EIGHTH EDITION Introduction to Solid State Physics CHARLES KITTELName Symbol Name Symbol Name Symbol Actinium ge Hafnium HE Praseodymium = Pr Aluminum — al Helium He Promethium = Pm Americium Am Holmium Ho Frotactinium Pa Antimony Sb Hydrogen H Radium Ra ‘Argon Ar Indium In Radon Rn Arsenic As Todine 1 Rhenium Re Astatine At Iridium Ir Rhodium Bh Barium Ba Iron Fe Rubidium Rb Berkelium Bk Krypton kr Ruthenium = Ru Beryllium Be Lanthanum = La Samarium Sm Bismuth, Bi Lawrencium = Le Scandium Se Boron B Lead Pb Selenium Se Bromine Br Lithiun Li Silicon Si Cadmium Cd Lutetium Lu Silver Ag Caleium Ca Magnesium = Mg Sodium Na Californium — CE Manganese Mn Strontium sr Carbon c Mendelevium Md Sulfur s Cerium Ce Mercury Hg Tantalum Ta Cesium Cs Molybdenum — Mo Technetium Te Chlorine Cl Neodymium Nd Tellurium Te Chromium Gr Neon Ne Terbium cy Cobalt Co Neptunium Np Thallium n Copper Cu Nicket Ni Thorium Th Curium Cm Niobium Nb Thulium Tm Dysprosium Dy Nitrogen N Tin Sn Einsteinium Es Nobelium No Titanium Ti Erbium Er Osmium Os Tungsten w Europium Eu Oxygen 0 Uranium u Fermium = Fm Palladium Pd Vanadium v Fluorine F Phosphorus P Xenon Xe Francium Fr Platinum Pt Yeterbium Yb Gadolinium — Gd Plutonium = Pu Yetrium y Gallium Ga Poloninm Po Zine Zn Germanium Ge Potassium K Zirconium ke Gold AuPeriodic Table, with the Outer Electron Configurations of Neutral Atoms in Their Ground States «notation used to describe the electronic configuration of atoms nd ions is discussed in all texthooks of introductory atomic physi The letters s, p, d, . . . signify electrons having orbital angular momentum 0, 1, 2, . units 4; the number to the left of the letter denotes the principal quantum number of one orbit, and the superscript to the right denotes the number of electrons in the orbIntroduction to Solid State Physics EIGHTH EDITION Charles Kittel Professor Emeritus University of California, Berkeley Chapter 18, Nanostructures, was written by Professor Paul McEuen of Cornell University. ® John Wiley & Sons, IncEXECUTIVE EDITOR Stuat Johnson SENIOR PRODUCTION EDITOR. Patricia MeFudden SENIOR MARKETING MANAGER Robert Smith DESIGN DIRECTOR Madelyn Lesure SENIOR MEDIA EDITOR Martin Batey PRODUCTION MANAGEMENT Suzanne Ingrao/lagrao Associates ‘This book was set in 10/12 New Caledonia by GOS Books Services, Alantie Highlands and printed and bound by Malloy Lithographing, The cover was printed by Phoenix Color. ‘This book is printed on actd free paper 2° Copyright © 2005 John Wiley & Sons, Ine. 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, eleetzonic, mechanieal, photocopying, recording, scanning or otherwise, ‘execpt ts permitted under Sections 107 or 108 ofthe 1976 United States Copyright Act, withoat either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc. 222 Rosewood Drive, Danvers, MA 01923, (975)750-8400, fax (975)646-8600, Requests to the Publisher for permission should be aeldeessed to the Permissions Department, Joba Wiley & Sons, Inc, 111 River Street. Hoboken, NJ 07030-5774, (201)748-601 1, fax (201)748.6008., To order books or for customer service please, call 1-800-CALL WILEY (225-5945), Lubrary of Congress Cataloging in Publication Data: Kittel, Charles, Introduction to solid state physies / Charles Kittel, 8th ed peem, ISBN 0-471.-41526-X 1. Solid state physies. 1. Title 26276.K5 2005, 330.41 de22 2004042850 ISBN 0-£71-11526. WIE ISBN 0-471-65057-5, Printed in the United States of America 987654About the Author Charles Kittel did his undergraduate work in physics at M.I.T and at the Cavendish Laboratory of Cambridge University. He received his Ph.D. from the University of Wisconsin. He worked in the solid state group at Bell Laboratories, along with Bardeen and Shockley, leaving to start the theoretical solid state physics group at Berkeley in 1951. His research has been largely in ‘magnetism and in semiconductors. In magnetism he developed the theories of ferromagnetic and antiferromagnetic resonance and the theory of single ferromagnetic domains, and extended the Bloch theory of magnons. In semi- conductor physics he participated in the first cyclotron and plasma resonance experiments and extended the results to the theory of impurity states and to electron-hole drops He has been awarded three Guggenheim fellowships, the Oliver Buckley Prize for Solid State Physics, and, for contributions to teaching, the Oersted Medal of the American Association of Physics Teachers. He is a member of the National Academy of Seience and of the American Academy of Arts and Sciences,Preface This book is the eighth edition of an elementary text on solid state/ condensed matter physics for seniors and beginning graduate students of the physical sciences, chemistry, and engincering. In the years since the first edi- tion was published the field has developed vigorously, and there are notable applications, The challenge to the author has been to treat significant new areas while maintaining the introductory level of the text. It would be a pity to present such a physical, tactile field as an exercise in formalism. At the first edition in 1953 superconductivity was not understood; Fermi surfaces in metals were beginning to be explored and cyclotron resonance in semiconductors had just been observed; ferrites and permanent magnets were beginning to be understood; only a few physicists then believed in the reality of spin waves, Nanophysics was forty years off. In other fields, the structure of DNA was determined and the drift of continents on the Earth was demon- strated. It was a great time to be in Seience, as it is now. I have tried with the successive editions of ISSP to introduce new generations to the same excitement. There are several changes from the seventh edition, as well as much clarification: + An important chapter has been added on nanophysies, contributed by an active worker in the field, Professor Paul L. McEen of Cornell University Nanophysics is the science of materials with one, two, or three small dimen- sions, where “small” means (nanometer 10~? m). This field is the most excit- ing and vigorous addition to solid state science in the last ten years. * The text makes use of the simplifications made possible by the universal availability of computers. Bibliographies and references have been nearly eliminated because simple computer searches using keywords on a search engine such as Google will quickly generate many useful and more recent references. As an example of what can be done on the Web, explore the entry http:/Avww-physiesweb.org/bestof/eond-mat. No lack of honor is in- tended by the omissions of early or traditional references to the workers who first worked on the problems of the solid state. * The order of the chapters has been changed: superconductivity and magnetism appear earlier, thereby making it easier to arrange an interesting one-semester course, ‘The crystallographic notation conforms with current usage in physics. Im- portant equations in the body of the text are repeated in ST and GGS-Gaussian units, where these differ, except where a single indicated substitution will translate from CGS to SI. The dual usage in this book has been found helpful and acceptable. Tables are in conventional units. The symbol ¢ denotes thePreface charge on the proton and is positive, The notation (18) refers to Equation 18 of the current chapter, but (3.18) refers to Equation 18 of Chapter 3. A caret () over a vector denotes a unit vector. Few of the problems are exactly easy: Most were devised to carry forward the subject of the chapter, With few exceptions, the problems are those of the original sixth and seventh editions. The notation QT refers to my Quantum Theory of Solids, with solutions by C. Y. Fong; TP refers to Thermal Physics, with H. Kroemer. This edition owes much to detailed reviews of the entire text by Professor Paul L. McEuen of Cornell University and Professor Roger Lewis of Wollongong University in Australia, They helped make the book much easier to read and un- derstand. However, I must assume responsibility for the close relation of the text to the earlier editions, Many credits for suggestions, reviews, and photographs are given in the prefaces to earlier editions. [have a great debt to Stuart Johnson, my publisher at Wiley; Suzanne Ingrao, my editor; and Barbara Bell, my per- sonal assistant. Corrections and suggestions will be gratefully received and may be ad- dressed to the author by email to kittel@berkeley.edu. The Instructor's Manual is available for download at: www.wiley.com/ college/kittel. Charles KittelContents ‘CHAPTER 1: CRYSTAL STRUCTURE Periodic Array of Atoms Lattice Translation Vectors Basis and the Crystal Structure Primitive Lattice Gell Fundamental Types of Lattices ‘Two-Dimensional Lattice Types Three-Dimensional Lattice Types Index Systems for Crystal Planes Simple Crystal Structures Sodium Chloride Structure: Cesium Chloride Structure Hexagonal Close-Packed Structure (hep) Diamond Structure Cubic Zine Sulfide Structure Direct Imaging of Atomic Structure Nonideal Crystal Structures Random Stacking and Polytypism Crystal Structure Data Summary Problems (CHAPTER 2: WAVE DIFFRACTION AND THE RECIPROCAL LATTICE Diffraction of Waves by Crystals Bragg Law Scattered Wave Amplitude Fourier Analysis Reciprocal Lattice Vectors Diffraction Gonditions Laue Equations Brillouin Zones Reciprocal Lattice to se Lattice Reciprocal Lattice to bee Lattice Reciprocal Lattice to fee Lattice ~ Few aonse 18 4 18 16 Ww 18 18 19 19 22, 23 25 26 a7 29 32 33 36 37Fourier Analysis of the Basis Structure Factor of the bec Lattice ‘Structure factor of the fee Lattice Atomic Form Factor Summary Problems CHAPTER 3: CRYSTAL BINDING AND ELASTIC CONSTANTS Crystals of Inert Gases ‘Van der Waals—London Interaction Repulsive Interaction Equilibrium Lattice Constants Cohesive Energy Tonic Crystals Electrostatic or Madelung Energy Evaluation of the Madelung Constant Covalent Crystals Metals Hydrogen Bonds Atomic Radi Tonic Crystal Radti Analysis of Elastic Strains Dilation Stress Components Elastic Compliance and Stiffness Constants Elastic Energy Density Elastic Stiffness Constants of Cubie Crystals Bulk Modulus and Compressibility Elastic Waves in Cubic Crstals ‘Waves in the [100] Direction ‘Waves in the [110] Direction Summary Problems CHAPTER 4: PHONONS I. CRYSTAL VIBRATIONS Vibrations of Crystals with Monatomic Basis First Brillouin Zone Group Velocity 288s aS BS azeageressssassa co 13 cy 7 8 80 8h 82. 85 89 geeContents ‘Long Wavelength Limit 94 Derivation of Force Constants from Experiment 4 ‘Two Atoms per Primitive Basis 95 Quantization of Elastic Waves 99 Phonon Momentum 100 Inelastic Scattering by Phonons 100 Summary 102 Problems 102 (CHAPTER 5: PHONONS 11, THERMAL PROPERTIES 105 Phonon Heat Capacity 107 Planck Distribution 107 Normal Mode Enumeration 108 Density of States in One Dimension 108 Density of States in Three Dimensions aul Debye Model for Density of States 2 Debye T° Law 14 Einstein Model of the Density of States, 14 General Result for D(w) ua Anharmonic Crystal Interactions 119 ‘Thermal Expansion 120 Thermal Conductivity 121 ‘Thermal Resistivity of Phonon Gas 123 Umklapp Processes 125 Imperfecions 126 Problems 198 CHAPTER 6: FREE ELECTRON FERMI GAS 131 Energy Levels in One Dimension 134 Effect of Temperature on the Fermi- Dirac Distribution 136 Free Electron Gas in Three Dimensions 137 Heat Capacity of the Electron Gas ul Experimental Heat Capacity of Metals 145 Heavy Fermions MT Electrical Conductivity and Ohm's Law a7 Experimental Electrical Resistivity of Metals 148 ‘Umklapp Scattering 151Motion in Magnetic Fields 152 Hall Effect 153 ‘Thermal Conductivity of Metals 156 Ratio of Thermal to Electrical Conductivity 156 Problems 157 (CHAPTER 7; ENERGY BANDS 161 Nearly Free Electron Model 164 Origin of the Energy Gap 165 Magnitude of the Energy Cap 167 Bloch Functions 167 Kronig-Penney Model 168 Wave Equation of Electron in a Periodic Potential 169 Restatement of the Bloch Theorem 173 Crystal Momentum of an Electron 173 Solution of the Central Equation 174 Kronig-Penney Model in Reciprocal Space 174 Empty Lattice Approximation 176 Approximate Solution Near a Zone Boundary 177 Number of Orbitals in a Band 180 Metals and Insulators 181 Summary 182 Problems 182, (CHAPTER 8: SEMICONDUCTOR CRYSTALS. 185 Band Gap 187 Equations of Motion 191 Physical Derivation of hk = F 193 Holes 194 Effective Mass 197 Physical Interpretation of the Effective Mass 198 Effective Masses in Semiconductors 200 Silicon and Germanium 202 Intrinsic Carrier Concentration 205 Intrinsic Mobility 208 Impurity Conductivity 208 Donor States 209 Acceptor States aun ‘Thermal Ionization of Donors and Acceptors 213CHAPTER 9: Thermoelectric Effects Semimetals Superlattices Bloch Oscillator Zener Tunneling ‘Summary Problems FERMI SURFACES AND METALS Reduced Zone Scheme Periodic Zone Scheme Construction of Fermi Surfaces Nearly Free Electrons Electron Orbits, Hole Orbits, and Open Orbits Calculation of Energy Bands ‘ght Binding Method of Energy Bands Wigner Seitz Method Cohesive Energy Pseudopotential Methods Experimental Methods in Fermi Surface Studies Quantization of Orbits in a Magnetic Field De Haas-van Alphen Effect Extremal Orbits Fermi Surface of Copper Magnetic Breakdown Summary Problems CuarTeR 10: SUPERCONDUCTIVITY Experimental Survey Oceurrence of Superconductivity Destruction of Superconduetivity of Magnetic Fields Meissner Effect Heat Capacity Energy Gap Microwave and Infrared Properties Isotope Effect Theoretical Survey ‘Thermodynamics of the Superconducting Transition London Equation Contents 214 215 216 217 27 217 218 221 225 226 228, 232 232 237 239 249. 242, 244 248 249 251, 252 252. 257 259 262, 262, 264 268 269 270 270 273Coherence Length 276 BOS Theory of Superconductivity 277 BCS Ground State 278 Flux Quantization in a Supercondueting Ring 270 Duration of Persistent Currents 282 ‘Type HI Superconductors 283 Vortex State 284 Estimation of Hs and Hf. 284 Single Particle Tunneling 287 Josephson Superconductor Tunneling 289 ‘De Josephson Effect 289 ‘Ae Josephson Effect 290 Macroscopic Quantum Interference 292 High-Temperature Superconductors 293 Summary 2904 Problems 294 Reference 296 (CuarTeR 11; DIAMAGNETISM AND PARAMAGNETISM 297 Langevin Diamagnetism Equation 299 Quantum Theory of Diamagnetism of Mononuclear Systems 301, Paramagnetism 302 Quantum Theory of Paramagnetism 302 Rare Earth ons 305 ‘Hund Rules 306 Iron Group Ions 307 Crystal Field Splitting 307 ‘Quenching of the Orbital Angular Momentum 308 Spectroscopic Splitting Factor aul ‘Van Vieck Temperature-Independent Paramagnetism ail Cooling by Isentropic Demagnetization 312 Nuclear Demagnetization 314 Paramagnetic Susceptibility of Conduction Electrons 315 Summary 37 Problems 318 (CHAPTER 12; FERROMAGNETISM AND ANTIFERROMAGNETISM 321 Ferromagnetic Order 323 Curie Point and the Exchange Integral 323Carter 13: ‘Temperature Dependence of the Saturation Magnetization Saturation Magnetization at Absolute Zero Magnons ‘Quantization of Spin Waves ‘Thermal Excitation of Magnons Neutron Magnetic Scattering Ferrimagnetic Order Curie Temperature and Susceptibility of Fesrimagnets Tron Garnets Antiferromagnetie Order Susceptibility Below the Néel Temperature Antiferromagnetic Magnons Ferromagnetic Domains Anisotropy Energy Transition Region between Domains Origin of Domains Coercivity and Hysteresis Single Domain Particles Geomagnetism and Biomagnetism Magnetic Force Microscopy Summary Problems MAGNETIG RESONANCE Nuclear Magnetic Resonance Equations of Motion Line Width Motional Narrowing, Hyperfine Splitting Examples: Paramagnetic Point Defects F Centers in Alkali Halides Donor Atoms in Knight Shift Nuclear Quadmpole Resonance Ferromagnetic Resonance Shape Effects in PMR Spin Wave Resonance Antiferromagnetic Resonance Contents 396 328, 330 333 334 336 338, 339 340 343 344 346 349) 351 352, 354 356 357 361 363 370 371, 373 315 376 376 3i7 379 379 383Cuarrer 14: Carter 15: Electron Paramagnetic Resonance Exchange Narrowing ‘Zero-field Splitting Principle of Maser Action Three-Level Maser Lasers Summary Problems. PLASMONS, POLARITONS, AND POLARONS Dielectric Function of the Electron Gas Definitions of the Dielectric Function Plasma Optics Dispersion Relation for Electromagnetic Waves ‘Transverse Optical Modes in a Plasina ‘Transparency of Metals in the Ultraviolet Longitudinal Plasma Oscillations Plasmons Electrostatic Screening Screened Coulomb Potential Pseudopotential Component U(0) Mott Metal-Insulator Transition Screening and Phonons in Metals Polaritons. LST Relation Electron-Electron Interaction Fermi Liquid Electrou-Electron Collisions Electron-Phonon Interaction: Polarons Peierls Instability of Linear Metals Summary Problems OPTICAL PROCESSES AND EXCITONS Optical Reflectance Kramers-Kronig Relations Mathematical Note 386 386 386 386 388 389 390 391 393 395 395 396 397 398 398 398 401 403 407 407 409 410 a4 4lT AIT ay 420 492, 424 424 427 429 430 432