tditors The Science and Technology of Carbon Nanotubes The Science and Technology of Carbon Nanotubes Edited by Kazuyoshi Tanaka Kyoto University,Japan Tokio Yamabe Kyoto University,Japan Kenichi Fukui t Institutefor Fundamental Chemistry, Japan '999 Elsevier Amsterdam - Lausanne - New York - Oxford - Shannon - Singapore - Tokyo ELSEVIER SCIENCE Ltd The Boulevard, Langford Lane Kidlington, Oxford OX5 IGB, UK 1999 Elsevier Science Ltd All rights reserved This work is protected under copyright by Elsevier Science and the following terms and conditions apply to its use: Photocopying Single photocopie, of single chapters may be made for personal use as allowed by national copyright laws Permission of the Publisher and payment of a fee is required for all other photwopying including multiple or systematic copying, copying for advertising or promotional purpose\, rewle and all forms of document delivery Special rates are available for educalioiial mslilutions that wish to make photocopics 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advancer in the medical hciences in panicular independent verification of diagnores and drug dorages should be made First edition 1999 Library of Congress Cataloging in Publication Data A catalog record from the Library of Congress has been applied for British Library Cataloguing in Publication Data A catalogue record from the British Library has been applied for ISBN: 08 042696 @The paper used in this publication meets the requirements of ANSI/NISO 239.48-1992 (Permanence of Paper) Printed in The Netherlands V EDITORIAL Carbon nanotube (CNT) is the name of ultrathin carbon fibre with nanometersize diameter and micrometer-size length and was accidentally discovered by a Japanese scientist, Sumio Iijima, in the carbon cathode used for the arcdischarging process preparing small carbon clusters named by fullerenes The structure of CNT consists of enrolled graphitic sheet, in a word, and can be classified into either multi-walled or single-walled CNT (MWCNT or SWCNT) depending on its preparation method It is understood that CNT is the material lying in-between fullerenes and graphite as a quite new member of carbon allotropes It should be recognised that while fullerene has established its own field with a big group of investigators, the raison d'&tre of the CNT should become, and actually has become, more and more independent from that of fullerenes As a novel and potential carbon material, CNTs would be far more useful and important compared with fullerenes from practical points of view in that they will directly be related to an ample field of "nanotechnology" It seems that a considerable number of researchers have been participating into the science of CNTs and there has been remarkable progress in the both experimental and theoretical investigations on MWCNT and SWCNT particularly during the last couple of years Moreover, almost at the same time, an obvious turning point has been marked for the research of CNT toward explicit application targeting, e.g., electronic and/or energy-storing devices These circumstances have assured us that it is high time to prepare an authentic second-generation monograph scoping as far as practical application of CNT in succession of the book earlier published [ I ] covering the results of rather firststage studies on CNT Undcr this planning the present monograph is entitled "The Science and Technology of Carbon Nanotubes" as the successive version of ref for the benefit of actual and potential researchers of these materials by collecting and arranging the chapters with emphasis on the technology for application of CNTs as well as the newest science of these materials written by top-leading researchers including our own manuscripts In Chaps 2-4 most updated summaries for preparation, purification and structural characterisation of SWCNT and MWCNT are given Similarly, the most recent scopes of the theoretical treatments on electronic structures and vibrational structures can be seen in Chaps 5-7 The newest magnetic, optical and electrical solid-state properties providing vital base to actual application technologies are described in Chaps 8- 10 Explosive research trends toward application of CNTs including the prospect for large-scale synthesis are introduced in Chaps 11-14 It is the most remarkable feature of this monograph that it devotes more than a half of the whole volume (Chaps 8-14) to such practical aspects The editors truly appreciate that all of the authors should like to offer the readers the newest developments of the science and technological aspects of CNTs vi It is our biggest sorrow that in the course of preparation of this monograph one of the Editors, Professor Kenichi Fukui, Nobel Laureate of 1981 in Chemistry, passed away on January 9, 1998 As one of the editors he was eager to see actual utilisation of CNT in nanotechnologicaldevices as he described in Chap from the profound scientific viewpoint Finally we would like to express our sincere gratitude to Dr Vijala Kiruvanayagam of Elsevier Science for her kind cooperation as well as encouragementtoward publication of this monograph KAZUYOSHI TANAKA Chief Editor Reference Carbon Nanotubes, ed M Endo, S Iijima and M S Dresselhaus, Pergamon, Oxford, 1996 vii CONTENTS Editorial K Tanaka (Chief Editor) 111 Chapter Prospect late K Fukui Chapter Synthesis and Purification of MultiWalled and Single-Walled Carbon Nanotubes M.Yumura Chapter Electron Diffraction and Microscopy of Carbon Nanotubes S Amelinckx, A Lucas and P Lambin 14 Chapter Structures of Multi-Walled and SingleWalled Carbon Nanotubes EELS Study T Hanada, Y Okada and K Yase 29 Chapter Electronic Structure of Single-Walled Carbon Nanotubes K Tanaka, M Okada and Y Huang 40 Chapter Phonon Structure and Raman Effect of Single-Walled Carbon Nanotubes R Saito, G Dresselhaus and M S Dresselhaus 51 Chapter Behaviour of Single-Walled Carbon Nanotubes in Magnetic Fields H Ajiki and T Ando 63 Chapter Electronic Properties of Carbon Nanotubes Probed by 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108 atomic force microscope (AFA.4) 168, 180 atomic scattering factor 22 ballistic regime I I band gap (bandgap) 42,45, 167 band structure 42 bead-string structure 158 Bessel function 24 bond alternation 43 boron-nitride nanotubes 159 Bruggeman model (BM) 95,100 Brunauer-Emmett-Teller (BET) analysis 147 buckybundle 157 bundle 47, 112, I 19, 144 c 77 13C nuclear magnetic resonance (NMR)42 capillarity I3 capillary effect 177 capillary filling 129, 138 carbolite 158 carbon electrode 160 carbon nanotube (CNT) cavity 132, 136 junction 123 tip 136 carbyne 150 catalyst metal catalytic decomposition of hydrocarbon cathode ray tube (CRT) I77 chemical vapour deposition (CVD) 155 chiral angle 19 chiral vector 41, 108 chiral (or helical)-type carbon nanotube (CNT) 41, 45, 55, 108 185 Clausius-Mossotti expression 140 Clausius-Mossotti model 95 coaxial cylinder model 16 cobalt monoxide (COO)filament I36 coherent quantum wire 170 collar 144 conduction electron spin resonance (CESR) 77 core-loss region 35 coronae 19 Coulomb blockade 120 Coulomb charging energy 17I Curie law 77 current-bias voltage 169 cyclotron orbit 66 density of states (DOS) 167 diamagnetism 78 dielectricconstant 140 dielectric function 95 differential susceptibility 72 diffraction vector 20 dipole moment 96 dirty chemistry I54 disordered stacking model I9 doped carbon nanotube (CNT) 82 dynamical matrix 53 Dysonian 85 effective medium 95, 100 elastic constant 54 electrical conductivity 10 electrochemicalcapacitor I electrolysis 149 electron diffraction (ED) pattern 14 electron energy loss spectroscopy (EELS) 32 electron irradiation 150 electron spectroscopic image (ESI) 33 electron spin resonance (ESR) 77 electron spin resonance (ESR) linewidth 78,90 Endo pyrolytic carbon nanotube (Endo PCNT) 146 energy dispersive X-ray spectroscopy (EDX) 139 energy-loss near-edge structure (ELNES) 32 Ewald’s construction 23 exciton 69 extended energy-loss fine-structure (EXELFS) 32 far infrared (FIR) absorption 93 186 Fermi energy I 16 field emission 7, 123, 159, 175 field-effect transistor ( E T ) 172 filling material droplet 137 force constant 52 Fowler-Nordheimmodel 176 g-value 78 Gatan imaging filter (GIF) 33 graphene sheet 159 graphite electron mobility 154 154, 160 intercalation compound (GTC) sound velocity 154 thermal conductivity 154 helical (or chira1)-type carbon nanotube (CNT) 41,45,55, 108 hexagonal lattice I8,59 high-resolution electron micrograph (HREM) 133, 136 high-resolution transmission electron microscopy (HRTEM) 26 77, highly oriented pyrolytic graphite (HOPG) 92, 116 hologram generation 159 homogeneous shear model 19 host medium 101 hydrogen arc 158 hydrogen storage 160, I78 Hyperion pyrolytic carbon nanotube (Hyperion PCNT) 147 inelastic mean free path I I I inter-chain barrier 166 inter-layer hopping 166 intercalatedcarbon nanotube 158 intercalated graphite 82 intercalation 122, 180 interlayer interaction 47 intertube interaction 47 K-shell3 KekulC distortion 69 KekulC type 44 kinematical diffraction theory 20 Korringa-like relation 42 Kramers-Kronig transformation 92 k*pequation 65 L-shell3 Landau level 66, I 16 187 laser ablation 4,9,144 laser vapourisation 144 lattice distortion 69 lattice fringe 16 lead-compound filling 137 light-emitting diode 164 linewidth (see electron spin resonance linewidth) liquid surface tension 13I liquid-solid contact angle 131 lithium-ion (secondary) battery 160, I78 local-density approximation (LDA) I77 localised orbital 177 longitudinal acoustic (LA) mode 54 Lorentz-Drudemodel 97 low-temperature graphitisation 155 luminescence intensity 177 magnetic length 78 magnetic moment 73 magnetic susceptibility I magnetisation 72 magnetoconductance 17 magnetoresistance 74, 115, 159 matrix display 177 Maxwell-Garnett (GM) model 94,95 mean free path I IO mesoscopic system metal catalyst 144, 145 metal phthalocyanine I56 metal-insulator transition 43 metallic (propertye) 42,46, 92, 165 mirror symmetry 69 moire pattern I7 nanoparticle nanorod 132,136,158 nanoscale device (nanodevice) 164, 168 nanoscale void 178 nanotechnology 165 nanowire 158 narrow-gap semiconductive 46 optical absorption 67 optical conductivity 92, 103, 167 p-n junction 158 x plasmon 34 188 x-conjugated conducting polymer I n-electron bonding 153 n-electron material 153, 157 Pauli spin matrices 64 Pauli susceptibility 42, 77, 90 Peierls transition , 108 percolation limit 100 phonon density of states (DOS) 53 phonon dispersion 52 photovoltaic device 179 plasmon loss 34 polarisability 140 polarisation 67, 96 polyacetylene 43, 164 polymer/C60 interface 179 purification 8, 10 pyrolytic carbon nanotube (PCNT) 146 quantum transport I5 Raman intensity 55 Raman spectra 52,59 Raman-active mode 52 rectifying effect I78 reflectivity 92, 103 reflexion 18 relativistic Dirac equation 70 resonant tunnelling 115 rope 16, 23, 47, 12, 171 rotating-cathode arc-discharge Russian-doll structure 158 scanning electron microscope (SEM) 7, 158 scanning force microscopy (SFM) 173 scanning tunnelling microscope (STM) 3, 167 scanning tunnelling spectroscopy (STS) 167 scattering density 23 Schradinger-cat state I scooter mechanism 157 semiconductor I65 semimetallic behaviour 84 silicon carbide 148 simple two-band (STB) model 115 single electron tunnelling 170 single microbundle I 13 single-molecule transistor 120 soluble carbon nanotube (CNT) 180 189 spin susceptibility 83 streaked spot 14 superconductingquantum interferencedevice (SQUID) 77 superconductivity 48 surface tension threshold 129 thermal oxidation 130, 133 thermoelectric power (TEP) 121 tight-binding 42, 65 tight-binding molecular dynamics (TBMD) 52 transmission electron diffraction (TED) 30 transmission electron microscope (or -py) ( E M ) 8,30,32, 134, 156 transverse acoustic (TA) mode 53 transverse optical (TO) phonon mode 93 twisting acoustic (TW) mode 54 two-dimensional (2D) graphite 52,64, I59 ultra-fine probe I64 universal conductance fluctuation (UCF) 117,159 van der Waals force 15, 140 vapour-grown carbon fibre (VGCF) 143, 145 weak localisation I I , 165 wetting 131 Weyl's equation 64 wide-gap semiconductive46 Young's modulus 54 zigzag-type carbon nanotube (CNT) 41,45,53,55, 108 190 AUTHOR INDEX Ago, H 164 Ajiki, H 63 Amelinckx, S 14 Ando, T 63 Bommeli, F 89 Bonard, J -M 128 Charlier, J -C 107 Ch2telain, A 128 de Heer, W A 89, 128 Degiorgi, L 89 Dresselhaus, G 51 Dresselhaus, M S 51 Endo, M 143 Forro, L 89 Fukui, K Hanada, T., 29 HSU,W -K 143 Huang, Y 40 Issi, J -P 107 Kosaka, M 76 Kroto, H W 143 Lambin, P 14 Lucas, A 14 Okada, M 40 Okada, Y 29 Saito, R 51 Stockli, T 128 Takeuchi, K 143 Tanaka, K 40, 143 Tanigaki, K 76 191 Terrones, M 143 Ugarte, D 128 Walton, D R M 143 Yamabe, T 164 Yase, K 29 Yoshimura, S 153 Yumura, M ... this planning the present monograph is entitled "The Science and Technology of Carbon Nanotubes" as the successive version of ref for the benefit of actual and potential researchers of these materials... The Science and Technology of Carbon Nanotubes The Science and Technology of Carbon Nanotubes Edited by Kazuyoshi Tanaka Kyoto University,Japan... 1271 It would be of most importance to establish the controllability of the diameter and the helical pitch in this kind of synthesis of SWCNT toward the development of novel kinds of electronic