DEPARTMENT OF PHYSICS

UNIT I
ELECTRICAL PROPERTIES

Dr.S.J
Fig .1.1
Fig .1.2
 How do electrons populate the bands?
Probability of Occupation (Fermi Function) Concept
 Now that we know the number of available states at each energy,
then how do the electrons occupy these states?
 We need to know how the electrons are “distributed in energy”.
 Again, Quantum Mechanics tells us that the electrons follow the
“Fermi-distribution function”.

 F(E) is the probability that a state at energy E is occupied.

 1-F(E) is the probability that a state at energy E is unoccupied.
Fermi-Dirac distribution and the Fermi-level
Density of states tells us how many states exist at a given energy
E. The Fermi function F(E) specifies how many of the existing
states at the energy E will be filled with electrons. The function
F(E) specifies, under equilibrium conditions, the probability that
an available state at an energy E will be occupied by an electron.
It is a probability distribution function.

= 1.38 1023 J/K = 8.6  105 eV/K

Fig 1.4
 Fermi-Dirac distribution: Consider T > 0 K
If E = EF then F(EF) = ½
 E  EF 
exp    1
If E  EF  3kT then  kT 
 (E  EF ) 
F (E )  exp  
 kT 
Thus the following approximation is valid:
i.e., most states at energies 3kT above EF are empty.
 E  EF 
exp    1
 kT 
If E  EF  3kT then  E  EF 
F (E )  1  exp  
 kT 
Thus the following approximation is valid:
So, 1F(E) = Probability that a state is empty, decays to zero.
So, most states will be filled.
kT (at 300 K) = 0.025eV, Eg(Si) = 1.1eV, so 3kT is very small in comparison.
Temperature dependence of Fermi-Dirac distribution
Fig 1.6 Fig 1.7
PARTICLE IN A THREE DIMENSIONAL POTENTIAL BOX

The solution of one-dimensional potential box can be extended for a three dimensional
potential box. In a three dimensional potential box, the particle (electron) can move in any
direction in space. Therefore instead of one quantum number ‘n’. We have to use three
quantum number and corresponding the three co-ordinate axis (ie) x, y and z
respectively.

Particle in a three dimensional potential box

Let us consider a particle enclosed in a 3-dimensional potential box of length a, b and c along x,
y and z axis respectively as shown in fig 1.7
Since the particle inside the rectangular box has elastic collisions
with the wall, the potential energy of the electron inside the box
is constant and can be taken as zero for simplicity.
∴ We can say that outside the box and on the wall of the box,
the potential energy is .
∴ The boundary conditions are
 SI no Boundary condition Interference
1. V (x, y, z) = 0 when 0 < x < a Within this boundary the particle exist …(1)
V (x, y, z) = 0 when 0 < x < b and we need to find the energy values and
V (x, y, z) = 0 when 0 < x < c wave function.
2. V (x, y, z) = when 0 ≥ x ≥ a In this area the particle does not exist and
V (x, y, z) = when 0 ≥ x ≥ b therefore the wave function = 0 …(2)
V (x, y, z) = when 0 ≥ x ≥ c

To find the wavefunction of the particle within the boundary conditions (1). Let us consider the
3-dimensional schrodinger time independent wave equation, i.e.,

…(3)
Since V = 0 [For a free particle], we can write eqn (3) as
…(4)
Equation (4) is a partial differential equation, in which Ψ is a function of three variables x, y & z.
∴ We can solve this using method of separation of variables.
∴ The solution for eqn (4) can be written as

Which means Ψ is a function of x, y and z and ia equal to product of 3 functions i.e., X, Y and Z.
Where X is a function of x only
Y is a function of y only
and Z is a function of z only
∴ We can write the solution for equation (4) as Ψ = XYZ …(5)
Differentiating eqn (5), Partially with respect to ‘x’ twice, we get

…(6)
Similarly differentiating eqn (5) partially with respect to ‘y’, twice , we get

…(7)
Similarly differentiating eqn (5) partially with respect to ‘z’, twice, we get

…(8)

Substituting equations (5), (6), (7) and (8) in eqn (4)we get

Dividing by XYZ on both sides we get

…(9)

…(10)

…(11)
In equation (10), L.H.S is independent of each other and is equal to a constant in R.H.S, ∴ we can
equate term of L.H.S to each constant in R.H.S
∴ We can write

…(12)

…(13)

…(14)
Equations (12), (13) and (14) represents the differential equations in x, y and z co-ordinates. The
solution for equation (12) can be written as
…(15)
Where Ax and Bx are arbitrary constants, which can be found by applying boundary conditions.
i.e., (i) when x = 0 ; X =0
∴ Equation (15) becomes
0 = 0 + Bx
∴ Bx = 0 …(16)
(ii) when x = a ; X = 0
∴ Equation (15) becomes

Here
[Because, if Ax =0, then X(x) becomes zero, which implies that the particle is not there, and is
meaningless]

we know
Comparing the above two equations we can write
…(17)
Substituting equations (16) & (17) in eqn we get
…(18)
Equation (18) represents the un-normalized wave function.
Normalization
Eqn (18) can be normalized by integrating it with in the limits i.e., boundary conditions 0 to a,
∴ We can write

Solving we get

(or) …(19)
Substituting eqn (19) in (18) we get
…(20)
Similarly by solving equation (13) and equation (14) with the boundary conditions 0 to b and
…(21)

…(22)
Eigen functions
The complete wave function, for equation (4) can be written as

Substituting equations (20), (21) and (22) in the above equation, we get

…(23)
Equation (23) represents the eigen function for an electron in a rectangular box.
Eigen values
From equation (11) we can write

…(24)

From equation (17) we can write

Similarly we can write

Substituting these values in eqn (24), we get

…(25)

Equation (25) represents the energy eigen values of an electron in a rectangular box.
Cubical box
For a cubical box, a=b=c,
∴ We can write equation (25) as
…(26)

The corresponding normalized wave function of an electron in a cubical box can be obtained
from equation (23), as
…(27)
From equations (26) and (27) we can note that, several combinations of the three quantum
numbers (nx, ny, and nz) leads to different energy eigen values and eigen functions.
Example
If a state has quantum numbers nx = 1 ; ny = 1 ; nz = 2

Similarly for nx = 1 ; ny = 2 ; nz = 1 combination and nx = 2ny =1; ny = 1 ; nz = 1 combination w

have

…(28)
The corresponding wave functions can be written as

…(29)
DEGENERACY AND NON-DEGENERCY
(i) Degeneracy : It is seen from equation (28) and equation (29), for several combination of
quantum numbers we have same energy eigen value but different eigen functions. Such
states and energy levels are called Degenerate State.
the three combination of quantum numbers (112), (121) and (211), which givws same
eigen value but different eigen functions are called 3 fold degenerate state.
If we have 6 combinations to give the same energy level and 6 eigen functions, it is called 6 fold
degenerate state.
(ii) Non –Degeneracy : For various combinations of quantum number if we have same energy
eigen value and same (one) eigen function then such states and energy levels are called
Non-Degenerate State.

Example
Fig 1.8
Fig 1.9

Fig 1.10
 (7 )

(8 )

(9 )
 (10)

(11)

(11)
(12)

(13)
 (1)

(2)

(3)
Fig 1.11
 Distribution of carriers Fig 1.12 (a)

Distribution of carriers = DOS probability of occupancy Metal

= g(E) f(E)

= X Fig 1.12 (d)

Fig 1.12 (b) Fig 1.12 (c) Fermi-Dirac distribution

The product of the The density of allowed function describing the
distribution function and states for a metal as a probability that an allowed state
the density-of-states function of energy at energy E is occupied by an
function
ELECTRON IN PERIODIC POTENTIAL
In quantum free electron theory of metals the electrons were assumed to be moving
in a region of constant potential and hence it moves freely about the crystal. But it fails to
explain why some solids behaves as conductors, some as insulators and some an
semiconductors etc.
Therefore instead of considering an electron to move in a constant potential, I Zone
theory of solids the electrons are assumed to move in a field of periodic potential.
In a metal piece, the positive ions are arranged in a regular and proper order,
therefore a periodic potential (i.e) the potential field which varies periodically with the same
period as the lattice, exists in the metal. Also the potential is minimum near the centre of
positive ions and is maximum between the centres of ions as shown in fig. 1.13.
Therefore the potential energy of the electron near by the centre of positive ion is maximum
and will not be able to move freely, but the electrons which are above these potential peaks are
free to move inside the metal and hence they are termed as free electrons.

ENERGY SPECTRA IN ATOMS, MOLECULES AND SOLIDS

To picture the energy spectra in atoms, molecules and solids let us consider a metal say sodium,
which consists of 11 electrons with electronic configuration of 1s2 2s2 2p6 3s1. The energy
spectrum of a single atom is as shown in fig. 1.14. When two sodium atoms and assembled to
form a sodium molecule, the energy spectrum of the molecule is as shown in fig. 1.15. It is
found that for a sodium molecule each atomic levels are splitted into two closely spaced levels.
Similarly if ‘N’ number of atoms are assembled to form a solid, then we have N number of very
closely spaced sub levels so called as energy band as shown in fig. 1.16.
It can be found that each energy band is separated by the gaps and are known as Energy gap
(or) forbidden band gap energy.
It can be seen that the electrons present in the outermost energy band (3s1) are mixed together
and they are free to move over the metals. These free electrons are responsible for the
conduction to occur.
Conclusion
Thus we can conclude that the electron moving in a periodic potential lattice will have
discontinuous energy values (i.e) they are separated as allowed and forbidden zones (or) bands.
In the case of electron moving in constant potential lattice (quantum theory) it has quasi
continuous energy values.
BLOCH THEOREM
Bloch theorem is a mathematical statement of an electron wave function moving in a perfectly
periodic potential. These functions are called bloch functions.
Explanation
Let us consider an electron moving in a periodic potential. The one dimensional Schroedinger
wave equation for an electron moving in a periodic potential shall be written as
Suppose the electron moves along X-direction in a one dimensional crystal, then the potential
energy of the electron should satisfy the condition

Where a is the periodicity of the potential.

The solution for equation (1) is

Here represents the plane wave and represents the periodic function.
∴ Equation (3) is called Bloch theorem and Equation (4) is called Bloch function.
Proof
If equation (1) has the solutions with the property of equation (2), we can write the property of
Bloch functions i.e., equation (3) as
Since , we can write the above equation as

Since , we can write the above equation as

is a single-valued function, then

We can write Thus Bloch theorem is proved.
This equation is similar to that of eqn(2) and eqn(4) i.e., If the potential is a function of ‘x’ and
‘a’, then the wave function is also a function of ‘x’ and ‘a’.

BEHAVIOUR OF AN ELECTRON IN A PERIODIC POTENTIAL – THE KRONIG – PENNEY MODEL

(QUALITATIVE TREATMENT)
Kronig and Penney treated a simplest example for one dimensional periodic potential. In this
model it is assumed that the potential energy of an electron has the form of a periodic array of
square wells as shown in fig. 1.17.
Here we have two regions. Viz.
 Region (i) In this region, between the limits 0 < x < a, the potential energy is zero hance the
electron is assumed to be a free particle. ∴ The one dimensional Schroedinger wave equation
for a free particle is

Region (ii) In this region between the limits –b<x<0, the potential energy of the electron is Vo
∴ The one dimensional Schroedinger wave equation is
For both the region, the appropriate solution suggested by Bloch is of the form,

Differentiating equation (3) and substituting it in equation (1) and (2) and then further solving it
under the boundary conditions, we get

Where , is called as Scattering power of the potential barrier, which is the measure of
the strength with which the electrons are attracted by the positive ions.
In equation (4), there are only two variables (i.e) α and k. We know cos ka can take values only
from – 1 to 1. Therefore the left hand side of equation (4) must also fall in this range. A plot is
made between the LHS of equation (4) and αa for a value of (arbitrary) as shown in
fig.1.18.

Fig 1.18
Conclusion

From the fig. 1.18 the following conclusions can be made.

(i) The energy spectrum has a number of allowed energy bands denoted by solid jorizontal line
separated by foebidden band gaps denoted by dotted lines.
(ii) The width of allowed energy band (shaped portion) increases with the increase in αa.
(iii) When P is increased, the binding energy of the electrons with the lattice points is also
increased. Therefore the electron will not be able to move freely and hence the width of the
allowed energy band becomes infinitely narrow and the energy spectrum becomes a line
spectrum as shown in fig.1.19.
(iv) When P is decreased, the binding energy of the
electron decreases and thus it moves freely
over the lattice points and hence we get a wide
range of allowed energy levels as shown in fig 1.19.
(v) Thus by varying P from zero to infinity we get the
energy spectra of all ranges.
TIGHT BINDING APPROXIMATION
Before discussing about the tight binding approximation, Let us know about free electron
approximation.

Free electron approximation

We know in solids, there exist the Ionic core which are tightly bounded to the lattice location,
while the electrons are free to move here and there throughout the solid. This is called the
free-electron approximation.

In free electron approximation the following points are observed. Viz.

1. The potential energy of the electron is assumed to be lesser than its total energy.
2. The width of the forbidden bands (Eg) are smaller than the allowed bands as shown in fig
1.20(a).
3. Therefore, the interaction between the neighbouring atoms will be very strong.
4. As the atoms are closer to each other, the inter atomic distance decreases and hence the
wave functions overlap with each other as shown in fig 1.20.
Tight binding approximation
Tight binding approximation is exactly an opposite approach of discussing the atomic
arrangements, when compared to free electron approximation.
Here instead of beginning with the solid core, we begin with the electrons, i.e., All the electrons
are bounded to the atoms. In other way we can say that the atoms are free, while the electrons
are tightly bounded. Hence, this is called tight binding approximation.
The following points are observed in tight binding approximation, viz.
1. The potential energy of the electrons is nearly equal to the total energy.
2. The width of the forbidden bands (Eg) are larger than the allowed bands, as shown in fig 1.20
(b).
3. Therefore, the interactions between th neighbouring atoms will be weak.
4. As the atoms are not closer, the interatomic distance increases and hence the wave function
will not overlap, as shown in fig 1.20.

Explanation
Let us consider the atoms with larger inter atomic distance (a2) as shown in fig. 1.20. Here
the atoms are far apart, and all the bounded electrons have fixed energy levels. Therefore when
a solid is formed by using the same element, then the energy levels occupied by the electrons in
each atom will be identical, which lead to tight binding approximation.
Now, when we bring the atoms closer to each other to form the solid, then inter atomic
distance (a1), decreases. Therefore, the outer shell electrons begin to overlap and energy levels
also splits as shown in fig 1.20.
If the inter atomic distance is further reduced, then the splitting of energy level happens for the
Inner shell electrons also, which lead to free electron approximation.
Note: For, better understanding about the width of allowed energy bands and forbidden band
gaps, the flat band diagrams corresponding to various inter atomic distances is also shown in fig.
1.20(a) and 1.20(b), for free electron approximation and tight binding approximation,
respectively.

EFFECTIVE MASS OF AN ELECTRON AND CONCEPT OF HOLE

Definition : Effective mass of an electron is the mass of the electron when it is accelerated in a
periodic potential and is denoted by m*.
Explanation : When an electron of mass ‘m’ (9.11 x 10-31 Kg) is placed in a periodic potential and
if it is accelerated with the help of an electric (or) magnetic field, then the mass of the electron
will not be a constant, rather it varies with respect to the field applied. That varying mass is
called as effective mass (m*).
Expression : To study the effect of electric field on the motion of an electron in one dimensional
periodic potential, let us consider the Brillouin Zone which contains only one electron (1st
Brillouin Zone) of charge ‘e’ in the state k, placed in an external field ‘E’. Due to the field applied
the electron gains a group velocity (vg) [Quantum mechanically] and therefore the acceleration
changes.
The group velocity with which the electron can travel is

Where k wave vector

ω Angular velocity of the electron
We know ω = 2π

Substituting equation (2) in equation (1) we get

Group velocity

If the field (E) is applied to the electron for a time say dt seconds then
Change in field (or) Work done = Force x distance
dE = Force x Velocity x Time
dE = eE vg dt [Since Force = eE] …(4)
Substituting equation (3) in equation (4) we get
 We know Acceleration
Substituting for vg from equation (3) we get

Substituting equation (5) in equation (6) we get

Acceleration

Equation (7) resembles with the newtons force equation

(i.e) F = eE = m*a …(8)
Where m* is the effective mass of the electron.
Comparing equation (7) and (8), we can write
Equation (9) represents the effective mass of a electron in a periodic potential, which depends
on

Special cases
Case (i) If is + ve, then effective mass m* is also +ve.

Case (ii) If is –ve, then effective mass m* is also –ve.

Case (iii) If is 0, then effective mass m* becomes .

Thus we can say that it is not so the effective mass (m*) should always be greater than real mass
(m), it may also have negative value.

Negative effective mass (or) Concept of hole

To show that the effective mass has negative value, let us take the Energy – wave vector (E-k)
curve of a single electron in a periodic potential i.e., consider the 1st Brillouin Zone (alloed
energy band) alone as shown in fig 1.21.
In the E – k curve, the band (1st Brillouin Zone) can be divided
into two bands viz, upper band and lower band with respect to point (P)
called as Point of inflection.

Point of inflection is a point in the curve from which the curve changes
from concave upward to concave downward and viceversa as shown in fig
1.22.
From the E – k curve (fig 1.21) we can say that
(i) In the Lower band the value of is a decreasing
function (Indicated by arrow mark) from the point
of inflection. ∴ is + ve, and hence m* should be + ve in
the lower band.
If the plot is made between m* and k for various values of
we get the curve as shown in fig 1.23. In which we can see
that m* has + ve curve.
(ii) In the Upper band of E – k curve (fig. 1.21) the value of
is found to be increasing from the point of inflection.
∴ is – ve and hence m*should also be – ve in the upper
band. If a plot is made between m* and k (fig. 1.23) we can
see that, if is – ve, the effective mass (m*) has – ve
value.
(iii) At the point of inflection = 0 [Fig 1.21] and hence in
m*-k plot, effective mass goes to as shown in fig 1.23.
Physically speaking we can say that, In the upper band [Fig. 1.21], the electron has negative
effective mass.
Hole : The electron with the negative effective mass is called Hole, in the other words the
electron in the upper band behaves as a positively charges particle called hole. It has the same
as that of an electron but with positive charge.
Conclusion :
If a single electron is taken in a one dimensional periodic potential. We get the 1st Brillouin Zone
(i.e.,) only one allowed energy band.
If that energy band is divided into two bands (i.e) upper band and lower band. The electron is
found to exist with positive effective mass in the lower band and with negative effective mass
(hole) in the upper band as shown in fig. 1.24.
Therefore, the advantage of the concept of hole is, for a nearly filled band with ‘n’ number of
empty states as shown in fig. 1.25 ‘n’ number of holes (empty states) arises.
In other words we can say that the presence of hole is attributed to an empty state, for an
electron to be filled. Thus, based on the hole concept several phenomenon like Thomson effect,
Hall effect etc are well explained.

ENERGY BANDS IN SOLIDS

According to the energy band theory of solids, the free electrons move in a periodic potential
produced by positive ion cores. The electrons are treated as weakly perturbed by the periodic
potential.
In solid sodium, the electrons experience a periodic potential since the atomic arrangement is
periodic.
A simple qualitative explanation of the formation of energy bands in asolid is given below.
A solid contains an enormous number of atoms packed closely together. Each atom when
isolated has a discrete set of electron energy levels, 1s, 2s, 2p….
If we imagine the N atoms on the solid to be isolated from one another, they would have
completely coinciding schemes of energy levels.
The energies of electrons within any one isolated atom obey the following conditions.
(i) There are specific electronic energy levels in each atom (fig 1.26). Electrons cannot space
between these levels.
(ii) Electrons fill the lowest energy levels first. A specific quantity of energy, called a quantum of
energy must be supplied to move an electron to the next higher level.

(iii) Pauli’s, exclusion principle states that no two electrons can occupy the same quantum
state. Not more than two electrons can occupy any energy level.
Two electrons shall occupy the same energy level because they have opposite electron spins
(fig 1.26 (b)).
 When the atoms are brought in close proximity to form a solid, the valance electrons
of adjacent atoms interact and constitute a single system of electrons common to the entire
crystal, and their outermost electronic orbits overlap.

Therefore, N electrons will now have to occupy different energy levels, which may be
brought about by the electric forces exerted on each electron by all N nuclei.
As a result of these forces, each atomic energy level is split up into large number of
closely spaced energy levels.
A set of such closely spaced energy levels is called an energy band.
Consider 11 electrons of a neutral sodium atom, each occupying a specific energy level
as indicated in fig 1.27. the energy levels of sodium become bands when the atoms lie close
together.
In figure 1.27, r0 represents the spacing between atoms in solid sodium. When the
atoms are part of a solid, they interact with each other and the electrons have slightly different
energies.
In an energy band, allowed energies are almost continuous. These energy bands are
separated by ranges of energies that have no allowed energy levels.
These regions are known as forbidden bands or energy gaps. (fig 1.28).
The amount of splitting is not the same for different levels. The levels filled by valance electrons
are distributed to a greater extent, while those filled by electrons of inner shells are disturbed
only slightly.
Fig 1.27 shows the splitting of levels as a function of the distance r between atoms.
If there are N atoms in a solid, there are N allowed quantum states in each band. Each quantum
state is occupied by a maximum of two electrons with opposite spins. Thus, each energy band
can be occupied by 2N electrons.
The valance band consists of a group of states containing the outermost electrons or valance
electrons of an atom. The band formed from atomic energy levels containing valance electrons
is called valance band.
These electrons have the highest energy. The band is obviously the highest occupied band.
Above the valance band, there exists the band of next higher permitted energies called
conduction band. It is separated from the valance band by a gap (fig 1.29). The gap represents
the range of energy which electrons cannot posses.
The conduction band corresponds to the first excited states and it is normally the lowest unfilled
energy band.
In conduction band, the electrons can move freely and they are generally called conduction
electrons.
According to free electron theory, the potential energy of the electron inside the crystal through
which an electron moves is supposed to be constant (zero) and so it is completely free to move
through out the crystal, restrained only by the surface of the crystal.

CLASSIFICATION OF METALS, SEMICONDUCTORS AND INSULATORS

On the basis of width of forbidden gap valance and conduction band the solids are classified
into insulators, semiconductors and conductors.
Insulators
•In case of insulators, the forbidden energy band is very wide as shown in the fig 1.30. due to
this, electrons can not jump from valance band to conduction band. In insulators, the valance
electrons are bound very tightly to their parent atoms.
•For example, in the case of material like glass, the
valance band is completely full at 0K and the energy
gap between valance band and conduction band is of
the order of 10 eV.
• Even in the presence of high electric field, the electrons cannot jump from the valance band to
conduction band.
• When a very large energy is supplied, an electron may jump across the forbidden gap. Increase
in temperature also enables some electrons to go to the conduction band.
•This explains why certain insulators become conductors at high temperature. The resistivity of
insulators is of the order of 107 Ωm (ohm metre).
Semiconductors
•In semiconductors, the forbidden gap is very small as shown in fig 1.31. Germanium and silicon
are the best examples of semiconductors.
•In Germanium, the forbidden gap is of the order of 0.7 eV while in case of silicon, it is of the
order of 1.1 eV.
•Actually, a semiconductor is one whose electrical properties lies between those of insulators
and conductors. At 0K there are no free electrons in conduction band and valence band is
completely filled.
•When a small amount of energy is supplied, the electrons can easily jump from valence band to
conduction band, since the forbidden gap is very small.
•In semiconductors, the conductivities are of the order of 102 Ωm (ohm metre).
Conductors
•In case of conductors, there is no forbidden gap, both valence and conduction bands overlap
each other as shown in the fig 1.32.
•In conduction band, plenty of free electrons are available
for the process of electric conduction. The electrons from
valence band freely enter into the conduction band.

•The most important fact in conductors is that due to the

absence of forbidden gap, there is no structure to
establish holes. The total current in conductors is simply
the flow of electrons.