Preface to the Second Edition ix

Preface to the First Edition xi

1 Introduction 1

1.1 Motivation 1

1.2 The Defect Concept: Point Defects as the Main Actors 3

References 11

2 Bonding Aspects: From Atoms to Solid State 13

2.1 Chemical Bonding in Simple Molecules 13

2.1.1 Ideal Covalent Bonding 13

2.1.2 Polar Covalent Bonding 17

2.1.3 The Ionic Bonding 19

2.1.4 Metallic Bonding 20

2.1.5 Further Intermediate Forms of Chemical Bonding 21

2.1.6 Two-Body Potential Functions 21

2.2 Many Atoms in Contact: The Solid State as a Giant Molecule 23

2.2.1 The Band Model 23

2.2.2 Ionic Crystals 36

2.2.3 Molecular Crystals 41

2.2.4 Covalent Crystals 43

2.2.5 Metallic Crystals 44

2.2.6 Mixed Forms of Bonding in Solids 46

2.2.7 Crystal Structure and Solid State Structure 47

2.2.8 Atomistic Modelling 49

References 51

3 Phonons 55

3.1 Einstein and Debye models 55

3.2 Deviations From Ideality 58

References 61

4 Equilibrium Thermodynamics of the Perfect Solid 63

4.1 Preliminary Remarks 63

4.2 The Formalism of Equilibrium Thermodynamics 63

4.3 Examples of Equilibrium Thermodynamics 76

4.3.1 Solid-Solid Phase Transition 76

4.3.2 Melting and Evaporation 77

4.3.3 Solid-Solid Reaction 78

4.3.4 Solid-Gas Reaction 78

4.3.5 Phase Equilibria and Mixing Reactions 79

4.3.6 Spatial Equilibria in Inhomogeneous Systems 88

4.3.7 Thermodynamics of Elastically Deformed Solids 90

4.3.8 The Thermodynamic Functions of State of the Perfect Solid 91

References 93

5 Equilibrium Thermodynamics of the Real Solid 95

5.1 Preliminary Remarks 95

5.2 Equilibrium Thermodynamics of Point Defect Formation 96

5.3 Equilibrium Thermodynamics of Electronic Defects 110

5.4 Higher-Dimensional Defects 119

5.4.1 Equilibrium Concentration 119

5.4.2 Dislocations: Structure and Energetics 120

5.4.3 Interfaces: Structure and Energetics 124

5.4.4 Interfacial Thermodynamics and Local Mechanical Equilibria 130

5.5 Point Defect Reactions 139

5.5.1 Simple Internal Defect Equilibria 139

5.5.2 External Defect Equilibria 143

5.6 Doping and Freezing Effects 158

5.7 Interactions Between Defects 179

5.7.1 Associates 179

5.7.2 Activity Coefficients 187

5.8 Boundary Layers 194

5.8.1 General 194

5.8.2 Concentration Profiles in the Space Charge Zones 200

5.8.3 Conductivity Effects 204

5.8.4 Defect Thermodynamics of Interface: The Core-Space Charge Picture 209

5.8.5 Examples and Supplementary Comments 216

References 234

6 Kinetics and Irreversible Thermodynamics 243

6.1 Transport and Reaction 243

6.1.1 Transport and Reaction in the Light of Irreversible Thermodynamics 244

6.1.2 Transport and Reaction in the Light of Chemical Kinetics 249

6.2 Electrical Mobility 256

6.2.1 Ion Mobility 256

6.2.2 Electron Mobility 265

6.3 Phenomenological Diffusion Coefficients 267

6.3.1 Ion Conduction and Self-Diffusion 268

6.3.2 Tracer Diffusion 269

6.3.3 Chemical Diffusion 272

6.3.4 A Comparison of the Phenomenological Diffusion Coefficients 276

6.4 Concentration Profiles 278

6.5 Diffusion Kinetics of Stoichiometry Change 282

6.6 C