Organic Molecular Solids

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1 Markus Schwoerer, Hans Christoph Wolf Organic Molecular Solids BICENTENNIAL BICENTENNIAL WILEY-VCH Verlag GmbH & Co. KGaA

2 VII Contents 1 Introduction What are Organic Solids? What are the Special Characteristics of Organic Solids? 1.3 Goals and Future Outlook 15 Problems for Chapter 1 16 Literature 24 2 Forces and Structures Forces Inductive Forces Van der Waals Forces Repulsive Forces Intermolecular Potentials Coulomb Forces Structures Crystals of Nonpolar Molecules Crystals of Molecules with Polar Substituents Crystals with a Low Packing Density, Clathrates A Crystals of Molecules with Charge Transfer, Radical-ion Salts Polymer Single Crystals: Diacetylenes Thin Films Inorganic-Organic Hybrid Crystals 57 Problems for Chapter 2 52 Literature 54 3 Purification of Materials, Crystal Growth and Preparation of Thin Films Purification Highest Purity 61 Organic Molecular Solids. M. Schwoerer and H. C. Wolf Copyright 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN:

3 VIIII Contents 3.3 Crystal Growth Mixed Crystals Epitaxy, Ultrathin Films 71 Problems for Chapter 3 72 References 73 4 Impurities and Defects Foreign Molecules, Impurities, and X traps Structural Defects Point Defects Dislocations Grain Boundaries Dipolar Disorder Characterisation and Analysis of Impurities Characterisation of Defects 84 Literature 86 5 Molecular and Lattice Dynamics in Organic Molecular Crystals Introduction Intramolecular Vibrations Phonons The Eigenvector The Wavevector The Frequencies Q (K) Excitations Experimental Methods Inelastic Neutron Scattering Raman Scattering and Infrared Absorption The 12 External Phonons of the Naphthalene Crystal Dispersion relations Pressure and Temperature Dependencies Analytic Formulation of the Lattice Dynamics in Molecular Crystals Phonons in other Molecular Crystals Hindered Rotation and Diffusion Nuclear Magnetic Resonance Benzene Crystals Methyl Groups Diffusion 120 Problems for Chapter References 123

4 Contents IX 6 Electronic Excited States, Excitons, Energy Transfer Introduction Some historical remarks Optical Excited States in Crystals Davydov Splitting and Mini-Excitons Frenkel Excitons Excitonic States, Fundamental Equations Polarisation and Band Structure Coherence Charge Transfer (CT) Excitons Surface Excitons Excimers Exciton Processes, Energy Conduction Sensitised Fluorescence Delayed Fluorescence by Triplet Excitons Excitonic Processes Excitonic Processes in other Systems Future Developments 273 Problems for Chapter Literature Structure and Dynamics of Triplet States Introduction and Historical Remarks Spin Quantisation in Triplet States The Dipole-Dipole Interaction, Fine Structure Zero Field (Bo = 0) Zeeman Splitting (B o # 0) Powder Spectra Mini-Excitons Triplet Excitons Anthracene and Naphthalene Crystals: Two-dimensional Triplet Excitons Dibromonaphthalene Crystals: coherent, one-dimensional Triplet Excitons Optical Spin Polarisation (OEP) Optical Nuclear-Spin Polarisation (ONP) Perspectives 214 Problems for Chapter Literature Organic Semiconductors Preliminary Historical Remarks Conductivity and Mobility of nearly-free Charge Carriers 223

5 Contents 8.3 Charge Carriers in Organic Semiconductors: Polarons, Shallow Traps and Deep Traps Generation of Charge Carriers and Charge Transport: Experimental Methods The TOF Method: Gaussian Transport Photogeneration of Charge Carriers Contacts, Injection, Ejection, and Dark Currents Space-Charge Limited Currents Charge-Carrier Mobilities in Organic Molecular Crystals Band-or Hopping Conductivity? Temperature Dependence and Anisotropy of the Mobilities Electric-field Dependence Band Structures Charge-Carrier Traps Charge Transport in Disordered Organic Semiconductors The Bassler Model Mobilities in High-Purity Films: Temperature, Electric-Field, and Time Dependence Binary Systems Discotic Liquid Crystals Stationary Dark Currents 292 Problems for Chapter Literature Organic Crystals of High Conductivity Donor-Acceptor Systems Strong CT Complexes, Radical-ion Salts The Organic Metal TTF-TCNQ - Peierls Transition and Charge-Density Waves Other Radical-ion Salts and CT Complexes Radical-Anion Salts of DCNQI Radical-Cation Salts of the Arenes Direct-current Conductivity X-Ray Scattering Optical Reflection Spectrum Magnetic Susceptibility Spin Resonance of the Conduction Electrons (ESR) Charge-Density-Wave Transport 343 Problems for Chapter Literature Organic Superconductors Introduction 352

6 Contents XI 10.2 Mainly One-dimensional Charge-Transfer Salts as Superconductors; Bechgaard Salts Quasi-Two-dimensional Charge-Transfer Systems as Superconductors The Nature of the Superconducting State in Organic Salts Three-dimensional Superconductivity in Fullerene Compounds 361 Literature Electroluminescence and the Photovoltaic Effect Electroluminescence: Organic Light-Emitting Diodes (OLEDs) Historical Remarks The Principle of the OLED Multilayer OLEDs Electro-optical Properties Photovoltaic Effect: Organic Photovoltaic Cells Exciton Dissociation Photovoltaic Characteristics CuPc/C 60 Solar Cells 386 Literature Towards a Molecular Electronics What is Molecular Electronics and What Will it Do? Molecules as Switches, Photochromic Effects Molecular Wires Light-Induced Phase Transitions Molecular Rectifiers Molecular Transistors Molecular Storage Units 406 Appendix: Coloured Plates 42 2 Index 427

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