a C2 dependence for the same reason. The absence of a linear k term in the phonun dispersion relations along the z axis of graphite comes from the threefold rotational axis. Phonon dispersion relations for nanotubes ~ ~ o ~ 9. The method of folding the phonon dispersion curves for a given chiral vector c h ( n .3).2. (3. bk.28)] is an even function of k around the I' point. and w ( L ) thus becomes an even function of X: which is obtained from the sum of the differential phase factors eik'ARij given by Eq. such as for the inplane modes.4(b)]. b). the w ( k I . Because of this symmetry.1 Zone j u ~ ~ ~ ~ g e 2 As a first approximation. 9. where N = 2(n2 m2 nm)/dR and d s are defined in Eqs. (2. and the phonon density of states shows a step function which is known as a twodimensional vanHove singularity [see Fig. we get w ( k ) = 2 m l s i n k a l 0: J k l .25) when discussing the electronic structure. The optical outofplane transverse branch (. respectively (see also Table. When the force constant matrix depends on the atom locations. Thus there is neither a phase velocity nor a group velocity for the z component of the vibrations at the J? point.fi If we consider only the three nearestneighbor atoms.rn) is the same as that for electrons. the dynamical matrix for the z components in a two0 dimensional system becomes its complex conjugate. axis. It is clear that Ill*[= 11for the Hermitian matrix D. C3 along the z direction. Since there are 2 N carbon atoms in the unit cell of a carbon nanotube.a term proportional to might appear poi% ). this invariant condition applies to the product of the force constant matrix and the phase difference factor.7). the phonon dispersion relations for a singlewall carbon nanotube are determined by folding the phonon dispersion curves of a twodimensional graphene layer. ils discussed in f 41. and the quadratic form of k$ kg is also invariant. for a onedimensional spring constant model with the force constant. and thus the eigenvalues are even functions of k: around k: == 0 (the r Even though w(k) is an even function of k. 93 .3.9. This is why we get a k2 dependence for w ( k ) for the outofplane branch. For example. 3. The simpiest invariant form is a constant. (9. (2.1.3. PHONON DISPERSION RELATIONS FOR NANOTUBES 171 does not depend on the coordinate.  + + . can be invariant under a 2a/3 rotation around the k. in w ( K. However. Icy) should have threefold rotational symmetry around the C. The energy dispersion relation thus obtained [see Eq. which generally has a linear k term in w ( k ) . Thus when w e change k: to k. and ky.. the sum of the differential phase factors is nothing but f ( k ) obtained in Eq. the phase factor eik'AR*j goes into its complex conjugate if we change k: to k.
(3.20) ). which corresponds to a breathing mode with nonzero frequency f1931 as shown in Fig. 4 and dti* in the ~ i ~ c u ~ f e r e n t i a l . (3. However. PHONON MODES OF CARBON NANOTUBES dispersion relations for the x . .5(a) on the right. only the inplane force constants. On the other hand. the two directions which are perpendicular to the nanotube axis do not correspond ‘Since there is no vibration in the direction of the nanotube axis in the breathing mode. 9. (3.M ) and diameter of the carbon nanotube.5(a) on the left do not give zero energy at the r point when rolled into a nanotube as shown on the right. In the breathing mode.8). Thus the force constant &i is necessary to describe the breathing mode. it has been pointed out [193] that zonefolding alone does not always give the correct dispersion relation for a carbon nanotube. L directions. For example. Here. and this results in a finite frequency at the I? point.1)].y. where wrD (lc) denotes the twodimensiona~ energy dispersion relations for a graphene sheet. in accordance with the periodic boundary conditions of the chiral vector. the outofplane tangential acoustic (TA) modes of a graphene sheet shown in Fig. The phonon dispersion relations of a carbon nanotube also depend on the chirality (n. especially in the low frequency region. However. djrection of the tube are related t o the vibration. at k = 0. The idea of zone folding is applicable for almost all the phonon modes of a carbon nanotube. k is a onedimensional wave vector. all the carbon atoms of the nanotube move radially in an outofplane radial acoustic vibration.172 CHAPTER 9. and z v~brationsfor each atom are foIded into the onedimensional Brillouin zone of a carbon nanotube along the K2 direction (Eq.20) and (4. we generally expect three acoustic modes which correspond to vibrational motions in the 2 . since the phonon wave vector in the circumferential direction becomes discrete for every K1 vector [see Eqs. and some additional physical concepts must be introduced. when we consider the vibrations of a carbon nanotube in the context of threedimensional space. the bond angle of the hexagon network is modified. The corresponding onedimensional phonon energy dispersion relation wyg (k) for the nanotubes is given by. g. 9. d t . and T is the m a ~ n i t u d e of the onedimensional translation vector T given in Eq.
(b) An acoustic mode of a carbon nanotube whose vibration is perpendicular to the nanotube axis (right) corresponds to a linear comb~nationof both inplane and outofplane graphitederived modes (left). to form the acoustic mode of the nanotube shown on the right.3. However. the graphitederived inplane and outofplane modes do couple to each other. as shown on the lefthand side of Fig. PHONON DISPERSION RELATIONS FOR ~ A ~ O T U ~ E S 173 Fig.2 Force constant tensor of a carbon nanotube In order to avoid these difficulties.5: (a) The outofplane tangential acoustic modes at Ic = 0 (left) in a single layer of graphite give rise to a radial breathing mode in the carbon nanotube with nonzero frequency (right). to any tw5dimens~onalg r ~ p h i t e phonon modes. when the graphene strip is rolled up into a nanotube.9. but do couple for the nanotube because of the curvature that is introduced by rolling up the sheet. 9. In a graphene sheet.3.5(b). we solve the threedimensional carbon nanotube dynamical matrix problem directly using the force constant parameters . 9. the inplane and outofplane modes are decoupled from each other. 9. These modes do not couple in the case of a single graphite layer.
then (b) rotating the tensor by an angle (p/2 around the z axis.10) p . (9. Since we have 2N carbon atoms.16) + + + + . (3. .6).1.6 (a). the chiral angle 0 defined in Eq. . (BpAq). (3. is obtained by: (a) rotating the tensor of Eq. When ( q . and V ( B i B j ) . N . Here we denote the 2 N atoms as Ai and B j ( i . N ) . j = 1 . we then consider (2N)' = 4 N 2 small ) matrices. Here the angles 0. .0 around the z axis. .) (9. + . Thus we can generate all force constant tensors from the nonzero tensor related to A1 or B1.N ) . as discussed in 3.4. where the N Ai (or N B j ) atoms are geometrically .1 ) I 0 sin(p. 'p and I are. . + Ap. (b) and (c). (9. In fact.14) = cos(p . and finally (c) rotating by I around the z axis. the angle (o between A1 and B1 around the z axis.174 CHAPTER 9.1 ) I sin(p . When we put atom A1 on the z axis. When we consider I d A l B p ) or IdBIBJ'). The corresponding force constant tensor I d A p B q ) is calculated using where U is a unitary matrix for rotation by an angle I = 2 r / N around the nanotube axis. . we use ( N q . (3.4). . . . WheIl a pair (i (ApBq). (or (ApAq).p 1) for ( q . are we will consider V(ApBq). the position of each Ap (or Bp) atom can be obtained by operation of the symmetry vector R defined in Eq.p 1).1 ) I o ( 0 0 1 1 . and the angle 9 between A1 and A p around the z axis defined by 2 ( p . j = 1.4). the effect of the curvature has been taken into account. and B1 RP. Then UP' is defined in Eq.1  Bp.D(BiAj).16) as UP' where the z axis is taken for the nanotube axis. 9. equivalent to each other. as shown in Fig.l ) n / N in Eq. D ( A i A j ) .1 times on A1 (or B l ) : A1 RP1  When we divide the big 6N x 6N dynamical matrix into the 3 x 3 small matrices V ( A i B j for a pair of Ai and B j atoms.15). ( p = l . For example.p 1) is negative or zero in Eq.(3. let us consider the case of (see Fig. respectively. . D ( A i B j ) . .9) by (7r/6) . the dynamic matrix to be solved becomes a 6 N x 6 N matrix. . (9. respectively. 9. PHONON MODES OF CARBON NANOTUBES listed in Table 9.1 ) I cos(p. (BpBq)) within the 4th neighbor distance.
Using the force constant tensor thus obtained and multiplying by exp ikAzij. and the angle yo is defined in this figure by the angle between A1 and €31 in the xy plane around the z axis. The force constant tensor is obtained by (a) rotating the tensor of Eq.7(a). the dynamical matrix for a Ic vector is obtained. of which 12 modes are nondegenerate and 54 are doubly degenerate. 9. Bi. For the 2N = 40 carbon atoms per circumferential strip for the (10. (9.6: The geometry of the A1 atom and its nearest neighbor atoms. (3. we have 120 vibrational degrees of freedom.lO) nanotube. B1.B on a 2D graphene plane.4).Y l ) i 5. where T denotes the ~ a g n i t u d of the unit vector along the tube axis (see Eq.5)). The phonon energy dispersion relation is determined by solving the dynamical matrix for many k points in the onedimensional Brillouin zone. For II(APBq). Here B is the chiral angle defined in Eq.fl Fig. (9.B j . The upper open circle in (a) represents the projection of B1 on the yz plane and the lower open circle represents its location after rotation by n/6 . we further rotate in (c) the force constant tensor by 9 around the z axis (see Eq.16)).lO) armchair carbon nanotube e are given in Fig. (3. but because of mode degeneracies there are only 66 distinct phonon branches. 9. The results thus obtained for w(lc) for a (l0.8 around the z axis and by (b) rotating the force constant tensor by an angle rgf2 around the z axis.9) by ( n / 6 ) . where Azij is the component of Al&j along the z or nanotube axis. The number of distinct phonon branches can be obtained by point group theory for atoms .
(b) Phonon density of states of (10.0 0. .4(b)] since the phonon dispersion relations are.lO) armchair nanotube. 9. 9. 9.2 0. When we integrate the phonon density of states with respect to the energy.lO) nanotube and for 2D graphite. and the direct product of the reducible representation for the atomic sites* with the representations for 2 . in principle. z is decomposed into the irreducible representations for the phonon modes.lO) nanotube in units of states per C atom per cml.176 CHAPTER 9. y . PHONON MODES OF CARBON NANOTUBES 1600 1200 aoo 400 n  0.lO). in the unit cell.lO) nanotubes. In Fig. The phonon density of states for the (10.7: (a) The calculated phonon dispersion relations of an armchair carbon nanotube with c h = (10.4 0. Since we use the same units for the phonon density of states for 2D graphite [see Fig. In the case of the (10.0 0. we can directly compare the phonon density of states for the (10. D l o h is the point symmetry group.4(b)]. 9. given by the zonefolding of *The character of the atomic sites for an operation 0 of the point group is defined by the number of atoms which do not change their position when the operation 0 is carried out.6 0.0 kT/ 'IC 1. The number of degrees of freedom is 120 and the number of distinct phonon branches is 66.8 1. we get 3 states/Catom as the total number of states.lO) nanotube is close to that for 2D graphite [see Fig. 1x10* states/l Catom/cm' Fig.7(b) we show the phonon density of states for the (10.
In Fig. since all acoustic modes of the (10. as is commonly observed in the solid state.lO) armchair car' bon nanotube near the I point.8.lO) carbon nanotube. the phonon dispersion curves around the J? point are shown on an expanded scale for the (10.8: Phonon dispersion relations of the (10.3.4 kT/a Fig. and have 2 and y vibrations perpendicular to the nanotube ( z ) axis (see Fig. at However.7(b). which is known as the twodimensional van Hove singu~arity the band edge. P ~ O N O N ~ ~ S P RELATIONSO N NANOTUBES ~ ~ ~ FOR 177 200 '6 100 3 0 Ll 0. 9. It is noted that we integrated the phonon states within an accuracy of 10 cml. 0. The difference in the phonon densities of states appear in the small peaks due to the onedimensional van Hove singularities. Another difference between the (10. Since the djsplacements of all the acoustic modes are three dimensional. 9. The three lines near w = 0 which intersect at k = 0 correspond to the acoustic modes of a carbon nanotube. The corresponding phonon density of states is proportional to . 9. we have no phonon density states at w = 0 as shown in Fig. The lowest energy modes are the transverse acoustic (TA) modes.9. which are doubly degenerate.0 02 . the z longitudinal acoustic mode (LA).lO) nanotube and graphite relates to the phonon density of states at w = 0 cm'. those for 2D graphite. Since there is k 2 dependence in the outofplane TA mode for 2D graphite.lO) carbon nanotube. the frequencies of the phonon dispersion relations are proportional to k for all three phonon branches. including the lower energy 2. The TW mode is related to the rotation of a nanotube along its axis. doubly degenerate). 9. There are four acoustic modes in this cylindrical solid.5(b) right).y transverse acoustic modes (TA. we get a finite density of states at w = 0 cml. The highest energy mode is the longitudinal acoustic (LA) mode in the direction of the nanotube axis.lO) nanotube have a k dependence as shown below. and the twisting mode (TW). Let us focus our attention on the acoustic modes of the (10.
When we assume the triangular lattice of the nanotubes ( s o called rope) with the lattice constants of a =16. Details will be discussed in Chapter 11 on elastic constants.35 km/s. respectively. Since the driving force for this wave motion is a twisting motion of the nanotube.95A and c =1.178 CHAPTER 9.9. vgiD 9. which is related t o a rotation around the nanotube axis at k = 0. 'u = in which p is the density of carbon atoms. The difference of the sound velocity is due to the existence or absence of the interlayer interaction between graphene layers for 3D graphite and a 2D graphene sheet. . we call this mode a twisting mode (TW).9 Force constant corrections due to curvature of 1D nanotubes The threedimensional phonon dispersion relations of a carbon nanotube can be obtained by the methods discussed in the previous subsection. In addition. PHONON MODES OF CARBON NANOTUBES the energy while the phonon density of states of 2D graphite is constant because of the k2 dispersion relation for the outofplane TA graphite mode. for which = 12. tThe Young modulus.196]. The sound velocities of the TA and LA phonons for a (l0. This small Y value arises from the small mass density of the rope. since the sound velocity for the zonefolded outofplane TA mode is zero because of the k2 dependence as discussed above. The sound velocity of the T W mode is 15. respectively. It is noted that the sound velocities that we have calculated for 2D graphite are similar t o those observed in 3D graphite [9]. Y can be estimated by the LA velocity. which is the same as the calculated value of the inplane TA mode for 2D graphite. The reason why the T W modes have the same velocity as the TA graphite mode is that the displacements associated with the T W mode are in the cylindrical plane and are perpendicular to the tubular axis.43 km/s and 20.lO) armchair carbon nanotube are estimated as 9. the density p becomes 1. there is a fourth acoustic mode for the carbon nanotube. When we consider a single carbon nanotube as an infinite onedimensional material. This value is smaller than other calculated Y values.0 km/s.1 are not well defined on the curved surface of the nanotube by merely considering the planar graphene force constants.00 km/s. However it should be mentioned that the force constant parameters of Table 9. fi.44x&A.28 x lo3 kg/m3 from which the Young modulus gives Y = 532 GPa.? These results cannot be obtained by the zonefolding method discussed in the previous subsection. a rotation around the nanotube axis is possible [83.3 km/s and vgjD = 21.
PHONON DISPERSION RELATIONS FOR NANOTUBES 179 For example. we can find a small radial component of the motion which is perpendicular to the cylindrical surface and is due to the effect of curvature on the force constant parameters. Thus as a first approximation. the calculated result for the (10.. negative w 2 ) frequencies for the acoustic phonon modes. In order to treat the curvature effect correctly with the given force constant parameters of twodimensional graphite. the two vectors u and G u are not in the plane which is defined by the dotted line and tube axis. which gives a nonzero value of w at k = 0. we show the effect of the rotational motion of the twisting mode with k = 0 on the cross section of the carbon nanotube in which all vectors of the motion should be parallel to the cylindricaI surface and perpendicular to the nanotube axis. Actually the calculated results using the force constant parameters in Table 9. for this kind of rotational motion. Thus we do not use the elasticity theory approach to the curved coordinates of carbon nanotubes. The ratio of the components of the motion in the radial direction to the cylindrical direction is on the order of The curvature effect will also apply to all of the other modes by an amount up to ~ 1 cm' even for the (5. It is a physical requirement that we have a rotational mode with w = 0 at k = 0 in this system. this effect can be neglected compared with general nanotube phonon frequencies which are on the order of lo3 cml.1 give less accurate values than the approach of the previous subsection.lO) carbon nanotube gives a finite value of w = 4 cm' at k = 0 for the twisting mode when we use the method of the previous subsection with the force constant parameters of Table 9.5) 0 armchair nanotube. The other three acoustic modes correctly give w = 0 cmI at k = 0.9.1. Actually when we examine the eigenvectors of the motion. the force associated with the tangential outofplane force constant. When we consider a curved chemical bond. However this treatment requires a different method from that used for a lattice of springs. Sometimes the calculated results even give imaginary (i.3. we could consider the dynamical matrix on a curved coordinate reflecting the cylindrical surface.9.1 cannot be applicable to the curved coordinates. 4to artificially introduces a force on the motion. 9. . we find that the force constant parameters in Table 9. When we denote a nearestneighbor bond as the dotted line in Fig. which would mix the force constant parameters with each other depending on the curvature and the bond length.e. Thus. However. in Fig.9. 9. This p h en o ~ en o ncan be treated by elasticity theory for a thin film.
17) and (b) correction of the force constants of 4.180 CHAPTER 9. the rotational motion appears to have a tangential outofplane motion in the plane defined by the dotted line and the nanotube axis. 9..9: The dependence of the twisting mode at k = 0 of a carbon nanotube on its cross section is shown. x Y Fig. On the other hand. Figure (a) illustrates the section of a plane perpendicular to the nanotube axis. 9. (9. (9. when we denote the bond ij by the thick line.18) and (9. 9. When we consider the interaction between the two atoms along the dotted line. PHONON MODES OF CARBON NANOTUBES Fig.19). When we consider the tangential outofplane mode for the ith site on the cylindrical surface as shown in Fig. which are given by Eqs.10: (a) Correction of the force constant #do. whose subtended angle around the tube . we have proposed the following approximation in which the force constants are scaled depending on their bond lengths. and &. To avoid the difficulty of the curved coordinates. and (b) illustrates a plane corresponding to an unrolled graphite sheet. which is given by Eq.10 (a)zthe motion is in the direction perpendicular to the cylindrical surface.
(9. the frequency of the twisting mode becomes very small (Iwl < cml)  *We could also consider other corrections of the force constant.10) armchair carbon nanotube./cos(cp/2). we conclude that 4..17).* The correction of Eq.10(a). and thus we do not adopt it. #ti are corrected by the following formulae. this correction diverges at 'p = R. When we calculate the motion using the tangential outofplane dto force constant for a given bond. 9. = #r and + 4. Here we scale the force constant #to by do= 4 t o + d t o (1 .Q) (1 .3. When the bond length is large. respectively. In this case.17) becomes relatively large with increasing bond length or increasing p.17) as an empirical correction for the force constant. such as r#~t. 9. the Component of the force constant in the direction perpendicular t o the cylindrical surface becomes 4 ~ o c o s ( ~ / Z )In order to obtain the same amplitude of the motion in . which reIates to the corresponding bond length becoming shorter than that in a twodimensional graphite plane. The difference between the two directions is the angle 912 which depends on the bond length. we add #bo(l cos(cp/2)) to #to. Thus this bond ~e ngth dependent correction is used to describe the v~brations perpendicular to the cylindrical surface. this direction as is obtained in the case of twodimensional graphite. A justification for the correction of Eq. Using the scaled force constants. cos(n/6 0) and sin(a/6 .cos (5. However. we calculate an improved version of the phonon dispersion relations for a (10. . this correction gives the same effect. (9. Since we consider only the horizontal component of the force by a rotation of 9/2 around the z axis.19) where n/64 is the angle of the bond from the horizontal zy plane [see Figs. (9.6 (a)].18) (9.. (9. (9. PHONON DISPERSION RELATIONS FOR NANOTUBES 181 axis is p as shown in Fig.as that of Eq. For small cp. but not so large as the origina~ force co n st~ n t.10 (b) and 9. the correction for the force constant becomes large. the tangential outofplane direction for that bond is defined to be perpendicular to that bond.17) is as follows.4) are the components to be corrected.cos (~)). Similarly. 4.9.cos () . the force constants of 4Sp.
lO) carbon nanotube is 17 cml. The observation of the Ramanactive modes. It is interesting to note that the lowest phonon mode with nonzero energy at k = 0 is an Ezg mode in which the cross section of the carbon nanotube is vibrating with the symmetries corresponding to xy and x 2 . 9.lO) armchair nanotube. The only mode where the correction is significant is the E2. Since this mode is a Ramanactive mode and its frequency is sensitive to the radius of the carbon nanotube. symmetry) shown in Fig.5(a). the corrections are generally small (less than 5 cml). Another important mode for experimental study is the Ramanactive low frequency breathing mode (Al. The calculated frequency of the E2.y2. mode which gives a large softening after this correction from 22 cm' to 17 cml. PHONON MODES OF CARBON NANOTUBES at k = 0. This mode frequency quickly decreases to 0 cm' with increasing radius. are discussed in the following chapter. As for the other modes. The frequency of the breathing mode appears at 165 cm' for the (10. the above arguments show the importance of investigating this mode experimentally. mode for the (10. .182 CHAPTER 9.
2 Raman or infrared active modes of carbon nanotubes Among the 6 N calculated phonon dispersion relations for carbon nanotubes whose unit cell contains 2N carbon atoms. x2 . Point group theory of the unit cell. and z ) for the infraredactive modes. zy. A review is given in Sect.2 of Raman scattering experiments on purified s i n g ~ ~ w a l i nanotubes and arrays of carbon nanotubes. 10. only a few modes are Raman or infrared (IR) active. yz and )z for the Ramanactive modes. As discussed in Chapter 9. 10.5. 10. Raman Spectra of Carbon Nanotubes The Ramanactive and infrareda. 3. z 2 .CHAPTER 10. The Raman and infrared(IR. or as a vector . 10.y 2 . called ropes.3. as specified by the symmetry of the phonon modes. To analyze the unique Raman spectra that are observed. Thus 6N4 optical phonons ' are considered in this section. predicts the number of Ramanactive modes and IRactive modes. 10.1. as discussed in Sect. y.ctive phonon modes of carbon nanotubes are described on the basis of group theoretical arguments in Sect. there are four acoustic modes including the rotation around the nanotube axis ( R z )at the I point. form (8. results €rom bond polarization theory are presented in Sect. Since only k vectors very close to k = 0 are coupled to the incident light because of the energymomentum conservation requirements for the photons and phonons. 10. we need only consider the symmetry of the nanotube zonecenter vibrations at the I? point (k = 0).)active modes correspond to modes whose irreducible representations transform as a quadratic form (z2 y2. The dependence of the Raman mode frequencies on the nanotube diameter is discussed in Sect.4 and the dependence of the Raman mode ~ntensities nanotube orientatioii is discussed in on Sect. The relationship between an + 183 .6.
When we consider the nanotube axis to be in the t direction.R.YP (RX. ( +Y 2 7 W zIR.Y2lR (x2 6 6 Total 6N4 16(6) 1 5 0 Numbers without and with parentheses denote the numbers of Raman and IR active modes. E2 E2 . The number of opticallyactive modes is calculated by the decomposition of the reducible representation of the vibration. groups. An eigenfiinction can be identified with an irreducible representation by applying a projection operator for the irreducible representation of the group to the phonon normal modes [197]. the eigenfunction belongs to the corresponding irreducible representation.1. respectively (see Section 3. and therefore have A1 or A symmetry in the Dn or C . CNfn Achiral Chid " . The other Ramanactive modes belong to the El and E2 symmetry types. and t transforms according to A2 ( A ) symmetry. we can directly assign the symmetries of the Ramanactive modes and IRactive modes among the 6 N .Y2r . Each type of nanotube is classified by its symmetry. If the projected eigenfunction is not zero.6). which is given by the direct + . denote Ramanactive and infraredactive modes. respectively.) ("7y)IR } Az AI Az A A (2j. Basis functions D. RAMAN SPECTRA OF CARBON NANOTUBES Table 10. 9 21 2j A1 2j+1 R. If we know the irreducible representation of the calculated eigenfunctions of the phonon modes.1 are listed the basis functions for the irreducible representations of the carbon nanotubes and the number of Ramanactive modes for each irreducible representation. the Raman modes whose vibrational amplitudes transform as t 2or z 2 y2 are invariant under any operation of the group.4 phonon modes. In Table 10. Pib. The superscripts and I R .m) (1) 6(5) 4 (4) El El EI 5(5) E 2 irreducible representation and its basis function is given in the character tables. as shown in Table 10. ( x z .1: Basis Functions for Point Groups Dnd and Numbers of Raman and IR Active modes.2j) 4 (0) 4(7) 8 16(7) others 3 (n. the basis functions 2 and y are partners of a twofold degenerate mode with El ( E ) symmetry. In the case of the IRactive modes. The numbers of the Ramanactive and IRactive modes for the solid can be predicted by group theory once the lattice structure and its symmetry are specified.184 CHAPTER 10. respectively.
using the ort ~ o g o ~ i relations between the characters of the irreducible re ~ r e s ~ n ta tjo n s .6. ~~ty the number of times an irreducible representation is contained in rvib the is number of phonon modes which belong to that irreducible representation. we symmetry types of the Raman (Alg. R tIn Eq. * The point group symmetries of armchair C h = ( n . the symbols are as follows: transiational fE A ) . l . E l ) modes. The representations which correspond to x$ y. If j is odd [such as for ( n .s. respectively. we can easily find the number of Raman and IR modes.1 for the groups of nanotubes which are discussed in Section 3.1 RAMAN OR INFRARED ACTIVE MODES OF NANOTUBES 185 product of the two representations of the group as foilows (10.: R. If the a1 to t r a n ~ l a t i o ~(Elu: z.4. l ) g +8E(jl)u + *The symmetries are for achiral nanotubes.) modes.s. m )= (6. 4 +~ ~ + 2B1g 242a (10.8. From the as character Tables 3. n ) and zigzag C = (n.5 and 3. When we into decompose rvib the irreducible representations of the group. Raman (A. E l . and the irreducible representations which belong t o the vector components 2. and the symmet~y chiral nanotubes is the of nonsymmorphic kbelian group CN. For chiral nanotubes.t respectively. which is discussed in Sect. rotational ( A ) .: z) and r ~ t a . . t i o ~(Az.2). the representations of the atomic sites are.y. the 4 and 8 are interchanged in the last two terms in Eq.6. y. (10.) motion be~ong the al and IR (Az. + 8E2$ +4Ezu + * * * + 4 E ( j . depending h on whether n =odd or n =even.O) nanotubes are either Dnd or D n h . Since we know which irreducible representations correspond to the Ramanactive and IRactive modes. z. El. E2) and I ( A . and rz.. r$y = 4Aig + 2A1.1) where I'a. 3. are listed in Table 10.2) we assume that j is even. + 4BzU + 4E1. A2.10. z .2) + 2B2. + 8E1.6)].y. we get the decomposition of rvib follows 11981: for armchair nanotubes (even n = 2 j with Dnh symmetry)t a) . given by are the number of atoms in the unit cell that remain invariant under an operation of the group. 3. The characters for I'a. + 4 $431. (10. for the equivalence transformation. E l g . subtract the number of those modes from the optically active modes in compiling Table l O .
The difference between Dzj and Dzj+l for armchair nanotubes comes from the different numbers of El and Ez modes in the decomposition of rvib in Eqs. refer t o the numbers of Raman and IRactive modes. only armchair nanotubes with even number indexes (2j. (10.1 we see that the numbers of Raman and infraredactive modes for a carbon nanotube do not depend much on the nanotube diameter and chirality. From Table 10. Among achiral nanotubes.O). because of the existence of an inversion center.3) For armchair and zigzag nanotubes (odd n = 2 j rvib zj+l + 1 with D. Raman and I R active + + t The g and u come from the traditional notation of the German words 'gerade' and 'ungerade'. 2j) have a different numbers of Raman and IR modes from others such as armchair nanotubes with odd number indexes ( 2 j 1 .d 3A2. though the total number of phonon modes 6 N .186 CHAPTER 10.4 is very different for different chiralities. RAMAN SPECTRA OF CARBON NANOTUBES (10.1 the numbers of Raman and IR active modes for achiral and chiral nanotubes in which the numbers without and with parentheses.2) and (10. + 6E2g + 6Ezu + + 6Ejg + 6Eju (10. 2 j 1) and zigzag nanotubes (n. symmetry): = 3Alg I.4) For chiral nanotubes: We list in Table 10.3A1. Group theory selection rules indicate that there are 15 or 16 Ramanactive modes and 6 to 9 IRactive modes for a singlewall carbon nanotube. Since the basis functions of achiralnanotubes consist of even ( 9 ) and odd ( u ) t functions. .4). respectively. +6E1g * ' ' 3Azg + 6E1. respectively.
the (10.4. we have only six or seven intense Ramanactive modes for any nanotube chirality.4 nm. however. though similar results were obtained on singlewall nanotubes synthesized by the carbon arc method 1521. the diameter range is 1. In fact. 10. atomic vibrations prevent the for . while thinner nanotubes with diameters of 0.01. This situation may be explained by the probability for generating a pentagon. modes with A and El symmetry are both Raman and IRactive. especially the growth temperature.lO) armchair nanotube is the dominant species in the rope. Even when the same catalysts are used. when 1. the probability of closing a carbon pentagonal ring increases. a higher growth temperature gives a larger diameter. At a higher temperature.2) [55. because of the lack of an inversion center. Most of the Raman studies on singlewall carbon nanotubes were made on nanotubes synthesized by the laser vaporization method [55] with transition metal catalysts. When the temperature is lowered. in general. In both of these synthesis methods.200]. However. 5.83. However for chiral nanotubes. A phonon mode can be Raman and IR active simultaneously in the lower symmetry chiral nanotubes.2 weight % of Ni/Co catalyst is used in the sample synthesis at a temperature of 1150OC in 500 torr Ar.99. the singlewall carbon nanotubes grow in a triangular lattice t o form a bundle or ‘rope’ containing 1050 nanotubes (see Sect. the Raman spectra also have similar shapes. 10. and thus the caps that are generated tend to be smaller.81. 10.3. as shown in Sect. the Raman samples have a narrow distribution of diameters and chiralities.199]. which depend sensitively on the catalysts that are used in the synthesis and the growth conditions. as shown by the calculations in Sect.modes can be found for several different irreducible representat~ons. Even though group theory may indicate that a particular mode is Ramanactive. in these cases the intense Raman modes are generally weak IR modes and vice versa. Under some synthesis conditions.4% Rh/Pd catalyst with growth at llOO°C [99]. For example. Since similar eigenfunctions give similar Raman intensities for any kind of nanotube. However.2 Raman experiments on singlewall nanotubes This section mainly describes Raman experiments on singlewall carbon nanotubes [52.0 nm are obtained in the case of a 2. this mode may nevertheless have a small Raman cross section.
1 shows Raman spectra for the singlewall nanotube rope using a laser excitation wavelength of 514. Between 1550 and 1600 cm'. the experiments show a few intense lines and several weaker lines. The strong lines between 1550 and 1600 cm' may be assigned t o the . and the lower panels show the calculated intensities for armchair nanotubes (n. n ) . 10. n = 8 t o 11.1 [83]. 10. N mation of relatively unstable pentagonal rings. n ) nanotubes. n = 8 to 11. Ramanactive modes [83]. respectively. a illustrated in Fig. compared with hexagonal rings.5 nm.188 CHAPTER 10. The four bottom panels are the calculated Raman spectra for armchair ( n . RAMAN SPECTRA OF CARBON NANOTUBES Fig. which correspond to the graphite E2$ optic mode a t 1582 cm' which has been extensively studied in HOPG (highly oriented pyrolytic graphite) [9.1: Raman spectra (top) of the rope of single wall carbon nanotubes taken with 514. 10. so the lower growth temperatures favor the growth of smaller diameter tubes. The features in the spectrum denoted by the symbol "*" are assigned to secondorder Raman scattering. The arrows in the panels indicate the positions of the remaining weak. s The top panel of Fig. two strong features are observed at 1567 cm' and 1593 cm'. Among the 15 or 16 Ramanallowed zonecenter modes.5 nm excitation at 2W/cm2.201].
[83] assigned the two strong modes of 1567 cm' and 1593 cml to the E2. respectively [202].2. and Elg or A l . In Fig. The dashed lines are theoretical LO and TO energy dispersion curves for graphite along I'M as a function of q and q / 2 for n = 1 and n = 2 (first harmonic vibrat~on). The Raman frequencies in this high frequency region do not vary much with carbon nanotube diameter. 10. E l g . (8.1.55 nm). Ezg and Al. respectively. (b) Co ( P = 0. 10. respectively. the observed Raman spectral frequencies are shown for three singlewall nanotube samples prepared with different catalysts and under different growth conditions yielding nanotubes with different mean diameters (radii) and different distribu . 10.65 nm).9) tubes.2: Plot of the observed Raman frequencies for several different singlewall carbon nanotube samples. modes in carbon nanotubes with different diameters. Rao et al. ent mean nanotube radii P : (a) Fe/Ni ( = 0. Solid dots and the symbol 'T' correspond to the observed frequencies of the peaks and shoulders in the Raman spectra.8). The Raman frequencies in the range 15501600 cml can be understood by zonefolding of the graphite phonon dispersion relations [202]. (9. as shown in the lower panels of Fig.0 nm).Fig. prepared with different catalysts under different growth conditions yielding differ. and (c) La (r = 1.
TO (n = l ) . It is important to note that the Raman intensity for graphite in the 13001600 cm' region is sensitive t o sample quality. and Ez.l(a) [see Fig. of (360 has a frequency of 497. the Raman spectra may change if we change the frequency of the excitation laser. Because of the strong dependence of the frequency of the A l .1 may come from a symmetrylowering effect. these El. bending of the nanotube. breathing mode is found in Fig. breathing mode on nanotube diameter (see Sect. Figure 10. However. Generally the intensity of the Ezg modes of graphitic materials is sharp and strong when the sample is highly crystalline and defect free. Even for a given sample.M direction corresponds t o the wave vector along the equator of the nanotubes. respectively. due to defects or nanotube caps. it is difficult t o observe Raman lines in the very low frequency region. At 186 cml. Thus LO (n = l ) . Raman modes. while disordered graphites and carbons show a broad feature around 1350 cm' [9. respectively. but their intensities are expected t o be lower than that for the Al.5(a) on the right]. and TO ( n = 2) correspond to the Al. mode. (b) Co ( T = 0.65 nm).201. lO. and the presence of carbon nanoparticles and amorphous carbon. where the background Rayleigh scattering is very strong.2 shows a clear relationship between 1 / and q on the ~ zonefolded phonon energy dispersion curves.3). and E2.lO) nanotubes.5 cml [198]. the calcvlations predict nanotubespecific El. RAMAN SPECTRA OF CARBON NANOTUBES tions of diameters (radii). and Ez. modes around 116 cm' and 377 cml. mode can also be clearly seen in fullerenes. . as shown in the lower panels of Fig. 9.1.190 CHAPTER 10. the A1.55 nm). El. In the very low frequency region below 30 cm'. which will be explained in the theoretical analysis in Sect. breathing mode can be used as a marker for assigning the approximate diameter of the carbon nanotube.203.204]. The 1347 cm' signal seen in Fig. In armchair nanotuhes.4. 10. The dashed lines are theoretical LO and TO energy dispersion curves in graphite along I?M as a function of wavevector q and q/2 in units of lo9 cm' for n = 1 and n = 2 (first harmonic vibration). 10. modes are important since they also show a diameter dependence of their mode frequencies. the frequency of the A1. Specifically the catalysts and resulting average radii are: (a) Fe/Ni ( T = 0.0 nm). a strong Al. However. The radial breathing A1..* In the low frequency region. When the excitation energy is close to an energy 'For example. and (c) La ( T = 1. a strong low frequency Ramanactive Ezg mode is expected. for (10. the r . 10. 10.
a I/@ singularity is expected for the energy dependence of the onedimensional density of states (see Fig. R A M A N EXPERIMENTS O N SINGLE. thereby enhancing the Raman signal through the electronphonon coupling process. 4. Under resonant conditions. the Raman intensity is enhanced.3: Room temperature Raman spectra for purified singlewall carbon nanotubes excited at five different laser frequencies. the Raman modes that are preferentially enhanced shift to higher frequencies.7).2. and these singularities are known as vanHove singularities. The 1/fi singularities for the 1D density of states results in a much stronger resonant Raman effect than would be . In Fig. of high “optical” absorption. the density of states of the 1~ band becomes singular by folding the twodimensional energy bands of the graphene layer into the onedimensional bands of the carbon nanotube. as in a carbon nanotube. and the laser frequency matches a peak in the optical absorption.2.10. showing the resonant enhancement of the Raman intensity associated with the vanHove singularities in the nanotube density of states [83]. since the resonance effect is most pronounced when the joint density of states of the carbon 1~ band is large. 10. and this effect is known as the resonant Raman effect.WALL NANOTUBES 191 Fig.3 are shown Raman spectra obtained with different laser excitation frequencies. Each trace is labeled by the wavelength and power level of the laser light. more light can be absorbed. 10. When the laser frequency increases. As discussed in the 5 4. For every onedimensional band edge.
since the phonon frequencies for the low frequency normal modes increases with decreasing n. respectively. . The Raman intensity for h/ atoms in the unit cell is calculated by the empirical bond polarizability model [205. (10. RAMAN SPECTRA OF CARBON NANOTUBES observed for a 2D graphene sheet or for 3D crystalline graphite. Here W L and w s are the incident and scattered light frequencies.The a and .192 CHAPTER 10. x .3 Bond Polarizability Theory of Raman Intensity for Carbon Nanotubes In this section we discuss the nonresonant bond polarization theory for calculating the Raman intensity. mode provides the value of the nanotube diameter that is in resonance electronically. 10. (10. The Raman resonance condition thus selects the particular carbon nanotube ( n . while ( n ( w f ) = l/(exp(hwf/hBT)1) is the phonon occupation number at temperature T. w j is the ) frequency of the fth normal phonon mode. which is also useful for the interpretation of the Raman spectra. r] and r]' are the corresponding unit vectors for the polarization of the light.7) . z . the resonant Raman effect may be seen in different nanotubes for different laser excitation frequencies. which is given by [205]. When we consider only armchair nanotubes ( n . and Pap. The observed phonon frequency of the low frequency A1.n ) . Clearly the energy separation of these singularities in the 1D density of states increases as the number of energy bands decreases.6) denote Cartesian components of the vector or tensor. Thus the resonance effect is a quantum effect that can be understood in terms of both the electronic and phonon dispersion relations of the nanotubes.206].B subscripts in Eq.m) which has a singularity in its electronic density of states at the laser frequency. g . Since nominal singlewall carbon nanotube samples consist of nanotubes with different diameters and chiralities.j is the derivative of the electronic polarization tensor for the fth normal mode. the energy separation between the vanHove singularities becomes large with decreasing n.
The term x.(L.7) is approximated by a sum over the bond polarization contributions as follows Pap = 1 [ c l.B ) R(&. Both translational and rotational acoustic modes are included in f for simplicity.3 BOND P O ~ A ~ Z A ~ r ~ r T Y OF AN ~ ~ T E ~ S ~193 Y THEORY T where Pap is the electronic polarization. (10. B ) are the a component and the length of R(&. ) . respectively. B ) + .(. When we denote the bond vector without the displacements of the two atoms of the bond as Ro(4.  $6Qd)] (10.B ) =&(jJ? (10. for the t t h atom.B ) . B ) and R(4. Here we assumed that q ( B ) and a l ( B ) are functions of only the length R(L. then R(t. respectively.B ) = &(&. and the derivative is performed with respect to the yth Cartesian displacement. the acoustic modes do not contribute t o the Raman in tensity. (10. and R ( t .11) and . (10. However. and aql(B) and a ~ ( 3 are the static molecular B ) polarizabilities for the bond B in the directions parallel and perpendicular t o the bond.9) while the derivative on u..B { a l p ) + W B ) } 6.B ) can be defined by R(4.(tlf) is the y component of the unit vectors of the f t h normal modes of the t t h atom. in Eq.10) €3 dR(t. B> Here the summation is taken over the bonds connected to the 1th atom and we use the following relations: (10.7) is expressed by the derivative on R(t. u.Bf is the corresponding vector from the 4th atom to the neighbor atom l' specified by B . The term Pap in Eq.B ) as follows: a d d R ( t .B ) .el) .10.@ 3 + {9l(B) .(l).a(e).Q ( B ) ) ( RU(eJ B)Rp(e8 B.B)2 where B denotes a bond which is connected to the Gth atom in the unit cell. The quantities R.8) R(t.
and making use of Eqs. we have terms .2 do not converge well for carbon materials. RAMAN SPECTRA OF CARBON NANOTUBES When we calculate Pap. . and aR("B) in 8% .After some calculation au. because of the different results that have been reported by various groups. Although the calculated values are within a reasonable range for carbon materials.j in Eq. I ( B ) . (10. The values of a l ~ ( B ~.10)' (10. Then we fit the values so as to reproduce the Raman signal for randomly oriented nanotubes. (10. we start by interpolating between the values for the polarizability parameters for single (1. (10. (el .194 CHAPTER 10. In order to obtain values for the parameters for carbon nanotubes. the values for the polarizability parameters listed in Table 10.40di) carbon bonds in c 6 0 and related materials [205.46A) and double (1. and these values are listed for carbon nanotubes in Table 10.2.(l.7). da dR.13) where all(B)and a y ( B ) are the radial derivatives of q ( B ) and a l ( B ) .207].B) du.that is ) all(B)and aL(B) are given empirrespectively.11) and (10:12). 7 du. we obtain an explicit form for Pap.!. ically as a function of the bond length between two carbon atoms or between carbonhydrogen atoms.
6) for the Bose distribution function for phonons.016 4.07 0. Snoke and M.96 4.40) SWCNC) C = C (1. Saito et al.28 f 0.09 1.60 2.00 f0.50 2. The lowest Ez9 mode is found to be most sensitive to the parameter a11. ' Here we consider two possible geometries for the polarization of the light: the VV . (10.60 If: 0. ' Molecule Bond Lengths (YI~ 2 a ~ ( ~ 1 1 Q L +  + CH4") C .20 0. Cardona [207].36 1. [208]. and the polarization parameters are obtained using bond polarization theory [205]. the relative intensities for the Raman modes are not so sensitive to small changes in the values of the bond polarization parameters except for the lowest E29 mode.50) CZH4&) C = C (1.30 f 0. Richter et al. The Raman intensity is calculated using the eigenvectors for the vibrational modes.4 Raman Spectra of Nanotubes with Random Orientations The Raman intensities for the various Ramanactive modes in carbon nanotubes are Calculated at a phonon temperature of 300 K which appears in the formula of Eq.04 cf21 d21  c60b) c . (Y' 20'1 Q a.32) [A1 1~33 [k31 1. Guha et al.7 2.70 5. R. The eigenfunctions for the various vibrational modes are calcufated numerically at the I point (k = 0). that the polarizability parameters of carbon are similar for a variety of carbon materials. E. [205].890 C = C (1.28 0.c (1.46) C = C (1. I t is known. obtained by solving the dynamical matrix.42) Ceoa) 3.30 f 0.28 f 0. however. 10. are used for calculating appro xi mat^ Raman intensities.35 f 0.40) C . (unpublished data which is used in their work[83]).28 1.40 1.46) 1.Table 10.01 7.2: Bond lengths and Raman polarizability parameters for singlewall carbon nanotubes and for various carbonrelated molecules.55 f 0.30 2.K (1. W.13 6.20 4.944 2. D.47 4 .C (1.32 It 0.50 f 0.31 2.a ~ Thus the fitted values .50 5. Furthermore.O ~ ~ ~ '1 S.40 f 0.30 5.09) C ~ H G ~ )c c (1.42) SWCNd) C = C (1.20 0.65 1.
196 CHAPTER LO. . This anisotropy is due to the low dimensionality of carbon nanotubes. The Raman intensity is averaged over the sample orientation of the nanotube axis relative to the Poynting vector of the light. Thus Fig. The degenerate vibrations of the E modes. whose eigenfunctions 500 cml. We present the sample orientation dependence of the Raman spectra of a (10.4.4. 10. When we compare the VV with the V H polariz~tions(see Fig. Since we consider randomlyoriented nanotubes in this section. In Fig. Generally the cross section for Raman scettering is a function of the scattered angle of the light. modes are not suppressed as much.66A. we show the calculated Raman intensities for the (10. while they are perpend~cu~ar each to other in the V H direction. However. rU. while the lower frequency El. (17. respectively. and thus the calculated results cannot distin~uish between forward and backward scattering of the light. 10. we need the directions of V and H for calculating the Raman intensity of a nanotube.lO) armchair.1 Lower ~ r ~ ~ R ~ e~ Spectra ~ n c ~ ~ n Here we discuss the Raman intensity for the lower frequency modes below The Raman intensity is normalized for each nanotube to a maximum intensity ( A l . and middle (500 cmI 5 w 5 1500 cml) frequency ranges. On the other hand. Then we discuss the phonon density of states for the Ramanactive modes which depend strongly on the chirality.s) chiral nanotubes. and 6. Most importantly. in the V V configuration) of unity. the Raman intensity shows anisotropy.47A and are close to one another. whose radii are. 10. We divide the discussion into the following three frequency regions: the lower (w _< 500 cm').7S& 6. in which we rotate the nanotube axis by fixing the polarization vectors. mode at 165 em' is suppressed in the VH configuration. weighted by the solid angle for that direction. we do not need t o mention the direction of the polarization vector for the V V and V W configurations. RAMAN SPECTRA OF CARBON NANOTUBES and V H configurations.4). 6.4 is the calculated result for r~domIyorientednanotubes. in which the average is calculated by summing over many ( w 50) directions. the A l . higher (w 2 1500 cml). the incident and the scattered po~arizationsare parallel to each other. In the VV configuration.O) zigzag and (11.lO) nanotube in the next section. and E2. the formulae for the bond polarization theory consider only Smattered waves [205].
(b) (17. RAMAN SPECTRA WITH RANDOM ORIENTATIONS 197 vv . and (c) (11. 1591 400 600 1200 1600 Raman Shift [ cm’1 Fig. From the figure we see that the relative intensities for the same mode between the V V and VII polarizations are different but are on the same order for all the E modes.O) zigzag.4: The polarization dependence of the Raman scattering intensityfor (a) (10. 10. VH .lO) armchair. 4 A* 1687 1581 o 400 11 388 400 800 1200 1600 % 1581 BOO 1200 woo 1580 1571 400 600 1200 1600 0 400 BOO 1200 1600 I  1% E. The left column is for the V V scattering configuration and the right column is for the VH configuration.8) ehiral nanotubes and the tube radius are given on the right.4. are orthogonal to each other. When we compare the lower frequencies of these Raman modes for nan . are relevant to V N signals. €4.10.
m) in the range (8 5 n 5 10. mode a t 1587 cm' does not show a suppression between the V V and V H geometries. is approximately quadratic and may reflect the effect of which curvature on the nanotube. the frequencies are inversely proportional to r making only a small deviation from the predictions of Fig.5 we give the calculated mode frequencies for the lower frequency Ramanactive modes on a loglog plot as a function of the carbon nanotube radius r for ( n . we do not see a strong dependence on P . respectively. As for the lowest E2.4.5 clearly shows straight line dependences for all four Raman modes. with vaiues of w ( 10. modes exist in a similar frequency region. we conclude that.15) should be useful to experimentalists in interpreting their spectra. In Fig. 10. It is the noted that the El. the frequency w z S ( r ) has a dependence of r1~95f0~03.0017f0. the experimental Raman spectra between 100 to 300 cml are dominated by the A l . and A1. 1 0 ) are.=6. since the frequencies of the higher frequency optical modes are more sensitively determined by the local movements of the atoms. the frequency and radius of the (10. 1. RAMAN SPECTRA OF CARBON NANOTUBES otubes. However.3.and r ~ 1 0 . modes depend on the orientation of the nanotube axis. 0 5 m 5 n). which is relevant t o the Raman active E2. since the intensity of the El. In the next section we will see that the A1.1 and 10.lO) armchair l~) nanotube. thus indicating a power dependence of u ( r ) on r. As for the higher frequency Raman modes. This fact shows that . mode. except for the lowest E2.0007 1 ( 10.10)= 165 cm. which is consistent with the fact that the energy gap of a semiconducting nanotube and the strain energy depend only on the nanotube radius and not on the chiral angle B [81. the frequency shifts systematically with increasing diameter. mode that is valid in the region 3hi 5 r 5 7A 4) = q l 0 . S o ) .2 Higher Frequency Raman Modes It is interesting that the higher frequency A1.10) and ~ ( 1 0 .209]. mode. This dependence is closely related to the circumferential length of the nanotube. From the slopes of ~ ( rfor this range of ) r . The fitted power law for the A l . Figure 10. 10. No chirality dependence is found for the mode frequencies for these modes. mode of graphite.?85& respectively. [+ y(lo. mode as shown in Figs. 10. mode.198 CHAPTER 10.5. Here w(10. modes is not as strong as that for the Al. 10.
mode the A and B atoms move in the same way (inphase). because of the relation of these modes to the Eag mode of graphite.6 (e) to ( g ) .1000 R 9 fj 100 U 3 0 0 .6 (e) to (g) are similar to the motion of the Ramanactive E2. It is reasonable that the outofphase motions of the higher frequency Raman modes of a nanotube have a large Raman intensity.6 (a) to (d) show inphase motion. 10. 10. mode is different from the polarization vector. 10. the lattice can be split into two sublattices consisting A and B atoms.which corresponds t o C=C bond stretching motions for one of the three nearest neighbor bonds in the unit cell. The motions shown in Fig. In the nanotube. In the higher frequency A l . mode of graphite at 1582 C M .6 we show the normal mode disp~acements seven Raman modes for a (lO . When we see the motion of the higher or the lower Ramanactive modes of a nan . In Fig. 10. while in the lower frequency A l .1 rIAl 10 Fig. The outofphase motions observed in Fig. It is clear from Fig. that the modes are outofphase between nearest neighbor carbon atoms. lO } for nanotube which have a relatively large intensity.6 are independent of the chirality. 10.5: Loglog plot of the lower Raman mode frequencies as a function of carbon nanotube radius. a V H signal can be expected when the vibration of the A1. while the modes of Fig.~ . 10. the A and B atom moves in opposite directions (outofphase) in the unit cell. mode. Thus this motion is an outofphase motion.
respectively. respectively [see Fig. ~~A~ ~ SPECTRA OF CARBON N A ~ O ~ U B ~ S ~ T ~ A].6: The calculated Raman mode atomic displacements. We show the displacements for only one of the two modes in the doubly degenerate El. El9 and E2. modes are functions with zero. 1. otube.lO) nanotube modes which show strong Raman intensity. and . the envelope functions for the Al. and four nodes around the tube zaxis. frequencies. 165cm' Ezs 368cmI El. 1591cm' Fig. The symmetry and the frequencies for these modes are almost independent of the chirality of the nanotube. 1585cm' AI.200 G ~ A 10. we can consider an envelope function for the amplitude of the vibration. modes. and symmetries for those (l0. ( e ) . For example.6 (f).587~111' E2. and Ez. multiplying it by the abovementioned outofphase or inphase motions. two.. We can say that the envelope function should satisfy the symmetry for the Ramanactive modes among the many phonon modes. 10. 10.
4. 10. When we investigate the vibration of the higher frequency A l . respectively. once purified aligned samples become available. We can say within the discussion of the envelope function that we see a homogeneous elastic cylinder. in C60t since all 60 atoms are equivalent.5. no carbon atom can move in an outofphase direction around the C axes for either of the two A l . 10. When we focus our attention on armchair nanotubes. and (a) for inphase motion]. In . modes. The Raman experiments on singlewall Raman modes around 12001~00 nanotubes show weak features which have been assigned to armchair modes {83].9 Medium Frequency Raman Modes It could be very interesting to discuss the Raman frequency in the intermediate frequency region where the frequency may be the most chirality dependent [210]. show almost no intensity for the ~ n t e r m e d ~ a t ~ em'. however. RAMAN SPECTRA WITH RANDOM ORIENTATIONS 20 1 fg) for outofphase motion. However. lo. as shown in discussing the angular dependence of the Raman int~nsities. the vibration corresponds to the folded vibration of one of the higher Ez9 modes of graphite. Although these higher frequency modes are difficult to distinguished from one another because of their similar frequencies. and (c). This is the reason why we get similar Raman spectra for different chirality nanotubes. so that both modes show similar s polarization behavior to each other [198].4. in the cyli~drical geometry. The calculated results.2. mode at 1587 cml. Thus. modes are different for armchair and zigzag nanotubes. which is reviewed in Sect.10. we may get a result that is not so polarization sensitive. Thus the curvature of the nanotube affects the frequency of these mode. Thus the envelope functions with a given symmetry are similar to one another for nanot~ubes with any (n. From the calculation we cannot explain why these low intensity peaks appears. which is understood by the zonefolding method and is discussed in Sect. The peaks might come from a lowering of the symmetry of the nanotube. it will be possible to identify the different modes experimentally. On the other hand. rn) values. the directions of the outofphase motions of the A1. In fact the C=C bondstretching motions can be seen in the horizontally and the vertically vibrating C=C bonds for armchair and zigzag nanotube. the higher Raman frequencies depend on the radius of the nanotube l / r via the wave vector q around the equatorial direction 12021. (b).
broad Raman peaks around the 1347 cm'l are observed experimentally [83. 11. Because of the large number of states for the (11.O) nanotubes have 40 and 68 carbon atoms in their 1D unit cells. the chirality dependence of the Raman spectra is not clearly observed except for the frequency. When we caIcuIate the Raman intensity for a nanotube with open ends. Note that if the nanotube is deformed to a 2 x 2 structure for any reason. However when we consider the absoIute Raman intensity. the amount of disorder in carbon fibers [212] and in graphite nanoclusters [214]. the (10. For example. which implies a high phonon density of states * f216]. 10. the (11. The three nanotubes in Fig. the M point ' phonon can be folded to the I point and the folded modes becomes Ramanactive A .8) nanotube has 364 carbon atoms in its unit cell. in small aromatic molecules. it is i m p o r t ~ n to consider also the effect of the phonon t density of states. this situation may occur only in the case of intercalated nanotubes [135]. However. bending of the nanotube and the other possible defects are likely to turn on the Raman intensity for this Mpoint mode. Moreover.4 have almost the same diameters.lO) and (17. As shown in Fig. ~ AN SPECTRA OF CARBON ~ T ~ A ~ O T U fact. The relative intensity of the broad peak around 1350 cml to the strong EQ mode at 1582 cml is sensitive to the lowering of the crystal symmetry of graphite [211.4. since a Peierls instability is unlikely. so that these M point phonon modes becomes Raman active [217] and have a large intensity [214.202 C ~ A P 10. However.135]. However the number of carbon atoms per 1D unit cell is very different. These peaks are known to be associated with symmetrylowering effects in disordered graphite [211] and carbon fibers [212] for which a broad peak is observed around 1350 cml. it *See Fig. The observed Raman signal in Fig. 10. In this case we can see a flat band appearing below 1300 c m 1 . the intermediate frequency Raman modes have a small intensity relative to the strong peaks in the higher and the lower frequency regions. modes.1 in the intermediate frequency region can be relevant to the finite length of a nanotube. The nonzonecenter phonon mode a t 1365 cm' has a flat energy dispersion around the M point in the Brillouin zone of graphite.218]. respectively. 10. as is discussed in Sect. 9. the frequency and the normal mode displacements are modified by the finite size effect. The amount of disorder in these systems can be controlled by the heat treatment temperature THTor by ion implantation 12151.3.213]. Thus some symmetrylowering effects such as the effect of the end caps.s) nanotube.4 for 2D graphite.
8) nanotube within the reso~ution the STM because the singu~arities of occur so close to one another. ( i = 1 . at for the V V configuration.y.7 we see that the Raman intensity for the Al. Thus the resonant Raman effect for chiral nanotubes should also be re~ative~yi ~ c u t~ tobserve compared with the case of d o achiral nanotubes. mode a t 1587 cml as a function of 81 has a m a x i ~ u m 81 = 0.7. However since the symmetry of these modes are d i ~ e ~ e n t . while the El. 3 ) as shown in Fig. while 83 is the angle of the nanotube axis around the z axis from the x to the y axis. In Fig. respectively for the V and H polarizations. and these three rotations are denoted by Bi. As a result. mode at 1.7. In Fig. we show the relative Raman intensities for the (10.lO) armchair nanotube for the VV and V H configurations for the various Raman modes of a (10.should be difficult to observe the singularities in the electronic density of states in a (11.lO) carbon nanotube as a function of &. 10.2. Then we consider the effect of rotating the nanotube axis from the z axis. which corresponds to 82 = 83 = 0. 10. Even for the VV configuration. the rotations by 81 and 42 are not equivalent to each other in the case of the (10. In Fig.4.o f ~ p h ~ e mode of graphite.7.(i = 1 . 2 . 2 . Here 81.lO) armchair nanotube has a tenfold symmetry axis ( C ~which is not compatible with the Cartesian O) axes. three rotations of the nanotube axis are possible for the VV and the V H ~onfiguratjons. 81 and 42 are different from each other for the V H configuration. Since we put the horizontal polarization vector along the x axis. 10. z axes so that we put a carbon atom along the 2 axis when 83 = 0'.585 cml has a maximum . In this geometry. since the (10. 10. Here we define the x. 3 ) .lO) armchair nanotube as a function of sample orientation. 10. respectively. we see that the high frequency Raman modes originate from the o u t . mode can be separated from one these another by exploiting special experimental geometry conditions.5 Sample Orientation Dependence In Sect. we show the intensities of the various Ramanactive modes for the (10. Here we fix the polarization vectors to lie along the z and x axes. 10. the frequencies of the Raman Ezs modes in the high frequency region are close to one another. It would be interesting to be able to assign the chirality of a nanotube from the Raman spectra by using many laser excitation frequencies.lO) armchair nanotube. and 82 are the angles of the nanotube axis from the z axis to the x and y axes.
where V and H correspond to the light polarization in the direction of the z and z axes. mode at 1591 cml becomes reversed for the VV configuration relative to the V H configuration. 93 is the corresponding angle around the z axis from the z t o the y axes. When 81 increases t o 45O. the relationship between the intensities of the A1. Thus. There is also an E2g mode at 1591 cm' at . respectively. we can distinguish these two closelying modes from each other experimentally if we have an axially aligned sample. The left and right hand figures correspond t o the VV and V H polarizations.lO) armchair nanotube.204 CHAPTER 10. mode at 1587 cm' and of the E2. el = 45'. 61. and 62 are angles of the nanotube axis from the z axis toward the z and y axes. respectively.7: The polarization dependence of the Raman intensities as a function of the orientation of the nanotube axis for a (10. 10. RAMAN SPECTRA OF CARBON NANOTUBES vv VH EJ591 0 30 60 E$68 80 Fig.
we can see the difference between these EzS modes. and this envelope function is sensitive only to the homogeneous elastic cylinder. The symmetry analysis may be difficult even if we can get an aligned nanotube sample for which the direction of the carbon atoms is ordered. as shown in Fig. Thus an averaged angular dependence for 01 and 02 in the V V geometry is expected for a general aligned sample. In summary. the intensity of the Al. we expect to see a large c h i d dependence of the phonon density of states which is reflected in the absolute intensity. modes at 368 and 1591 cm'l have almost the same intensity in the VV configuration.9) armchair nanotube is of special interest. The Raman intensity is explained by the envelope function of the amplitude of the vibration. The sample orientation dependence of the Raman intensity shows that not only the symmetry but also the direction of the displacements give rise to their own angular dependence. since the Al. As for the other Ramanactive modes. 10. since the E2. therefore. we 1 has a m ~ i m u m can also distinguish them by their frequencies. In Fig. detailed in angledependent selection rules can be expected.10. zigzag. Thus we can see only a single line in the VV configuration of the figure. Even in this case. it is clear from the figure that the angular dependence with respect t o 81 and 6 2 is different for the V H geometry since the horizontal polarization is taken in the x direction. and this angular dependence can be used for distinguishing between the symmetry assignments for the higher frequency Raman . for (9. The (9. the Raman intensity of armchair. SAMPLE ORIENTATION DEPENDENCE 205 which can be distinguished from the Al. N o significant dependence on chiral angle is found for the Raman spectra. However in the 8 2 dependence of the V H configuration. and chiral nanotubes is discussed in Sects. the two Ez. 10. and El. mode at 165 cml has a different angular dependence from that of the A l . For example. modes.9) n an o tu b ~ s a trjanguiar lattice.lO) nanotube does not satisfy the symmetry of the trian~u l a r nanotube lattice.5 as a function of their polarization geometry and sample orientation.7. Even the modes belonging to the same irreducible representation do not always have the same angular dependence with regard to the polarization of the light.7. the signal for this mode will be clearly seen. mode a t 1587 cm' is independent of 03. However. mode a t 1587 cm'. 10. mode intensity at 8 = 90'. since it is one of a few examples where the nfold symmetry of the nanotube matches the triangu~a~ lattice. Further.5.4 and 10. since the 10fold symmetry of the (10.
RAMAN SPECTRA OF CARBON NANOTUBES modes.206 CHAPTER 10. . Such a symmetry analysis will also be useful for identifying the chirality of carbon nanotubes.
and these are summarized in Sect. 11. The fundamental atomic forces consist of strong c. as shown in the following three sections. in carbon nanotubes are discussed in Sect. Although the three forces differ from oneanother regarding their orders of magnitude. respectively. the total energy of the nanotube is increased by the strain energy associated with the curvature of the nanotube. single wall nanotubes are rather flexible in the direction normal t o the nanotube surface.4. three kinds of forces between carbon atoms produce their characteristic elastic properties. Elastic Properties of Carbon Nanotubes Since the C=C bond in graphite is the strongest bond in nature.CHAPTER 11. so that a nanotube with a small diameter may be less stable than a nanotube with a larger diameter. The static elastic properties of carbon nanotubes are discussed in Sect. 11. 11. In graphitic materials. The unusual aspects of the Peieris instabilit~} associated with the distortion which makes an energy gap a t the Fermi energy. all three forces are essential for describing the elastic properties of carbon nanotubes. Multiwall carbon nanotubes have unique properties that do not appear in single wall nanotubes.rbonding and nbonding forces between intralayer C=C bonds and weak interlayer interactions. Furthermore.3. By rolling a graphene sheet to form a single wall carbon nanotube (SWCN). The strain energy thus increases with decreasing nanotube diameter. 11.2.1 Overview of Elastic Properties of Carbon Nanotubes In graphite and in carbon nanotubes. sp2 covalent 207 . E each section we give an overview of the relationn ship between the properties and the force. a carbon nanotube is widely regarded as the ultimate fiber with regard to its strength in the direction of the nanotube axis.
their extensibility. and these ridges can relax elastically when the stress is released. Computer simu~ations 12221 further indicate that when the c o m p r ~ ~ i o norl shear stress is a released. In addition to these amazing predictions for their tensile properties. In fact. singlewall nanotubes show remarkable flexibility. Whereas carbon fibers fracture easily under compression. 11. we discuss in Sect. carbon nanotubes form kinklike ridges under compression. and can be bent around small circles or about sharp bends without breaking [ l l O ] . and their ability to withstand compression without fracture. singlewall carbon nanotubes have a number of other desirable nanotube properties with regard to their flexibility. It should be possible to utilize these excellent mechanical properties for applicat~ons directly. in many cases.219].2 the rigidity of carbon nanotubes and the weak chirality effects expected for their elastic properties. we expect a rather soft surface in SWCNs for a force applied perpendicular to the surface of a carbon nanotube. Single wall carbon nanotubes have no interlayer interactions.2. a perpendicular deformation is not always stable and the cross section of carbon nanotubes is easily flattening by applying a force normal to the nanotube axis [220] and a large bending of single wall nanotubes is observed without breaking the skeleton [221]. ELASTIC PROPERTIES OF CARBON NANOTUBES bonds mainly form the D skeleton of the honeycomb lattice. 11. Singlewall carbon nanotubes are believed to possess many of the desirable mechanical properties of carbon fibers. and molecular dynamics simulations [222] indicate that an increase in length (elongation) of several percent without fracture might be possible [95. Just as for the carbon fibers that are produced commercially for aerospace applications. in addition. the original circular crosssection of the nanotube can.208 CHAPTER 11. Using elastic continuum theory to describe the elastic properties of nanotubes. carbon nanotubes show excellent strength characteristics under extension. Thus the strength in the direction of the nanotube axis may be considered as an elastic thin film for which classic elastic theories can be applied [219]. be restored [219]. their ability to withstand crosssectional and twisting distortions. since a hollow vacuum core exists inside each nanotube. as shown in Sect. the 7~ contribution is nevertheless . or in conjunction with their use for manipu~ating other nanostructures [53]. Although the 7~ electron contribution to the elastic energy is relatively small compared with that from the c electrons. but. On the other hand. and this feature of SWCNs can also be explained by consider in^ a tangential force on the abond skeleton.
the interlayer stacking can become correlated. The Peierls instability is known to cause a metalinsulator transition. by opening an energy gap at the Fermi energy to benefit from the eIectronic energy gain which is introduced by the distortion of the lattice into a doubled unit cell. in some cases.225]. in which the energy gain associated with the electronlattice interaction of the T electrons is balanced by the energy loss of the potential energy of the Iattice. relative t o those on the inner layer of the nanotube. However.2). and it is well known that the Peierls instability is favored in low dimensional systems 12231.3. we focus our attention on the reason why the Peierls distortion is suppressed in carbon nanotubes in Sect. the relatively weak interaction between two adjacent layers determines their relative stacking structure. in discussing multilayer nanotubes we require that in the limit of large nanotube diamet. and experimental evidence has been found for faceting in some multilayer nanotubes [224. The lattice structure of the inner and the outer layers are generally incommensurate with each other. 11. which denotes the positions of the atom sites on the outer layer.4. Multiwall carbon nanotubes have many interesting properties that are not observed or explained by the physics of singlewall nanotubes.21. These topics are briefly summarized in Sect. Although one third of the possible carbon nanotubes that can be formed are onedimensional metals. which describes the turbostratic structure of multiwall carbon nanotubes. 11. . In multiwall nanotubes. Because of the weak and incommensurate electronic interaction between the two layers.1 OVERVIEW OF ELASTIC PROPERTIES OF NANOTUBES 209 important for obtaining the lattice distortion known as the Peierls distortion (see Sect. Furthermore.er. Starting from a general theory of the Peierls instability.3. 11. The values of the distortion are determined by minimizing the total energy as a function of the distortion. the electronic structure between two adjacent carbon layers is considered in terms of a sum of the electronic structures of the constituent nanotubes. all the nanotube properties should correspond to those of graphite. This turbostratic structure affects shear stress between the nanotube shells. the associated lattice distortion can be negligible in the case of carbon nanotubes because of the following physical situation.
is inversely proportional to the diameter of carbon nanotube.e. the strain energy per carbon atom is inversely proportional to the square of the nanotube diameter: (11. This is because the abundance of nanotubes is determined by the initial formation of the end cap of the carbon nanotube. T is the length of the carbon nanotube per 1D unit cell in the direction of the nanotube axis [see Eq.. and this weak dependence may be due to: (1) chiralitydependent directions of the three equivalent u bonds with respect to the nanotube axis. as shown in Fig./N on chirality. given in Eq.9)] is also proportional to dt (i. (11./N on d t 2 is confirmed by a more detailed first principles calculation of the strain energies of many carbon nanotubes with different diameters and chiralities [209]. (3. The small deviations of the strain energy as a function of nanotube diameter (or radius) suggests that the dependence of E.2) This simple argument for a dependence of E. (3. the strain energy E. Since the number of carbon atoms per unit cell N = 2LT/&a2 [see Eq. and d f is the thickness of the thin film.446. experimental results for the diameter distribution of single wall carbon nanotubes do not show the same diameter distribution for different catalysts [57].2 Strain Energy of Carbon Nanotubes When we consider a singlewall carbon nanotube as an elastic sheet.210 CHAPTER 11. the abundance of a given diameter carbon nanotube should not depend on the chirality. The solid curve in the figure depicts the (l/dt)' dependence of E . dt: [12]. Although the total energy depends on the nanotube chirality and thus should be related to the stability of the carbon nanotube.1). showing that we can understand the functional dependence of the strain energy of a carbon nanotube from the simple arguments given above for an elastic thin film. (11.1. 11. is very weak. depending on whether there is an energy gap or not in the dispersion relations. which can be considered as the interplanar distance between two turbostratic graphene layers (3. Since the diameter and chirality cannot .).1) where E is the elastic modulus of the sheet. L = 2sdt). ELASTIC PROPERTIES OF CARBON NANOTUBES 11. In fact.5)]. and (2) chiralitydependent contributions of the K bonds.
' I where Si. are the outer and inner about its axis. .1). Their calculated result shows that the beam rigidity is 200 times greater than a Pr bar of the same size. The solid curve depicts the ( l / d t ) 2 dependence of E. and r. The lower limit of the diameter of a single wall carbon nanotube seems to be the diameter of CG0.226]. (11. denotes the compliance tensor. we may use the Ci values for graphite to obtain a value l for Y for carbon nanotubes. STRAIN ENERGY OF CARBON ~ A ~ O T ~ 3 E S 211 Fig. calculated the beam rigidity of a carbon nanotube in the same geometry. given in Eq. we expect Y for a carbon fiber (N 800 GPa) Z to be somewhat smaller than 4 1 for graphite. However.ff3 (11. As a first approximation* we use Y= where the elastic modulus Cl1 for a carbon fiber for Y .219. in which r. this result might show that the diameter and chirality that are obtained in the growth process depend mainly on the shape of the caps generated by the catalytic particle. In fact there is no report of observation of a nanotube with a diameter smaller than that of (360. since we expect Clz in a nanotube to be reduced relative to graphite. to as described by the Young's modulus Y [220]. using the Keating potential whose parameters are given by the local density functional calculation [227].2. the deflection d of the beam with a force f at its free end is given by [219] d = . 11. When we consider a cantilever beam of length 4. respectively [220]. be changed in a singlewall nanotube unless a defect exists. the nanotube bends. Overney et al.11. C11= 1060 GPa [9. I = Z(Y: radii of an elastic cylinder. The  'The Young's modulus Y is given by (S). Since C ~ = 220 GPa is not negligible in a carbon fiber.1: Strain energy per carbon atom E.3) 3Y I where I is the areal moment of inertia of the crosssection of the nanotube r i ) / 4 . as a function of nanotube radius ri = d t / 2 [Sl]. When a force acts pe~pendicular the nanotube axis.
(W. The spring constant is estimated by directly observing the amplitude of the thermal vibration as a function of temperature within the standard deviation u2 = k BTCn 1 (11.5) cn given by statistical physics. can be used. On a nanometer (nm) scale. P c exp(E/kBT).44A. TEM photos of a collapsed nanotube look similar to the bending of a rubber nanotube [228]. A novel method for measuring the Young’s modulus of individual nanotubes has been developed.)=kBT. There are many calculations for the Young’s modulus whose value varies from 500 to 1500 GPa. The relationship between c. we may use Eq. whereby the amplitude of a thermal vibration of the nanotube is observed as a function of temperature [229]. the average of the vibrational ( energy. or (W. Since the averaged value of W. The experimental observation of the Young’s modulus of a single nanotube is difficult because of its small diameter. When we consider a single wall nanotube.). and the Young’s modulus Y is given by use of elasticity theory for continuum media (11. ELASTIC PROPERTIES O F CARBON NANOTUBES calculated Young’s modulus for a carbon nanotube is about 1500 GPa.6) . (11.3) and we can consider the wall thickness to be 3.4) where c.212 CHAPTER 11. At a high temperature T where a classical Boltzmann distribution of probabilities. the nanotube seems to be rather soft in the direction perpendicular to the nanotube axis. The TEM observations show evidence for nanotubes collapsing into a flattened or bent nanotube without breaking the nanotube structure. is proportional to the square of the amplitude t: we can write i. depending on the potential model and on the estimation for the cross section. When the diameter of single wall nanotube increases. becomes k B T . is a spring constant. (11. the nanotube is unstable in the direction perpendicular to the surface. where ]cg is Boltzmann’s constant. for a vibrational mode. n . which is the interlayer separation between turbostratically stacked graphene layers [9].
developed initially for polyacetylene (CH). 4.3. cosp.1 The Peierls Instability of Nanotubes Bond Alternation Next we discuss the effect o f t electrons on the elastic properties. This effect is known as the Peierls instability. 7. becomes a function of the distortions of atoms from their originai positions. coshp.6) for By various nanotubes.d i ~ e n s i ~ n f materials.1. . The leading numerical values for Bra.0 eVfA). In the SSH model. +  + 11.3. fin can be found by the approximation fin (a 1 1 2 ) ~ .9955 and for larger Pn values.3. b. fitting a. /234]. (11. the energy dispersion relations are folded in half and an energy gap is opened at the Fermi energy a t the zone boundary of the foided Brillouin zone. .5 3..8751.. a tightbinding Hamiltonian describing bondalternat~on is solved in a large unit cell in which the transfer integral between the nth and mth atoms.6941. the absolute value  . comparable to CIl for graphite. the corresponding unit cell in reciprocal space is reduced by a factor of 2. and subsequently for CSO and its ions [2312331. (11. and L to Eq.3 11. Therefore. In their experiments the authors used a clamped hollow cylindrical cantilever of length L 12293. t:.) are ( 1. /. 1 = 0. When the two atoms are close to each other. x. is the transfer integral without bond alter.8548 and 10. the estimated results for Y are found to be in the range of 1000 G P a . and 2 In Eq. .2 eV) and a denotes the electronphonon coupling constant ( w 5. For partially filled bands. When electrons occupy about half o the valence energy band of # n e . such a distortion leads to a lowering of the energy of the system a. . the energy bands are unstable to a distortion of the lattice into a doubled unit cell. An example of the Peierls instability is the bond alternation or the Kekul6 structure of neutral carbon nanotubes [230]. For the doubled unit cell in real space. which has been discussed 12302331 in terms of the SuSchriefferHeeger (SSH) model.11. nation (2. f is defined by and t. THE PEIERLS INSTABILITY OF NANOTUBES 213 where the values 3 are solutions to the equation. n = 0.7>.2.s the lower energy bands become occupied and the higherlying energy bands remain empty.
2.l ) n z ~leading to two transfer integrals tl and t2. (11. and thus the optimized value of 20 is given by minimizing the total energy. decreases by opening the energy gap. The electronic energy of those electrons which are in the occupied valence energy band (E+ band in Fig.7).2 a q and tz = t o 2az0. In the case of polyacetylene (CH). wesee that an energy gap of 2)tltzI = 8azo = 0. 11. 11.lO). (2.2 for the values of tl = 1.12) Thus the total energy EM = Eel + ESP a minimum.the energy difference of the electronic energy is given by + . (tl = to .11) where I< is a spring constant. Comparing Figs. (a 'IT < k < ). ELASTIC PROPERTIES OF CARBON NANOTUBES of the transfer integral' becomes large. 11. a 'IT ( 11. (ll. + tleika/2 + taeika/2 f2p . with It11 < 1t21).9.(tf t t. s = 0 in Eq. . When we neglect the overlap integral. (11. the elastic energy increases by ESP= 4Kzi (1 1. (11. = 0.4 is opened at k = f a / a because of the bond alternation. N A B of Eq./"'a a d k d dA 'IT n/a 8x0 *It is noted that tOnm < 0 and a > 0 in Eq.1 and t2 = 0.2azo and t2 = to 2az0 into Eq.E 2tlt2 cos ka) 1 (11.8) = (fgp .9) The solution of Eq.E)2.10) which are plotted in Fig.9) yields the dispersion relations Ef(z) czP f Jtt + t i = + 2tlt2 coska. Putting tl = to .2).E tleika/2 + tZe+ika/2 (11. (2. the bond alternation problem can be solved by using a doubled unit cell with a distortion zn = ( .20) for simplicity. On the other hand.214 CHAPTER 11.13) 8Kzo = .17) becomes + N A B = t l e ikal2 + t2eika/2 and the secular equation is given by f2p .2 and 2.. dEtot/dzo = 0 when has + B cos La.
14) where K ( z ) .5 1. (11.l 0. :+.4 in these = units.i) for bondalternating polyacetylene given by Eq. where A and B denote A = 2t$ f 8a2x$ and B = 2t$ .2B AfB 14(?) * (11.15) In Eq. The integration of Eq.2: The energy dispersion relation I3k.1 < 1 w e can expand K ( z ) and E ( z ) around le = 0 to obtain: K. (11. 11. respective1yJ the complete elliptical integrals of the first and the second kind defined by..14) z is a function of xo which is given by 2 z 2 = . (11.t. = () 2 {+ 1 ($2 + (E)’. t l = 1. and qz.0  1.13) is given analytically by ( 11..t 2 l = 8 ~ ~ x 00.16) To solve Eq. we use the mathematical formula cos 28 = 1.8a2x:.0 kdz 0.0 0.4) 1.)22+(2.2sin2 6.1 and t 2 = 0. (11.} + 224 . .and obtain a solution for 20 over a reasonable range of a > 0. t When 1. (11. and & ( z ) are. respectively.10) using values for the parameters ~2~ = 0. K(2) = LTf2 HB vczzT and & ( a ) = Jld *P d B u .=2{l(.5 0.9. The energy gap at k = f a / a arising from the bond alternation has a value of 2 ] t l .14).0 Fig...3 2 respectively.*}.215 rr.
is plotted as a function of the normalized electronphonon interaction z 4 a 2 / ( ~ l t o l K ) The inset shows a . §There are no pure one or two dimensional solids in three dimensional space. The Peierls instability is thus a kind of JahnTeller effect which occurs in the solid state. this instability does not always occur. as a function of 1/x.3 we plot . linear dependence of . Egap3 8azo/ltol. clearly showing a linear dependence of . which is the solution of Eq. $The Peierls instability is sometimes called a band JahnTeller effect.§ In a carbon nanotube. 11. which lowers the symmetry and splits the degenerate levels so as to open an energy gap between the filled and unoccupied states. bond alternation is always found in a onedimensional metal. Because of this lowering of the total energy. The corresponding lattice deformation is called the Peierls distortion. as a function of the normalized electronphonon interaction z z 4a2/(rlto IK). In the inset of Fig. 11. ELASTIC PROPERTIES OF CARBON NANOTUBES ‘I I/x / / X I 1 1 Fig.log(EgaP)as a function of l / z . In a molecule which has degenerate and partiallyoccupied levels associated with the high symmetry of the molecular geometry. (11. The Peierls instability occurs when the shape of the Fermi surface is close to that of a onedimensional .. the degenerate states become unstable under a lattice distortion. 11. In Fig.log( Egap) .17) The functional form of the energy gap is similar to that for the superconducting energy gap according to BCS theory.216 C H A P T E R 1 1 .ln(Egap) on l / z which is numerically fitted by (11.$ In higher dimensions. simply because the energy gain in a small region around the Fermi energy is not always larger than the energy loss associated with the elastic energy. Egap 3 8azo/ltol.3 we plot the normalized energy gap. This effect which is similar to the Peierls instability is called the JahnTeller effect in quantum chemistry.14).3: The normalized energy gap of polyacetylene.
respectively. the electronic structure becomes close to that of graphite as the diameter increases. . $1. thereby lowering the electronic energy. In Fig. 11. and (c) an outofplane bond alternation.3. which we will discuss in this section. Thus a dimensional crossover associated with bond alternation occurs at 0 K.(b) a quinoid type inplane bond alternation.4: Possible bond alternation for a honeycomb lattice. respectively.4. T H E PEIERLS INSTABILITY O F NANOTUBES 217 Fig. In the case of inplane bond alternations.3. an energy gap would appear.4(a) and (b). denote shrunk and surface. 11. Whether this symmetrylowering distortion does occur or not depends on the strength of the electronphonon coupling constant.2 PeierEs Distortion of graphite and carbon nunotubes In chapter 2 we show that twodimensional graphite has no energy gap between the bonding and antibonding T bands because there are two equivalent carbon atoms in the unit cell which give rise to a symmetryimposed degeneracy at the Brillouin zone corner. 11.11. 11. and (c) an outofplane bond a~ternation. If the two atoms were not equivalent to each other. respectively.2. In the honeycomb lattice we can consider three kinds of lattice deformations as shown in Fig.(b) a quinoid type in plane bond alternation.3. (a) a Kekul6 type of inplane bond a~ternation. denote shrunk and elongated bonds. while solid and open circles in the outofplane bond alternation denote deformations in the +z and z directions. (a) a Kekul6 type inplane bond alternation. thick and thin lines. as described in Sect. although the geometry is onedimensional. thick and thin lines. ur when two Fermi surfaces are parallel to each other over large areas in the Brillouin zone (the nesting condition).
SOC. When the distortion is included.* In a single layer of graphite. Even if we deform the lattice by an outofplane deformation.25). the A and B sites in the unit cell deform in the +t and 2 directions.26) for simplicity. in the case of a single layer carbon nanotube. ELASTIC PROPERTIES OF CARBON NANOTUBES elongated bonds. while the unit cell for outofplane deformations does not change.24) and Eq. For example the A and B sites are inequivalent in threedimensional graphite. Here we neglect the effect of the overlap matrix S and we put czP = 0 in Eq. and thus there is no relative difference in the transfer energy between the A and B sites. Japan 52. If we assume that the site energy for the A and B carbon atoms is shifted by &aro/2 in which a is the electronphonon coupling constant per distortion t o . the calculated energy dispersion E ( k ) becomes This relation implies an energy gap of 2azo at the K point. the energy dispersion of the distorted T bands of graphite is given by solving the perturbation Hamiltonian . (2. Saito and H. However. all CC bonds are still equivalent to each other. See. (1983) 407.218 CHAPTER 11. respectively. J. 31= a t 0 ( tf(k)) at0 . (2. (11. there is no relative difference in the site energy between the A and B sites. in which the A sites have carbon atoms above and below the atom but the B sites do not. Kamimura. the electronlattice interaction affects both the transfer integral and site energies. respectively. for example. After deformation] the unit cell becomes twice as large as the original unit cell in the case of inplane deformations. (2. When the site energies have different values for the A and B sites.18) tf(k)* where t and f(k) are defined by Eq. R. Generally. . In the case of an outofplane deformation. The value of t o is obtained by minimizing the total energy which is given by the sum of the ~ *In the SSH Hamiltonian they consider only the change of the transfer energy by the lattice deformation. Phys. Here we consider only the change of the site energy by the lattice deformation. there is a difference between the inner and outer directions. Thus for simplicity we consider the case of an outofplane deformation. the two sites are not equivalent.
(11. . we obtain the following gap equation for the (n. This situation is explained below as the limit of a carbon nanotube. The 4% energy dispersion relations of the distorted (n.0) zigzag nanotube Eq. (11. for ~ i m p ~ ~ iSince the size of the unit cell does not change in the case of an outty. = / 4 c o s ( ~ ) / . and in which X(z) is the complete lipt tical integral of the first kind defined in B4 are given by A. (11. and A. 0)zigzag nanotube n. (11. ofplane ~ i s ~ o r t i othe electronic structure of a distorted (n. E&(k). in which IC is a spring constant. Here we consider only outofplane distortions for the case of a zigzag carbon nanotube. No distortion from the honeycomb lattice is observed in crystalline graphite because the density of states at the Fermi level is zero in the case of twodimensional graphite.electronic energy and potential energy of the lattice.= (y) 2 + 1 + 4 c o s 2 ( ~ ) and 8 . and Eq.14).7).0).O) zigzag nanotube.23) which directly follows from the definition of K in the footnote of the previous subsection. are expressed as Taking account of the potential energy of the lattice as K $ f 2 per unit cell of graphite.22) respectively. is obtained by zo~efoldingas discussed in Eq. (4.21) is obtained by use of the mathematical formula. (n. Let us consider the Peierls instability of a carbon nanotube.
the energy gap has nonzero values for small values o 2.17) to polyacetylene and carbon nanotubes is that the factor appearing in the exponent of Eq.6  0.o 1.5 X I . we see that the dependence of the energy gap of the nanotube on the electronphonon coupling constants is very close to that for the 2D case. 6. From the figure. for metallic zigzag nanotubes (la.(233] and Viet et a1.0). 11. 12. 11. Actually in the case of zigzag nanotubes. as a function of = . As for the other types of d~stort~onscarbon n ~ o t u b e shown in Fig.17) depends on n for (la. dashed. dotted. (11. and bold solid lines. (11. (11. of s Harigaya et a1. 11.5: The normalized energy gap Egap a2zo/ltol for metallic zigzag nanotubes. 6.220 CHAPTER 1 1 .which is normalized by x which is the electronphonon interaction a2 normalized by IiltoI so that 2 a Z / ( I i l t ~(lt) < 0). respectively. 11. we plot the energy gap Egap 2 a z 0 / ( t 0 I . namely n = 3.[235] independently calculated the energy gap l t o l .00. while the elastic energy loss comes from all of the 27a carbon atoms in the unit cell [71]. we obtain the twodimensional case in which a In the limit of nonzero value of zo appears only when cx2/Kjtoi > 1.5 is made for special values of n that are multiples of 3. Thus for large R : a larger interaction x is necessary for opening an energy gap.01. corresponding to 2D graphite) denoted by solid. is plotted as a function of the normalized electronphonon interaction 2 E a2/(Iilltl)(t < 0 ) for special valuesof n = 3.17).0 0. its seen in Eq. 0) zigzag nanotubes as 0 exp(nA/z) (A is constant) [711. + 00. = 0. and that an energy gap appears due to the finite values of the interaction. respectively.4. The reason why we get the present results is that the electron energy gain comes only from two of the 4n energy bands which cross the Fermi energy. 12. dashed. which is essentially 2D graphite) denoted by solid. the normalized interaction of a 2 / I C J t ~ l satisfies a2/K1tOl < 1. and 999 (.5 In Fig.8 0. Since there is no experimental distortion in 2D graphite.01. o The plot in Fig. although f these values can be exponentially small. O ) .5. dotted. and 999(w m. ( n . The difference between the application of Eq. and bold solid lines. ELASTIC PROPERTIES OF CARBON NANOTUBES Fig.
A magneticinduced distortion can however occur in a nanotube since the density of states at the Fermi energy is enhanced by the presence of a magnetic field by forming the l = 0 Landau level. using the SSH model for twodimensional graphite. though metallic 1D energy bands are generally unstable under a Peierls distortion^ the Peierls energy gap obtained for metallic nanotubes is found to be greatly suppressed by increasing the nanotube diameter. The electronelectron repulsion interaction.4. in which the twobody effect is calculated mostly within the HartreeFock approximation. distortion. is also expected to be important in carbon nanotubes.~ Nanotubes a~l In this section.  . The calculated result shows a similar functional dependence of the energy gap on the electronphonon interaction. since they are aIso P owdimens~ona~ materials. while keeping selfconsistency between the charge and the lattice distortion [233].71]. Thus if we. Although multilayer nanotubes have not been characterized in detail for their physical properties. as discussed in detail by Ajiki and Ando [lSO].For larger U . Thus the Peierls gap quickly approaches the zeroenergy gap of 2D graphite [69. is independent of the lattice deformation. depending on the chirality of the carbon nanotube. Within the reasonable range of U N Itol.t In conclusion. it is believed that eV) cannot be observed experimentally. The such a small Peierls gap (< coexistence of metallic and semiconducting carbon nanotubes.11..) are taken into account in the SSH Hamiltonian.W A ~ ~ NAMOTUBES 221 as a function of the chiral vector or the intensity of the electronphonon interaction. [see Eq. the lattice distortion is determined by the electronphonon interaction (a). we list several interesting features that can be seen only in multiwa. Onsite ~ ~and offsite electron ~ ~ interactions (Uijlai. Since the transfer energy t in the SSH Hamiltonian is a function of (sn 3 c n + l ) . which is considered to be large in conjugate polymers.).4 Properties of ~ u l t i . because of the difficulty of making measurements on the individual shells of the nanotube and of sample preparation of tThere is an kinetic exchange interaction J N it12/U which favors the ~ t i f e r r ~ m a g n e t i c interaction. { 1 7 ] J depends on the deformation. consider finite temperatures or fluctuation effects. This effect is known as the spinPaerls 1.11 nanotubes. PROPERTIE§ OF ~ ~ ~ T I .nj. N ~ +  11. a spinPeierls interaction may occur in which the interaction between the two spins is now a function of the deformation of the lattice: ( J ]itI2/V = JO a3(zn zn+l)).
Thus the lattice constant along the z axis has a 1 to 1 commensurate ratio. m) nanotubes. Further for (n. should be much reduced in the multiwall nanotube. One nanotube may move smoothly with respect to the other in the attractive force between the two walk. a periodic function. T .8)]. no periodicity appears along the z axis. n l ) and (n2. both for the inner and outer nanotubes. the shear modes between two graphite layers. the length of the chiral vector c = L is proportional t o an h irrational number L = adnz m2 nm. This means that when we put carbon atoms on the x axis. the coaxial nanotubes provide an interesting geometry. When we consider two coaxial n ~ n o tu b es which share the same n ~ o t u b e axis. the potential becomes flat. since their ratio of lengths in the circumferential direction is scaled by the ratio of the two diameters.O) (where T = d u ) . Since we have two degenerate shear modes in the x and y directions in + + .(n2. are the same for two armchair nanotubes (721. which is observed at 42 cm' in graphite. It is clear that an armchair nanotube and a zigzag nanotube cannot be commensurate in the direction of the z axis. The only commensurate cases are the cases of the achiral coaxial nanotubes. the elastic potential is. however. the commensurate ratio is expressed by n1/n2. since the ratio of T is l/&. since the average of the interatomic potentials a t different distances does not depend much on +. with a period that is the larger value of the T vectors for the constituent nanotubes. the ratio of the T vectors for the two nanotubes will be an irrational number. When we slide the inner nanotube along the z axis relative to the outer nanotube. As for the circumferential direction. cyclic boundary conditions always imply a commensurate relation. However. When the number of carbon atoms in the unit cell of the constituent nanotubes becomes large.222 CHAPTER 1 1 . In this sense. In the case where the two are general chiral nanotubes. which give the radii of the constituent nanotubes and the interlayer spacing between them. as shown below. the chiral vectors of the inner and outer nanotubes can be determined separately. ELASTIC PROPERTIES OF CARBON NANOTUBES a welldefined and structurally characterized multiwall nanotube. since the translation vectors.O). we will not see any two atoms in a line parallel to the 2 axis. but is not scaled in the direction of the nanotube axis. n2) (where T = a ) or for two zigeag nanotubes (nl. since the length of T = f i L / d ~is an irrational number in units of a [see Eq. In the case of ~ncommensurate coaxial nanotubes. In achiral nanotubes. (3. the structures of the two nanotubes will not be commensurate to each other in almost all concentric nanotubes.
graphite shear mode at 42 cml. where A = l / a is an empirical damping factor. rnl) and (n2. Thus.0)(18.4. Chandrabhas et ai. The authors attributed the upshift to defects in the nanotube axis.rnz) nanotubes.. If we could have an ideal coaxial multiwall nanotube with open ends. m l . . Anticrossingoccurs as a result of the interaction between the two energy bands.. where d. The normal mode for the shear displacement of the two constituents of a twowalled nanotube is a mixture of a translation and a rotation around the P axis. [236]. n l . most nanotubes have end caps which prevent mode can be expected to result the sliding motion. it would be interesting to study the nanoforces associated with sliding the inner nanotube with respect to the outer nanotube. As for the wave functions with different symmetries. we can expect another shear mode in the nanotube which corresponds to the rotation around the z axis. relative to the shear mode in graphite. the energy dispersion relations can cross each other. the smaller is the value of d. we expect a downward shift for the shear stress between the adjacent walls of a multiwail nanotube. however. the interlayer interaction between two carbon atoms on two different nanotube shells with a separation r is assumed to be 7 expfAT).0) nanotubes show an anticrossing* of two energy dispersion curves with the same symmetry of wave functions belonging to the two different nanotubes. Except for a few nanotubes with open ends.O. The direction of the normal mode d i s p ~ a ~ e m e ~ t sbe d ~ t e r ~ i n by the two chiral vectors. In the tightbinding calculation. since the wave functions remain orthogonal to each other even in the presence 'Anticrossing means that two energy dispersion curves repei each other at the crossing point. PROPERTIES OF MULTI. and m2 for the ( n l .5)(10. the rotation around the z axis has a periodicity of Znld. In that case a v~brat~onal from the sliding motion. The calculated 1 results for the commensurate (5. like the micro~copic motion of a muscle.WALL NANOTUBES 223 the graphitic plane. 712. we expect the motion to be smoother.35 eV for the two A carbon atoms with a separation (O.11. have reported an upshift of the two shear modes to 49 cml and 58 em" from the Ezs. In will ed all cases. The electronic structure of a multiwall nanotube has been calculated for a commensurate doublewall carbon nanotube by a tight binding calculation 1761. In this calculation. is the common divisor of the four integers. Since there are two chiral vectors in a horizontal plane perpendicular to the nanotube axis. the value used for the largest interlayer iiiteraction in graphite associated with the overlap of the wave functions of the two ?r electrons was y1 = 0.c).lO) and (9.
. In the STM experiment on single crystal graphite. In graphite. Since the energy gap of a BN nanotube is the same as that for the bulk BN semiconductor. i n a multiwall nanotube and even in a singlewall carbon nanotube. the electrons and holes near the Fermi energy mainly corresponds to B atom wavefunctions. ELASTIC PROPERTIES OF CARBON NANUTUBES of the interlayer interaction. although the reason for this is still not clear. Thus the calculated results show that the constituent nanotubes of a coaxial nanotube remain either metallic or semiconducting. it becomes easy to understand the topological STM and the transport STS experiments in which only the outermost nanotube contributes to the STM image and STS conductance measurements. a triangular lattice is observed because of the ABAB stacking of the graphite layers. we do not see the onset of an energy gap at the Fermi energy for metaimetal and meta~semicon~uctor coaxial nanotubes. This observation suggests further possibilities for a variety of other nanotube complexes. the calculated result [76] shows that the electronic properties of a twoshell coaxial nanotube look like the sum of the electronic structure of the two independent nanotubes except for the anticrossing phenomenon. Even when this anticrossing appears near the Fermi energy. since high insulation by the EN nanotube can be expected.224 CHAPTER 11. a triangular pattern is observed in the STM image. Thus when a small voltage is applied. Thus when we cover a carbon nanotube by a BN nanotube. The arc method of synthesis using a carbon rod with the materials for the BN nanotube included in the central portion of the carbon anode yields a coaxial multiwall nanotube in which a severalwall BN nanotube is surrounded by a severalwall carbon nanotube on both the outside and the inside [137]. which clearly shows that the A and B atoms are not equivalent to each other [54]in the nanotube plane. From this result. the nanotube complex will be more interesting than carboncarbon coaxial nanotubes for device applications. respectively. which do not have a neighboring atom directly above or below them on the adjacent graphite layers. a large energy gap of about 5 eV is expected for BN nanotubes. Although we take account of the interlayer interaction. the STM can only see the electrons and the holes at the B sites which form a triangular lattice. depending on the chirality of the constituent nanotube.237]. we can expect that it will be possible to fabricate coaxial conducting wires or capacitors shielded by semiconducting nanotubes which are suggested in the literature [141. If the electronic structure of a mu~tiwallnanotube can be understood in terms of the electronic structure of the constituent singlewall nanotubes.
for two coaxial armchair nanotubes. were obtained. the greatest part of the individual layers more quickly approach that of graphite than through the cylindrical growth of multiwall nanotubes.with an energy stabilization of 14 meV/atom [147]. In the multilayer structure.23 meV/atom and 0. A similar calculation for dou~lelayeredhyperfull~renes also been has carried out.WALL NANOTUBES 225 A more sophisticated calculation was done for ~ u l t i . The faceting may occur in order to gain the cohesive energy of graphite through the ABAB stacking. the multiwa~~ nanotube starts t o exhibit a hexagonal pillar shape. which is related t o the growth of multiwall nanotubes in the radial direction by an accretion method. yielding an interlayer spacing of 3. estimates €or the translationa~ and rotationa~ energy barriers of 0. The fact that the interlayer separation is somewhat less than the 3. with an energy stabi~i~ation 48 mev~carbon of atom.52 meV/atom. similar to the occurrence of faceting in carbon fibers 191.524 A between the two shells of C60@C240. In the faceting. and thus the multiwall structure would be advantageous for obtaining high strength per unit area in the nanotube axis direction. The result of this c a h l a t i o n yielded a 3. respectively. By faceting the layers. when the diameter increases to more than 1020 nm.Z 1.44 A separation expected for turbostratic graphite may be explained by the interlayer correlation between the carbon atom sites both along the nanotube axis and the circumferential directions. multilayer carbon nanotubes [59].238].4.2381 confirm the tightbinding results [76] mentioned above. we can expect multiwall carbon nanotubes to have the properties of graphite. It is important to note that the faceting is not generafly found in pyrolytically generated. In addition. PROPERTIES OF MULTI. Detailed band calculations for various interpfanar geometries for a t~o.l a y n ~ o t u b e w i t h ~ n ~r s the local density approximation t o establish the optimum interlayer distance between an inner (5. .5)armchair nanotube and an outer armchair (10.39 A interlayer separation [196. the curvature of the nanotubes becomes concentrated a t the corners of the pillars as the interlayer correlation becomes established over a large area with a structure that is close to that of graphite. However.ayer red coaxial armchair nanotube 1196. In the limit of large diameter. the cross section of the hollow core becomes relatively small with increasing numbers of carbon layers.lO) nanotube. suggesting significant translational and rotational interlayer mobility for individual shells of ideal nanotubes at room temperature.
.
we show first a simple program for generating parameters of an (n.m) carbon nanotube In this Appendix. The atomic coordinates for an ( n .m) carbon nanotube are generated in the unit cell of the nanotube by the second program. we obtain output for the parameters in a standard output format. When you input n.3.m) ==> d i s gcd(n. o u t Enter n.m) carbon nanotube using a standard input method. Example: Input and output of the program A1 tube% a l .m f o r Ch 10. See details of the definitions given in Tables 3. which is discussed in Chapter 3.Appendix: Programs for a (n.lO Ch = ( 10. = 30 R L/a = square r o o t <== input ==> Chiral vector (n. The source codes are written in Fortran 77. The third program gives more coordinates for several unit celIs.2 and 3. which generally means a keyboard. m) carbon nanotube. m values for an ( n . 10) d = 10 d . A1 Parameters for an (n. Any reader can use these codes by citing the book.2m~n) . of 300 ==> Length o f Ch 227 . R and T.m) ==> dR i s gcd(Zn~m. We show below an example of the inputoutput on a workstation. carbon nanotube m) The first program A1 generates the characteristic vectors such as Ch. other related parameters.
xyz has a format for the xmol program* which can display the structure in its xyz format and can convert the results to many formats consistent with other software.yi.xyz2 is a work file which will be used in the program A3. . A2 Coordinates for a (n. The first line of tube.zi) ( i = 1 . 0) ==> = 10 ==> T T/a N R M rt = 6.m) nanotube. z i ) coordinate in A units are listed from the third line for the number of carbon atoms.m) CARBON NANOTUBE = 13. .228 d .xyz includes the atomic coordinates of carbon atoms in the unit cell for the ( n . the program generates two files: Output files for A2: (No Input file) tube. The file inputoutput is specified by the OPEN statement of Fortran codes.56955AA = ( 1. and dba Minnesota Supercomputer Center Inc. .. The z axis is taken to be along the nanotube axis. After a blank line in the second line.m ) carbon nanotube. 1) ==> = I ==> = 20 ==> = ( 1.m) carbon nanotube The program A2 generates (xi. . zi) (i = 1.2) Length of T Number of hexagon in the unit cell Symmetry vector number of T in N R Here the diameter and the radius are in A unit.xyz2 : work file which will be used in the program A3.xyz is the number of carbon atoms in the unit cell.42A. . 2N) coordinates in the unit yi. The lengths of C and T are h shown in units of a . the atomic symbol C and ( q . the output is shown above for convenience. m values are input in the same way as in the example for the A1 program. The CC bond distance is taken as 1. . cell for an ( n . The other file en. When n . The file tube. If you want to change *xmol is a graphic software package with a Copyright by Research Equipment Inc.78478AA ==> diameter and radius Translation vector (t_I. y i . The file tube. . Since these values are a square root of an integer in units of a .t. 2N) en. .xyz : 2N and coordinates (xi. t APPENDIX: PROGRAMS FOR A (n.
A3 COORDINATES FOR SEVERAL UNIT CELLS this value. When you enter the number of unit cells Nu from the keyboard. A4 Source Codes Here we list the source cords.m for Ch’ read(*. 2 N x ~ .m . Nu) If you want a large numbers of carbon atoms (more than 5000).xyz2 which is generated by the A2 program.xyz2 : (Input) the work file made by the program A2. before we run the A3 program.*) n. by R. Saito. G . A€ Parameters for a (n.m) nanotube C C C C C C C C C C Parameters for a (n. .xyz : (Output) the coordinates (ti. nnq $00) itest=l i t e s t l=O < C write(*...xyz has the same format as tube. the parameters in the program should be changed. the program A3 outputs a fiIe tubel. Thus. The file tubel.m) nanotube Rade by 10/16/96 R.*) ’Enter n.xyz but the number of carbon atoms becomes Nu x 2N. 229 A3 Coordinates for several unit cells The program A3 reads the en. Dresselhaus dimension nnp I 100) . 6 zi) ( i = 1. and M.xya.. Dresselhaus. the parameter in the program shouid be changed. Input and Output files for A3: en. we need to run the A2 program.S. Saito Reference: “Physical Pxoperties of Carbon NanotubesSJ Imperial College Press. Anybody that uses these source codes or their mo~i~ed versions is required to cite the book. tubel.
32) dt.21) ndr format(’ dR = ’.rt rt ~ ’ ~ f 1 0 . 10) n .le.eq.eq.m format(’ Ch = <’.5.1) mite(. 40 41 c N 50 c R nn=2*12/ndr if(itest.eq. i4) ichk=O if (nr. . .tiO) nn format(’ N = ’.’)’) nt2=3*12/ndr/ndr nt=int (sqrt ( loat(nt2f>+eps) f if ((nt2nt**2) eq.’)’) if(itest. ’\AA nra (2*m+n) /ndr nsa(2*n+m)/ndr if(itest.3*nd). i4) else if(ite9t.O) then if(ite9t.e 1 write(*.20) nd format(’ d = ’.i) write(*.0) then if(ite9t.0) then n60=1 else n60llr endif C itest2=0 .eq. ’\AA’) format(’ dt = ’.1e.eu.’.30) 1 formato L7: = I.41) nt2 format( ’ T7. i ) 6 endif 42 .m) if(mod((nm).). .i3.eq.1) nrite(*.0’ l=int (sqrt (float ( 2 ) e s 1)*p) if((121**2). = >.e 1 write(*.3i) 12 format( J a = square root o f ’ .i3) a=sqrt(3. 1) write(*. 5 .O) then ndr=3*nd else ndr=nd endif if (itest. f10.il write(*.i3) if (itest .421 eps=l. i3) else ) if(itest. = square root of).13.5 if(itest.230 APPENDIX: PROGRAMS FOR A (qm)CARBON NANOTU3E nd=igcm(n.eq.Oe5 10 2 0 2 1 C C L 30 31 32 C T l2=n*n+m*m+n*m if (12. i6) endif dt=a*sqrt ( loat(12) )/3.13.I> write(*.eq.e i) write(*.1415926525 f rt=dt*O.40) nt ) format(’ T7.422 m a s format(’ T = fl.13.e . eq.0) stop ’12.0)*1.1) wite(*.
n: . ndr write(*.ns=’ .m.ne.0) then write(*.Mq(i).ichk if((m*nnp(i)n*nnq(i)). ’ .A4 SOURCE CODES C 231 67 61 60 C do 60 np=abs(n60) .*) ’n.m. i3) stop more than 1 palr of p.67) n.and.0) then 77 C if(itestl.n*nq if(itest2.nr. j1.ichk.i=l.nn.12.eq.m.nn) continue endif goto 777 m write (* .lt.eq. ndr= . j2 jl.ichk) .lt.q strange!!’ endif C itest3=l C if (ichk.abs(nbO) do 61 nqabs(ns) . .ichk.np. format( ’n. .*) ’ichkm . ns.2) then if (itest3.nq.1) then jl = m *np .66) ( n ( ) .*) ’n.nr.m.iChk) 66 format(’ (’.m.n:m.jl. i3. 1 .ge .gt. mnpi*n() stop ’ more than 1 pair of p.eq.nn j2ihen f ichk=ichk+l nnp(ichk)=np nnq(ichk)=nq endif endif continue continue if(ichk.nr 1 8 .nq.nn.eq.ns stop ’ not found p.y.nr.ns.n.abs(ns) 52 7 nr*nq .q strange!!’ endif endif 777 continue 62 C .6i4. n ( ) ( * n ( ) n n q i ) npi nqi.i2!’) mpnq = ’.ne.1) then do 77 i=l.0 .?s=’.and.0 C .ns*np if(32.eq. ndr=’.m.1) then write(*.*> ’n.(m*Mp(i)n*nnq(i)) .i=l. ’ N=’.nr. ndr write(*.nr. 1) arite(*.*) ’ichk=’.ns=’.ns write(*.nrps write(*.q strange!!’ endif if(nr.n.2i6P i ( jl.66) <nnv(:) .
) C en. 0) then igcm=j return else .*)’ R = (’. Dresselhaus c Input: n.m (from keyboard) c Output: tube. C by R.’. Takeya and R . nq .m C C C c a l l genll(n. nanotube in the unit cell rn) C c Atomic Coordinates i n t h e u n i t c e l l of a (n. G. .xyz2 ( a work f i l e f o r the program A3) C implicit real*8 (ah.232 C APPENDIX: PROGRAMS FOR A (n.42d0) parameter (nk=1300) dimension x(nk) .m.*) n.y(nk) .S.nq. 0) then igcm=i return endif continue ir=mod(i. Dresselhaus.ndr) write(*. S a i t o . ’.m) CARBON NANOTUBE c c a l c u l a t e t h e highest common d i v i s o r C integer function i g c m ( i i . j j ) i=abs ( i i ) j=abs (jj) i f ( j g t i) then fw= j J 1 . ’1’ . np.m)’ read(*. See d e t a i l i n t h e above book. and M.m) nanotube C c Made by 10/31/95 C C C by T.z(nk) C write(*. parameter (acc = 1.m f o r Ch=(n. Saito c Reference: “Physical Properties of Carbon Nanotubes” Imperial College Press.xyz (coordinates. 1‘4 J =lr endif got0 10 end A2 Atomic Coordinates for a ( n .oz) C c C acc: CC bond distance.np. .*)’ Enter n. j > i f (ir eq. i=iw 10 endif i f (j eq.
.q4*i80.OdO) *acc C c C r. a: t h e length of t h e u n i t vector sq3 = 1.nk) s t o p 'parameter nk is too small' C rs=c/(2. . OdO) a z s q r t (3.*) write (* .OdO)ql) C C C C C C C C C C write(*.ql*l80. df l o a t (n*n+m*m+n*~) write (*.nn*2 C C rs: r a d i u s of t h e tube if(2*nn.OdO*pi/dfloat (nn) q6~acc*cos((pi/6..OdO) pi=4.lC.IRI .4) C C C nn: t h e number of hexagon i n t h e u n i t c e l l M nnt2*(n**2*m**2+m*n)/ndr C c C write(*. t . 190)~/2.732.. The A atom .hl .OdO/pi ' Calculate 2*nn atoms i n t h e u n i t c e l l .gt.OdO*atan ( 1.OdO/pi C c I 9 0 format(' r a d i u s ='.OdO/pi 'q5 : 3 . c.*) ' N ='.OdO)ql)/c*2~OdO*pi C C C C hi : h2: Delta z between t h e A and B atoms hlsabs ( t ) /abs (sin(q3) ) hZ=acc*sin( (pi/6.0dO/pi 'q2 : =' .*) 'ql: ='.*) write(*. *) write (* .t .q5*180.. sq3=sqrt(3.A4 SOURCE CODES C 233 c C p i = 3. l T I r=a*sqrt (df l o a t (np*np+nq*nq+np*nq)) c=a*sqrt(dfloat(n*n+m*m+n*m)~ t = s q r t (3 .OdO/pi 'q4: =' .141592.OdO) *c/dfloat (ndr) I w r i t e (* .OdO*pi) C C C C C q l : t h e c h i r a l angle f o r Ch 42: t h e ' c h i r a l ' angle f o r R 93: t h e angle between Ch and R ql=atan( (sq3*df l o a t (m) /df l o a t (2*n+m) ) q2=atan( (sq3*df loat (nq) /df l o a t (2*np+nq)1 q3=qlq2 C C C C 94: a period of an angle f 5 r t h e A atom q5: t h e d i f f e r e n c e of t h e angle between the A and B atoms q4=2.q2*180.f10.*) t= .
lt.and.O.02) then zl=zl+t*dfloat (kk2) endif ii=ii+i x (ii) =xi y(ii)=yl z(ii)=zl C C C The B atoms zd=(dfloat (i)*abs(r)dfloat ii=ii+l C (k)*hl)*sin(q3)h2 c Check the C B atom is in the unit cell 0 < 23 < t x2 =rs*cos (dfloat (i) *q4+q5) if((z3.01) then z2=z2+t*dfloat(kk) endif x(ii)=x2 y(ii)=y2 z(ii)=z2 endif continue 100 C .gt.le.0l)then z2=z2t*dfloat (kk) endif if(z2.gt.tO.t0.nn1 xi0 yl=O zl=O k=int(df loat ( i *abs(r) /hl ) xl=rs*cos(dfloat (i)*q4) yl=rs*sin(dfloat (i)*q4) zl=dfloat (d loat(i)*abs ( r ) (f dfloat (k)*hl)) *sin(q3) kk2=abs(int (zl/t))+l C c Check the A atom is in the unit cell 0 < zl < t C if(z1.m) CARBON NANOTUBE do 100 i=O.234 ii=O APPENDIX: PROGRAMS FOR A (n.O2))then c yes y2 =rs*sin(dfloat(i)*q4+ 5) 22 =dfloat (dfloat (i)*abs?r) dfloat(k)*hl )*sin(q3)h2 x(ii)=x2 y(ii)=y2 z (ii)=22 else c no x2 =rs*cos (dfloat(i) *q4+q5) y2 =rs*sin(dfloat(i)*q4+ 5) 22 =dfloat (dfloat (i)*abs?r)dfloat(k+l)*hl)*sin(q3)h2 kk=abs(int(z2/t))+l if(z2.0.t0.02).(z3.lt.02)then zl=zlt*dfloat(kk2) endif if(zl.ge.0.
z(i> end do format ( ’C’ .np.m) if (mod((nm) .ii8)t.20) 116 close(60) stop end C c This subroutine calculates np.acc format (2f25.xyz ’1 write (60.0’ l=int (sqrt (dfloat (12) )+eps) dt=a*sqrt (dfloat (12)) /3.*) 2*nn write (60.O) stop ’12.ndr) dimension nnp(iO0) .116)i.3*nd) .nn*2 write(60.y(i) .nnq(iOO) C nd=igcm(n. f ile= ’tube.y(i) .m.nq.*)2*~ write(60.eq.le.6) do i=i.*) ’ ’ do i=l.x(i) .3f10.file=’en. ii7)x(i) .le.(2*m+n)/ndr ns=.nq and ndr from n.xyz2 C I18 open(60.eq.xyz2’) write(60.z(i) end do fornat (ii5.0) then n60=i else n60m endif C itest21 .A4 SOURCE CODES c Out put to the file tube.O) then ndr=3*nd else ndr=nd endif C L 12=n*n+m*m+n*m if (12.nn*2 write(60.1415926525 c T nr.m C subroutine genll(n.(2*n+m) /ndr nt2=3*12/ndr/ndr nt=int (sqrt (dfloat (nt2))+eps) c N nn=2*12/ndr c R ichk=O if (nr.xyz C 235 117 C open(60.5) close(6O) c Out put to the file en.3f25.
eq.n*nq i ( jl.m) CARBON NANOTUBE do 60 np=abs (n6O) .lt.1) then stop ’ more than 1 pair of p. j1.1) then np=nnp ( 1) nq=nnq( 1) endif continue return continue stop end c calculate the highest common divisor C integer function igcm(ii.eq.nn) goto 777 endif endif 777 continue C 2 1 C if (itest .i) then lu=j J 1 i=iw .abs(ns) j2 = nr*nq .2) then if (itest3.ichk if ((m*nnp(i)n*nnq(i)) continue endif .and.0) then stop ’ not found p.ns*np if(j2.ne.gt.eq.ne.236 C APPENDIX: PROGRAMS FOR A (n.nn ) then f ichk=ichk+l nnp(ichk)slp nnq(ichk)slq endif endif continue continue if (ichk.O) then C 77 C if (itestl.ge.0 . jj ) i=abs(ii) ) j=abs(jj if(j.gt.1) then do 77 i=l.l) then J l = m *np .q strange!!’ endif if(nr.0 .and.q strange!!’ endif 61 60 C C itest31 C if(ichk.lt.abs( 1 0 16) do 61 nq=abs(ns) .eq. ns.eq.
0) then igcm=i return endif continue ir=mod(i.*)t do 10 i = l .*)j . 02) parameter (nk=5000. j ) i f (ir.~yz2’) read(dl. Saito c Reference: “Physical Properties of Carbon Nanotubes” Imperial College Press. S a i t o .n1 iii=ii+i+j ’*ii z ( i i i ) = z (ij+df l o a t ( jj + l ) *t C . G. Dresselhaus C c Input : n (from keyboard. statusi’keep ’1 write(*.iZ(nk. t h e number of the u n i t c e l l .3) .*)n open(Gl. nanotube rn) c Atomic Coordinates f o r several unit c e l l s of a (n. n n read(61.m) nanotube C c Made by 10/31/95 C C by T. 10 A3 Atomic Coordinates for several unit cells of a (n.z(nk) dimension iic(nkT. n*nn if(n*nn. Dresselhaus.gt.nk) stop ’change parameter nk t o a l a r g e r value’ ii=nn do 20 i = l . C by R.0) then igcm=j return else :=J J‘lr endif got0 10 end 237 . Takeya and R . n n do 21 jj=O. z ( i ) continue c l o s e ( 6 l .A4 SOURCE CODES endif i f ( j eq.42) dimension x(nk).xyz2 (a work f i l e made by t h e program A2) c Output: tubel. aa=1.S.*) ’Number of t o t a l atoms = ’. (nk) .ic(nk.eq. and M.xyz (atomic coordinates) C i m p l i c i t real*8(ah.3) C 10 C write(*. ) C : en.FILE=’en.*)nn read(6l. x ( i ) .*) ’enter the number of the unit c e l l Nu =’ read(*. y ( i ) .
y (i) .FILE=’tubel .*) ’ ’ do 100 i=l.n*nn nrite(60.m) CARBON NANOTUBE x (iii)=x (i) y (iii)=y (i) continue cont inue open(GO.7OO)x(i) .z (i) continue format (’Cl.xyz’) arite(60.238 APPENDIX: PROGRAMS FOR A (n.*)n*nn write (60.5) close(60) stop end 21 20 C 100 700 C . 3f 10.
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Index
9 25 caxis crystallite sizes L , ...........89 CN group ........................ 184 D, group ......................... 184 D, point group .................... 48 d R ................................. 39 dt ................................. 38 E2, optic mode ................... 188 K point ........................... 60 k . p perturbation theory ..........106 k2 dependence .................... 170 L .................................. 38 Mpoint mode .................... 202 N ................................. 40 Smatrix ......................... 145 sp hybridization .................... 5 sp2 hybridization ...................7 sp3 hybridization ...................8 sp" hybridization ................... 5 THT............................... 89 VH configurations ................196 VV configuration ................. 196 rvib .............................. 185 T bands of 2D graphite H j j i .......................... 26 S jr ........................... 27 j energy dispersion relations .... 27 T bands ........................... 26 T bond ............................. 7 11, .................................. 41 u bands of 2D graphite ............ 29 H.j ........................... 29
acc
1s Core Orbitals ....................
..............................
........................... ............................. al a2 .............................
Sij
u bond
K I K ............................ z
bl b .............................. 2
R .................................
Ch ................................
T .................................
29 7 38 47 47 41 39 37
2D graphite acoustic modes .............. 170 Brillouin zone ................. 25 force constant parameters ....169 graphite ...................... 25 Landau level ................. 106 optical modes 170 phonon dispersion relations . . 166 reciprocal lattice unit vectors . 25 unit cell ...................... 25 unit vectors ................... 25
................
A
AB effect ......................... 110 ABAB stacking., .................. 87 abundance of nanotubes .......... 210 acetylene ........................... 7 additive property ................. 148 AharonovBohm effect ............108 amorphous carbon ................. 12 amorphous graphite ................12 Anderson localization ............. 147 angle of rotation around the nanotube axis 11, ......... 41
253
254
antibonding r* bands .............. 24 arc method ........................ 77 areal moment of inertia. ..........211 armchair nanotube ................. 36 atomic s i t e s . . .................... 185 axis of cone ....................... 121 beam rigidity ................211 Brillouin Zone ................45 circumferential length .........38 curvature., ...................70 density of states .............. 66 38 diameter ...................... dynamical matrix ............ 173 electronic structure in a magnetic field ...........108 electronic structure ........... 59 energy gap .................... 66 growth rate ...................78 oxidation., ...................84 parameters ...................46 Peierls instability ............219 phonon dispersion relations .. 171 quantum transport .......... 152 reciprocal lattice vectors ...... 45 157 resistivity .................... solid state properties .......... 66 strain energy ................210 35 structure ..................... the number of hexagons N .... 40 45 unit cell ...................... carbon whisker ...................2,82 carbonization temperature .........87 carbyne ............................ 13 catalytic chemical vapor deposition . .2 CGS units ......................... 95 CH, ............................... 22 channels .......................... 142 chemical potentials ...............142 39 chiral angle B ...................... 36 chiral nanotube .................... 37 chiral vector C h ................... 35 chirality ........................... classic elastic theories ............. 208 classical conductance ............. 139 classical transport ................ 144 classification ....................... 35
ballistic transport ................ 139 bamboo structure .................. 81 band JahnTeller effect ........... 216 121 bending angle .................... 81 bending ........................... 80 benzene gas ....................... bias window ...................... 157 156 bistability ........................ Bloch's theorem ...................17 224 BN nanotube ..................... 213 bond alternation .................. bond polarization theory ..........192 167 bondbending ..................... 167 bondstretching ................... 24 bonding x bands ................... breathing A1, mode .......... 172,190 Bright model ..................... 160 broad Raman peaks around the 1347 cm' .......... 202 bulk modulus ...................... 15
C
Cz absorption process .............. 89 cantilever beam ...................211 81 capping ............................ 79 carbide ............................ carbon arc synthesis ............... 73 carbon fiber with high THT....... 147 carbon fibers ....................14,15 carbon nanotube
.. 5 core electrons ........... commensurate doublewall carbon nanotube .. 155 crystallite size along the caxis L.. diamagnetism for graphite .... F faceting .....................95 255 de Broglie wavelength XB .............. ......224 encapsulated metal cluster ........... edge states ..................... 138 electronphonon coupling constant .........130 electronic structure ................... diffusion constant D .............138 elastic thin film.................. 61 energy stabilization ............................112 disorder in carbon fibers . .. ....138 desorption temperature hydrogen ....... 152 ensemble average ....................................215 conductance G[O].. 100 focusedion.....beaminduced deposition .............................. 127 137 conductivity ...........................INDEX coaxial nanotubes ................................... ......... Fermi wavelength XF . 165 123 126 EELS ...... 192 electronic properties of a twoshell coaxial nanotube .............. conductance .... .......... ...... ...... 178 ........ 11 electronelectron interaction ......................210 electron energy loss spectra .................225 enhanced backward scattering ............... 154 force constant model ................... 150 envelope function ....................................200 equation of motion ...89 dynamical matrix D ( k ) . 202 flux quantum .. 138 finite size effect .............223 complete elliptical integrals ........ 89 current operator ..151 elastic modulus Cxl . 9 Coulomb charging effect ........ 95 cyclotron radius T ...... ............... ................ ..... 88 88 oxygen ....... core orbitals ........... 221 electronelectron scattering .......132 eccentricity ............... ....222 132 cobalt catalyst ................................ dimensionless inverse magnetic length L/2irC ...........................202 distorted columnar structures ............ 139 121 dihedral angle ............ 213 electronic polarization tensor .......... ...134 222 commensurate . 137 141 conductance regimes ........... 163 Euler theorem....................... ........ 110 Einstein relation ..... 11 effective mass ......... .127 CVD .......................... ....... coiled carbon nanotubes ............ 225 138 Fermi sphere .................... ........ 79 energy dispersion armchair and zigzag nanotubes ........... .... ...... 106 11 diamond ................... 138 coherence ................................. 2 cyclotron frequency wc .....................210 elastic scattering ................. 163 correction of force constant ............. 151 diffusive motion ......
.............221 McClure ............132 heptagonal defect ............ JahnTeller effect ............... ........ 213 Kekule structure ............... .......................224 metalmetal junction ....... 124 ........... 184 J..177 Lorentz force ....216 joint density of states ... 95 irreducible representation ........ 4 in zero magnetic field .......................................... shape of a junction ...............................120 211 Keating potential ........ 147 localization phenomenon .................................... ................................................ 111 inphase motion .. 95 97 Landau radius ......................................256 force constant tensor ..............147 longitudinal acoustic mode .. L H heat treatment temperature THT .........213 HOPG ..222 infraredactive modes... 138 mesophase pitch fibers .. 104 111 carbon nanotube ...... 15 mesoscopic systems ..........87 89 growth mechanism ............ 2 hollow cylindrical cantilever ....................138 metalmetal coaxial nanotubes .... Landau degeneracy .. laser vaporization method ............................81.............207 inversion center ......... magneticinduced distortion ....84 length of cone axis ...................71 localization length L ......107 intercalated graphite with fluorine ........ 225 highly oriented pyrolytic graphite ........ graphitization temperature ... 89 incommensurate coaxial nanotubes .........191 115.................................................. helical pitch ............ Landau gauge .........................147 interlayer interaction ...... K G Gaussian broadening .................183 interband coupling ...........131 helixshaped structure ..............................107 local density approximation ... 95 Iijima ..........123 junction ...........127..... 186 ...........123 linear k dispersion .......... 2 hybridization .................. free electron in a magnetic field ................... ... 199 inplane bond alternation ...217 inplane crystallite sizes La ............ 5 Landau energy bands twodimensional graphite .. 116 high strength per unit area .........124 132 genus .74 layerbylayer removal .......202 ...167 164 Fourier transform .... 186 gerade ............. 97 144 Landauer formula ..163.... 133 helically coiled nanotube .. 106 mean free path L .....
....................... ...151 phase diagram of carbon .......... 138 Peierls distortion ............. 198 projection operator ................187 Raman mode of carbon nanotube atomic displacements .......................... 89 outofphase motion ..... .. . ... 171................... 52 nonzonecenter phonon mode .. ....... 143 quantized current ... .143 quantum confinement .... 192 photoelectron spectroscopy ........... .. 116 116 negative curvature .......... 84 Q quantized conductance Go ........... .. ......199 outofplane deformation dotfill 218 overlap integral matrix . negative magnetoresistance . 163 phonon occupation number ..193 momentum relaxation length L .... 160...................... . 70 Peierls instability ..................................... ....... . . 187 PES .... 198 lower frequency modes ... 14 polarizability parameters ..... .14......................... 10 phasecoherent motion ..... .207 pitch fiber ......151 Landau level formation ..209.. ......... 15 PAN fibers ...95 R radial ...... 194 192 polarization ....10 a bond .......... 221 257 Pauli exclusion principle ... 13 phase relaxation time t . ... .... ....202 192 normal mode .200 higher frequency modes ... ........ . ...22........ ............. normalized electronphonon 216 interaction ... .138 momentum relaxation time t .......143 quantized resistance Ro ................................. .. . 201 PAN (polyacrylonitrile) . ... 187 nonsymmorphic translational group . Ni/Co catalyst .............. ..139 phaserelaxation length L .....124 8 methane . 0 open ends . (see alse transpolyacetylene) 7......... ...........INDEX metalsemiconductor coaxial nanotubes ... .......138 phonon density of states .. .. ... . 7....... ........9 5 molecular polarizabilities ..... polyacetylene (CH). ......... ...........216..... 224 metalsemiconductor junction ............ .......................19 oxidation ........ .... ........... ....... . ... ........151 . 167 Raman experiment ...............2 13 normalized energy gap ............... . power law for the A1........... . mode ..... 32 ... ... ............ . 139 Mott localization . ..........2 parameters of 2D graphite tight binding method .......213 pentagon ............. .... .... .... ........202 phonon mode ... 184 N nanotube junctions .215 2 polyacrylonitrile . MKS (SI) units ... 196 medium frequency modes ..12........... . 147 multiwall nanotubes .. ..
.. 137 resistance....... 223 sound velocity ......191 187 Rh/Pd catalyst ................ resistance of a mesoscopic wire R.........224 SuSchriefferHeeger (SSH) model 213 199 sublattices ................... semitoroidal structure...221 ................. .190 120 regular triangle .....................205 polarization dependence . .......... 17 ... 19 S j .43 spinPeierls interaction ....... 22 unit vector .. .. 205 symmetry vector R .7 sp3 hybridization ... 10) armchair nanotube .................. ................................... 178 sp2 hybridization ..........22 energy dispersion relations .................................... j! 19 tilt and twist boundaries ..........203 scaled force constant ......223 STM image ..79 Rayleigh scattering ................89 timereversed processes A: .........43 rotation around the z axis . 127 resolvent . 133 superlattice ...8 space group symmetry operation R = ( $ 1 ~ ) .......... 203.......... 134 semimetal ........................ Edison ... 22 Brillouin zone ......... 22 transfer integral matrix ...................79 translation r .. 210 strongly localized regime .. 98 tight binding method ......20 secular equation ......139 sample orientation dependence ...........222 207 abonding ...................156 resonant Raman effect ............ 22 ' F I J J I ........................ ..181 secondrank tensor .................. 24 Bloch orbitals .......130 shear modes between two graphite layers ..........147 STS experiments ........ ...................... ................. 1 tight binding approximation in a static magnetic field ........ ...............212 Thomas A ... 224 strain energy per carbon atom ................ 186 selection rules ..... 19 139 transit time t t .. ..................................... ................ 187 rotation angle II...................187 thermal diffusion length L T . 24 reciprocal lattice vector.............................. . 150 rareearth metals ..................... symmetry assignment .168 165..... resonance tunneling ............. 144 137 resistivity.......................151 toroidal carbon nanotube .................................................................. T (10............ ..........................................151 thermal vibration ........................ 43 njjl sample length L ............ 15 tows ........................................ 195 Raman spectra angular dependence ............... sliding motion....... 197 Ramanactive modes .............133 130 torus c 3 6 0 ...........................Raman polarizability parameters .................................................... rope ....... transpolyacetylene irbands ..183 random phase ...................... transition metals .. 23 SJJI .........41 202 symmetrylowering effects ............
...... .....59 ungerade ..123 turbostratic graphite.. ....... ....................Y...............161 valence electrons ..... 9 Young’s modulus Y ..169.132 twisting motion .......... 159 transverse acoust>icmode ... . 80 vaporization temperature ... .......177 tube opening ....... 191 vapor grown carbon fiber ........127. 41 translational vector T ....... 85 tubule axis length .123 tunneling conductance ............................... .. ..... ..............14.....64 zigzag nanotube ............ .... 89 weakly localized regime ..... ..100 twodimensional graphite (see 2Dgrphite) twodimensional van Hove singularities ....... ..........125 twopoint resistance .... 36 zone folding phonon mode .... 211 zerogap semiconductor .. 186 unitary matrix . .. . 77.. . z XPS ....... 172 zonecenter vibrations .................................................. .. 89 twisted helical carbon nanotube ............2...... ... 144 w wavy ribbons ........... 88 vector potential .... .155 259 X...... ...... 123 wrinkled layers ............ .................. ...163............ ...... . 168 universal conductance fluctuations (UCF)127..... ...........160 twodimensional cosine band in a magnetic field .. ........... ...37 transmission probability . 9 5 voltage drop. 183 zonefolding Energy dispersion ......... ........... ...79 vapor growth method ........... 89 ...178 twoband semimetal model .. ....... ...........148..INDEX translation in the direction of T r .... 147 wire frame model ....... 5 vanHove singularities . ......... 144 transport experiments ........
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