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Molecular Electronics from Principles to Practice Molecular Electronics From Principles to Practice Michael C. Petty School of Engineering and Centre for Molecular and Nanoscale Electronics, Durham University, UK John Wiley & Sons, Ltd Molecular Electronics Wiley Series in Materials for Electronic and Optoelectronic Applications Series Editors Dr Peter Capper, SELEX Sensors and Airborne Systems Infrared Ltd, Southampton, UK Professor Safa Kasap, University of Saskatchewan, Canada Professor Arthur Willoughby, University of Southampton, Southampton, UK Published Titles Bulk Crystal Growth of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper Properties of Group-IV, III–V and II–VI Semiconductors, S. Adachi Charge Transport in Disordered Solids with Applications in Electronics, Edited by S. Baranovski Optical Properties of Condensed Matter and Applications, Edited by J. Singh Thin Film Solar Cells: Fabrication, Characterization and Applications, Edited by J. Poortmans and V. Arkhipov Dielectric Films for Advanced Microelectronics, Edited by M. R. Baklanov, M. Green and K. Maex Liquid Phase Epitaxy of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper and M. Mauk Forthcoming Titles Luminescent Materials and Applications, Edited by A. Kitai Photovoltaic Materials: From Crystalline Silicon to Third-Generation Approaches, Edited by G. J. Conibeer CVD Diamond for Electronic Devices and Sensors, Edited by R. S. Sussmann Silicon Photonics: Fundamentals and Devices, J. Deen and P. K. Basu Zinc Oxide Materials for Electronic and Optoelectronic Device Applications, Edited by C. Litton, D. C. Reynolds and T. C. Collins Molecular Electronics From Principles to Practice Michael C. Petty School of Engineering and Centre for Molecular and Nanoscale Electronics, Durham University, UK John Wiley & Sons, Ltd Copyright ß 2007 John Wiley & Sons Ltd. The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (þ44) 1243 779777 Email (for orders and customer service enquiries): [email protected] Visit our Home Page on www.wileyeurope.com or www.wiley.com All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to the Publisher should be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England, or emailed to [email protected], or faxed to (þ44) 1243 770620. 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Anniversary Logo Design: Richard J. Pacifico British Library Cataloguing - in - Publication Data Petty, Michael C. Molecular electronics : from principles to practice / Michael C. Petty. p. cm. – (Wiley series in materials for electronic and optoelectronic) Includes bibliographical references and index. ISBN 978-0-470-01307-6 (cloth) – ISBN 978-0-470-01308-3 (pbk.) 1. Molecular electronics. I. Title. TK7874.P457 2007 621.381–dc22 2007041701 A catalogue record for this book is available from the British Library ISBN 978-0-470-01307-6 (HB) 978-0-470-01308-3 (PBK) Typeset in 10/12 pt Times by Thomson Digital, Noida, India Printed and bound in Great Britain by Antony Rowe Ltd, Chippenhan, Wiltshire, England This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production. Dedicated to Gareth Gwyn Roberts (1940–2007) Contents Series Preface xv Preface xvii Acknowledgements xix Symbols and Abbreviations xxi 1 Scope of Molecular Electronics 1 1.1 Introduction 1 1.2 Molecular Materials for Electronics 2 1.3 Molecular-Scale Electronics 5 1.3.1 Evolution of Microelectronics 5 1.3.2 Moore’s Laws 7 1.3.3 Beyond Moore 8 1.4 The Biological World 12 1.5 Future Opportunities 13 1.6 Conclusions 15 Bibliography 15 References 16 2 Materials’ Foundations 19 2.1 Introduction 19 2.2 Electronic Structure 19 2.2.1 Atomic Structure 19 2.2.2 Electrons in Atoms 20 2.2.3 Filling of Orbitals 24 2.2.4 The Periodic Table 24 2.3 Chemical Bonding 26 2.3.1 Bonding Principles 26 2.3.2 Ionic Bond 27 2.3.3 Covalent Bond 29 2.3.4 Metallic Bonding 32 2.3.5 Van der Waals Bonding 33 2.3.6 Hydrogen Bonding 34 viii CONTENTS 2.4 Bonding in Organic Compounds 35 2.4.1 Hybridized Orbitals 35 2.4.2 Isomers 37 2.4.3 Double and Triple Bonds 42 2.5 Crystalline and Noncrystalline Materials 45 2.5.1 States of Matter 45 2.5.2 Phase Changes and Thermodynamic Equilibrium 47 2.5.3 The Crystal Lattice 48 2.5.4 Crystal Systems 49 2.5.5 Miller Indices 50 2.5.6 Distance Between Crystal Planes 52 2.5.7 Defects 52 2.5.8 Amorphous Solids 56 2.6 Polymers 57 2.6.1 Molecular Weight 57 2.6.2 Polymer Structure 59 2.6.3 Polymer Crystallinity 60 2.7 Soft Matter: Emulsions, Foams and Gels 63 2.8 Diffusion 63 Bibliography 64 Reference 64 3 Electrical Conductivity 65 3.1 Introduction 65 3.2 Classical Theory 65 3.2.1 Electrical Conductivity 66 3.2.2 Ohm’s Law 68 3.2.3 Charge Carrier Mobility 69 3.2.4 Fermi Energy 70 3.3 Energy Bands in Solids 72 3.3.1 Quantum Mechanical Foundations 73 3.3.2 Kronig–Penney Model 80 3.3.3 Conductors, Semiconductors and Insulators 85 3.3.4 Electrons and Holes 86 3.3.5 Intrinsic and Extrinsic Conduction 88 3.3.6 Quantum Wells 92 3.3.7 Disordered Semiconductors 93 3.3.8 Conductivity in Low-dimensional Solids 94 3.4 Organic Compounds 96 3.4.1 Band Structure 96 3.4.2 Doping 107 3.4.3 Solitons, Polarons and Bipolarons 109 3.4.4 Superconductivity 112 3.5 Low-Frequency Conductivity 112 3.5.1 Electronic Versus Ionic Conductivity 113 3.5.2 Quantum Mechanical Tunnelling 114 CONTENTS ix 3.5.3 Variable Range Hopping 116 3.5.4 Space-Charge Injection 118 3.5.5 Schottky and Poole–Frenkel Effects 120 3.6 Conductivity at High Frequencies 121 3.6.1 Complex Permittivity 121 3.6.2 Impedance Spectroscopy 125 Bibliography 127 References 127 4 Optical Phenomena 129 4.1 Introduction 129 4.2 Electromagnetic Radiation 129 4.3 Refractive Index 130 4.3.1 Permittivity Tensor 132 4.3.2 Linear and Nonlinear Optics 133 4.4 Interaction of EM Radiation with Organic Molecules 135 4.4.1 Absorption Processes 135 4.4.2 Aggregate Formation 140 4.4.3 Excitons 141 4.4.4 Effect of Electric Fields on Absorption 143 4.4.5 Emission Processes 144 4.4.6 Energy Transfer 147 4.5 Transmission and Reflection from Interfaces 149 4.5.1 Laws of Reflection and Refraction 149 4.5.2 Fresnel Equations 150 4.5.3 Ellipsometry 152 4.5.4 Thin Films 152 4.6 Waveguiding 154 4.7 Surface Plasmons 156 4.7.1 The Evanescent Field 156 4.7.2 Surface Plasmon Resonance 157 4.8 Photonic Crystals 162 4.8.1 Subwavelength Optics
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