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’.
 V
Periodic positive ion cores V =∞
Inside metallic crystals.
+ + + + + + +

+ + + + + + +

+ + + + + + +

+ + + + + + + X

+ + + + + + + One dimensional periodic

potential in crystal.
 Bloch’s Theorem
• Bloch’s Theorem states that for a particle
moving in the periodic potential, the
wavefunctions ψ(x) are of the form

ψ ( x ) = u k ( x )e ± 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 Schrödinger equation
d 2ψ 8π 2 m
+ [ E −V ]ψ = 0
dx 2 h2 1

• The periodic potential V(x) may be defined by means

of the lattice constant a as V(x)=V(x+a)
I
d 2ψ 8π 2 m
+ 2 [ E − V ( x + a)]ψ = 0
dx2 h

Bloch has shown that the one dimensional solution

of the Schrödinger equation is
ψ k ( x) = exp(ikx)U k ( x) 2

In3 − D
ψ K (r ) = exp(ikr )U k (r )
Where U k (x) is a periodic with periodicity 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)
ψ k ( x + Na) = U k ( x + Na) exp{ik ( x + Na)
ψ k ( x + Na) = exp(ikNa)U k ( x) exp(ikx)
ψ k ( x + Na) = ψ k ( x) exp(ikNa)..........(4)

• This is refered to as Bloch condition.Similarly, the

complex conjugate of eq(4)
∗
ψ k ( x + Na) = ψ *k ( x). exp(−ikNa).......(5)
FromEq(4)and (23)
ψ k ( x + Na)ψ * k ( x + Na) = ψ k ( x)ψ *k ( x)
 Bloch’s Theorem

V ( x) = V ( x + a)
The probability of finding an
electron at any atom in the solid
is the same!!!

• Each electron in a crystalline

solid “belongs” to each and
every atom forming the solid
• 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 Schrödinger 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
V between the atoms.

U2(x)
U1(x)

x
X=0 X=a

X=−b

We will eventually let

V→∞ and b →0 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 Schrödinger equations for the
two regions:

d 2ψ 2m
+ 2 Eψ = 0 for 0 < x < a..............1
dx 2

d 2ψ 2m
+ ( E − V0 )ψ = 0 for − b < x < 0........2
dx 2  2
• Let us define real quantities α and β by
2mE 2m(V0 − E )
α2 = andβ 2
= ; ( E < V0 )...............3
2 2

• Now ,since the wave function must have Bloch form

,we may expect that

ψ ( x) = eikxU k ( x)..........4

• Substituting eq (4) in eq(2) we get the following the

equation for uk(x)

2
d u1 du1
2
+ 2ik + (α − k )u1 = 0 for0 < x < a
2 2
5
dx dx
 d 2u 2 du2
2
+ 2ik − ( β 2
+ k 2
) = 0 for− b < x < 0 6
dx dx
The soln of these equations may be written as

u1 = Aei (α − K ) x + Be − i (α + k ) x for0 < x < a

u 2 = Ce ( β −ik ) x + De −( β +ik ) x for− b < x < 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 8
 du   du 
(u 1 ) x = a = (u2 ) x = − b ;  1  =  2 
 dx  x = a  dx  x = − b
• The first two condition are imposed because of
the requirement of continuity of the wave
function Ψ and its derivative dΨ/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(α − k ) − Bi(α + k ) = C ( β − ik ) − D( β + ik ),
9
(α − k ) a − i (α + k ) a − ( β − ik ) b ( β + ik ) b
Ae + Be = Ce + De

The coefficient A,B,C,D can be determined by solving these equation s,and

Wave functions calculated.this leads to the following equations;

β 2 −α 2
sinh β bsin α a + coshβ bcosα a = cos K (a + b)
2α β 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  Sinα a + cosα a = coska 11
 α 

mV0ba
If we define the quantity P by
p= 2

• Eq (11) reduces to
sin αa
p + cos αa = cos Kα
αa 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 αa 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

sin(αa )
Boundaries are for αa = nπ . P + cos(αa )
αa

-π 3π
- 0 2π
π π α a
-2π

-1
No solution
exists, k2 < 0

Regions where the equation is satisfied, hence where

the solution exists.

In general, as the energy increases (α a 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

sin αa
p +cos αa
αa
• Conclusions:
• **Allowed ranges of αa 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 α 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 .
tends
• to infinite the allowed band reduces to one
gle energy level :
p→ ∞

0 αa
If P tends to zero no energy levels exist,
all energies are allowed to the electrons.
cosα a = coska
α =k
α 2 = k2
2mE
p→ 0 k2 = α 2 =
2
2 2
E = ( )k
2m
h 2 2π 2
αa E = ( 2 )( )
8π m λ
h2 1
E=( ) 2
2m λ
h2 p2 p2 1 2
E=( ) 2 = = mv
2m h 2m 2
 Brillouin zones

• 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.
E-k diagram :
E

Energy gap Allowed

bands

Energy gap

−
3π
a
−
2π
a
−
π
a
π
a
2π
a
3π
a k
First
Brillouin zone
 Insulators, Semiconductors,
Metals
• The last completely filled (at least at T = 0 K)
band is called the Valence Band
• The next band with higher energy is the
Conduction Band
– The Conduction Band can be empty or partially
filed
• The energy difference between the bottom of
the CB and the top of the VB is called the
Band Gap (or Forbidden Gap)
 Insulators, Semiconductors,
Metals
• Consider a solid with the empty
Conduction Band
• If apply electric field
to this solid, the
electrons in the
valence band (VB)
cannot participate in
transport (no
current)
 Insulators, Semiconductors,
Metals
• The electrons in the VB do not
participate in the current, since
– Classically, electrons in the
electric field accelerate, so they
acquire [kinetic] energy
– In QM this means they must
acquire slightly higher energy
and jump to another quantum
state
– Such states must be available,
i.e. empty allowed states This solid
– But no such state are available in would behave
the VB!
as an insulator
 Insulators, Semiconductors,
Metals
• Consider a solid with the half filled
Conduction Band (T = 0K)
• If an electric field is applied
to this solid, electrons in the
CB do participate in
transport, since there are
plenty of empty allowed
states with energies just
above the Fermi energy
• This solid would behave
as a conductor (metal)
 Band Overlap
• Many materials are
conductors (metals) due
to the “band overlap”
phenomenon
• Often the higher energy
bands become so wide
that they overlap with the
lower bands
– additional electron energy
levels are then available
 Band Overlap
• Example: Magnesium (Mg; Z =12):
1s22s22p63s2
– Might expect to be insulator; however, it is a
metal
– 3s-band overlaps the 3p-band, so now the
conduction band contains 8N energy levels,
while only have 2N electrons
– Other examples: Zn, Be, Ca, Bi
Insulators, Semiconductors, Metals
• There is a qualitative difference between
metals and insulators (semiconductors)
– the highest energy band “containing”
electrons is only partially filled for Metals
(sometimes due to the overlap)
• Thus they are good conductors even at very low
temperatures
• The resisitvity arises from the electron scattering
from lattice vibrations and lattice defects
• Vibrations increases with temperature ⇒ higher
resistivity
• The concentration of carriers does not change
appreciably with temperature
Insulators, Semiconductors, Metals
• The difference between Insulators and
Semiconductors is “quantitative”
– The difference in the magnitude of the
band gap
• Semiconductors are “Insulators”
with a relatively small band gap
– At high enough temperatures a fraction of
electrons can be found in the conduction
band and therefore participate in transport
 Insulators vs Semiconductors

• There is no difference between Insulators

and Semiconductors at very low
temperatures
• In neither material are there any electrons in
the conduction band – and so conductivity
vanishes in the low temperature limit
 Insulators vs Semiconductors

• Differences arises at high temperatures

– A small fraction of the electrons is thermally excited
into the conduction band. These electrons carry
current just as in metals
– The smaller the gap the more electrons in the
conduction band at a given temperature
– Resistivity decreases with temperature due to higher
concentration of electrons in the conduction band
1 q2
nτ
=σ =
ρ m*
 Conduction

Electrical current for holes and electrons in the same direction