ELECTRON ENERGY

BANDS
CHAPTER-7

by Dr. E. Zacharias
The classical and quantum free electron theory could not satisfactorily explain a
number of properties of materials.
• Positive Hall coefficient in some materials
• Number of conduction electrons per atom in some metals could not be
estimated correctly
• Couldn’t explain why some materials are conductors while others are
insulators
• Continuous parabolic energy curves being incapable of explaining sharp
resonance like optical spectra of solids

by Dr. E. Zacharias
Band Theory of solids replaces the free electron theory to be able to explain
completely the behavior of solids.

The constant potential energy of electrons in Sommerfield theory is replaced by a

periodic non-vanishing potential energy, the rectangular potential box is replaced
by an infinite periodic potential with the periodicity of the crystal and neglects
the surface effects.

One electron Schrodinger equation is solved to obtain the allowed energy states
of the electron. The allowed energy states appear as a bunch of closely spaced
levels forming a band. Separating bands are the forbidden gap or band gap.

The band theory distinguishes between electrons in the outer most shell and
those inside, treating the inner electrons as heavier.
by Dr. E. Zacharias
CONSEQUENCES OF PERIODICITY
Consider a periodic potential energy function, 𝑉 𝒓 = 𝑉(𝒓 + 𝒕) (7.1)
𝒕 is an arbitrary transl vector in the direct space lattice 𝒕 = 𝑛1 𝒂 + 𝑛2 𝒃 + 𝑛3 𝒄

Since 𝑉 𝒓 is a periodic function, it can be expanded in a fourier series as

𝑉 𝒓 = σ𝒈 𝑉𝒈 𝑒𝑥𝑝(𝑖𝒈. 𝒓) (7.2)
𝒈 is the reciprocal lattice vector.

One electron, time-independent Schrodinger equation is

ℏ2 2
𝐻ψ 𝑟 = − 𝛻 + 𝑉 𝒓 ψ 𝑟 = 𝜀ψ 𝑟 (7.3)
2𝑚
Let the solution to (7.3) be ψ 𝑟 = σ𝒌 𝐶𝒌 exp(𝑖𝒌. 𝒓) (7.4)

Substituting (7.2), (7.4) in (7.3) gives,

by Dr. E. Zacharias
 ℏ2 2
− 𝛻 + 𝑉 𝒓 ψ 𝑟 = 𝜀ψ 𝑟
2𝑚

ℏ2 2
− 𝛻 + σ𝒈 𝑉𝒈 𝑒𝑥𝑝(𝑖𝒈. 𝒓) σ𝒌 𝐶𝒌 exp(𝑖𝒌. 𝒓) = 𝜀 σ𝒌 𝐶𝒌 exp(𝑖𝒌. 𝒓)
2𝑚

ℏ2 𝑘 2
σ𝑘
2𝑚
𝐶𝒌 exp 𝑖𝒌. 𝒓 + σ𝑘 σ𝑔 𝐶𝒌 𝑉𝒈 exp[𝑖(𝒌 + 𝒈). 𝒓] = 𝜀 σ𝑘 𝐶𝒌 exp 𝑖𝒌. 𝒓 (7.5)

Equating coefficients of exp 𝑖𝒌. 𝒓 on both sides, gives

ℏ2 𝑘 2
( − 𝜀)𝐶𝒌 + σ𝑔 𝐶𝒌−𝒈 𝑉𝒈 = 0 (7.6)
2𝑚

The total number of allowed 𝑘 values of the electron waves is equal to the total
number of unit cells, 𝑁 . Therefore, there would be 𝑁 equations (7.6)
corresponding to different values of 𝑘. These 𝑁 equations replace Schrodinger
time-independent equation. by Dr. E. Zacharias
 ℏ2 𝑘 2
Solution of( − 𝜀)𝐶𝒌 + σ𝑔 𝐶𝒌−𝒈 𝑉𝒈 = 0 corresponding to each 𝑘 (for eigen
2𝑚
value 𝜀𝒌 ) is of the form
ψ𝑘 𝒓 = σ𝑔 𝐶𝒌−𝒈 exp[𝑖(𝒌 − 𝒈). 𝒓] (7.7a)

ψ𝑘 𝒓 = σ𝑔 𝐶𝒌−𝒈 𝑒𝑥𝑝 −𝑖𝒈. 𝒓 . 𝑒𝑥𝑝[𝑖𝒌. 𝒓] (7.7b)

ψ𝑘 𝒓 = 𝑢𝑘 (𝒓) 𝑒𝑥𝑝[𝑖𝒌. 𝒓] (7.7c)

with 𝑢𝑘 (𝒓) = σ𝑔 𝐶𝒌−𝒈 . 𝑒𝑥𝑝 −𝑖𝒈. 𝒓 (7.7d)

𝑢𝑘 (𝒓) is the periodic term that modulates the plane wave 𝑒𝑥𝑝[𝑖𝒌. 𝒓] so that it is
a solution to time-independent Schrodinger equation (7.3) of the single electron.
It is periodic in the direct lattice ie. 𝑢𝑘 (𝒓 + 𝒕) = 𝑢𝑘 (𝒓) (7.8)
by Dr. E. Zacharias
Blochs theorem:
the wave function for an electron in a periodic potential has the form
ψ𝑘 𝒓 = 𝑢𝑘 (𝒓) 𝑒𝑥𝑝 𝑖𝒌. 𝒓 , where 𝒌 is the wave vector, 𝒓 is a position vector,
and 𝑢𝑘 (𝒓) is a periodic function that satisfies 𝑢𝑘 (𝒓 + 𝒕) = 𝑢𝑘 (𝒓), for all
vectors 𝒕 of the Bravais lattice of the crystal.

Bloch's theorem is interpreted to mean that the wave function for an electron in
a periodic potential is a plane wave modulated by a periodic function.

by Dr. E. Zacharias
Proof of Bloch theorem:
Consider a crystal of length 𝐿 along the 𝑥-direction with 𝑁 atoms and inter-
atomic spacing 𝑎.

The eigen state of an electron with wave vector 𝒌 near an atom positioned at 𝑥 is
given by Bloch function, ψ𝑘 𝒙 = 𝑢𝑘 (𝒙) 𝑒𝑥𝑝[𝑖𝒌. 𝒙] (7.9)

When the electron moves a distance 𝑎, the wave function becomes,

ψ𝑘 𝒙 + 𝒂 = 𝑢𝑘 (𝒙 + 𝒂) 𝑒𝑥𝑝[𝑖𝒌. (𝒙 + 𝒂)]
= 𝑒𝑥𝑝[𝑖𝒌𝒂] 𝑢𝑘 (𝒙) 𝑒𝑥𝑝[𝑖𝒌. 𝒙]

ψ𝑘 𝒙 + 𝒂 = 𝐶ψ𝑘 𝒙 (7.10)
where 𝐶 = 𝑒𝑥𝑝[𝑖𝒌. 𝒂] (7.11)
by Dr. E. Zacharias
If the crystal is an 𝑁-atom ring, then movement of electron through 𝑁𝑎 brings
the electron back to initial position, the function becomes (using 7.10)
ψ𝑘 𝒙 + 𝑁𝒂 = 𝐶 𝑁 ψ𝑘 𝒙 = ψ𝑘 𝒙 (7.12)
⟹ 𝐶 𝑁 = 1 = 𝑒𝑥𝑝(𝑖2𝜋𝑛)
⟹ 𝐶 = 𝑒𝑥𝑝(𝑖2𝜋𝑛/𝑁) (7.13)

Using (7.11) and (7.13), 𝐶 = 𝑒𝑥𝑝[𝑖𝒌. 𝒂] = 𝑒𝑥𝑝(𝑖2𝜋𝑛/𝑁)

2𝜋𝑛 2𝜋𝑛
𝑘= = (𝑛 = 0, ±1, … , 𝑁/2) (7.14)
𝑁𝑎 𝐿
The number of
𝑁 𝜋
For 𝑛 = , 𝑘 = ± , the two 𝑘 values differing by one reciprocal lattice spacing
2 𝑎
2𝜋
.
𝑎
The number of unique allowed 𝑘 values in the first Brillouin zone is 𝑁.
by Dr. E. Zacharias
 2𝜋 2𝜋 2𝜋
For 3D-crystal, 𝑘𝑥 = 𝑛𝑥 , 𝑘𝑦 = 𝑛𝑦 , 𝑘𝑧 = 𝑛𝑧 . (7.15)
𝐿 𝐿 𝐿

Identical to what was obtained for phonons confirming the appropriateness of

Bloch function to describe the motion of electrons through periodic lattice.

Periodicity of Bloch functions and their eigen values:

Bloch functions are periodic in the reciprocal lattice and have periodicity given
by reciprocal lattice vectors.
𝜓𝒌+𝑮 (𝒓) = 𝜓𝒌 (𝒓) (7.16)

Schrodinger equation for eigen state 𝜓𝒌+𝑮 (𝒓) is

𝐻𝜓𝒌+𝑮 (𝒓) = 𝜀𝑘+𝑔 𝜓𝒌+𝑮 (𝒓) (7.17)

by Dr. E. Zacharias
Using (7.16), (7.17) can be rewritten as
𝐻𝜓𝒌 (𝒓) = 𝜀𝒌+𝒈 𝜓𝒌 (𝒓) (7.18)

(7.18) is the Schrodinger equation for state 𝜓𝒌 𝒓 .

Therefore, 𝜀𝒌+𝒈 = 𝜀𝒌 (7.19)

This means that eigen values have same periodicity as Bloch functions.

Consequences of these periodicities:

• 𝜀𝒌 obtained in terms of 𝑘 can be treated as a quantum number.
• It is sufficient to know the allowed values of 𝑘 in the first Brillouin zone for a
complete description of eigen states and values in the entire crystal.
• The periodic energy surfaces 𝜀𝒌 gives rise to electron energy bands and band
gaps.
by Dr. E. Zacharias
WAVE MECHANICAL INTERPRETATION OF ENERGY BANDS
A crystal is an assembly of atoms. An isolated atom has discrete energy levels. Let
𝜙𝐴 be the wave function of an electron in an atom 𝐴 and 𝜙𝐵 in an atom 𝐵.

If the two atoms 𝐴 and 𝐵 come closer, the electron shares its space between the
two atoms. The electron oscillates between the two atoms at a fixed frequency.
The wave functions 𝜙𝐴 and 𝜙𝐵 overlap.

The two states between which the electron oscillates can be expressed as
1
𝜓 ± = [𝜙𝐴 ±𝜙𝐵 ] [7.20]
2

If 𝜀0 is the electron energy in the isolated atom, the eigen values for the two
states are 𝜀 ± = 𝜀0 ± 𝜀1 [7.21a]
The difference in the two eigen states is 2𝜀1 .
by Dr. E. Zacharias
2𝜀1 = ℏ𝜔 (7.21b)
𝜔 is the frequency with which the electron oscillates between the two states
𝜓 ± .
𝜀1 can be interpreted as a measure of the overlap of wave functions or the
interaction of the electron with the core of the two atoms 𝐴 and 𝐵.

If atoms 𝐴 and 𝐵 are isolated and far away, 𝜀0 is the doubly degenerate level
associated with wave functions 𝜙𝐴 and 𝜙𝐵 .

If the crystal is made up of 𝑁 atoms, the electron interacts with 𝑁 atoms and the
𝑁-fold degenerate level splits into 𝑁 closely spaced levels and forms an energy
band. Similar bands are formed by splitting of discrete levels of isolated atom.

Splitting between degenerate levels in a band increases with decrease in atomic

spacing. by Dr. E. Zacharias
THE KRONIG-PENNY MODEL
The energy bands of crystals are mostly centered about their parent discrete
levels. Kronig-Penny model demonstrated the existence of forbidden gaps
between bands.
Each atom is represented by a finite square well of width 𝑎 and depth 𝑉𝑜 and
separated by potential barrier of width 𝑏.
by Dr. E. Zacharias
If the potential barrier 𝑏 is thin such that 𝑏𝑉0 is negligible, the electron can
move freely through the lattice for any energy given by free electron dispersion
ℏ2 𝑘 2
relation, 𝜀𝑘 =
2𝑚
by Dr. E. Zacharias
If the potential barrier thickness 𝑏 is large, the electrons with potential energy
less than 𝑉0 have little probability of tunneling through the potential barrier and
behave like electron in a potential box of side 𝑎.
ℏ2 𝑘 2 2 1 ℎ 2
𝜀𝑘 = = 𝑛 ( )
2𝑚 2𝑚 2𝑎

In the Kronig-Penny model, 𝑏 << 𝑎 and small enough so that tunneling of

electrons have a non-zero probability for electrons with potential energy less
than 𝑉0 .

The energies and wave functions of electrons associated with this model can be
calculated by solving time-independent one-dimensional Schrödinger’s wave
equations for the two regions shown in the figure.

by Dr. E. Zacharias
The Schrodinger equation for region I is
𝑑2 𝜓 2𝑚𝜀𝑘
2 + 2 𝜓=0
𝑑𝑥 ℏ
𝑑2 𝜓 2𝑚𝜀𝑘
or 2 + 𝛼 2 𝜓 = 0 for 0 < 𝑥 < 𝑎 where 𝛼2 = (7.22a)
𝑑𝑥 ℏ2

by Dr. E. Zacharias
𝑑2 𝜓 2𝑚[𝜀𝑘 −𝑉0 ]
+ 𝜓 = 0 for region II
𝑑𝑥 2 ℏ2
𝑑2 𝜓 2𝑚[𝑉0 −𝜀𝑘 ]
or 2 − 𝛽2 𝜓 = 0 for −𝑏 < 𝑥 < 0 where 𝛽2 = (7.22b)
𝑑𝑥 ℏ2

According to Bloch's theorem, the wave function solution of the Schrödinger

equation when the potential is periodic is a Bloch function of the form
𝜓 𝑥 = 𝑢 𝑥 𝑒𝑥 𝑝 𝑖𝒌. 𝒙 .
where 𝑢 𝑥 is a periodic function. 𝑢 𝑥 = 𝑢 𝑥 + 𝑎

Using Bloch theorem and applying the conditions:

• The wave function and its first derivative should both be continuous at the
interface of region I and II
• The product of 𝑏 and 𝑉0 is kept a constant.
by Dr. E. Zacharias
Differentiating Bloch’s function twice gives
𝑑2 𝜓 𝑑2 𝑢 𝑑𝑢
= ( 2 + 2𝑖𝑘 − 𝑘 2 𝑢)𝑒𝑥𝑝𝑖𝑘𝑥 (7.22c)
𝑑𝑥 2 𝑑𝑥 𝑑𝑥

Substitute (7.22c) in (7.22a) and (7.22b) gives

𝑑2 𝑢 𝑑𝑢
+ 2𝑖𝑘 − 𝑘 2 − 𝛼 2 𝑢 = 0 (7.22d)
𝑑𝑥 2 𝑑𝑥
𝑑2 𝑢 𝑑𝑢
+ 2𝑖𝑘 − 𝑘 2 + 𝛽 2 𝑢 = 0 (7.22e)
𝑑𝑥 2 𝑑𝑥

Solutions of (7.22f) and (7.22g) are respectively,

𝑢 = 𝑒𝑥𝑝𝑖𝑘𝑥 [𝐴𝑒𝑥𝑝𝑖𝛼𝑥 + 𝐵𝑒𝑥𝑝−𝑖𝛼𝑥 ] (7.22f)
𝑢 = 𝑒𝑥𝑝𝑖𝑘𝑥 [𝐶𝑒𝑥𝑝−𝛽𝑥 + 𝐷𝑒𝑥𝑝𝛽𝑥 ] (7.22g)

by Dr. E. Zacharias
Applying the boundary condition
𝑢(𝐼) = 𝑢 𝐼𝐼 at 𝑥 = 0 and
𝑑𝑢 𝑑𝑢
𝐼 = 𝐼𝐼 at 𝑥 = 0
𝑑𝑥 𝑑𝑥

𝑢(𝐼) = 𝑢 𝐼𝐼 at 𝑥 = 𝑎 and
𝑑𝑢 𝑑𝑢
𝐼 = 𝐼𝐼 at 𝑥 = 𝑎
𝑑𝑥 𝑑𝑥

Gives four equations in 𝐴, 𝐵, 𝐶 and 𝐷.

Using the four equations the four coefficients can be eliminated and gives the
condition for solution to exist for the Schrodinger equation.

by Dr. E. Zacharias
It is seen that the solution to the Schrodinger equation exists only if
sin 𝛼𝑎
𝑃[ ]+ cos 𝛼𝑎 = cos 𝑘𝑎 (7.23)
𝛼𝑎
is satisfied.
2𝑚𝜀𝑘 1/2 𝑏𝑉0 𝑚𝑎
where 𝛼 = ( 2 ) and 𝑃 = 2 (7.23 a,b)
ℏ ℏ

by Dr. E. Zacharias
 sin 𝛼𝑎
Plotting the LHS of 𝑃[ ]+ cos 𝛼𝑎= cos 𝑘𝑎 as a function of 𝛼, for a fixed
𝛼𝑎
value of 𝑃=2, shows that the absolute magnitude of ordinate crosses unity when
𝜋
𝛼 crosses multiples of ± . This is found to be consistent and independent of the
𝑎
value of 𝑃.

From RHS, the ordinate has to lie between +1 and -1. The energies corresponding
to range of 𝛼 values where ordinate exceeds permitted level of unity are not
possible and are forbidden.

The allowed energies form bands separated by band gaps.

Kronig-Penny model thus successfully predicts existence of band gaps.

by Dr. E. Zacharias
 sin 𝛼𝑎 2𝑚𝜀𝑘 1/2 𝑏𝑉0 𝑚𝑎
In𝑃[ ]+ cos 𝛼𝑎= cos 𝑘𝑎, where 𝛼 = ( 2 ) and 𝑃 =
𝛼𝑎 ℏ ℏ2
with increase of 𝛼𝑎, the allowed energy states for a electron increases there by
increasing the width of the bands, i.e., the strength of the potential barrier
diminishes. This also leads to increase of the distance between electrons and
the total energy possessed by the individual electron.

Conversely, if the effect of potential barrier dominate i.e., if 𝑃 is large, the

resultant plot shows a steeper variation in the region lies between +1 to -1. This
results in the decrease of allowed energy and increase of forbidden energy gap.

𝑃 → 0 and 𝑃 → ∞ correspond to free electron dispersion relation and electron

trapped in an infinite potential well respectively.
by Dr. E. Zacharias
by Dr. E. Zacharias
DISPERSION RELATION OF FREE ELECTRON:

by Dr. E. Zacharias
Dispersion relation of electron in a crystal:

by Dr. E. Zacharias
INSULATORS, SEMICONDUCTORS AND METALS
Insulators, semiconductors and metals can be distinguished based on the
qualitative differences in the band structure.

Number of energy states in a band is equal to the number of primitive cell 𝑁. The
number of electrons that can be accommodated is 2𝑁 with each cell occupied by
two electrons of opposite spins.

If the primary cell contributes even number of electrons, the band is fully
occupied.
Ex. In a monoatomic crystal having one valence electron per atom, the band is full
if there are two atoms in the primitive cell.
If the monoatomic crystal has two valence electrons per atom, and the primitive
cell has one atom, the band is fully occupied with 2𝑁 electrons.
by Dr. E. Zacharias
Solids in which one or more bands are completely filled and other bands are
empty, behave as insulators at 0 K. The forbidden gap between the lowest
allowed empty band and the highest filled band is greater than 5 eV. Applied
electric fields are insufficient to excite the electrons across the band gap.

Solids in which the band gap is of the order of 1 eV, the conductivity value is
intermediate between an insulator and a conductor.

If the number of valence electrons per primitive cell is odd, the top most
occupied band is partially filled. Such materials are metals and conduct electricity
on applying electric field. Ex. Alkali and noble metals have one valence electron
per primitive cell and the highest occupied band is half filled.
by Dr. E. Zacharias
Sodium: Belongs to group Alkali metal, BCC structure, rhombohedral primitive
cell. 1 atom per primitive cell, electronic configuration [1s2,2s2,2p6],3s1 , 5 filled
bands (2 from s and 3 from p) and 6th half filled highest band. Hence metal.

Magnesium: belongs to group Alkaline earth metal, 2 valence electrons per

primitive cell, electronic configuration [1s2,2s2,2p6],3s2. All filled bands, but a
metal because of the overlapping of filled 3s and empty 3p bands. Electrons can
get excited from 3s to 3p bands on application of field. 𝜀𝐹 is at 90 percent of the
filled 3s band. These are semi metals.

by Dr. E. Zacharias
Diamond: isolated C electronic configuration is 1s2,2s2,2p2. 2s and 2p wave
functions in tetrahedrally bonded diamond crystal results in sp3 hybridization. sp3
hybrid bands further split into two, each can accommodate 4 electrons. The
lower hybrid band is filled with 2 electrons each from 2s and 2p, leaving the
other sub-band empty.

by Dr. E. Zacharias
The forbidden gap between the two sub bands is 5 eV at 0 K. Hence insulator.

by Dr. E. Zacharias
by Dr. E. Zacharias
by Dr. E. Zacharias
EFFECTIVE MASS OF ELECTRON:
The mass of an electron in the periodic potentials of a crystal is different from
the free electron mass and is usually referred to as the effective mass.
According to de Broglie hypothesis, a moving electron is associated with a wave.
𝑑𝜔 1 𝑑𝜀
The velocity of an electron 𝑣 is equal to the group velocity 𝑣𝑔 = =
𝑑𝑘 ℏ 𝑑𝑘

Differentiating with respect to time,

𝑑𝑣𝑔 1 𝑑 𝑑𝜀 1 𝑑 𝑑𝜀 𝑑𝑘 1 𝑑2 𝜀 𝑑𝑘
𝑎= = [ ] = [ ][ ] = [ ]
𝑑𝑡 ℏ 𝑑𝑡 𝑑𝑘 ℏ 𝑑𝑘 𝑑𝑘 𝑑𝑡 ℏ 𝑑𝑘 2 𝑑𝑡

Momentum of the electron is 𝑝 = ℏ𝑘

Differentiating with respect to time,
𝑑𝑝 𝑑𝑘
= ℏ[ ]
𝑑𝑡 𝑑𝑡
Using this in the equation for acceleration gives
by Dr. E. Zacharias
 1 𝑑2 𝜀 𝑑𝑘 1 𝑑2 𝜀 𝑑𝑝 1 𝑑2 𝜀
𝑎= [ ] = [ ] = 𝑚∗ 𝑎
ℏ 𝑑𝑘 2 𝑑𝑡 ℏ2 𝑑𝑘 2 𝑑𝑡 ℏ2 𝑑𝑘 2

ℏ2
The effective mass 𝑚∗ = 𝑑2 𝜀
[ 2]
𝑑𝑘
−𝜋
The effective mass is positive between < 𝑘<
2𝑎
+𝜋 −𝜋 −𝜋
and negative between <𝑘< and
2𝑎 2𝑎 𝑎
+𝜋 +𝜋
between <𝑘< .
2𝑎 𝑎

When the magnitude of 𝑘 increases (with the

𝜋
applied electric field) beyond the value , the
2𝑎
electron starts to move along the applied field
behaving like a positive charge.
by Dr. E. Zacharias
The effective mass of an electron in an energy band is positive near the bottom
𝑑2 𝜀
of the band where [ 2 ]. It is negative near the top of the band. Change in sign
𝑑𝑘
occurs at the point of inflexion of the dispersion curve.

At the Brillouin boundary, ie the top of the band, there is decrease in momentum
of the electron even though field is applied. The electron transfers more energy
to the lattice than it receives from the field. This means the effective mass
becomes negative.
The influence of the lattice on the movement of electrons make the movement
of these electrons different from that of a free electron in an applied field.

By using effective mass 𝒎* of electrons instead of real mass 𝒎, their behavior

becomes identical to that of electrons in the free electron gas model.
by Dr. E. Zacharias