Block's theorem is interpreted as the wave function for an electron in a periodic potential is a

plane wave modulated by a periodic function.

In order to understand the physical properties of the system, it is required to solve the
Schrödinger’s equation. However, it is extremely difficult to solve the Schrödinger’s equation
with periodic potential described above. Hence the Kronig – Penney Model is adopted for
simplification.
KRONIG -PENNEY MODEL:

According to this theory, the electrons move in a periodic potential produced

by the positive ion cores. The potential of electron varies periodically with periodicity of ion core
‘a’ which is nothing but inter-atomic spacing. It is assumed that the potential energy of the
electrons is zero near nucleus of the positive ion core and maximum when it is lying between the
adjacent nuclei as shown fig. Note that, it is extremely difficult to solve the Schrödinger’s
equation for this periodic potential.

Fig. One dimensional periodic potential

Kronig and penny proposed a simpler potential model in the form of rectangular wells as
shown in fig. The width of the potential well and barrier are ‘a’ and ‘b’ respectively. The potential
energy of an electron in the well is zero and in the barrier is V 0. The periodicity of the potential is
(a+b). This model is highly artificial, but it illustrates many of the characteristics features of the
behavior of electrons in periodic lattice. The energies and wave functions of electrons
associated with this model can be calculated by solving the Schrödinger’s wave equation for two
regions I and II. The Schrödinger’s equations are
d 2 2m
 E  0 for region-I 0 < x < a
dx 2  2
d 2 2m
and  2 E  V0 )   0 for region-II -b < x < 0
dx 2 
Since E less than Vo, define two +ve quantities, α2 = 2mE/ ħ2 and β2 = 2m(V0– E )/ħ2
d 2
  2  0 for region 0 < x < a
dx 2
d 2
2
  2  0 for region -b < x < 0
dx
According to Bloch theorem, the solutions of above eqn’s can be written as

Ψ ( x ) = UK (x) eiKx

This consists of a plane wave eiKx modulated by the periodic function UK(x), where this UK(x) is
periodic with the periodicity of the lattice. i.e UK(x) = UK(x+a)

where K is propagating constant along x-direction and is given by K =2π/λ. K is also known as
propagation wave vector. In order to simplify the computations, an assumption is made
regarding the potential barrier. As Vo increases the width of the barrier ‘b’ decreases so that the
product Vob remains constant. After tedious calculations, the possible solutions for energies are
obtain from the relation
sin∝𝑎
𝑃 + cos ∝ 𝑎 = cos 𝐾𝑎----------- (1)
𝛼𝑎

where P = mVo ab /ħ2 is scattering power of the potential barrier. It is a measure of electrons
in a crystal are attracted to the ions on the crystal sites.

The left hand side of the equation (1) is plotted as a function of αa for the value of P=3π/2. The
right side of the equation imposes a limitations on the values of left side function, i.e., between -
1 to +1 as indicated by the horizontal lines in fig. Hence only certain range of α are allowed.

The permitted values of energy are shown as shaded portions between white portions. This
gives rise to the concept of ranges of permitted values of  for a given ion lattice spacing a.
Detail analysis results following interesting conclusions:
1. The allowed ranges of a which permit 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.
2. As the value of a increases, the width of allowed energy bands also increases and
the width of the forbidden bands decreases.
3. If the potential barrier strength P is large, the function described by the left hand side
of the equation crosses +1 and -1 region at a steeper angle. Thus the allowed bands
are narrower and the forbidden bands are wider.
4. If 𝑃 ⟶ ∞, the the allowed band reduces to one single energy level corresponding to
the discrete energy level of an isolated atom.
 n 2 2
P  is follows from equation (1) that Sina=0, a = n ;  = 2
.
a2
n 2 2 2mE
∴ 2  2
 2
a 

 n 2 2  2   n 2    2 h 2  n 2 h 2
E 2 
  2 

 2ma   2m   4  8ma
2

Here E is independent of k. The energy levels in this case are discrete and the result is
similar to the energy levels of a particle in a constant potential box of atomic dimensions.

5. The other extreme case, when P0, leads to

Cos a = cos Ka
=K
i.e. 2 = K2
2 mE
K2 = 2 =
2
 2  2  h 2   2 
2

E =   k E =  2   
 2m   8 m    
 h2  1
E    2
 2m  
 h2  p2 p2 1 2
E =   2   mv
 2 m h 2m 2

Equation is appropriate to completely free particles. Hence no energy levels exist; that means all
energies are allowed to the electrons.
Thus by varying P from zero to infinity we cover the whole range, from the completely free
electron to the completely bound electron.

BRILLOUIN ZONES:
The motion of electrons in a periodic lattice
is characterized by the bands of allowed
energy regions separated by forbidden regions.
From equation(1), it is possible to plot the
total energy E of the electron versus K,
the wave number or propagation vector.
The right side of the eqn becomes ±1
for values of K= nπ/a.
Hence the discontinuities in the
E versus K graph occur at K= nπ/a,
where n= ±1,±2, ±3, …..etc.
 2  2
The dotted curve shows the free electron parabola =   k . From the graph, the electron
 2m 
has allowed energy values in the regions or zones extending from K= -π/a to K= +π/a. the zone
is called the first brillouin zone. After a break in the energy values called the forbidden region or
band or zone, we get another allowed zone of energy values in the region from K= -π/a to -2π/a
and +π/a to +2π/a. This zone is called the second Brillouin zone. Similarly the other higher order
Brillouin zones can be defined.

Effective mass of electron

An electron in crystal may behave as if it had a mass different from the free electron mass m0.
There are crystals in which the effective mass of the carriers is much larger or much smaller
than m0. The effective mass may be anisotropic, and it may even be negative.
When an electron in a periodic potential of lattice is accelerated by an electric field or magnetic
field, then the mass of the electron is called effective mass (m*).
Let us consider an electron of charge ‘e’ and mass ‘m’ moving inside a crystal lattice of electric
field E. The acceleration a =eE/m is not a constant in the periodic lattice of the crystal. It can be
considered that its variation is caused by the variation of electron’s mass when it moves in the
crystal lattice
𝑒𝐸
∴ 𝑎𝑐𝑐𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = ∗
𝑚
The electrical force on the electron, F= m*a --------------- (1)

Considering the free electron as a wave packet, the group velocity 𝑣𝑔 corresponding to the
particle’s velocity can be written as
𝑑𝜔 𝑑𝜈 2𝜋 𝑑𝐸 1 𝑑𝐸
𝑣𝑔 = = 2𝜋 = = − − − − − −(2)
𝑑𝑘 𝑑𝑘 ℎ 𝑑𝑘 ℏ 𝑑𝑘

where the energy E=hν and ℏ = ℎ/2𝜋

dv gd  1 dE  dk 1 d 2 E dk
a    
dt dk   dk  dt  dk 2 dt
𝑑𝑘 𝑑𝑝 𝑑𝑘 𝐹
Since ℏ𝑘 = 𝑝, ℏ = = 𝐹, =
𝑑𝑡 𝑑𝑡 𝑑𝑡 ℏ

1 d 2E 2
∴𝑎= 2 F or F  2 a ---------(3)
 dk 2 d E 2
dk
This equation indicates that the effective mass is determined from
𝑑2 𝐸
𝑑𝑘 2
a ) Variation of E with k :
The variation of E with k seen in the Fig.(a) for the first allowed band.
Using this type of variation of E with k and Eq(1), velocity can be
calculated.
b) Variation of v with k:
The variation of velocity with k is illustrated in the Fig.(b). We find that for
k=0 the velocity is zero and as the value of k increases
(i.e.,the energy E increases), the velocity increases reaching its
maximum value at 𝑘 = 𝑘0 . 𝑘0 corresponds to the point of inflexion on the
𝐸 − 𝑘 curve. Beyond this inflexion point the velocity begins to decrease and finally assumes the zero
value at 𝑘 =π/a. →𝑘

c) Variation of m* with k:
It is shown in fig.(c). Near k=o, the effective mass approaches m. As the value of k increases, m *
increases, reaching its maximum value at the point of inflection on the E-k curve. Above the point of
inflection, m* is negative and as k tends to π/a, it decreases to small negative value.
Experimentally, Effective mass can be obtained from cyclotron resonance experiment.
From fig.(b) it is clear that beyond the inflection point k0 velocity decreases i.e., acceleration negative.
This means that in this region of k the lattice exerts a large retarding force on the electron. This means
that in this region of k the electron behaves as a positively charged particle referred to as hole.
 Basic concept of band theory (Origin of Energy Bands in Solid)

Fig: Splitting of Energy levels due to inter atomic interaction

In an 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 adjacent atoms and is largest for
outer most atomic electrons.
In a solid many atoms are brought together so that the split energy levels form a set of very
closely spaced levels with forbidden energy gap between them. Overlapping of these bands
occurs for smaller equilibrium spacing r0.
These electrons present in higher energy bands are important in determining many of the
physical of solids.
Example: Formation of energy bands in Lithium:
Let us consider the element Lithium belonging to Group I
in the periodic table. The electronic configuration of
lithium atom is 1s22s1. The 1s shell is closed and there is
only one electron as the 2s level. In solid lithium, 1s and
2s bands form corresponding to the 1s and 2s levels. Both
1s and 2s bands have N levels each. The 1s band is
completely filled as 2N electrons occupy N energy levels
where as the 2s band is half-filled because the N available
electrons fill N/2 lower levels in the band leaving the band
leaving upper N/2 levels vacant.
In general, the solid of Group-I elements form such half-
filled energy bands at the top and therefore belong to the group of conductors.
Distinction between Insulators, Semiconductors and Conductors