Charles kittel introduction to solid state physics wiley (2005)

Contents Periodic Array of Atoms Lattice Translation Vectors Basis and the Crystal S t ~ c t u r e Primitive Lattice Cell Fundamental Types of Lattices Two-Dimensional Lattice Types Thre

Name Symbol Name Symbol Name Symbol Actinium

P o l o n i ~ ~ m Potassium

Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium Samarium Scandium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium

-

H'

Periodic Table, with the Outer Electron Configurations of Neutral

L i :, Be'

T h e notation used to descrilx the electronic configuratior~ of atoms 8"' N' OX FY Nel0

;nrd ions is discussed in all textl,nokc uf introdoctory atomic physics

The letters s, p , d, signifj flectrorrs having nrlrital angular 2y "' tnomentum 0, 1 , 2, in units fi; the rruml,er to the left of the Zs22p 2 ~ ~ 2 ~ ' 25122~1 2~~211' 2sZ2pi 2*'2p0

~ ~ ~ > ~ letter dcwotrs the principal quantum nurnl~er $ i 2 of o n e c~rl)it, and the ~ 1 4 3 sit4 PI-S'~ cln7 A ~ ~ X

superscript to the right denotes t h e nrlrnher of electn)rrs in the r~rl)it

Introduction to

E I G H T H E D I T I O N

Charles Kittel

Pr($essor Enwritus L'nitiersity of Cal$c~nlia, Berkeley

B

!

I

Professor Paul McEuen of Cornell University

John Wiley & Sons, Inc

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About the Author

Charles Kittel did his undergraduate work in physics at M.1.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 Science 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 fur seniors and beginning grad~rate students of the physical sciences, chemistry, and engineering In the years since the first edi- tion was pnhlished the field has devcloped \,igoronsly, 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 editic~n in 1953 superconductivity was not lmderstood; Fermi snrfaces in metals were beginning to he 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 Science, as it is now I have tried with the successivt: editions of lSSY to introduce new generations to the same excitement There are several changes from the seventh edition, as well as rnucll clarification:

An important chapter has been added on nanophysics, contributed by an active worker in the field, Professor Paul L McEuen 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 simplificati(~ns made possible hy the nniversal availability of computers Bibliographies and references have been nearly eliminated because simple computer searches using keywords on a search engine slreh as Google will quickly generate many useful and rnore recent references As an cxamplc of what can ho dons on the Web, explore the entry http://\mw.physicsweb.org'hestof/cond-mat No lack of honor is in- tended by the omissions of early or traditiorral references to the workers who first worked on the problems of the solid state

The order nf the chapters has been changed: superconducti\ity 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 SI and CGS-Gaussian units, where these differ, except where a single indicated substitution will translate frnm CGS to SI The dual usage in this book has been found helpful and acceptable Tables arc in conventional units The symbol e denotes the

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 nnit 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 QTS refers to my Quantum Theory of Solirls, 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 I 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 rmail to kittelQberke1ey.edu

The Instructor's Manual is available for download at: \m.wiley.coml collegelkittel

Charles Kittel

Contents

Periodic Array of Atoms Lattice Translation Vectors Basis and the Crystal S t ~ c t u r e Primitive Lattice Cell

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 (hcp) Diamond Structure

Cubic Zinc Sulfide Structure Direct Imaging of Atomic Structure Nonideal Crystal Structures

Random Stacldng and Polytypism Crystal Structure Data

Summary Problems

CHAPTER 2: WAVE DIFFRACTION AND THE RECIPROCAL

Fourier Analysis of the Basis

Structure Factor of the bcc Lattice Structure factor of the fcc Lattice Atomic Form Factor

Summary

Problems

Crystals of Inert Gases

Van der Wads-London Interaction Repulsive Interaction

Equilibrium Lattice Constants Cohesive Energy

Ionic Crystals

Electrostatic or Madelung Energy Evaluation of the Madelung Constant Covalent Crystals

Constants

Elastic Energy Density Elastic Stiffness Constants of Cubic Crystals Bulk Modulus and Compressibility

Elastic Waves in Cubic Crstals

Waves in the [I001 Direction Waves in the [I101 Direction Summary

Problems

CIIAPTER 4: PHONONS I CRYSTAL VIBRATIONS

Vibrations of Crystals with Monatomic Basis First Brillouin Zone

Group Velocity

Long Wavelength Limit Derivation of Force Constants from Experiment Two Atoms per Primitive Basis

Quantization of Elastic Waves

Phonon Momentum

Inelastic Scattering by Phonons

Summary

Problems

CHAFTER 5: PHONONS 11 THERMAL PROPERTIES

Phonon Heat Capacity

Planck Distribution Normal Mode Enumeration Density of States in One Dimension Density of States in Three Dimensions Debye Model for Density of States Debye Law

Einstein Model of the Density of States

General Result for D(w)

Anharmonic Crystal Interactions

Thermal Expansion Thermal Conductivity

Thermal Resistivity of Phonon Gas Umklapp Processes

Imperfecions Problems

CHAPTER 6: FREE ELECTRON FERMI GAS

Energy Levels in One Dimension

Effect of Temperature on the Fermi-

Motion in Magnetic Fields

Hall Effect Thermal Conductivity of Metals

Ratio of Thermal to Electrical Conductivity Problems

CHAPTER 7: ENERGY BANDS

Nearly F r e e Electron Model

Origin of the Energy Gap Magnitude of the Energy Gap Bloch Functions

Approximate Solution Near a Zone Boundary

Silicon and Germanium Intrinsic Carrier Concentration

Intrinsic Mobility Impurity Conductivity

Donor States Acceptor States Thermal Ionization of Donors and Acceptors

Thermoelectric Effects

Semimetals Superlattices Bloch Oscillator Zener Tunneling Summary Problems

C ~ E 9: R FERMI SURFACES AND METALS

Reduced Zone Scheme Periodic Zone Scheme Construction of F e r m i Surfaces Nearly Free Electrons

Electron Orbits, Hole Orbits, and Open Orbits Calculation of Energy Bands

Tight Binding Method of Energy Bands Wigner-Seitz Method

Cohesive Energy Pseudopotential Methods Experimental Methods in F e r m i Surface Studies Quantization of Orbits in a Magnetic Field

De Haas-van Alphen Effect Extremal Orbits

Fermi Surface of Copper Magnetic Breakdown Summary

Problems

CHAPTER 10: SUPERCONDUCTIVITY

Experimental Survey Occurrence of Superconductivity Destruction of Superconductivity of Magnetic Fields Meissner Effect

Heat Capacity Energy Gap Microwave and Infrared Properties Isotope Effect

Theoretical Survey Thermodynamics of the Superconducting Transition London Equation

Coherence Length BCS Theory of Superconductivity BCS Ground State

Flux Quantization in a Superconducting Ring Duration of Persistent Currents

Type I1 Superconductors Vortex State

Problems Reference

Langevin Diamagnetism Equation Quantum Theory of Diamagnetism of Mononuclear Systems

Paramagnetism Quantum Theory of Paramagnetism Rare Earth Ions

Hund Rules Iron Group Ions Clystal Field Splitting Quenching of the Orbital Angular Momentum Spectroscopic Splitting Factor

Van Vleck Temperature-Independent Paramagnetism Cooling by Isentropic Demagnetization

Nuclear Demagnetization Paramagnetic Susceptibility of Conduction Electrons Summary

Problems

CHAPTER 12: FERROMAGNETISM AND ANTIFERROMAGNETISM

Ferromagnetic Order Curie Point and the Exchange Integral

Temperature Dependence of the Saturation Magnetization

Saturation Magnetization at Absolute Zero Magnons

Quantization of Spin Waves Thermal Excitation of Magnons Neutron Magnetic Scattering

Ferrimagnetic O r d e r

Curie Temperature and Susceptibility

of Ferrimagnets Iron Garnets Antiferromagnetic O r d e r

Susceptibility Below the NBel 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

CHAPTER 13: MAGNETIC 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 Silicon Knight Shift

Nuclear Q u a d m p o l e Resonance Ferromagnetic Resonance Shape Effects in FMR Spin Wave Resonance Antiferromagnetic Resonance

Electron Paramagnetic Resonance

Exchange Narrowing Zero-field Splitting Principle of Maser Action

Three-Level Maser Lasers

Summary

Problems

CHAPTER 14: 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 Plasma

Transparency of Metals in the Ultraviolet Longitudinal Plasma Oscillations Plasmons

Electrostatic Screening Screened Coulomb Potential Pseudopotential Component U(0) Matt Metal-Insulator Transition Screening and Phonons in Metals Polaritons

LST Relation Electron-Electron Interaction Femi Liquid

Electron-Electron Collisions Electron-Pbonon Interaction:

Polarons Peierls Instability of Linear Metals

Summary Problems

CHAPTER 15: OPTICAL PROCESSES AND EXCITONS

Optical Reflectance Kramers-Kronig Relations Mathematical Note

Example: Conductivity of collisionless Electron Gas

Electronic Interband Transitions Excitons

Frenkel Excitons Alkali Halides Molecular Crystals Weakly Bound (Molt-Wannier) Excitons Exciton Condensation into Electron-Hole Drops (EHD)

Raman Effects in Crystals Electron Spectroscopy with X-Rays Energy Loss of Fast Particles in a Solid Summary

Problems

CHAPTER 16: DIELECTRICS AND FERROELECTRICS

Maxwell Equations Polarization Macroscopic Electric Field Depolarization Field, E,

Local Electric Field at an Atom Lorentz Field, E,

Field of Dipoles Inside Cavity, E3

Dielectric Constant and Polarizability Electronic Polarizability

Classical Theory of Electronic Polarizability Stmctural Phase Transitions

Ferroelectric Crystals Classification of Ferroelectric Crystals Displacive Transitions

Soft Optical Phonons Landau Theory of the Phase Transition Second-Order Transition

First-Order Transition Antiferroelectricity Ferroelectric Domains Piezoelectricity Summaq Problems

CHAPTER 17: SURFACE AND INTERFACE PHYSICS

Reconstruction and Relaxation Surface Crystallography Reflection High-Energy Electron Diffraction

Surface Electronic Structure Work Function

Thermionic Emission Surface States Tangential Surface Transport Magnetoresistance in a Two-Dimensional Channel

Integral Quantized Hall Effect (IQHE) IQHE in Real Systems

Fractional Quantized Hall Effect (FQHE) p-n Junctions

Rectification Solar Cells and Photovoltaic Detectors Schottky Barrier

Heterostructures

n-N Heterojunction Semiconductor Lasers

One-Dimensional Subbands Spectroscopy of Van Hove Singularities 1D Metals - Coluomb Interactions and Lattice Copnlings

Localization

Voltage Probes and the Buttiker-Landauer Formalism

Electronic Structure of OD Systems

Quantized Energy Levels

Quantized Vibrational Modes

Monatomic Amorphous Materials

Radial Distribution Function

Structure of Vitreous Silica, SiO,

Color Centers

F Centers Other Centers in Alkali Halides Problems

Shear Strength of Single Crystals Slip

Dislocations Burgers Vectors Stress Fields of Dislocations Low-angle Grain Boundaries Dislocation Densities Dislocation Multiplication and Slip Strength of Alloys

Dislocations and Crystal Growth Whiskers

Hardness of Materials Problems

General Considerations Substitutional Solid Solutions- Hume-Rothery Rules

Order-Disorder Transformation Elementary Theoly of Order Phase Diagrams

Eutectics Transition Metal Alloys Electrical Conductivity Kondo Effect

Problems

APPENDIXA: TEMPERATURE DEPENDENCE OF THE REFLECTION LINES 641

APPENDIX B: EWALD CALCULATION OF LATTICE SUMS 644

Ewald-Kornfeld Method for Lattice Sums

APPENDIX C: QUANTIZATION OF ELASTIC WAVES: PHONONS

Phonon Coordinates Creation and Annihilation Operators

APPENDIX F: BOLTZMANN TRANSPORT EQUATION

Particle Diffusion Classical Distribution Fermi-Dirac Distribution Electrical Conductivity

APPENDIX G: VECTOR POTENTIAL, FIELD MOMENTUM,

AND GAUGE TRANSFORMATIONS

Lagrangian Equations of Motion Derivation of the Hamiltonian Field Momentum

Gauge Transformation Gauge in the London Equation

Crystal Structure

PERIODIC ARRAYS O F ATOMS

Lattice translation vectors

Basis and the crystal structure

Primitive lattice cell

FUNDAMENTAL TYPES O F LATTICES

Two-dimensional lattice types

Three-dimensional lattice types

INDEX SYSTEM FOR CRYSTAL PLANES

SIMPLE CRYSTAL STRUCTURES

Sodium chloride structure

Cesium chloride structure

Hexagonal close-packed structure

Diamond structure

Cubic zinc s d d e structure

DIRECT IMAGING O F ATOMIC STRUCTURE 18

NONIDEAL CRYSTAL STRUCTURES 18

Random stacking and polytypism 1 9

CHAPTER 1: CRYSTAL STRUCTURE

PERIODIC ARRAYS O F ATOMS

The serious study of solid state physics began with the discovery of x-ray diffraction by crystals and the publication of a series of simple calculations of the properties of crystals and of electrons in crystals Why crystalline solids rather than nonclystalline solids? The important electronic properties of solids are best expressed in crystals Thus the properties of the most important semi- conductors depend on the crystalline structure of the host, essentially because electrons have short wavelength components that respond dramatically to the regular periodic atomic order of the specimen Noncrystalline materials, no- tably glasses, are important for optical propagation because light waves have a longer wavelength than electrons and see an average over the order, and not the less regular local order itself

We start the book with crystals A crystal is formed by adding atoms in a

constant environment, usually in a solution Possibly the first crystal you ever saw was a natural quartz crystal grown in a slow geological process from a sili- cate solution in hot water under pressure The crystal form develops as identical building blocks are added continuously Figure 1 shows an idealized picture of the growth process, as imagined two centuries ago The building blocks here are atoms or groups of atoms The crystal thus formed is a three-dimensional periodic array of identical building blocks, apart from any imperfections and impurities that may accidentally be included or built into the structure

The original experimental evidence for the periodicity of the structure rests on the discovery by mineralogists that the index numbers that define the orientations of the faces of a crystal are exact integers This evidence was sup- ported by the discovery in 1912 of x-ray diffraction by crystals, when Laue de- veloped the theory of x-ray diffraction by a periodic array, and his coworkers reported the first experimental observation of x-ray diffraction by crystals The importance of x-rays for this task is that they are waves and have a wave- length comparable with the length of a building block of the structnre Such analysis can also be done with neutron diffraction and with electron diffraction, hut x-rays are usually the tool of choice

The diffraction work proved decisively that crystals are built of a periodic array of atoms or groups of atoms With an established atomic model of a crys- tal, physicists could think much further, and the development of quantum the- ory was of great importance to the birth of solid state physics Related studies have been extended to noncrystalline solids and to quantum fluids The wider field is h o w n as condensed matter physics and is one of the largest and most vigorous areas of physics

Lattice Translation Vectors

An ideal crystal is constn~cted by the infinite repetition of idenbcal groups

of atoms (Fig 2) A group is called the basis The set of mathematical points to which the basls is attached is called the lattice The lattice in three dimensions may be defined by three translabon vectors a,, a,, a,, such that the arrange- ment of atoms in the crystal looks the same when viewed from the point r as when viewed from every polnt r' translated by an mtegral multiple of the a's:

Here u,, u,, u , are arhitraryintegers The set of points r' defined by (1) for all

u,, u,, u, defines the lattice

The lattice is said to be primitive if any two points from which the atomic

arrangement looks the same always satisfy (1) with a suitable choice of the in- tegers u i This statement defines the primitive translation vectors a, There

is no cell of smaller volume than a, a, x a, that can serve as a building block for the crystal structure We often use the primitive translation vectors to de-

fine the crystal axes, which form three adjacent edges of the primitive paral-

lelepiped Nonprimitive axes are often used as crystal axes when they have a simple relation to the symmetry of the structure

Figure 2 The crystal srmchre is formed by

the addition af the basis (b) to evely lattice

point of the space laisice (a) By looking at

( c ) , one oan recognize the basis and then one

can abstract the space lattice It does not

matter where the basis is put in relation to a

lattice point

1 Crystal 5

Basis and the Crystal Structure

The basis of the crystal structure can be idendled once the crystal mes

have been chosen Figure 2 shows how a crystal is made by adding a basis to

every lamce pomnt-of course the lattice points are just mathematical con-

structions Every bas~s in a given crystal is dentical to every other ~n composi-

tmn, arrangement, and orientation

The number of atoms in the basis may be one, or it may be more than one

The position of the center of an atom3 of the basis relahve to the associated

lattice point is

We may arrange the origin, wl~ich we have called the associated lattice point,

so that 0 5 x,, yj, zj 5 1

Fieure 3a Latttce nomts of a soam lnmce m two &mensrons AU ~ a r s of vector? a,, a, are trans-

twice the area of a primitive cell

Figare 3b Primitive ccll "fa space lattice in three dimensions

Figure 3c Suppose these points are identical atoms: Sketchin on the figure a set of lattice points,

choice ofprimitive axes, aprimitivc cell, and the basis of atoms associatedwith alattice point

F i p e 4 A primitive cell may also be chosen fol-

lowing this procedure: (1) draw lines to connect a

given lattice point to all nearby lattice points: (2) at

the midpoint and normal to these lines, draw new

lines or planes The smallest volume enclosed in this

way is the Wigner-Seitz primitive cell All space may

be filled by these cells, just as by the c e h of Fig 3

Primitive Lattice Cell

The parallelepiped defined by primitive axes al, a,, a, is called a primitive

cell (Fig 3b) A primitive cell is a t).pe of cell or unit cell (The adjective unit is superfluous and not needed ) A cell will fill all space by the repetition of suit- able crystal b-anslatlon operationq A primitive cell is a m~nimum-volume cell There are many ways of choosing the prnnitive axes and primitive cell for a given lattice The number of atoms m a primitive cell or primtive basis is alwap the same for a given crystal smllcture

There is always one lattice point per primitive cell If the primitwe cell is a parallelepiped with lattice po~uts at each of the eight corners, each lattice point is shared among e ~ g h t cells, so that the total number of lattice points in the cell is one: 8 X = 1 The volume of a parallelepiped wrth axes a,, %, a3 is

V, = (a, - as X a, 1 , (3)

by elementary vector analysis The basis associated wrth a primitive cellis cdued

a prim~tive bans No basis contans fewer atoms than a pnmibve basis contains Another way of choosing a primitive cell is shown in Fig 4 This is h o w n to physicists as a Wigner-Seitz cell

FUNDAMENTAL TYPES OF LATTICES

Crystal lattices can be carried or mapped into themselves by the lattice

translations T and by vanous other symmetzy operattons A typical symmetry

operation is that of rotation about an axis that passes through a lattice point Lattices can be found such that one., two-, three., four., and sixfold rotation axes cany the lattice into itself, corresponhng to rotatrons by ZT, 2 ~ 1 2 , 2 d 3 ,

2 ~ 1 4 , and 2 ~ 1 6 radians and by integral multiples of these rotations The rota- tion axes are denoted by the symbols 1,2, 3, 4, and 6

We cannot find a lattice that goes into itself under other rotations, such as

by 2.d7 rachans or 2 ~ / 5 rachans A single molecule properly designed can have any degree of rotational symmetry, but an Infinite periodic lattice cannot We can make a crystal from molecules that individually have a fivefold rotation ms,

but we should not expect the latbce to have a fivefold rotation m s In Fig 5 we show what happens if we try to construct a penodic latbce havlng fivefold

Figure 5 A fivefold t u i s of symmetry can-

not exist in a periodic lattice because it is not ~ossible to fa thc area of a plane with

a mmected m a y of pentagons We can, however, fill all the area oTa plane with just

two distina designs of "tiles" or elemeutary potysms

Figure 6 (a) A plane of symmetry to the faces of a cube (b) A diagonal plane of s)rmmehy

in a cube (c) The three tetrad xes of a cube (d) Thc four trid axes of a cube (e) The six diad axes

a lattice point The inversion operation 1s composed of a rotation of v followed

by reflection in aplane normal to the rotation axis; the total effect is to replace r

by -r The symmetry axes and symmetry planes of a cube are shown in Fig 6

The lattice in Fig 3a was d r a m for arbitrary al and as A general lattice

such as this is known as an oblique lattice and is invariant only under rotation

of rr and 27r ahout any lattice point But special lattices of the oblique type can

he invariant under rotation of 2 ~ 1 3 , 2 ~ 1 4 , or 2 d 6 , or under mirror reflection

We m i s t impose restrictive conditions on a, and a% if we want to construct a lat- tice that will he invariant under one or more of these new operations There are

four distinct types of restriction, and each leads to what we may call a special

lattice type Thus there are five distinct lattice types in two dimensions, the oblique lattice and the four special lattices shown in Fig 7 Bravais lattice is

the common phrase for a distinct lattice.%e; we say that there are five Bravdrs lattices in two dimensions

Figure 7 Four special lattices in twodirnmsions,

1 St-ture

Three-Dimensional Lattice Types

The point symmetry groups in three dimensions require the 14 different lattice types listed in Table 1 The general lattice is triclinic, and there are

13 special lattices These are grouped for convenience into systems classified according to seven types of cells, which are triclinic, monoclinic, orthorbom- bic, tetragonal, cubic, higonal, and hexagonal The division into systems is expressed in the table in terms of the adal relations that describe the cells The cells in Fig 8 are conventional cells: of these only the sc is a primitive cell Often a nonprimitive cell has a more obvious relation with the point symmetry operations than has a primitive cell

There are three lattices in the cubic system: the simple cubic (sc) lattice, the body-centered cubic (hcc) lattice, and the face-centered cubic (fcc) lattice

Table 1 The 14 latlioe types in three dimensions

Table 2 Characteristics of oubic lattices"

a

Volume primitive cell a3 ZQ 1 3 xa 1 3

Lattice points p e r unit volume l/a3 2/aR 4/a3

Numher of nearest neighbors 6 8 12

Nearest-neighbor distance a 3u2a/2 = 0.866a a/2'" 0.707a

Packing fractionn ZW &V5 i d 5

"The packing fraction is the manirnum proportion of the available volume that can be filled with hard spheres

Figure 10 Pnmibve translation vectors of the body-

~ i ~ , , , ~ 9 ~ ~ d c,lbic ~ lattice, shouing ~ a ~ ~ centered cubic lattice; ~ ~ ~ these ~ vectors connect d the lattice prilnitive ~h~ rimifive she%,,,, is a rhonl+,o point at the origin to lattice points at the body centers hedron ,,f edge ; 2 3 a, and the angle behen adja The primitive ceU is obtained on completing the rhody- cent edges is 109"ZR' huhedron In terms of the cube edge a, the primitive

translation vectors are

a l = i a ( i + i - 2 ) ; a s = $ ~ ( - i + j + L i )

a 3 = ; a ( % - f + i ) Ifere i , j , i are the Cartesian untt vectors The charactenstics of the three cubic lattxes are summanzed in Table 2 A

prirmhve cell of the bcc lattice is shown in Fig 9, and the primtive tran~lation vectors are shown in Fig 10 The primitive translabon vectors of the fcc lathce are shown In Fig 11 Primitive cells by definition contain only one lattice point, but the conventional bcc cell contains two lattice points, and the fcc cell contains four lattice points

I Crystal Stwctun 11

Figore 11 The rhombohedra1 primitive cell of the hce-centered Figore 12 Relation of the plimitive cell

cubic clystal The primitive translation vectors a,, a,, connen in the hexagonal system (heavy lines) to the lattice point at the origin with lattice points at the face centers, a prism of hexagonal symmew Here

The angles between& axes are 60'

The pos~hon of a point in a cell is spec~fied by (2) in terms of the atomic

coordinates x , y, z Here each coordinate is a fraction of the axla1 length a,, a,,

a, in the direction of the coordinate axis, with the origin taken at one corner of

the cell Thus the coorhnate? of the body center of a cell are ;$$, and the face

1 1 1 1

centers include i i O , 0,s; 5% In the hexagonal system the primitive cell is a

right prism based on a rhomhu3 with an included angle of 120" F ~ g u r e 12

shows the relabonship of the rhombic cell to a hexagonal prism

INDEX SYSTEM FOR CRYSTAL PLANES

The orientahon of a crystal plane is determined by three points in the

plane, provided they are not collinear If each point lay on a different crystal

axis, the plane could be specdied by giving the coordinates of the points in

terms of the latbce constants a,, a,, a3 However, it turns out to b e more useful

for structure analysis to specify the orientation of a plane by the indices deter-

mined by the followlug rules (Fig 13)

Find the intercepts on the axes in terms of the lattice constants a,, a,, a,

The axes may be those of a primitive or nonprimibve cell

Figure I3 This plane intercepts

the a,, +, a, axes at 3a,, Za,, Za,

The recrprocals of these numbers

, I &

are 5, ., The smallest three mte-

gers havlng the same rabo are 2, 3,

3, and thus the m&ces of the plane

For the plane whose intercepts are 4 , 1 , 2 , the reciprocals are $, 1, and $: the

smallest three integers having the same ratio are (142) For an intercept at infin- ity, the corresponding index is zero The indices of some important plades in a cubic crystal are illustrated by Fig 14 The indices (hkl) may denote a single plane or a set of parallel planes If a plane cuts an axis on the negative side of the origin, the corresponding index is negative, indicated hy placing a minus sign

1 Crystal

above the index: (hkl) The cube faces of a cubic crystal are (100) (OlO), (OOl),

(TOO), ( o ~ o ) , and (001) Planes equivalent by s y m m e q may he denoted by curly

brackets (braces) around indices; the set of cube faces is {100} When we speak

of the (200) plane we mean a plane parallel to (100) but cutting the a, axis at i n

The indices [uvw] of a direction in a clystal are the set of the smallest inte-

gers that have the ratio of the components of a vector in the desired direction,

referred to the axes The a, axis is the [loo] direction; the -a, axis is the [ o ~ o ]

direction In cubic crystals the direction [hkl] is perpendicular to a plane (hkl)

having the same indices, but this is not generally true in other crystal systems

SIMPLE CRYSTAL STRUCTURES

We di~cuss simple crystal structures of general interest the sohum chlo-

nde, cesium chloride, hexagonal close-packed, h a m o n d and c u h ~ c zinc sulfide

structures

Sodium Chloride Structure

The sohum chloride, NaCI, structure 1s shown in Figs 1.5 and 16 The

lattice is face-centered cublc: tile basis conslsts of one Na+ Ion and one C 1 ion

Figure 15 We may construct the soditzrn chloride

cvstal shuchlre by arranging Naf and C 1 ions alter-

nately at the lattice points o f a simple cubic lattice I n

the ctysral each ion is surrounded by six nearest neigh-

bors of the opposite charge The space lattice is fcc,

and the basis has one C I ion at 000 w d one Na'

L ? L

, , The 'figre shows one conventional cubi

The ionic diameters here are reduced in relation

cell in order to darify the spatial arrangement

c cell Fii tothe ?m

P :

p r e 16 M

d e r than th Singer)

ulll cirlnride

ns (Courtes

The sodium iuns are

y of A N Holden and

Pigure 17 Na1ui.d c~?stals of lead snlfide PbS whir11 lias the

NaCl crystal stmcturc ( P h u t a g ~ a p l ~ by R Burl?aon.)

Figure 18 The cesium chloride cqstal

struehne The space lattice is silnple

cubic, and &the basis has one Cst ion at

000 and one C 1 ion at i

separated by one-half the body diagonal of a umt cube There are four units of NaCl ~n each unit cube, with atoms in tlie pos~tions

Each atom has as nearest neighbors six atoms of the opposire kind Represen- tative crystals having the ~ k l arrangement include those in the following

table The cube edge a is given in angstroms; 1 if cm lo-'' m 0.1

nm Figure 17 is a photograph of crystals of lead sulfide (PbS) from Joplin, Missouri The Joplin specimens form in beautiful cuhes

Cesium Chloride Stnccture

The cesium chloride structure is shown in Fig 18 There is one molecule per primitive cell, with atoms at the comers 000 and body-centered positions

l i l

- - - , , of the simple cubic space lattice Each atom may he viewed as at the center

Figure 19 A close-packed layer of spheres is shown, with centers at points marked A A second and identical layer of spheres can he placed on top of this, above and patallel to the plane of the drawing, with centen over the points marked B There are two choices for a third layer It can go

in over A or over C Ifit goes in over A, the sequence is AEABAB and the structure is hexagonal close-packed If the third layer goes in over C, the sequence is ABCABCABC and the Struchlre

is face-centered cubic

A

B Figure 20 The hexagonal close-packed structure

c The atom positions in t h i s smcture do not constitute

a soace lattice The mace lattice is s i m ~ l e hexa~onal

I w i k a basis of hvo ;dentical atoms asiociatedwith

inhcated, where o is in the basal plane and c is the rnagmtude of the an? a, of R g 12

of a cube of atoms of the opposite kind, $0 that the number of nearest neigh- bors or coordination number is eight

Hexagonal Close-Packed Structure (hcp)

There are an infinite number of ways of arranging identical spheres in a regular array that maximuzes the packing fraction (Fig 19) One 1s the face- centered cub^ structure; another is the hexagonal close-packed structure (Fig 20) The fraction of the total volume occupled by the spheres is 0.74 for both structures No structure, regilar or not, has denserpaclung

Figure 21 The primitive cell has a, = h, with an

included angle of 120" The c axis (or a,) is normal

to the plane of a, and a, The ideal hcp s t m o h r e has

c = 1.633 a, The two atoms of one basis are shown

as solid circles One atom of the bais is at the ori-

gin; the other atom is at $Qb, which means at the

position r = $a, + +a, + $a,

Spheres are arranged in a single closest-packed layer A by placmg each sphere in contact with SIX others in a plane This layer may serve as either the basal plane of an hcp structure or the (111) plane of the fcc s h c t u r e A sec- ond s~milar layer B may be added by placlng each sphere of B in contact with

three spheres of the bottom layer, as in Figs 19-21 A third layer C may be added In two ways We obtam the fcc structure if the spheres of the third layer are added over the holes in the first layer that are not occupied by B We obtain the hcp structure when the spheres in the third layer are placed directly over the centers of the spheres in the first layer

The number of nearest-nelghbor atoms is 12 for both hcp and fcc stnlc- tures If the b~nding energy (or free energy) depended only on the number of nearest-neighbor bonds per atom, there would be no difference in energy between the fcc and hcp structures

Diamond Structure

The diamond structure is the structwe of the semiconductors silicon and germanium and is related to the structure of several important semicondnctor binary compouncLs The space lattice of damond 1s face-centered cubic The primitive basis of the diamond structure has two identical atoms at coordinates

000 and 2;; assoc~ated m t h each point of the fcc latt~ce, as shown in Fig 22 Because the convenbonal unit cube of the fcc lattice contains 4 latbce points,

i t follows that the conven~onal unit cube of the dlamond structure contams

2 X 4 = 8 atoms There is no way to choose a primitive cell such that the basis

of diamond contains only one atom

Figure 22 Atomic positions in the cubic cell uf the diamond Figure 23 Crystal structure of diamond,

s t ~ u c h ~ r r projected on a cub? face; fiacticms denote height showingthetetrahedralbondarrangement

above the hasp in units of a cubc edge The paints at 0 and $

are on the fcc lattice those at and are on a similar lattice

displvcerl along the body diagonal by one-fourth of its lengh

With a fcc space lattice, the basis consists of mia identical

atoms at 000 0 d i i ;

The tetrahedral bonding characteristic of the diamond structure is shown

in Fig 23 Each atom has 4 nearest neighbors and 12 next nearest neighbors

The diamond structure is relatively empty: the maximum proportion of the available volume which may he filled by hard spheres is only 0.34, which is 46

percent of the f11ling factor for a closest-packed stmcture such as fcc or hcp The diamond structure is an example of the directional covalent bonding found in column IV of the periodic table of elements Carbon, silicon, germa- nium, and tin can crystallize in the diamond structure, with lattice constants

n = 3.567, 5.430, 5.658, and 6.49 A, respectively Here a is the edge of the conventional cubic cell

Cubic Zinc Sulfide Structure

The diamond structure may be viewed as twn fcc structures displaced

from each other by one-quarter of a body diagonal The cubic zinc sulfide

(zinc blende) structure results when Zn atoms are placed on one fcc lattice and

S atoms on the other fcc lattice, as in Fig 24 The conventional cell is a cube The coordinates of the Zn atoms are 000; 0;;; $0;; $ $0; the coordinates of the

1 1 1 1 3 3 3 1 3 3 5 1

S atoms are 444; , 44; 2 j j; 4 4 4 The lattice is fcc There are four molecules '5-

ZnS per conventional cell About each atom there are four equally distafft atoms of the opposite kind arranged at the comers of a regular t e t r a h e d ~ w -

Figure 24

sulfide

Crystal structure of cubic zinc

The diamond structure allows a center-of-inversion symmetry operation

at the midpoint of every hne between nearest-neighbor atoms The inversion operation carries an atom at r into an atom at -r The cubic ZnS struc-

ture does not have inversion symmetry Examples of the cubic zinc sulfide structure are

The close equality of the lattice constants of several pairs, notably (Al, Ga)P and (Al, Ga)As, makes possible the construction of sem~conductor hetemjunc- tions (Chapter 19)

DIRECT IMAGING OF ATOMIC STRUCTURE

Direct images of crystal structure have been produced by transmission electron microscopy Perhaps the most beaubful Images are produced by scan- ning tunneling microscopy; in STM (Chapter 19) one exploits the large vana- tions in quantum tunneling as a function of the height of a fine metal tip above the surface of a crystal The image of Fig 25 was produced m t h ~ ~ way An STM method has been developed that will assemble single atoms Into an orga- nized layer nanometer structure on a crystal substrate

NONIDEAL CRYSTAL STRUCTURES l",v - ., ,

; ,.* ;> The ideal crystal of classical crystallographers is formed by the periodic

7 '

~

repetition of identical units in space But no general proof bas been given that

I Crystal Structure 19

Figure 25 A scanning tunneling microscope

image of atorns on a (111) surface of fcc plat-

inum at 4 K The nearest-neighbor spacing is

2.78 A (Photo courtesy of D M Eigler, IHM

R r e r a r c h Divi~irn.)

the ideal crystal is the state of minimum energy of identical atoms at the tem-

perature of absolute zero At finite temperatures this is likely not to be true We

give a further example here

Random Stacking and Polytypism

:d planes I

-

The fcc and hcp structures are made up of close-pack< 3f atoms

The structures differ in the stacking sequence of the planes, fcc having the se-

quence ABCABC and hcp having the sequence ABABAB Structures

are h o w n in which the stacking sequence of close-packed planes is random

This is known as random stacking and may be thought of as crystalline in two

dimensions and noncrystalline or glasslike in the third

Polytypism is characterized by a stacking sequence with a long repeat

unit along the s t a c h g axis The hest known example is zinc sulfide, ZnS, in

which more than 150 polytypes have been identified, with the lnngest period-

icity being 360 layers Another example is silicon carbide, Sic, which occurs

with more than 45 stacking sequences of the close-packed layers The polytype

of SiC known as 393R has a primitive cell with a = 3.079 A and c = 989.6 A

The longest primitive cell observed for S i c has a repeat distance of 594 layers

A given sequence is repeated many times within a single crystal The mecha-

nism that induces such long-range crystallographic order is not a la

force, but arises from spiral steps due to dislocations in the growtl

(Chapter 20)

~ng-range

I nucleus

CRYSTAL STRUCTURE DATA

In Table 3 we hst the more common crystal stmctureq and lattlce structures

of the elements Values of the atomic concentration and the density are glven in

Table 4 Many dements occur m several crystal structures and transform from