Band Theory of Solids

1 Introduction
In the starting of Crystal Structure lecture we mentioned it’s important for us
to understand the concepts of crytsallography before we procees to the next
section, now we would put these concepts at use.
The Free Electron Theory discussed earlier was useful in explaining vari-
ous electrical and thermal properties of metal.However there are various things
which could not be explained by this theory. For example,it could not explain
the difference between conductors, semiconductors and insulators.
The failure of Free Electron theory is due to the oversimplification of the model
that a conduction electron experiences constant zero potential inside the
crystal.In reality the potential due to ion cores is not constant and changes
with position inside the lattice (we later see that it changes periodically be-
cause our crystal is periodic). We make the approximation that the ion cores
are at rest and the potential experienced by electron inside lattice is periodic
with periodicity equals to lattice constant

One dimensional representation of potential experienced by electron in

perfectly periodic lattice

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2 Introducing Periodic Potential
The periodic potential we defined above forms the basis of band theory of
solids.We shall see that when the we solve for the motion of electron in this
periodic potential we observe the following results
1. There exists allowed energy regions separated by forbidden reigons or band
gaps
2. The electronic energy functions E(k) are periodic in wave vector k
If we recall the E(k) relation we obtained for free electron model was
h̄2 k2
Epkq “ 2m (Free Electron Model)
Here there is no limit on E and it takes discrete values based on discrete values
of k (k “ nπ
L ). So we see no such band gaps are there in free electron model.
Hence the formation of band gaps is one of the most important results
of band theory of solids.
Now our first step would be to determine electron wave function for periodic
lattice.

3 Bloch Theorem
Before we proceed to study motion of electron in the above periodic potential,
we should mention general properties of wavefunction in such periodic potential.
As described in free electron model one dimensional Schrodinger equation for
an electron moving in a constant potential of V0 is
d2 ψ 2m
` 2 pE ´ V0 qψ “ 0
dt2 h̄
Solution of above equation is of plane wave form
ψpxq “ e˘ikx
Similarly for an electron moving in one dimensional periodic potential V pxq
d2 ψ 2m
` 2 rE ´ V pxqsψ “ 0
dt2 h̄
Here the potential function V pxq is periodic with periodicity equals to lattice
constant a
V px ` aq “ V pxq
There is a theorem by Bloch that states that solution of the above
Schrodinger equation is of the from of plane waves multiplied by a
function uk pxq having same periodicity as that of the lattice

BlochF unction “ψpxq “ e˘ikx uk pxq

where
uk px ` aq “ uk pxq

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3.1 Proof of Bloch Theorem
Let gpxq and f pxq be the two real and independent solution of Schrodinger
equation with periodic potential V pxq, then general solution can be written as

ψpxq “ Af pxq ` Bgpxq (3.1)

since V px ` aq “ V pxq, so the equations f px ` aq and gpx ` aq also satisfy

the equation (3.1) .However since equation (3.1) cannot have more than 2 in-
dependent solutions we must be able to express f px ` aq, gpx ` aq in terms of
f pxq, gpxq.

f px ` aq “ α1 f pxq ` α2 gpxq

gpx ` aq “ β1 f pxq ` β2 gpxq

where

α1 , α2 , β1 , β2 are real functions of energy f pEq

So substituting above values in equation (3.1) we obtain

ψpx ` aq “ Af px ` aq ` Bgpx ` aq “ pAα1 ` Bβ1 qf pxq ` pAα2 ` Bβ2 qgpxq (3.2)

If we choose constants A and B such that

Aα1 ` Bβ1 “ λA
Aα 2 ` Bβ2 “ λB
loooooooooomoooooooooon (1)
p3.3q

then we can get

ψpx ` aq “ λψpxq (3.4)

For (3.4) to be true , there must exist a solution to the set of equations denoted
by (3.3). For a non zero solution to exist determinant of coefficients
must be equal to zero
 
pα1 ´ λq β1 

 α2 “0
pβ2 ´ λq
on solving we get

λ2 ´ pα1 ` β2 qλ ` α1 β2 ´ α2 β1 “ 0 (3.5)
To Prove: α1 β2 ´ α2 β1 “ 1 in above equation
We know that f pxq and gpxq are solution of the Schrodinger equation with
periodic potential. So substituting that we get

d2 gpxq 2m
` 2 rE ´ V pxqsgpxq “ 0
dx2 h̄

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 d2 f pxq 2m
` 2 rE ´ V pxqsf pxq “ 0
dx2 h̄
Multiplying the former by f(x) and the latter by g(x) and subtracting we obtain
d2 gpxq d2 f pxq
f pxq ´ gpxq “0
dx2 dx2
or
dgpxq df pxq
W pxq “ f pxq ´ gpxq “ constant (1)
dx dx
loooooooooooooomoooooooooooooon
W ronskian
We know f(x+a),g(x+a) in terms of f(x) and g(x) so we can express
„ ȷ
dgpx ` aq df px ` aq dgpxq df pxq
f px`aq ´gpx`aq “ pα1 β2 ´α2 β1 q f pxq ´ gpxq
dx dx dx dx
or
W px ` aq “ pα1 β2 ´ α2 β1 qW pxq “ constant
Hence we obtain
α1 β2 ´ α2 β1 “ 1
So equation (3.5) becomes
λ2 ´ pα1 ` β2 qλ ` 1 “ 0
From above we get two values of λ so that we can get periodic wave solu-
tion(Equation (3.4)).Hence two functions ψ1 pxq, ψ2 pxq

3.1.1 Case 1: For Energy Ranges pα1 ` β2 q2 ă 4

For Case 1 the equation would have complex roots λ1 , λ2 . Since coefficeints of
the polynomial are real they would be complex conjugate of each other. Hence
λ1 “ eika
λ2 “ e´ika
Using above λ and putting them in equation (3.4) we can write
ψpx ` aq “ e˘ika ψpxq (3.6)
The function having above relation behaves same as the Bloch function that we
studied earlier. To check we replace x by x+a in the Bloch function and we
obtain the same equation as (3.6)
ψpx ` aq “ e˘ikpx`aq uk px ` aq
Using uk px ` aq “ uk pxq
ψpx ` aq “ e˘ika ψpxq (3.6)
Hence this proves Bloch theorem for the Case 1

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3.1.2 Case 2: For Energy Ranges pα1 ` β2 q2 ą 4
Here the polynomial would have real roots which may be taken as
λ1 “ eµa

λ2 “ e´µa

µ is Real

The corresponding solution for Schrodinger equation are

ψ1 pxq “ eµx upxq and ψ2 pxq “ e´µx upxq
Though mathematically valid they are not acceptable solution as they are not
bounded. This is contradiction to assumption that wave function should remain
finite at all points in space because of probabilistic interpretation. In Case:1
this is always finite

ψpx`naq
Case 1 : ψpxq “ f inite

ψpx`naq
Case 2 : ψpxq “ 8 for n ÝÑ 8

Hence we get that

λ1 “ eika λ2 “ e´ika Allowed Roots (Energy)

λ1 “ eµa λ2 “ e´µa Forbidden Roots (Energy)

In three dimension Bloch function is written as

ψk prq “ eik.r uk prq

4 Kroing-Penney Model
As we had discussed in the introduction that rather than considering the free
electron model , now we would consider the model where the electron in lat-
tice experiences periodic potential with periodicity equals lattice constant a.
Same can be seen in figure 1, this model was further simplified by Kroing-
Penney, it would be easier for us to obtain the solution of Schrodinger
equation if we take a simplified potential function.Below we can see the
one-dimensional Kronig–Penney model of the periodic potential function, which
is used to represent a one-dimensional single-crystal lattice.

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The one-dimensional periodic potential function of the Kronig–Penney model

To obtain the solution to Schrodinger’s wave equation, we make use of Bloch

Theorem we just proved. We write Schrodinger equation for two regions
d2 ψ 2m
dx2 ` h̄2
Eψ “ 0 for 0 ă x ă a

d2 ψ 2m
dx2 ` h̄2
pE ´ V0 qψ “ 0 for ´b ă x ă 0

Assuming energy E of electron is less than V0 , we define two real quantities

2mE
α2 “ (4.1)
h̄2

2mpV0 ´ Eq
β2 “ (4.2)
h̄2
So above equation becomes

d2 ψ
` α2 ψ “ 0 f or 0 ă x ă a (4.3)
dx2
d2 ψ
´ β 2 ψ “ 0 f or ´ b ă x ă 0 (4.4)
dx2
Since the potential is periodic the wave solution must be of the form

ψpxq “ eikx uk pxq

where uk pxq is periodic function in x with periodicity a+b

Taking derivatives of Bloch function we get
dψ duk
“ ikeikx uk pxq ` eikx
dx dx
d2 ψ 2 ikx ikx duk
2
ikx d uk
“ ´k e uk pxq ` 2ike ` e (4.5)
dx2 dx dx2

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Substituing (4.5) in (4.3) and (4.4) we obtain

d2 u1 du1
` 2ik ` pα2 ´ k 2 qu1 “ 0 ; 0 ă x ă apRegion Iq (4.6)
dx2 dx
d2 u2 du2
` 2ik ´ pβ 2 ` k 2 qu2 “ 0 ; ´b ă x ă 0pRegion IIq (4.7)
dx2 dx
where u1 , u2 represent values of uk pxq in intervals of 0 ă x ă a and ´b ă x ă 0
respectively
The solution to equation (4.6) or Region I is of the form

u1 pxq “ Aeipα´kqx ` Be´ipα`kqx ; 0 ă x ă a

The solution to equation (4.7) or Region II is of the form

u1 pxq “ Ceipβ´kqx ` De´ipβ`kqx ; ´b ă x ă 0

where

A, B, C, D are constants determined from Boundary Conditions

We would apply 4 boundary conditions to solve for 4 unknowns (A,B,C,D).
Since the potential function vpXq is everywhere finite, both the wave function
ψpxq and its first derivative dψ
dx must be continuous. This continuity condition
implies that the wave amplitude function upxq and its first derivative du
dx must
also be continuous.
Boundary Condition 1
If we consider the boundary at x =0 and apply the continuity condition to the
wave amplitude, we have
u1 p0q “ u2 p0q
Substituting above in equation of Region I and Region II we obtain

A`B´C ´D “0 (B-1)

Boundary Condition 2
ˆ ˙ ˆ ˙
du1 du2
“
dx x“0 dx x“0
we obtain

pα ´ kqA ´ pα ` kqB ´ pβ ´ kqC ` pβ ` kqD “ 0 (B-2)

Boundary Condition 3
Due to continuity condition we can say that as u1 as x ÝÑ a is equal to u2 as
x ÝÑ ´b
u1 paq “ u2 p´bq

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Substituting above in equation of Region I and Region II we obtain

Aeipα´kqa ` Be´ipα`kqa ´ Ce´ipβ´kqb ´ Deipβ`kqb “ 0 (B-3)

Boundary Condition 4
The last boundary condition is
ˆ ˙ ˆ ˙
du1 du2
“
dx x“a dx x“´b

which gives

pα ´ kqAeipα´kqa ´ pα ` kqBe´ipα`kqa ´ pβ ´ kqCe´ipβ´kqb ` pβ ` kqDeipβ`kqb “ 0

(B-4)
We now have four homogeneous equations, Equations (B-1), (B-2), (B-3), and
(B-4), with four unknowns as a result of applying the four boundary conditions.
In a set of simultaneous, linear, homogeneous equations, there is a nontrivial
solution if, and only if, the determinant of the coefficients is zero. In our case,
the coefficients in question are the coefficients of the parameters A,B,C and D .
After equating the deteminant to 0 we would obtain.

´pα2 ` β 2 q
psinpαaqqpsinpβbqq ` pcospαaqqpcospβbqq “ coskpa ` bq (4.8)
2αβ

Equation (4.8) relates parameter k to the total energy E(through α)

and the potential function V0 (through β)
To simplify this equation Kroing Penney considered the case when V0 ap-
proaches infinity but b tends to 0, such that the potential barrier V0 b remains
constant(potential barrier becomes delta function). The quantity V0 b as
V0 ÝÑ 8 and b ÝÑ 0 is called barrier strength.
Kroing Penney equation on simplification becomes
ˆ ˙
mV0 b
sinpαaq ` cospαaq “ cospkaq
h̄2 α
where
mV0 ba
P “
h̄2
2mE
α2 “
h̄2
So the Final Kroing Penney equation we get is

sinpαaq
P ` cospαaq “ cospkaq (4.9)
αa

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4.1 Energy-k space Relation
4.1.1 Free Electron Case (V0 “ 0)
Let’s take the Kroing Penney Model(Equation (4.9)) and consider it for the free
electron case. For free electron V0 “ 0 and hence P “ 0. So the equation (4.9)
becomes
cospαaq “ cospkaq
α“k
Using equation (4.1) and above relation we get

h̄2 k 2
E“
2m
Hence for free electron case we obtain a parabolic relation between E and k ,
which we already knew

Parabolic E vs k curve for free electron

4.1.2 Electron in Potential Case (V0 ą 0)

We take left hand side of equation (4.9) and define it as f pαaq, then we get

sinpαaq
f pαaq “ P cospαaq
` looomooon (4.10)
αa
loooomoooon
f2 pαaq
f1 pαaq

So we get that
f pαaq “ cospkaq
We know that
´1 ď cospkaq ď 1

So
´1 ď f pαaq ď 1: Allowed Values of α

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aqf1 pαaq,bqf2 pαaq,cqf pαaq The shaded reigons represent allowed values of αa

Periodic Zone Scheme

Since αa is related to energy(E)(by equation (4.1)) and only certain values of α

are allowed to get a solution. We also get a bound on Energy(E)

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 E vs k diagram for allowed values of α, E

Extended Zone Scheme

From here we get the concept of allowed energy states and forbidden
energy states for particles in a crystal
Breaks appear in dispersion curve at k “ nπ
a . These discontinuities form the
boundary of Brilloun Zone
´π π
a ÝÑ a- 1st Brilloun Zone
π 2π ´2π ´π
a ÝÑ a , a ÝÑ a - 2nd Brilloun Zone
2π 3π ´3π ´2π
a ÝÑ a , a ÝÑ a - 3rd Brilloun Zone

Since cos(ka) is periodic by 2π, we may displace the E vs k curves by 2nπ, to

effectively shift them to first Brilloun Zone. This representation is known as
reduced-zone representation.

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 Reduced Zone Scheme

The principle result from the Kroing Penney model is that rather than all energy
states being available to electron, electrons in a crystal exist in certain
allowed energy bands and are excluded from the forbidden energy
bands.Similar band theory exists for 3 dimensional crystals. We would now
obtain certain properties of materials and electrons using this Kroing Penney
Model.

5 Distinction between Metal,Insulators and Semi

Conductors
Now firstly we would determine the number of available states in each energy
band to determine how the electrons fill in the crystal.

5.1 Allowed Number of States

If the solid contains N unit cells then the size of solid is given by

L “ Na
Bloch states are given by
2π 2π
kx “ L nx “ N a nx

Range of 1st Brilloun Zone(or any Brilloun zone for that matter(in reduced
scheme)) is given by

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 ´ πa ď kx ď π
a

which gives us
´ N2 ď nx ď N
2

So each band has N bloch states , taking a factor of 2 because of spin multiplicity
we get

No. of States in each band = 2N

No. of Electrons = N ˆ (No. of Valence electrons per unit cell)

5.2 Metal
A solid which would have a partly filled energy band would display metallic
charachters. For example Sodium has 1 valence electron per unit cell then
Number of States in Energy Band = 2N

Number of electrons = N ˆ 1(No. of valence electron)

Since Number of States ą Number of electron here the energy band remains
partly empty. If an electric field is applied electron in Conduction Band would
participate in transport since there are plenty of available states just above the
Fermi Level.

Energy Band Diagram of a Metal

Another case in which a solid can show metallic behaviour is when conduction
and valence band overlaps.The band splitting into allowed and forbidden energy
bands is a complex phenomenon, and below shows a case in which the conduction
and valence bands overlap at the equilibrium interatomic distance. This happens
in Magnesium

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 Overlapping Energy Bands

5.3 Insulators
A solid having certain number of energy bands completely filled and certain
bands completely empty is an insulator. Since Conduction Band is completely
empty if an electric feild is applied there are no particles to move and we would
observe no currents.
Number of States = Number of electrons

Energy Band Diagram of an Insulator

The situation in above figure can occur only at 0K. At temperature greater
than OK some electrons from topmost band(Valence Band) may get excited to
next energy band(Conduction Band). These electrons than start participating
in conduction process. The number of such electron depends on the value of
band gap between conduction and valence band.
The bandgap for insulators is in order of 3.5eV to 6eV or higher
so that even at room temperature there are essentialy no electrons
in conduction band. So due to large band gap value insulator has a high
resistivity.

5.4 Semiconductors
We just studied about insulators but what if the value of band gap was lower in
the previous case. In that case even at room temperature some electrons would
get excited from valence band to conduction band and start conducting. This
is the case with semi conductors

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 Energy Band Diagram of a semiconductor(lower band gap)

The examples of such material are silicon and germanium. The band gap is of
the order of 1eV.

1. At 0K semiconductors act like an insulator

2. Semiconductors are insulators with relatively smaller band gap
values

6 Effective Mass of Electrons

In free electron case we do not assume any periodic potential hence the effective
mass of electron comes out to be equal to exact mass of electron i.e m˚ “ me .
Here we try to determine the effective mass of electron in periodic potential
from energy-dispersion curve.
Consider effect of electric field ε on motion of electron present in Brilloun Zone.If
v is the velocity of electron and electric field ε acts for a time dt the change in
energy of electron is given by
ˆ ˙
eε dE
dE “ eεdx “ eεvdt “ dt
h̄ dk
To determine:Velocity of electron from E-k relationship
According to wave mechanical theory of particles. A particle moving with ve-
locity v is equivalent to wave packet moving with velocity vg

dω
v “ vg “ (1)
dk
Also E is given by
E “ h̄ω

15
So from above and (1) we can write
ˆ ˙
1 dE
v“ (2)
h̄ dk

So using the above velocity E-k relation we can write

ˆ ˙
eε dE
dE “ eεvdt “ dt
h̄ dk

We can write
dE
dE “ dk
dk
ˆ ˙
dE eε dE
dk “ dt
dk h̄ dk
dk eε
“ (6.1)
dt h̄
or
dk dp
h̄ “ “ F “ eε (6.2)
dt dt
Equation (6.2) in an analogue to Newton’s second law for an electron in periodic
lattice ( rate of change of momentum= Applied force). Hence we can say that
the accelration a is obtained by diffrentating v from (2) with respect to time

1 d2 E dk
ˆ ˙
dv
a“ “
dt h̄ dk 2 dt

Using equation (6.1) we obtain

eε d2 E
a“ (6.3)
h̄2 dk 2
For a free electron of mass m
eε
a“ (6.4)
m
Comparing (6.3) and (6.4) we get effective mass of electron(m˚ ) with which an
electron moves in a periodic crystal

h̄2
m˚ “ ` d2 E ˘ (6.5)
dk2

So the effective mass of electron is not constant but depends on the value of
d2 E
dk2 . Hence the curvature of bands determine the effective mass

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 Variation of Energy, Velocity and Effevtive Mass with k

d2 E
Note that dk2 can be positive,negative or zero

Now we introduce a factor which measures uptil which extent electron be-
haves as a free electron
m d2 E
ˆ ˙
m
fk “ ˚ “ 2 (6.6)
m h̄ dk 2
$
& ă 1 m˚ ą m Heavy particle
fk “ ą 1 m˚ ă m Light particle
“ 1 m˚ “ m F ree electron
%

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The concept of negative effective mass may be understood in terms of Bragg’s
reflection when k is close to ˘ πa .Due to Bragg’s reflection force applied in one
direction leads to gain in momentum in another direction leading to negative
effective mass.

6.1 Effective number of free electrons in Band

The measure of Nef f (Effective Number of Freee Electrons) helps us determine
conductivity of the material. For this we consider an energy band filled uptil
level k1 pk1 ă πa q.We defined fk earlier which represents the extent upto which
an electron behaves as free electron in k-space. Thus we can write that

Nef f “ Σfk

Energy Band filled upto state k1

Total number of states in interval dk is given by

L
dn “ dk
2π
Since each state has maximum of 2 electrons(because of spin). The total elec-
trons can be given by

L k1 L k1
ż ż
Nef f “ 2 fk dk “ fk dk
2π ´k1 π ´k1

Using (6.6)
ˆ ˙
2Lm dE
Nef f “ (6.7)
πh̄2 dk k“k1

From above we can make 2 comments-

• Nef f =0 when a band is completly filled because at k1 the term dE
dk is equal
to 0-Completley Filled Band

18
• Nef f is maximum when dE
dk is maximum (at point of inflection)-Partially
Filled Band

19