SOLID STATE

PHYSICS
(With An Introduction to Semiconductor Devices)
 SOLID STATE
PHYSICS
(With An Introduction to Semiconductor Devices)

THIRD EDITION

A J AY K U M A R S A X E N A
(M.Sc., M.Tech., PhD.
Department of Physics
A.P.S. University
Rewa (M.P.)-486003
India

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SOLID STATE PHYSICS

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AJAY KUMAR SAXENA

 Preface to the Second Edition

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 Contents

Preface to the Third Edition v

Preface to the Second Edition vii
Preface to the First Edition viii

1. CRYSTAL STRUCTURE 1
1.1 Crystalline and Amorphous Solids 1
1.2 Crystal Lattice and Crystal Structure 1
1.3 Translational Symmetry, Space Lattice, Unit Cell and Primitive Cell 2
1.4 Symmetry Elements in Crystals 3
1.4.1 Proper Rotation Axis 3
1.4.2 Plane of Symmetry 4
1.4.3 Inversion centre (Centre of Symmetry) 5
1.4.4 Rotary Inversion Axis 5
1.4.5 Screw Axis 6
1.4.6 Glide Planes 6
1.5 The Seven Crystal Systems (Types of Bravais Lattices) 6
1.5.1 Coordination Number 9
1.6 Some Important Crystal Structures 9
1.6.1 Simple Cubic Structue 9
1.6.2 Body Centred Cubic (BCC) Structure 9
1.6.3 Face Centred Cubic (FCC) Structure 10
1.6.4 Hexagonal Close Packed (HCP) Structure 10
1.6.5 Sodium Chloride Structure 14
1.6.6 Cesium Chloride Structure 14
1.6.7 Diamond Structure 14
1.6.8 Zinc Blende Structure 15
1.6.9 Fluorite Structure 15
1.6.10 Perovskite Structure 15
1.7 Wigner–Seitz Cells 16
1.8 Number of Lattice Points per unit Cell 17
1.9 Close Packing of Spheres in 3-Dimensions 19
1.10 Miller Indices 20
1.11 Miller–Bravais Indices 21
1.12 Indices of a Lattice Direction 22
1.12.1 Miller–Bravais Indices of a Direction 22
1.12.2 Important Features of Miller Indices 23
1.13 The Spacing of a Set of Crystal Planes 23
1.14 Point Groups 25
1.15 Schönflies System of Nomenclature for Point Groups 30
1.16 Space Groups 32
1.17 Quasicrystals 33
x Contents

1.18 Liquid Crystals 34

1.19 Graphite Structure 36
1.20 Fullerenes 36
1.21 Carbon Clusters 37
1.22 Carbon Nanotubes 38
1.22.1 Types and Structures of CNTs 38
1.23 Quantum Mechanics for Nano Science 40
1.23.1 Size Effects in Smaller Systems (Pre-Quantum) 40
1.23.2 Quantum Behaviour of Nanometric World 41
1.24 Properties of Carbon Nano Tubes 43
1.24.1 Nanotechnology 44
1.25 Polymers (‘Poly’: many; ‘mer’: part) 44
1.25.1 Classification 45
1.26 Coordination Number as a Function of Radius Ratio 46
Questions 51

2. X-RAY DIFFRACTION AND RECIPROCAL LATTICE 52

2.1 Choice of X-Rays, Electrons and Neutrons for Crystal Structure Determination 52
2.2 X-ray Diffraction According to Bragg 53
2.3 The Von-Laue Treatment 55
2.4 Reciprocal Lattice 56
2.4.1 Properties of Reciprocal Lattice 60
2.4.2 Reciprocal Lattice to Simple Cubic (SC) Lattice 62
2.4.3 Reciprocal Lattice to BCC Lattice 63
2.4.4 Reciprocal Lattice to FCC Lattice 64
2.5 The Bragg’s Condition and Ewald Construction 65
2.6 Brillouin Zones 67
2.6.1 One Dimensional Monoatomic Lattice 67
2.6.2 Two Dimensional Square Lattice 68
2.6.3 Brillouin Zone for a Simple Cubic Lattice 69
2.6.4 Brillouin zone of a FCC Lattice 70
2.6.5 Brillouin Zone of a BCC Lattice 70
2.7 Special Points and Special Lines in the 1st Brillouin Zone of a Two Dimensional
Square Lattice 71
2.8 Atomic Scattering Factor 75
2.9 Geometrical Structure Factor 77
2.9.1 Simple Cubic Crystals 78
2.9.2 Body Centred Cubic Crystal 78
2.9.3 Face Centred Cubic Crystal 79
2.10 Laue Method 80
2.11 Rotating Crystal Method 81
2.12 Powder Method 82
2.13 Scattering by a Unit Cell 83
2.14 The Crystallographic Zone-Axis 87
2.15 Electron Diffraction 89
2.16 Geometrical Nature of Electron Diffraction-Patterns 90
 Contents xi

2.17 Indexing of Electron Diffraction Spot Patterns 91

2.18 Electron Microscopes 93
2.19 Transmission Electron Microscopy 93
2.20 Image Formation in Transmission Electron Microscopy 95
2.21 Scanning Tunneling Microscopy (STM) 96
2.22 Scanning Electron Microscopy 97
2.23 Debye-Scherrer Technique 99
2.23.1 Analysis of the Powder Photographs 100
2.23.2 The Determination of Lattice Types and Space Groups 102
2.23.3 Crystal Structure Determination 103
2.24 The Powder Diffractometric Techniques 106
2.25 The Reciprocal Lattice in Terms of Fourier Transform 107
2.26 Comparison between Reflection and Diffraction 110
Questions 110

3. CRYSTAL IMPERFECTIONS 112

3.1 What is an Imperfection? 112
3.2 Importance of Lattice Imperfections 112
3.3 Types of Imperfections 112
3.4 Point Defects 113
3.4.1 Formation of Point Defects 113
3.4.2 Vacancy Defects in Elementals Solids 113
3.4.3 Schottky Defects in Ionic Crystals 116
3.4.4 Self-Interstitial Defects in Elemental Solids 117
3.4.5 Frenkel Defects in Ionic Solids 119
3.4.6 Interstitial or Substitutional Impurity 119
3.4.7 Colour or F-Centres 119
3.4.8 Polarons 121
3.4.9 Excitons 121
3.4.10 Frenkel Excitons 121
3.4.11 Weakly Bound Excitons (Wannier–Mott Excitons) 121
3.5 Dislocations 124
3.5.1 The Interpretation of Slip: Dislocations 125
3.5.2 Dislocation Model for Slip 126
3.5.3 Edge and Screw Dislocations 127
3.6 Dislocation Density 129
3.7 Estimation of Dislocation Density from X-ray Diffraction Measurements 130
3.8 Planar or Surface Defects 130
3.8.1 Grain Boundaries 130
3.8.2 Behaviour of Grain Boundaries 131
3.8.3 Tilt Boundaries 131
3.8.4 Twin Boundaries 131
3.8.5 Stacking Faults 132
3.9 Energies of Dislocations (Stress and Strains) 132
3.10 Stability of a Dislocation Loop (Critical Radius) 134
3.11 Origin of Dislocations 135
xii Contents

3.12 Solid Solutions 136

3.13 A Screw Dislocation Meeting a Surface 137
3.14 Interaction between parallel Dislocations 138
3.15 The interaction of a Dislocation with an Obstacle 139
3.16 Plastic Deformation 140
Questions 142

4. BONDING IN SOLIDS 143

4.1 Introduction 143
4.2 General Nature of Cohesion between Two Atoms in a Solid 143
4.3 Ionic Bond 144
4.3.1 The Bond Energy and Madelung Constant for NaCl Crystal 145
4.3.2 Properties of Ionic Solids 151
4.4 Covalent Bond 151
4.4.1 Heitler and London Theory of Covalent Bonding 152
4.4.2 Directional Nature of a Covalent Bond 155
4.4.3 Hybridization 156
4.4.4 Covalent Compounds 157
4.4.5 Properties of Covalent Compounds 158
4.5 Metallic Bond 159
4.5.1 Properties of Metallic Crystals 160
4.6 Van der Waal London Interaction and Lennard Jones Potential 161
4.7 Hydrogen Bonding 164
4.8 Born-Haber Cycle 166
Questions 167

5. LATTICE VIBRATIONS AND THERMAL PROPERTIES 168

5.1 Phonons 168
5.2 Experimental Determination of Dispersion Relation 169
5.3 Dynamics of a Linear Chain of Identical Atoms 170
5.3.1 Allowed Values of k (Normal Modes of Vibration) 172
5.3.2 Phase and Group Velocities 173
5.3.3 Frequency Distribution 174
5.4 Vibrations of a One Dimensional Lattice with a Basis (Linear Diatomic Chain) 174
5.4.1 Acoustic and Optic Branches 176
5.4.2 Particle Displacements in the two Branches 178
5.5 Phonon Processes 180
5.6 Phonon Density of States 181
5.7 The Debye Model 182
5.8 Thermal Properties of Solids 184
5.8.1 Specific Heat of Solids 184
5.8.2 The Classical Model 184
5.9 Einstein’s Theory of Specific Heat 185
5.10 Debye’s Theory of Lattice Heat Capacity 188
5.10.1 Limitation of the Debye Model 192
 Contents xiii

5.11 Thermal Expansion 192

5.11.1 Origin of Thermal Expansion 193
5.11.2 Gruneisen Relation 195
5.12 Classical Theory of the Lattice 197
5.12.1 Diatomic Interaction Potentials 199
5.12.2 Symmetry of the Interaction Tensor 200
5.12.3 Normal Modes of the Lattice 201
5.12.4 Dispersion Relation for FCC Lattice 202
5.13 Inelastic Scattering of Photons by Phonons 205
Questions 206

6. TRANSPORT PROPERTIES 207

6.1 Drude’s Model 207
6.2 DC Electrical Conductivity of a Metal according to Drude’s Model 208
6.3 Boltzmann Transport Equation 210
6.4 Lorentz Modification of Drude’s Model 211
6.5 Boltzmann Transport Equation For Electron and Lorentz Solution 211
6.6 Sommerfeld’s Theory of Electrical Conductivity 213
6.7 Thermal Conductivity 215
6.8 Wiedemann Franz Law 216
6.9 Sommerfeld’s Free Electron Model 218
6.10 Sommerfeld’s Free Electron Theory of Metals 219
6.10.1 Filling up of the Energy Levels 220
6.11 The Density of States 221
6.12 Concept of Fermi Energy and Fermi Level 224
6.13 The Number of Electrons/Volume, The Population Density and EFO 225
6.14 Variation of Electrical Resistivity of Metals (Matthiesen Rule) 226
6.15 The Hall Effect 227
6.15.1 Applications of Hall Effect 230
6.16 Magnetoresistance 231
6.16.1 Transverse Magneto resistance 231
6.16.2 Experimental Observations on Magnetoresistance 234
6.17 Transport Equations and Thermo-Electric Effects 235
6.17.1 Local Entropy Production 235
6.17.2 Electric Current Density and Heat Current Density 238
6.17.3 Transport Coefficients in Absence of a Magnetic Field 239
(Peltier and Seebeck Effects)
6.18 Seebeck Effect 243
Questions 244

7. BAND THEORY 246

7.1 Development of Energy Bands in Solids (Atomistic Approach) 246
7.1.1 Energy Bands in Sodium Crystal 247
7.1.2 Energy Bands in Diamond 248
7.2 Electron Motion in a Crystal (One-electron approach) 249
xiv Contents

7.3 Bloch Theorem 249

7.3.1 Proof of Bloch Theorem 250
7.4 Kronig–Penney Model 253
7.5 Number of Possible Wave Functions in a Band 257
7.6 Crystal Momentum 258
7.7 The Concept of Effective Mass 259
7.8 Effective Mass Tensor 261
7.9 Concept of Holes 262
7.9.1 Hole Band Construction 263
7.10 Metals, Insulators and Semiconductors 264
7.11 Reduced Zone Scheme 266
7.12 From Isolated Atoms to the Free-Electron Limit 268
7.13 The Nearly Free Electron Model 269
7.13.1 One Dimensional Free-Electron Case 269
7.13.2 Nearly Free-Electron Case 270
7.14 Energy Bands in One-Dimension 272
7.15 Tight Binding Approximation 273
7.15.1 Energy Surfaces 277
7.16 Velocity of the Bloch Electron (Qualitative Idea) 278
7.17 Wigner–Seitz Cellular Method 279
7.18 Orthogonalised Plane Wave (OPW) Method 281
7.19 Pseudopotential Method 283
7.20 Limit of the Band Theory (Mott Transition) 284
7.21 Density of States of a Lattice 285
7.22 Band Structure of Column IV Elements (Calculated by Tight Binding Method) 288
7.23 Dynamics of a Bloch Electron 292
7.23.1 Velocity of the Bloch Electron 292
7.23.2 Acceleration in the Reciprocal Space 293
Questions 294

8. FERMI SURFACES 295

8.1 Free Electrons 295
8.2 Square Lattice 296
8.3 Fermi Surface 297
8.4 Variations in the Free Electron Fermi Surface of a Square 299
Lattice according to the Valence of the Metal
8.5 Harrison Construction of Fermi Surface for Square Bravais Lattice 300
(Nearly Free Electrons)
8.6 Fermi Surface and Brillouin Zones 301
8.7 Divalent Metals 302
8.8 Constant Energy Contours 303
8.9 Fermi Surface for Three-Dimensional Lattices 304
8.9.1 FCC Lattice 305
8.10 Characteristics of Fermi Surfaces 306
8.11 Effect of Electric Field on Fermi Surface 306
8.12 Closed Orbits and Open Orbits 308
 Contents xv

8.13 Topology of Orbits in a Magnetic Field 309

8.14 Experimental Study of the Fermi Surface 310
8.14.1 Quantization of Orbits in a Magnetic Field 312
8.15 De Haas–Van Alphen Effect 314
8.16 Determination of Fermi Surface of Copper 317
8.17 Cyclotron Resonance in Metals 319
8.18 Difference between Energy Contours for Metals and Insulators 320
8.19 Electron Motion in a Magnetic Field (Origin of Landau Levels) 321
8.19.1 Effect of Perturbing Potential 325
8.20 Shubnikov–de Haas Effect 326
Questions 329

9. SEMICONDUCTORS AND SEMICONDUCTOR DEVICES 330

9.1 Conductor, Insulator and Semiconductor 330
9.2 Intrinsic Semiconductors 330
9.3 Extrinsic Semiconductors 332
9.4 Compound Semiconductors 333
9.5 Direct and Indirect Semiconductors 334
9.6 The Position of the Fermi Level in Semiconductors (Qualitative Idea) 336
9.7 The Effective Density of States and Carrier Concentration 337
9.7.1 The Equilibrium Electron-Hole Product 339
9.8 Variation of Carrier Concentration with Temperature 341
9.9 Intrinsic Conductivity and Mobility 343
9.10 Effect of Temperature on Mobility 343
9.11 Determination of Band Gap of Intrinsic Semiconductors 345
9.12 Kinetics of Extrinsic Case 346
9.13 Hall Effect in Semiconductors 348
9.14 Hall Effect Poynting Vector Measurements 349
9.15 Cyclotron Resonance 350
9.15.1 Effective Mass Tensor from Cyclotron Resonance 351
9.16 pn Junction 353
9.16.1 Formation of Depletion Region in pn Junction 354
9.16.2 Energy Band Diagram for pn Junction and Junction Barrier Voltage 354
9.16.3 Width of the Depletion Region 357
9.16.4 A pn Junciton Under Forward and Reverse Bias 359
9.16.5 Junction Capacitance 360
9.16.6 Current Across a pn Junction : The Rectifier Equation for a Forward Biased 361
pn Junction
9.17 Degenerate Semiconductors 364
9.18 Tunnel Diode 364
9.19 Bipolar Junction Transistor 366
9.19.1 Transistor Construction 366
9.19.2 Transistor Biasing 367
9.19.3 Transistor Operation 367
9.19.4 Transistor Input and Output Characteristics 369
9.19.5 Collector Cut off Current ICO 369
 Solid State Physics By Ajay Kumar
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