One-Dimensional Metals Conjugated Polymers,

Low-dimensional solids are of fundamental interest in materials science due to their anisotropic properties. Written not only for experts in the field, this book explains the important concepts behind their physics and surveys the most interesting one-dimensional systems and discusses their present and emerging applications in molecular scale electronics. Chemists, polymer and materials scientists as well as students will find this book a very readable introduction to the solid-state physics of electronic materials.

In this completely revised and expanded third edition the authors also cover graphene as one of the most important research topics in the field of low dimensional materials for electronic applications. In addition, the topics of nanotubes and nanoribbons are widely enlarged to reflect the research advances of the last years.

Siegmar Roth is founding director of Sineurop Nanotech GmbH Stuttgart, Germany, a company synthesizing carbon nanotubes, graphene and related materials. He has obtained his PhD in Physics at the University of Vienna, Austria, and his Habilitation at the University of Karlsruhe, Germany. After some years at Siemens in Erlangen, Germany, he joined the Institut Laue Langevin and later on the High Field Magnet Lab in Grenoble, from where he moved to Stuttgart to become leader of the Research Group on Synthetic Nanostructures at the Max Planck Institute for Solid State Research. Between 2009 and 2012 he was visiting professor at the School of Electrical Engineering of Korea University.

David L. Carroll is professor at the Wake Forest University. He is a trained materials scientist and received his PhD from Wesleyan University, Middletown, USA. After a stay as postdoctoral fellow at the department of materials science and engineering, University of Pennsylvania, Philadelphia from 1993-1995, he joined the Max-Planck-Institute for solid state research in Stuttgart, Germany. In 1997 he became Assistant Professor at Clemson University and 2001 Associate Professor. He moved with his group to Wake Forest University in 2003, where he founded the Center for Nanotechnology and Molecular Materials.

About the Authors XI

Preface to the Third Edition XIII

Preface to the Second Edition XV

Preface to the First Edition XVII

1 Introduction 1

1.1 Dimensionality 1

1.2 Approaching One-Dimensionality from Outside and from Inside 2

1.3 Dimensionality of Carbon Solids 7

1.3.1 Three-Dimensional Carbon: Diamond 7

1.3.2 Two-Dimensional Carbon: Graphite 8

1.3.3 One-Dimensional Carbon: Cumulene, Polycarbyne, Polyene 9

1.3.4 Zero-Dimensional Carbon: Fullerene 11

1.3.5 What about Something in between? 12

1.4 Peculiarities of One-Dimensional Systems 13

References 17

2 One-Dimensional Substances 19

2.1 A15 Compounds 23

2.2 Krogmann Salts 27

2.3 Alchemists’ Gold 29

2.4 Bechgaard Salts and Other Charge Transfer Compounds 31

2.5 Polysulfurnitride 34

2.6 Phthalocyanines and Other Macrocycles 36

2.7 Transition Metal Chalcogenides and Halides 38

2.8 Conducting Polymers 40

2.9 Halogen-Bridged Mixed-Valence Transition Metal Complexes 44

2.10 Miscellaneous 45

2.10.1 Poly-deckers 45

2.10.2 Polycarbenes 46

2.11 Isolated Nanowires 46

2.11.1 Templates and Filled Pores 46

2.11.2 Asymmetric Growth Using Catalysts 48

2.11.3 Carbon Nanotubes 49

2.11.4 Inorganic Semiconductor QuantumWires 51

2.11.5 Metal Nanowires 52

2.12 Summary 53

References 53

3 One-Dimensional Solid-State Physics 57

3.1 Crystal Lattice and Translation Symmetry 57

3.1.1 Classifying the Lattice 59

3.1.2 Using a Coordinate System 62

3.1.3 The One-Dimensional Lattice 63

3.1.4 Carbon Nanotubes as One-Dimensional Lattices 65

3.2 Reciprocal Lattice, Reciprocal Space 67

3.2.1 Describing Objects Using Momentum and Energy 67

3.2.2 Constructing the Reciprocal Lattice 68

3.2.3 Applying This to One Dimension 69

3.3 The Dynamic Crystal and Dispersion Relations 71

3.3.1 Crystal Vibrations and Phonons 71

3.3.2 Quantum Considerations with Phonons 79

3.3.3 Counting Phonons 81

3.4 Phonons and Electrons Are Different 83

3.4.1 ElectronWaves 84

3.4.2 Electron Statistics 85

3.4.3 The Fermi Surface 86

3.4.4 The Free Electron Model 87

3.4.5 Nearly Free Electron Model; Energy Bands, Energy Gap, and Density of States 91

3.4.6 The Molecular Orbital Approach 97

3.4.7 Returning to Carbon Nanotubes 98

3.5 Summary 102

References 102

4 Electron–Phonon Coupling and the Peierls Transition 105

4.1 The Peierls Distortion 107

4.2 Phonon Softening and the Kohn Anomaly 111

4.3 Fermi SurfaceWarping 112

4.4 Beyond Electron–Phonon Coupling 113

References 114

5 Conducting Polymers: Solitons and Polarons 117

5.1 General Remarks 117

5.2 Conjugated Double Bonds 119

5.3 A Molecular Picture 122

5.3.1 Bonding and Antibonding States 123

5.3.2 The Polyenes 123

5.3.3 Translating to Bloch’s Theorem 128

5.4 Conjugational Defects 132

5.5 Solitons 136

5.6 Generation of Solitons 144

5.7 Nondegenerate Ground-State Polymers: Polarons 146

5.8 Fractional Charges 151

5.9 Soliton Lifetime 153

References 156

6 Conducting Polymers: Conductivity 159

6.1 General Remarks on Conductivity 159

6.2 Measuring Conductivities 164

6.2.1 Simple Conductivity 164

6.2.2 Conductivity in a Magnetic Field 168

6.2.3 Conductivity of Small Particles 169

6.2.4 Conductivity of High-Impedance Samples 171

6.2.5 Conductivity Measurements without Contacts 171

6.2.6 Thermoelectric Power – the Seebeck Effect 172

6.3 Conductivity in One Dimension: Localization 175

6.4 Conductivity and Solitons 178

6.5 Experimental Data 182

6.6 Hopping Conductivity: Variable Range Hopping vs. Fluctuation-Assisted Tunneling 186

6.7 Conductivity of Highly Conducting Polymers 195

6.8 Magnetoresistance 197

References 202

7 Superconductivity 209

7.1 Basic Phenomena 209

7.2 Measuring Superconductivity 216

7.3 Applications of Superconductivity 218

7.4 Superconductivity and Dimensionality 219

7.5 Organic Superconductors 220

7.5.1 One-Dimensional Organic Superconductors 222

7.5.2 Two-Dimensional Organic Superconductors 225

7.5.3 Three-Dimensional Organic Superconductors 227

7.6 Future Prospects 229

References 231

8 Charge DensityWaves 235

8.1 Introduction 235

8.2 Coulomb Interaction, 4kF Charge DensityWaves, Spin PeierlsWaves, Spin DensityWaves 236

8.3 Phonon Dispersion Relation, Phase and Amplitude Mode in Charge DensityWave Excitations 240

8.4 Electronic Structure, Peierls–Fröhlich Mechanism of Superconductivity 242

8.5 Pinning, Commensurability, Solitons 243

8.6 Field-Induced Spin DensityWaves and the Quantized Hall Effect 248

References 250

9 Molecular-Scale Electronics 253

9.1 Miniaturization 253

9.2 Information in Molecular Electronics 257

9.3 Early and Radical Concepts 258

9.3.1 Soliton Switching 258

9.3.2 Molecular Rectifiers 261

9.3.3 Molecular Shift Register 262

9.3.4 Molecular Cellular Automata 264

9.4 Carbon Nanotubes 265

References 269

10 Molecular Materials for Electronics 271

10.1 Introduction 271

10.2 Switching Molecular Devices 272

10.2.1 Photoabsorption Switching 272

10.2.2 Rectifying Langmuir–Blodgett Layers 274

10.3 Organic Light-Emitting Devices 277

10.3.1 Fundamentals of OLEDs 277

10.3.2 Materials for OLEDs 284

10.3.3 Device Designs for OLEDs 284

10.3.4 Performance and Outlooks 285

10.3.5 Field-Induced Organic Emitters 286

10.3.6 Organic Lasers and Organic Light-Emitting Transistors 289

10.4 Solar Cells 294

10.5 Organic Field Effect Transistors 298

10.6 OrganicThermoelectrics 300

10.7 Summary 302

References 303

11 Even More Applications 307

11.1 Introduction 307

11.2 Superconductivity and High Conductivity 307

11.3 Electromagnetic Shielding 308

11.4 Field Smoothening in Cables 308

11.5 Capacitors 309

11.6 Through-Hole Electroplating 310

11.7 Loudspeakers 311

11.8 Antistatic Protective Bags 311

11.9 Other Electrostatic Dissipation Applications 313

11.10 Conducting Polymers forWelding of Plastics 314

11.11 Polymer Batteries 314

11.12 Electrochemical Polymer Actuators 316

11.13 Electrochromic Displays, SmartWindows, and Transparent Conducting Films 317

11.14 Electrochemical Sensors 319

11.15 Gas-Separating Membranes 320

11.16 Hydrogen Storage 321

11.17 Corrosion Protection 321

11.18 Holographic Storage and Holographic Computing 322

11.19 Biocomputing 323

11.20 Outlook 325

References 325

12 Finally 327

Reference 328

Glossary and Acronyms 329

Index 335

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One-Dimensional Metals Conjugated Polymers, Organic Crystals, Carbon Nanotubes and Graphene

Summary

Author Biography

Table of Contents

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