AUTONOMOUS

Band Theory of Solids

INTRODUCTION Bloch stated this theory in 1928. According to this theory, the free electrons moves in a periodic field provided by the lattice. This theory is also called Band theory of solids. The energy band theory of solids is the basic principle of semiconductor physics and it is used to explain the differences in electrical properties between metals, insulators and semiconductors.

Electron in a periodic potential Bloch

theorem

A crystalline solid consists of a lattice which is composed of a large number of positive ion cores at regular intervals and the conduction electrons move freely throughout the lattice. The variation of potential inside the metallic crystal with the periodicity of the lattice is explained by Bloch theorem.

+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +

 The potential of the solid varies periodically with the periodicity of space lattice and the potential energy of the particle is zero near the nucleus of the +ve ion in the lattice and maximum when it is half way between the adjacent nuclei which are separated by interatomic spacing distance a.

Periodic positive ion cores Inside metallic crystals.

+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +

V !g

One dimensional periodic potential in crystal.

Blochs Theorem
Blochs Theorem states that for a particle moving in the periodic potential, the wavefunctions (x) are of the form

] ( x ) ! u k ( x )e

s ikx

, where uk ( x) is a periodic function uk ( x) ! uk ( x  a )

uk(x) is a periodic function with the periodicity of the potential

The exact form depends on the potential associated with atoms (ions) that form the solid

 The one dimensional Schrdinger equation

d 2] 8T 2 m  [ E  V ]] ! 0 dx 2 h2

The periodic potential V(x) may be defined by means of the lattice constant a as V(x)=V(x+a)
d ] 8T m  2 [ E  V ( x  a)]] ! 0 dx 2 h
2 2

Bloch has shown that the one dimensional solution of the Schrdinger equation is

] k ( x) ! exp(ikx)U k ( x) In3  D ] K (r ) ! exp(ikr )U k (r )

Where U k (x) is a periodic with periodicit y of a crystal lattice.

 Let us consider a linear chain of atoms of length L in one dimensional case with N number of atoms in the chain
U k ( x ) ! U k ( x  Na ).............(3) ] k ( x  Na ) ! U k ( x  Na ) exp{ik ( x  Na ) ] k ( x  Na ) ! exp(ikNa )U k ( x) exp(ikx) ] k ( x  Na ) ! ] k ( x) exp(ikNa )..........( 4)

This is refered to as Bloch condition.Similarly, the complex conjugate of eq(4)

] k ( x  Na ) ! ] * k ( x). exp(ikNa ).......(5)


FromEq(4)and (23) ] k ( x  Na )] k ( x  Na ) ! ] k ( x)] k ( x)

* *

 This means that the electron is localized around any particular atom and the probability finding the electron the electron is same throughout the crystal .

 Behaviour of an electron in a periodic potential:(The Kronig-Penny Model): This model treats the potential found in actual crystal to the point of getting an exact solution of the Schrdinger equation. It assumes that the potential energy of an electron in a linear array of positive nuclei has the form of a periodic array of square wells as shown in fig.

The Kronig-Penney Model

Potential barrier between the atoms.

U2(x)

U1(x) x

X=0 X=b

X=a

We will eventually let Vpg and b p0 in the problem.

 The potential energy is equal to zero in the regions 0<x<a, and in the potential V0 in the regions - b<x<0.Each of the potential energy wells may be considered.. The wave functions associated with this model can be calculated by solving Schrdinger equations for the two regions:
d 2] 2m  2 E] ! 0 for 0 x a..............1 2 dx J d 2] 2m  2 ( E  V0 )] ! 0 for  b x 0........2 2 dx J

 Let us define real quantities

E2 !

and

by

2mE 2m(V0  E ) andF 2 ! ; ( E V0 )...............3 2 2 J J

Now ,since the wave function must have Bloch form ,we may expect that
] ( x) ! e ikxU k ( x)..........4

Substituting eq (4) in eq(2) we get the following the equation for uk(x)

d u1 du1  2ik  (E 2  k 2 )u1 ! 0 for 0 x a 2 dx dx

d 2u2 du2  2ik  ( F 2  k 2 ) ! 0 for b x 0 dx dx 2

The soln of these equations may be written as

u1 ! Aei (E  K ) x  Be i (E  k ) x for0 u2 ! Ce ( F ik ) x  De ( F  ik ) x for b

x x

a 0
7

Where A,B,C,D are the constants .These solutions must be subjected to the Following boundary condition

du1 du2 (u1 ) x !0 ! (u2 ) x !0 ; ! dx x !0 dx x !0 du2 du1 (u 1 ) x ! a ! (u2 ) x ! b ; ! dx x ! a dx x ! b

 The first two condition are imposed because of the requirement of continuity of the wave function and its derivative d /dx at x=0,and hence of u and du/dx;the remaining two conditions are required because of the periodicity of uk(x). The application of these boundary condition to eq(7) leads to the following four linear homogenous equations involving the constants A,B,C,D: A+B=C+D

Ai (E  k )  Bi (E  k ) ! C ( F  ik )  D( F  ik ), Ae
(E  k ) a

 Be

 i (E  k ) a

! Ce

 ( F ik ) b

 De

( F  ik )b

The coefficient A,B,C,D can be determined by solving these equation s,and Wave functions calculated.this leads to the following equations;

F E sinh Fbsin Ea  coshFbcos Ea ! cos K (a  b) 2EF

2 2

10

 This equation quite complicated ,.Kronig and Penny considered the possibility that Vo tends to infinity and b approaches zero in such a way that the product Vob remains finite . The quantity lim(Vob) representing the barrier strength. In this possibility , the equation (10) becomes
mV0b 2 SinEa  cos Ea ! cos ka JE
11

If we define the quantity P by

mV0ba p! 2 J

 Eq (11) reduces to
p sin Ea  cos Ea ! cos KE Ea 12

This is the condition for the solutions of the wave equation to exist. We see that this is satisfied only for those values of a for which its Left hand side lies between +1and -1;this is because its right hand side Must fall in this range .such values are represent the wave like solutions and are allowed.

Consequence of this equationcan be understood with fig.

The Kronig-Penney Model

Boundaries are for a = nT.

sin(Ea) P  cos(Ea) Ea
1

-2

3
Ea

-1 No solution exists, k2 < 0 Regions where the equation is satisfied, hence where the solution exists. In general, as the energy increases (Ea increases), each successive band gets wider, and each successive gap gets narrower.

 The part of the vertical axis lying between the horizontal lines represents the range acceptable to the left-hand side
p sin Ea  cos Ea Ea

 Conclusions: **Allowed ranges of a which permits a wave mechanical solution to exist are shown by the shadow portions. thus the motion of electrons in a periodic lattice is characterized by the bands of allowed energy separated by forbidden regions . ** As the value of increase the width of the allowed energy bands also increase and the width of the forbidden band decreases.

 ** if the potential barrier strength P is large ,the function described by the right hand side of the equation crosses +1 and -1 region at steeper angle. Thus the allowed bands become narrower and forbidden bands become wider . If P tends to infinite the allowed band reduces to one
single energy level :

ppg

Ea

If P tends to zero no energy levels exist, all energies are allowed to the electrons.
cos Ea ! cos ka E !k E2 ! k2
pp0

Ea

2mE k !E ! 2 J 2 J 2 E ! ( )k 2m h 2 2T 2 E ! ( 2 )( ) 8T m P h2 1 E !( ) 2 2m P h2 p 2 p 2 1 2 E !( ) 2 ! ! mv 2m h 2m 2
2 2

Brillouin zones (E-k Curve)

The Brillouin zone is a representation of permissive values of k of the electrons in one, two or three dimensions. Thus the energy spectrum of an electron moving in the presence of a periodic potential fields is divided into allowed zones and forbidden zones.

1 Ea -1

The Kronig-Penney model gives us DETAILED solutions for the bands, which are almost, but not, cosinusoidal in nature.
4 T T T 3 2 d d d  T d T d 2 T d 3 T d 4 T d

E-k diagram :

Energy gap

Allowed bands

Energy gap

3T  a

2T  a

T  a

T a

2T a

3T a

First Brillouin zone

 When a parabola representing the energy of a free electron is compared with the energy of an electron in a periodic field.this parabola is discontinuities in the parabola occur at values of k given by k=n /a Since k is the wave vector k=2 / n /a =2 / I 2a=n
This is in the form of Braggs law .

 The solution to the wave equation under this condition yields two standing waves ,showing that two electron positions of differing potential energy are possible for the same value of k.This is gives rise to break in E-K curve.

 From the graph we find that the electron has allowed energy values in the region or zone extending from k=- /a to + /a. this zone is called first Brillouin zone

Origin of energy band formation in solids When we consider isolated atom, the electrons are tightly bound and have discrete, sharp energy levels. When two identical atoms are brought closer the outer most orbits of these atoms overlap and interact. If more atoms are brought together more levels are formed and for a solid of N atoms , each of the energy levels of an atom splits into N levels of energy. The levels are so close together that they form an almost continuous band. The width of this band depends on the degree of overlap of electrons of adjacent atoms and is largest for outer most atomic electrons.

E1

E1 E2

E1 E2 E3 N atoms

N energy levels

 The energy bands in solids are important in determining many of physical properties of solids. The allowed energy bands (1) Valance band (2) Conduction band The band corresponding to the outer most orbit is called conduction band and the next inner band is called valence band. The gap between these two allowed bands is called forbidden energy gap.

Classifications of solids into Conductors, Semiconductors & Insulators On the basis of forbidden band or energy gap the solids are classified into insulators, semiconductors and conductors. Insulators: In case of insulators, the forbidden energy band is very wide as shown in figure. Due to this fact the electrons cannot jump from valance band to conduction band.

Conduction band Forbidden gap

INSULATORS
Conduction band

Valance band

SEMI CONDUCTORS
Forbidden gap Conduction band Valance band Valance band

CONDUCTORS

Semi conductors
In semi conductors the forbidden energy ( band ) gap is very small as shown in a figure. Ge and Si are the best examples of semiconductors. Forbidden ( band ) is of the order of 0.7ev & 1.1ev. Conductors In conductors there is no forbidden gap. Valence and conduction bands overlap each other as shown in figure above. The electrons from valance band freely enter into conduction band.

Effective mass of an electron The effective mass of an electron arises due to periodic potential provided by the lattice. When an electron in a periodic potential of lattice is accelerated by an electric field, then the mass of the electron varies, mass is called effective mass of the electron m*. Consider an electron of charge e and mass m acted on by electric field.
f ! eE ma ! eE a! eE m

Acceleration is not a constant in the periodic lattice of the crystal so mass of the electron replaced by its effective mass m* when it is moving in a periodic potential or crystal lattice.

eE a! * m

Consider the free electron as a wave packet moving with a velocity Vg

d[ vg ! dk where [ ! 2TR p angular . frequency k p wave.vector d[ vg ! dk dR v g ! 2T dk E dE E ! hR ,R ! ., dR ! h h 2T dE vg ! h dk 1 dE vg ! Jdk

dt 1 d 2E 1 a! Jdk dt 1 d 2 E dk a! Jdk 2 dt sin ce., J ! p k dp and .. !F dt p ) 1 d 2E ( J) a! Jdk 2 dt 1 d 2 E dp ( ) a! 2 2 J dk dt 1 d 2E a! 2 F 2 J dk d(

a!

dv g

The effective mass of an electron

1 d E a! 2 F 2 J dk 2 J F ! 2 a d E 2 dk 2 J m ! 2 d E 2 dk

a. Variation of E with K b. Variation of v with K

(a )

0 V

(b)

c. Variation of m* with K
(c )

0
m

d. Variation of fk with K The degree of freedom of an electron is generally defined by a factor.

fk

m m d E fk !  ! 2 { 2 } m J dk

(d )
 T a

k0

T a

pk

 Variation of v with K:
(a )

0 V

The variation of velocity with k fig (b).when k=0 The velocity is zero and the value of k increases The velocity is increase reaching its maximum (c ) Value at k=k0 .k0corresponds to that point of Inflexion on E-k curve .beyond this inflexion point The velocity begins to decrease .finally assumes the Zero value at k= /a

(b)

0
m

fk

(d )
 T a

k0

T a

pk

 Variation of m* with K
(a )

0 V

The variation of m*with k.near k=0 the effective mass (b) Approaches m.as the value of k increase m*increase ,reaching its maximum value at the point of inflexion On the E-K curve .above the point of inflexion m* (c ) Negative and as k tends to /a,it decreases to small Negative value.

0
m

fk

(d )
 T a

k0

T a

pk

 Variation of fkwith k:
The degree of freedom of an electron fk=m/m*

(a )

0 V

m d 2E fk ! 2 2 J dk

(b)
(c )

0
m

Fkis measure of the extent to which an electron In state k is free.if m*is large ,fk is small i.e the particle Behaves as a heavy particle . When fk=1 the electron behaves as a free electron . Note that fkis positive in the lower half of the band And negative in the upper half.

fk

(d )
 T a

k0

T a

pk