Tài liệu Tổng hợp, cấu trúc, tính chất và ứng dụng của ống nanocarbon

Contents
Foreword . V
References . IX
Preface . XI
Introduction to the Important and Exciting Aspects of
Carbon-Nanotube Science and Technology
David Tom´anek, Ado Jorio, Mildred S. Dresselhaus, and Gene
Dresselhaus 1
1 Introduction 1
2 Applications and Metrology 3
3 Synthesis . 4
4 Defect Control 5
5 Mechanical and Thermal Properties . 5
6 Electronic Structure and Atomic Arrangement 6
7 Advances in Photophysics 8
8 Transport Properties . 9
9 Double-Wall Carbon Nanotubes . 10
10 Chemical Reactivity . 10
11 Related Structures . 10
12 Graphene 11
13 Outlook 11
Index 12
Potential Applications of Carbon Nanotubes
Morinobu Endo, Michael S. Strano, and Pulickel M. Ajayan 13
1 Introduction 13
2 Applications of Carbon Nanotubes 16
2.1 Carbon Nanotubes in Electronics . 17
2.2 Carbon Nanotubes in Energy Applications . 22
2.3 Carbon Nanotubes for Mechanical Applications . 27
2.4 Carbon-Nanotube Sensors . 31
2.5 Carbon Nanotubes in Field Emission
and Lighting Applications . 36
2.6 Carbon Nanotubes for Biological Applications 38
XIV Contents
2.7 Carbon Nanotubes in Miscellaneous Applications . 42
2.8 Environmental and Health Effects of Carbon Nanotubes . 45
3 Conclusions . 46
References . 49
Index 61
Carbon-Nanotube Metrology
Ado Jorio, Esko Kauppinen, and Abdou Hassanien . 63
1 Introduction 63
2 Electronic Microscopy 65
2.1 Introduction . 65
2.2 Sample Preparation . 66
2.3 Morphology 67
2.4 Atomic Structure by HRTEM 68
2.5 Chiral Indices Determination by Electron Diffraction 70
2.5.1 Bessel-Function Analysis . 70
2.5.2 Intrinsic Layerline Distance Analysis . 70
3 Scanning Probe Microscopy . 71
3.1 Introduction . 71
3.2 Sample Preparation . 73
3.3 Imaging the Structure and Electronic Properties of SWNTs 73
3.4 Single-Electron States of SWNTs . 76
3.5 Defects 77
3.6 Local Vibrational Spectroscopy in SWNTs . 78
4 Optics . 79
4.1 Basic Principles 79
4.2 Optical Absorption . 82
4.3 Resonance Raman Spectroscopy 83
4.3.1 The Radial Breathing Mode (RBM) . 85
4.3.2 The Tangential Modes (G Band) 87
4.3.3 The Disorder-Induced Feature (D Band) . 89
4.3.4 Other Raman Features . 89
4.4 Photoluminescence 90
5 Summary and Outlook . 91
References . 93
Index 99
Carbon Nanotube Synthesis and Organization
Ernesto Joselevich, Hongjie Dai, Jie Liu, Kenji Hata,
and AlanH. Windle . 101
1 Introduction 102
2 Bulk Production Methods 103
2.1 Arc Discharge and Laser Vaporization . 103
2.2 Chemical Vapor Deposition (CVD) 103
2.3 Mass Production . 105
Contents XV
2.4 Toward Selective Synthesis . 106
3 Purification . 107
3.1 Dry Methods . 107
3.2 Wet Methods . 108
4 Sorting . 109
4.1 Classification of Sorting Methods and Selective Processes 109
4.2 Nondestructive Sorting 110
4.3 Selective Elimination 114
4.4 General Principles and Perspectives of Sorting 115
5 Organization into Fibers . 116
5.1 Processing Principles 117
5.2 Liquid Suspensions of Carbon Nanotubes 118
5.3 Spinning Carbon Nanotube Fibers from Liquid-
Crystalline Suspensions 119
5.4 Wet Spinning of CNT Composite Fibers . 120
5.5 Dry Spinning from Carbon Nanotube Forests . 122
5.6 Direct Spinning from Carbon Nanotube Fibers
from the CVD Reaction Zone 123
6 Organization on Surfaces . 125
6.1 Vertically Aligned Growth and Supergrowth 126
6.1.1 Supergrowth 126
6.1.2 SWNT-Solid 131
6.2 Organized Assembly of Preformed Nanotubes 133
6.3 Horizontally Aligned Growth . 137
6.3.1 Field-Directed Growth . 137
6.3.2 Flow-Directed Growth . 139
6.3.3 Surface-Directed Growth: “Nanotube Epitaxy” 141
6.3.4 Patterned Growth on Surfaces 147
7 Summary and Outlook . 148
References . 149
Index 163
Mechanical Properties, Thermal Stability and Heat
Transport in Carbon Nanotubes
Takahiro Yamamoto, Kazuyuki Watanabe, and Eduardo R. Hern´andez 165
1 Introduction 165
2 Mechanical Properties and Thermal Stability of Nanotubes . 167
2.1 Elasticity at the Nanoscale . 167
2.2 Mechanical Properties of Nanotubes: Elastic Regime 167
2.3 Beyond the Elastic Regime . 172
2.4 Thermal Stability of Nanotubes 175
2.5 Summary of Mechanical Properties and Thermal Stability . 177
3 Heat-Transport Properties 178
3.1 Ballistic Heat Transport in SWNTs . 178
3.1.1 Landauer Theory for Phonon Transport 178
XVI Contents
3.1.2 Quantization of Thermal Conductance . 180
3.1.3 Electron Contribution to the Thermal Conductance 181
3.2 Quasiballistic Heat Transport in SWNTs 182
3.2.1 Length Effect of the Thermal Conductivity . 182
3.2.2 Influence of Defects on the Thermal Conductivity . 184
3.3 Diffusive Heat Transport in SWNTs . 185
3.4 Heat Transport in MWNTs 186
3.5 Summary of Heat Transport . 188
4 Summary and Outlook . 188
References . 189
Index 194
Quasiparticle and Excitonic Effects in the Optical Response
of Nanotubes and Nanoribbons
Catalin D. Spataru, Sohrab Ismail-Beigi, Rodrigo B. Capaz, and
Steven G. Louie 195
1 Introduction 196
2 Methodology 197
3 First-Principles Studies of the Optical Spectra of SWNTs 199
4 Diameter and Chirality Dependence of Exciton Properties 204
5 Symmetries and Selection Rules of Excitons 206
6 Radiative Lifetime . 210
7 Pressure, Strain and Temperature Effects . 214
8 Related Structures: Boron-Nitride Nanotubes
and Graphene Nanoribbons . 216
9 Conclusion . 221
References . 222
Index 227
Role of the Aharonov–Bohm Phase in the Optical Properties
of Carbon Nanotubes
Tsuneya Ando . 229
1 Introduction 229
2 Effective-Mass Description 229
3 Excitons . 233
4 Exciton Fine Structure and Aharonov–Bohm Effect 236
5 Exciton Absorption for Crosspolarized Light 240
6 Optical Phonons 242
References . 246
Index 249
Excitonic States and Resonance Raman Spectroscopy
of Single-Wall Carbon Nanotubes
Riichiro Saito, Cristiano Fantini, and Jie Jiang . 251
1 Introduction 251
1.1 Outline 251
Contents XVII
1.2 Overview of Resonance Raman Measurements 252
1.3 Overview of the Raman Intensity Calculation 253
2 Measurement of Raman Spectra . 255
2.1 Raman Spectra of SWNTs . 255
2.2 The Radial Breathing Mode 255
2.3 G-Band . 257
2.4 D-Band . 260
2.5 G-Band . 261
2.6 Intermediate-Frequency Modes . 262
2.7 Other Two-Phonon Modes . 264
3 Resonance Raman Profile 264
3.1 Experimental Optical Transition Energies 264
4 Electron–Phonon and Electron–Photon Matrix Elements . 267
4.1 Extended Tight-Binding Method for Electrons and Phonons 267
4.2 Dipole Approximation for the Optical Matrix Element . 269
4.3 Electron–Phonon Matrix Element Calculation 270
4.4 Extension to the Exciton Matrix Element Calculation . 272
4.5 Raman Intensity Calculation . 275
4.6 RBM and G-Band: Length, Type, Chirality,
and Diameter Dependence . 276
5 Future Directions, Summary 279
References . 280
Index 285
Photoluminescence: Science and Applications
Jacques Lefebvre, Shigeo Maruyama, and Paul Finnie . 287
1 Introduction 287
2 Basic Photoluminescence Spectroscopy of Isolated Nanotubes . 288
2.1 Model . 288
2.2 Absorption . 290
2.3 Photoluminescence from Isolated SWNTs 291
2.4 Photoluminescence Excitation Map . 293
2.5 Exciton Picture . 296
3 Spectroscopic Properties of Nanotube Photoluminescence . 298
3.1 Lineshape 298
3.2 Polarization 299
3.3 Quantum Efficiency . 300
3.4 Photoluminescence Imaging 303
3.5 Time Dependence . 304
3.6 Phonons . 305
4 Physical and Chemical Effects 306
4.1 External Environment . 306
4.2 External Physical Parameters 308
5 Applications 310
5.1 Nanotube Research . 310
XVIII Contents
5.2 Wider Applications . 312
6 Conclusion . 313
References . 314
Index 318
Ultrafast Spectroscopy of Carbon Nanotubes
Ying-Zhong Ma, Tobias Hertel, Zeev Valy Vardeny,
Graham R. Fleming, and Leonas Valkunas . 321
1 Introduction 321
2 Background 322
2.1 Instrumentation for Ultrafast Spectroscopy . 322
2.2 Basics of Nonlinear Optics . 324
3 Metallic Tubes 327
4 Semiconducting Tubes . 328
4.1 Exciton Dynamics 329
4.2 Low Excitation Densities 330
4.2.1 Intersubband Relaxation . 331
4.2.2 Radiative Lifetime . 331
4.2.3 Correlation of the PL Decay Timescales
with the Tube Diameter 332
4.2.4 Environmental and Temperature Effects
on Exciton Population Dynamics 333
4.2.5 Transient Absorption of a Chirality-
Enriched SWNT Preparation . 336
4.3 High Excitation Densities 338
4.3.1 Spectroscopic and Dynamic Signatures of High-
Intensity Excitation . 338
4.3.2 Theoretical Advances 342
4.3.3 Exciton Dissociation . 343
5 Comparison of S-SWNTs with π-Conjugated Polymers . 344
6 Summary . 346
References . 347
Index 352
Rayleigh Scattering Spectroscopy
Tony F. Heinz 353
1 Introduction 353
2 Elastic Light Scattering 354
3 Experimental Technique 356
4 Application of the Technique 360
4.1 Electronic Transitions of Nanotubes
of Independently Determined Structure 360
4.2 Polarization Dependence of Nanotube Electronic Transitions . 361
4.3 Structural Stability Along the Nanotube Axis 362
4.4 Nanotube–Nanotube Interactions . 363
Contents XIX
5 Outlook 364
References . 366
Index 368
New Techniques for Carbon-Nanotube Study
and Characterization
Achim Hartschuh . 371
1 Introduction 371
2 Near-Field Optical Microscopy 371
2.1 Experimental . 372
2.2 Results 373
2.2.1 Nanoscale Optical Imaging . 373
2.2.2 Nanoscale Optical Spectroscopy . 375
2.3 Outlook . 377
3 Phonon Spectroscopy Using Inelastic Electron Tunneling . 378
3.1 Experimental . 378
3.2 Results 379
3.3 Outlook . 382
4 Coherent Phonon Generation and Detection 383
4.1 Results 384
4.2 Outlook . 389
References . 389
Index 392
High Magnetic Field Phenomena
in Carbon Nanotubes
Junichiro Kono, Robin J. Nicholas, and Stephan Roche 393
1 Introduction 393
2 Band Structure in Magnetic Fields 394
2.1 Parallel Field: Role of the Aharonov–Bohm Phase . 394
2.2 Perpendicular Field: Onset of Landau Levels . 395
3 Magnetization 397
3.1 Theory of the Magnetic Susceptibility . 397
3.2 Magnetic-Susceptibility Measurements . 399
4 Magneto-transport 400
4.1 Disorder and Quantum Interference . 401
4.2 Weak Localization and Magnetoresistance Oscillations . 401
4.3 Most Recent Experiments 404
5 Magneto-Optics . 405
5.1 Bandgap Shrinkage and Aharonov–Bohm Splitting 406
5.2 Magnetic Brightening of “Dark” Excitons: Theory 407
5.3 Magnetic Brightening of “Dark” Excitons: Experiment 410
5.4 Perpendicular Field Effects . 414
6 Summary and Remaining Problems 415
References . 416
XX Contents
Index 421
Carbon-Nanotube Optoelectronics
Phaedon Avouris, Marcus Freitag, and Vasili Perebeinos . 423
1 The Nature of the Optically Excited State 423
2 Exciton Properties 425
2.1 Low-Energy Exciton Bandstructure –
Dark and Bright Excitons 425
2.2 Exciton Radiative and Nonradiative Lifetimes 427
2.3 Exciton–Optical Phonon Sidebands in Absorption Spectra . 428
2.4 Impact Excitation, Auger Recombination
and Exciton Annihilation 430
2.5 Franz–Keldysh, Stark Effects and Exciton Ionization
by Electric Fields . 433
3 Overview of CNT Electronics – Unipolar and Ambipolar FETs 435
4 Photoconductivity and Light Detection 436
4.1 Types of Nanotube Photodetectors 436
4.2 CNT Photoconductor . 437
4.3 Photocurrent Spectroscopy and Quantum Efficiency . 437
4.4 Photovoltage in Asymmetric CNTFETs –
Schottky-Barrier Diodes . 439
4.5 Photovoltage in a CNT p–n Junction 440
4.6 Photovoltage Imaging . 441
5 Electroluminescence . 442
5.1 Ambipolar Mechanism . 442
5.2 Mechanism of the Spot Movement in Ambipolar Transistors 443
5.3 Electroluminescence Spectrum and Efficiency
of the Radiative Decay 444
6 Unipolar Mechanism for Infrared Emission 444
7 Conclusions – Future 446
References . 448
Index 453
Electrical Transport in Single-Wall Carbon Nanotubes
Michael J. Biercuk, Shahal Ilani, Charles M. Marcus,
and Paul L. McEuen 455
1 Introduction and Basic Properties . 455
1.1 Band Structure . 456
1.2 1D Transport in Nanotubes 458
2 Classical (Incoherent) Transport in Nanotubes 460
2.1 Contacts to Nanotubes: Schottky Barriers . 460
2.2 The Effect of Disorder . 463
2.3 Electron–Phonon Scattering in Nanotubes . 464
3 Nanotube Devices and Advanced Geometries . 466
3.1 High-Performance Transistors 467
Contents XXI
3.2 Radio-Frequency and Microwave Devices . 469
3.3 P–N Junction Devices . 470
4 Quantum Transport . 474
4.1 Quantum Transport in One Dimension 474
4.1.1 Luttinger Liquid 474
4.1.2 Ballistic Transport 476
4.2 Superconducting Proximity Effect . 476
4.3 Quantum Transport with Ferromagnetic Contacts . 478
5 Nanotube Quantum Dots . 479
5.1 Single Dots 480
5.2 Band and Spin Effects in Single Quantum Dots . 480
5.2.1 Shell Filling in Nanotube Dots 480
5.2.2 Nanotube Dots with Ferromagnetic Contacts . 481
5.3 Kondo Effects in Nanotube Dots 481
5.3.1 Nonequilibrium Singlet–Triplet Kondo Effect 482
5.3.2 Orbital and SU(4) Kondo 482
5.4 Multiple Quantum Dots . 483
6 Future Directions 484
References . 485
Index 492
Double-Wall Carbon Nanotubes
Rudolf Pfeiffer, Thomas Pichler, Yoong Ahm Kim, and Hans Kuzmany 495
1 Introduction 495
1.1 Fingerprints of Double-Wall Carbon Nanotubes . 496
2 Preparation of Double-Wall Carbon Nanotubes 496
2.1 DWNT Growth from Chemical Vapor Deposition . 497
2.2 DWNT Growth from Precursor Material . 501
2.2.1 DWNT Growth from Fullerene Peapods 501
2.2.2 DWNT Growth from Ferrocene . 503
2.2.3 DWNT Growth from Other Carbon Precursors 506
2.2.4 Theoretical Models for the Fullerene Coalescence 507
3 Properties and Applications of DWNTs 508
3.1 Electronic and Optical Properties, Transport . 508
3.1.1 Model Calculations 509
3.1.2 Experimental Results for Electronics and Structure 511
3.1.3 Transport 511
3.2 Raman Scattering 512
3.2.1 The Nature of the Radial Breathing Mode Response . 513
3.2.2 Tangential Modes and Overtones 513
3.2.3 Temperature, Pressure, and Doping Effects . 514
3.3 13C Substitution and Nuclear Magnetic Resonance 516
3.4 Thermal and Chemical Stability, Mechanical Properties 517
3.4.1 Thermal Stability . 518
XXII Contents
3.4.2 Pore Structure and Oxidative Stability
of the Bundled DWNTs . 518
3.4.3 Mechanical Properties . 520
4 Summary and Outlook . 521
4.1 Outlook . 522
References . 523
Index 530
Doped Carbon Nanotubes: Synthesis, Characterization
and Applications
Mauricio Terrones, Antonio G. Souza Filho, and Apparao M. Rao 531
1 Introduction 531
2 Exohedral Doping or Intercalation . 532
3 Endohedral Doping or Encapsulation 533
4 Inplane or Substitutional Doping 534
4.1 Substitutional Doping in Graphite 534
4.2 Substitutional Doping in Nanotubes . 534
4.3 Synthesis Methods for Substitutional Doped Nanotubes . 537
4.3.1 Arc-Discharge Method . 537
4.3.2 Laser-Ablation Method 537
4.3.3 Chemical Vapor Deposition . 538
4.3.4 B and N Substitution Reactions . 538
4.3.5 Plasma-Assisted CVD 540
5 Characterization Techniques for Studying Doped Nanotubes 540
5.1 Morphological and Structural Characterization . 540
5.1.1 Atomic Structure of N-Doped MWNTs . 541
5.1.2 Atomic Structure of B-Doped MWNTs . 542
5.1.3 Atomic Structure of Doped SWNTs . 542
5.2 Electronic and Transport Characterization . 543
5.3 Raman Characterization . 546
5.3.1 Nonsubstitutional n-Type Doped Nanotubes 546
5.3.2 Nonsubstitutional p-Type Doped Nanotubes 550
5.3.3 Raman Spectroscopy for Inplane Doped Nanotubes 551
6 Applications of Doped Nanotubes . 553
7 Perspectives and Challenges 555
References . 558
Index 566
Electrochemistry of Carbon Nanotubes
Ladislav Kavan and Lothar Dunsch . 567
1 Electrochemistry of Nanotubes: Fundamentals 567
1.1 Introduction . 567
1.2 Potential-Dependent Reactions . 568
1.3 Faradaic and Non-Faradaic Processes
in Nanocarbons (Nanotubes, Fullerenes) . 569
Contents XXIII
1.4 Doping of Nanocarbons 571
2 Experimental Techniques . 575
2.1 Materials in Electrochemical Studies of Nanotubes 575
2.2 Voltammetry . 575
2.3 Methods of Spectroelectrochemistry . 578
3 Practical Applications of Charge Transfer at Nanotubes 579
3.1 Electrochemical Synthesis and Behavior of Nanotubes . 579
3.2 Practical Devices . 580
4 Spectroelectrochemistry of Nanotubes 582
4.1 Vis-NIR Spectroelectrochemistry . 582
4.2 Raman Spectroelectrochemistry 585
4.2.1 SWNTs 586
4.2.2 Fullerene Peapods . 589
4.2.3 Double-Walled Carbon Nanotubes . 589
4.3 Combined Chemical/Electrochemical Doping . 592
4.4 Single-Nanotube Studies . 593
5 Summary and Outlook . 594
References . 595
Index 602
Single-Wall Carbon Nanohorns and Nanocones
Masako Yudasaka, Sumio Iijima, and Vincent H. Crespi . 605
1 Introduction 605
2 Geometrical Definition of the Cone 606
3 Structure, Production, and Growth Mechanism
of Single-Wall Carbon Nanohorns . 607
4 Properties of Single-Wall Nanohorns . 611
5 Applications of Single-Wall Nanohorns . 612
6 Comparison of Single-Wall Nanohorns
to Single-Wall Nanotubes . 616
7 Mechanical Response of Carbon Nanocones . 617
8 Electronic Properties of Carbon Cones . 619
9 Conclusion . 622
References . 622
Index 628
Inorganic Nanotubes and Fullerene-Like Structures (IF)
R. Tenne, M. Remˇskar, A. Enyashin, and G. Seifert . 631
1 Introduction 631
2 Synthesis of INT and IF Materials . 634
2.1 Physical Techniques . 634
2.2 Soft Chemistry “Chemie Douce” 637
2.3 High-Temperature Reactions . 639
3 Structural Characterization and Stability . 641
3.1 General Considerations 641
XXIV Contents
3.2 Strain-Relaxation Mechanisms in the Nanotubes 643
3.3 Studies of Some Specific Systems . 645
4 Physical Properties 649
4.1 Mechanical Properties . 649
4.2 Electronic and Optical Properties . 651
5 Applications 655
5.1 Tribological Applications 655
5.2 Towards High-Strength Nanocomposites . 656
5.3 Li Intercalation and Hydrogen Sorption in MS2 Nanotubes . 656
5.4 Solar Cells, Photocatalysis and Sensors 657
5.5 Biotechnology 658
5.6 Catalysis 658
6 Conclusions . 659
References . 660
Index 669
Electron and Phonon Properties of Graphene: Their
Relationship with Carbon Nanotubes
J.-C. Charlier, P. C. Eklund J. Zhu, A. C. Ferrari . 673
1 Introduction 673
2 Electronic Properties and Transport Measurements 675
2.1 Graphene 675
2.1.1 Electronic Band Structure 675
2.1.2 Transport Measurements in Single-Layer Graphene 678
2.2 Graphene Nanoribbons 681
2.3 Graphite and n-Graphene Layer Systems 684
3 Optical Phonons and Raman Spectroscopy . 686
3.1 Raman D and G Bands, Double Resonance
and Kohn Anomalies 686
3.2 Electron–Phonon Coupling from Phonon Dispersions
and Raman Linewidths 689
3.3 The Raman Spectrum of Graphene
and n-Graphene Layer Systems . 690
3.4 Doped Graphene: Breakdown of the Adiabatic Born–
Oppenheimer Approximation . 694
4 Implications for Phonons and Raman Scattering in Nanotubes 697
4.1 Adiabatic Kohn Anomalies . 697
4.2 Nonadiabatic Kohn Anomalies 698
4.3 The Raman G Peak of Nanotubes 698
5 Outlook 701
References . 701
Index 708
Index . 711