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Advances in Carbon Nanomaterials: Science and Applications
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ISBN 978-981-426-78-78 (Hardcover)
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Contents
Preface
xiii
1 Encyclopedia of Carbon Nanoforms 1
Irene Suarez-Martinez, Nicole Grobert,
and Christopher P. Ewels
1.1 Introduction 1
1.2 Graphene 5
1.2.1 The Structure of Graphene 5
1.2.2 Synthesis Methods for Graphene 6
1.2.3 Terminology 6
1.2.4 Graphene-Related Forms: Graphene Nanowalls
and Graphene Nanoribbons 7
1.2.5 Applications of Graphene 8
1.3 Carbon Nanotubes 9
1.3.1 The Structure of Carbon Nanotubes 10
1.3.2 Synthesis Methods for Carbon Nanotubes 14
1.3.3 Applications of Carbon Nanotubes 14
1.4 Carbon Nanoscrolls 16
1.4.1 The Structure of CNSs 17
1.4.2 Synthesis Method for CNSs 18
1.4.3 Applications of CNSs 20
1.5 Carbon Nanocones 20
1.5.1 The Structure of Carbon Nanocones 21
1.5.2 Terminology 22
1.5.3 Synthesis of Carbon Nanocones 24
1.6 Applications of Carbon Nanocones 24
1.7 “Bamboo” Nanotubes 25
1.7.1 Synthesis of Bamboo Nanotubes 25
1.7.2 Applications of Bamboo Nanotubes 26

vi
Contents
1.8 “Herringbone” Nanotubes 27
1.8.1 The Structure of Herringbone Nanotubes
and Nanofibers 27
1.8.2 Herringbone Synthesis 29
1.8.3 Herringbone Applications 29
1.9 Helical Nanotubes 30
1.9.1 Synthesis of Helical Nanotubes 31
1.9.2 Topology of Helical Nanotubes 32
1.9.3 Applications of Helical Nanotubes 33
1.10 “Necklace” Tubes/Nanobells 33
1.11 Fullerenes 35
1.11.1 Fullerene Synthesis 37
1.11.2 Fullerene Chemistry 38
1.11.3 Fullerene Applications 38
1.11.4 Ultra-Hard Fullerites 39
1.12 Onions 39
1.13 Nanotori and Circular Nanotube Bundles 43
1.14 Hybrid Nanoforms 45
1.14.1 Hybrid Forms Based on Filling
(Peapods etc.) 46
1.15 Hybrid Forms Based on Surface Interaction 48
1.16 Other Molecular Forms 49
1.17 Non-Hexagon-Based SP 2 Carbon Nanoforms 50
1.17.1 Schwarzites: Heptagon (and
Above)-Hexagon Networks 50
1.17.2 Haeckelites: Pentagon–(Hexagon)–
Heptagon Networks 51
1.18 Conclusions 52
2 Surfaces and Thin Films of Fullerenes 67
Roberto Macovez and Petra Rudolf
2.1 Introduction 68
2.2 Preparation of Fullerene Thin Films 70
2.3 Monolayer Systems 72
2.4 Properties of Multilayer and Thick C 60 Films 76
2.4.1 Electronic States 76
2.4.2 Molecular Orientations and Surface
Morphology 81

Contents
vii
2.5 Thin Films and Surfaces of Fullerides 85
2.5.1 Alkali Fullerides 85
2.5.2 Thin Films of AE and RE Fullerides 92
2.6 Thin Films of Endohedral Fullerenes 96
2.7 Conclusions and Outlook 103
3 High-Resolution Transmission Electron Microscopy
Imaging of Carbon Nanostructures 117
Kazu Suenaga, Yuta Sato, Zheng Liu, Masanori Koshino,
and Chuanhong Jin
3.1 Introduction 118
3.2 Experimental 118
3.3 Visualization of Atomic Defects in Carbon Nanotubes 119
3.4 Imaging of Fullerenes and Their Derivatives 123
3.5 In Situ Observation of Nano-Carbon Growth 127
3.6 Summary 129
4 Electronic and Optical Properties of Carbon Nanotubes 131
Christian Kramberger and Thomas Pichler
4.1 The Electronic Ground State 131
4.1.1 From Graphene to Carbon Nanotubes 134
4.1.2 Types and Families 138
4.1.3 Tight Binding versus First Principles 144
4.2 Electronic Excitations 147
4.2.1 Excitonic Inter-Band Excitations 148
4.2.2 Valence and Core Holes 151
4.2.3 Collective Plasma Excitations 152
4.3 Spectroscopic Methods 154
4.3.1 Optical Absorption Spectroscopy 155
4.3.2 Electron Energy Loss Spectroscopy 156
4.3.3 Luminescence Spectroscopy 157
4.3.4 Raman Spectroscopy 158
4.3.5 Photoemission Spectroscopy 159
4.3.6 X-Ray Absorption Spectroscopy 159
4.4 Spectroscopy on Nanotubes 160
4.4.1 Van Hove Singularities 161
4.4.2 Electronic Response 166
4.4.3 Opto-Mechanical Response 172

viii
Contents
4.4.4 Alignment 175
4.4.5 Metallic and Semiconducting Abundances 178
4.4.6 Diameter Distribution 179
4.4.7 Crystallinity 179
4.4.8 Purity 180
4.5 Summary 181
5 Fullerene-Based Electronics 189
James M. Ball, Paul H. Wöbkenberg,
and Thomas D. Anthopoulos
5.1 Introduction 189
5.2 Properties of Fullerenes 192
5.2.1 Electronic Properties 193
5.2.2 Thin-Film Processing 195
5.2.3 Why These Properties Are Desirable for
Electronics and Optoelectronics 197
5.3 Thin-Film Transistors, Integrated Circuits, and OPV 198
5.3.1 Thin-Film Transistors 198
5.3.2 Integrated Circuits 202
5.3.3 Organic Photovoltaics 205
5.3.4 Charge Transport in Organic Semiconductors 208
5.4 Electron Transport in Fullerene Thin-Film Transistors 211
5.4.1 Electron Injection 211
5.4.2 Electron Transport in C 60 ,C 70 ,andC 84 Devices 212
5.4.3 Electron Transport in Solution Processed C 60 -,
C 70 -, and C 84 - PCBM Devices 215
5.4.4 Electron Transport in Devices with Alternative
Fullerene Derivatives 216
5.5 Ambipolar Transport in Fullerene Thin-Film
Transistors 218
5.5.1 Ambipolar Transport in Fullerene
Transistors 219
5.6 Fullerene-Based Microelectronics 219
5.6.1 Unipolar Logic Circuits 220
5.6.2 Complementary Logic Circuits 220
5.6.3 Complementary-Like Logic Circuits 221
5.7 Fullerene-Based Optoelectronics 222
5.7.1 Fullerene-Based BHJ OPV 223

Contents
ix
5.7.2 Fullerene-Based Phototransistors and
Electro-Optic Circuits 227
5.8 Summary and Perspectives 230
6 Carbon Nanohorns Chemical Functionalization 239
Georgia Pagona and Nikos Tagmatarchis
6.1 Introduction 240
6.2 Chemical Functionalization of CNHS 243
6.2.1 Covalent Functionalization 243
6.2.1.1 1,3-dipolar cycloaddition of in situ
generated azomethine ylides 243
6.2.1.2 Aryl addition via in situ generated aryl
diazonium salts 246
6.2.1.3 Bingel cyclopropanation reaction 247
6.2.1.4 Anionic polymerization 249
6.2.1.5 Bulk free radical polymerization 250
6.2.1.6 NaNH 2 addition and amination
reactions 250
6.2.1.7 Oxidation 252
6.2.2 Non-Covalent Functionalization 257
6.3 Conclusions and Outlook 262
7 Endohedral Metallofullerene Functionalization 269
Yutaka Maeda, Takeshi Akasaka, and Shigeru Nagase
7.1 Introduction 270
7.2 Reduction and Oxidation 270
7.3 Disilylation 272
7.4 Reaction with Nitrogen Compounds 275
7.5 Prato Reaction 276
7.6 Cycloaddition of Diene and Benzyne 279
7.7 Addition of Carbene 281
7.8 Nucleophilic Addition 284
7.9 Radical Addition 287
7.10 Conclusion 290
8 Quantum Computing with Endohedral Fullerenes 299
Kyriakos Porfyrakis and Simon C. Benjamin
8.1 Introduction 299

x
Contents
8.2 Classical Information 300
8.3 Information Inside a Classical Computer 301
8.4 Introducing the Quantum Bit, or Qubit 303
8.5 Understanding the Qubit: The Bloch Sphere 304
8.6 More Than One Qubit: Entanglement 307
8.7 Basic Components of a Processor 308
8.7.1 Elements of a Classical Processor 308
8.7.2 A Notation for Qubits 309
8.7.3 Single-Qubit Gates 310
8.7.4 Two-Qubit Gates 313
8.8 Quantum Parallelism 315
8.8.1 Grover’s Search Algorithm 318
8.8.2 Decoherence and QEC 321
8.9 Synthesis of Endohedral Fullerenes 323
8.9.1 Endohedral Metallofullerenes 323
8.9.2 Synthesis of Endohedral Nitrogen Fullerenes 324
8.10 Purification of Endohedral Fullerenes 327
8.11 Quantum Properties of Endohedral Fullerenes 329
8.12 N@C 60 as a Spin Qubit 330
8.13 Scaling-Up of Endohedral Fullerene Nanostructures 332
8.13.1 Endohedral Fullerene Dimers 332
8.13.2 One-Dimensional and Two-Dimensional
Arrays and Beyond 335
8.14 Summary 337
9 Cell Biology of Carbon Nanotubes 343
Chang Guo, Khuloud Al-Jamal, Hanene Ali-Boucetta,
and Kostas Kostarelos
9.1 Experimental Techniques Used to Study the
Interaction Between Carbon Nanotubes and Cells
In Vitro 344
9.1.1 Optical Microscopy 344
9.1.2 Fluorescence Microscopy Techniques 344
9.1.3 Flow Cytometry 350
9.1.4 Electron Microscopy 350
9.1.5 Micro-Raman Spectroscopy 356
9.1.6 Intrinsic Photoluminescence (Via SPT) 356
9.2 Mechanisms Involved in the Cellular Uptake of CNTs 357

Contents
xi
9.2.1 Trafficking Pathways in the Cellular Uptake
of CNT 360
9.2.1.1 Types of CNT endocytosis leading
to internalization 361
9.2.1.2 Can CNTs pierce through cell
membranes as “nano-needles”? 362
9.2.1.3 Fate of CNTs after internalization 363
9.2.2 Parameters Involved in the Cellular Uptake
of CNTs 363
9.2.2.1 Surface modification of CNT:
non-covalent coating versus
chemical conjugation 363
9.2.2.2 CNT diameter and length 364
9.2.2.3 Concentration of CNT 364
9.2.2.4 Cell type 365
9.2.2.5 Duration of CNT interaction with
cells 365
9.3 Conclusion 366
Index 369

Preface
A promising class of nanostructured carbon-based materials, varied
from spherical empty fullerenes and endohedral fullerenes encapsulating
metal atoms to elongated carbon nanotubes and aggregated
nanohorns, has led to an explosion of research associated with
nanotechnology. Advances in Carbon Nanomaterials is a book that
offers a wide range of diverse information. Rather than focusing on
the latest developments in nanotechnology, the authors and editor
of the book, through an appealing collection of nine chapters, offer a
remarkably fresh and authoritative look at diverse areas and topics
of nanocarbon materials to scientists, researchers and students.
In Advances in Carbon Nanomaterials, contributions by experts in
diverse fields of chemistry, physics, materials science and medicine
provide a comprehensive survey of the current state of knowledge
of this constantly expanding subject. The book starts out with
Chapter 1 in the form of an encyclopedia of carbon nanoforms,
dealing with nomenclature and modelling of carbon nanomaterials,
with special emphasis on the topology and morphology of those
carbon nanostructures. Chapter 2 examines surfaces and thin films
of fullerenes, while focusing on morphology, electronic structure,
conduction and optical properties as well as phase transitions.
Chapter 3 gives an insight into the structure of carbon nanotubes
and the characterization of peapod materials with the aid of
high-resolution transmission electron microscopy. Subsequently in
Chapter 4, the novel electro-optical properties of carbon nanotubes
are analysed through a wealth of spectroscopic evidence. Then,
in Chapter 5, important advances in the field of fullerene-based
electronics, together with an outline of the major electronic
properties of fullerenes are presented. Moving into chemistry,
Chapters 6 and 7 deal with the chemical functionalization of carbon

xiv
Preface
nanohorns and endohedral metallofullerenes respectively Finally,
applications in quantum computing and medicine conclude this
fascinating overview of the field. Chapter 8 is dedicated to quantum
computing with endohedral fullerenes, while Chapter 9 deals with
the cell biology of carbon nanotubes
Finally, special acknowledgements go to all authors who contributed
to this book.
Nikos Tagmatarchis
Theoretical and Physical Chemistry Institute
National Hellenic Research Foundation
Athens, Hellas