I.

ELECTRICAL PROPERTIES OF METALS

• How does an electric current flow through a material? A current is a flow of charged
particles, which implies that either electron or ions are involved.

• In liquids, both of these types of particles take part in electrical conduction. But in
solids, the ions occupy fixed positions in the crystal lattice and are not free to move.
Some exception is there, but the conductivity is usually very small.

• So, the electrical conductivity of solids is almost entirely due to the movement of
the electrons. This implies that metals should be good electrical conductors because
they have a plentiful supply of free electrons. Whereas, all other materials should be
insulators because there are no free electrons.

• This picture is rather oversimplified. There are some non metals that can be reasonably
good electrical conductors.

• Here, we are first going to concentrate on the process of electrical conduction in metals.

A. Drude’s classical theory

First attempt to explain the behaviour of electrons in a metal was made by P. Drude in
1900, three years after the discovery of electron by J. J. Thomson. The theory is incorrect in
many respects, despite the fact that it gives several rather convincing results. It is therefore
important to examine this in details because it introduces some useful concepts.
Basic assumption of Drude’s model

• The electrons in a solid behave like classical ideal gas. They do not interact with each
other at all. There is no Coulomb interaction and they do not collide with each other.
This is known as ”Independent electron approximation”. This approximation is quite
good enough. The electrons do indeed not interact much with each other.

• The positive charge is located on immovable ion cores. The electron can collide with
the ion cores. These collisions instantaneously change their velocity. However, between
collisions, the electrons do not interact with ions either. This is known as ”Free electron
approximation”. This is not a very good approximation.

1
 • If there is no voltage applied, at each collision the electron is deflected in a different
direction so that the overall motion is quite random. Since the random motion of
the valence electrons appear to be similar to that of the molecules in an ideal gas,
Drude borrowed some of the concepts used in kinetic theory of ideal gas to describe
the properties of electron gas.

In kinetic theory, the average thermal velocity vt of a molecule with mass m at temper-
ature T is given by

1 3
m vt2 = kB T ,
2 r 2
3 kB T
vt = , (1)
m

where kB is Boltzmann constant. If we replace m by mass of electron me , then at room

temperature, we obtain vt = 105 m/s. This is the thermal velocity of electron. In between
collisons, the electrons move freely. The mean length of this free movement is called the
”mean free path (λ)”. If we assume that λ is of the order of a few atomic spacing, i.e,
λ ≡ 1 nm, then given vt = 105 m/s, one can compute the mean time between collisions to be

λ
τ= = 10−14 s . (2)
vt

τ is called relaxation time.

~ The equation
Let us consider what happens when we apply an electric field (voltage) E.
of motion of the electron in this electric field is given by

F~ = −e E
~,

me ~a = −e E ~,
d~v ~,
me = −e E
dt
~t
eE
~v (t) = − . (3)
me
~ This is called drift motion. If we
The electrons will flow opposite to the direction of E.
assume that the drift motion is destroyed in a collision with the ions and that on average
the time for a collision free drift is τ , then the average drift velocity can be obtained from
~τ
eE
< ~v >= − . (4)
me

2
 ~ = 10 Volt/m. This is
By putting all the numbers, we obtain | < ~v > | = 10−2 m/s for |E|
very slow compared to the thermal movement of the electrons. Now the question is: why is
the drift velocity so small?

• It is because even when an electric field is applied to the metal, the electrons will collide
with the ions and they continue to follow a more or less random trajectory with just
a very slight tendency to move toward the positive end of the sample. Consequently,
we arrive at a rather surprising result. When current flows in a metal, the valence
electrons are not all moving towards the positive terminal. Infact, at any instant in
time, there are nearly as many electrons traveling in the opposite direction.

What evidence do we have that Drude’s theory is correct?

• First of all, we can use it to provide a qualitative explanation of the phenomenon of

electrical resistance. When an electron collide with an ion, the excess energy that the
electron has gained from the electric field is transfered to the ion. This increases the
vibration of the ion, and so leads to an increase in temperature of the sample. The
KE of the electron is converted into thermal energy. This is familiar effect. If we
pass on electric current through a metal wire, it gets hot. If the resistance of the wire
is increased, the wire gets hotter. Resistance can be thought of as a measure of the
amount of electrical energy that is converted to heat energy.

We are now going to show that Drude’s model is consistent with Ohm’s law. Let us for
the time being neglect the random thermal motion of the electrons — average of this in any
direction is zero. So we can assume that the electrons are traveling at a velocity < v >
along the wire. This means that in a time interval t, each electron moves a distance < v > t
along the wire. So the number of electrons passing through the cross section A in this time
is equal to n < v > t A, where n is the number of valence electrons per unit volume.
Curren is defined as the amount of charge passing through the wire per unit time. Since
each electron carries a charge of −e, the current in the wire is

I = n < v > A (−e) = −e n A < v > . (5)

The current density J is defined as the current per unit area, so that
~ 2 ~
~ = −e n < ~v >= −e n −e E τ = n e E τ = σ E
J~ = I/A ~, (6)
me me

3
 n e2 τ
where σ = me
is the conductivity of the material.

~ and proportional to the field strength.

• Current density is in the same direction of E
This is familiar Ohm’s law.

• J~ is proportional to e2 . We would get same results for charge carriers with positive
charge and with negative charge.

Now we are going to introduce another useful definition called mobility. Mobility is defined
as the ratio of the drift velocity to the applied electric field, i.e,

|<v>| eτ
µ= = . (7)
E me

Using µ , we can write σ as

σ = nµe. (8)

The concept of mobility can be useful for solids in which the electron concentration can be
changed by some internal parameters without changing the scattering mechanism inside the
solid, i.e, without changing the relaxation time τ .

B. Failure of classical model

Let us first compare the conductivities of different metals. We see that the conductivity
of a metal σ is defined as

σ = nµe. (9)

So, it is evident that

• σ is directly proportional to n, where, n is the number density of valence electrons.

• σ is also directly proportional to µ, mobility.

Now the question is: How does µ vary from one metal to another. We know that µ ∝ τ ∝ λ,
where λ is the mean free path. Mean free path λ depends on the size of the ions and in
the percentage of the total volume that is occupied by the ions. Since most matelic ions
tend to be of more or less uniform size (ionic radius of order of 0.15 nm) and form a closed

4
packed crystal structure, we can assume that λ will not vary substantially between different
metals. Hence µ will also not vary from one metal to another. So, the conductivity should
be proportional to the valence electron concentration only, i.e, σ ∝ n. Howver, this is not
in good agreement with experimental data. It appears that those metals which have the
highest electron concentration tend to have lowest σ and vice versa.
Similarly, the dependence of resistivity ρ on T is also at odds with experimental obser-
vation. If λ is constant with T , it can be shown that ρ ∝ T 3/2 . But experimentaly it was
found that ρ ∝ T . Hence, we see that although, Drude’s model is consistent with the Ohm’s
law, it however, fails to explain various experimental data. We need to look for a quantum
theory.

C. Quantum theory

We can not assume the electrons in a metal to be classical ideal gas. Again, we can not
ignore the electrostatic interaction of the electrons with the ions (electron-ion interaction)
and between valence electrons themselves (electron-electron interaction). Electron-electron
interaction was found to be fairly insignificant in most cases, so we can neglect this effect.
Unlike classical theory, we are not dealing with collision between electrons and ions, rather
the electrons are deflected or scattered by the ions. To describe the motion of an electron in
a solid, we need to extend this idea to a large number of ions in close proximity. It follows
that, in order to describe the interaction between the valence electrons and the ions, we
must use a quantum theory.

1. Band theory of solids

• The properties of the electrons in an atom are determined by four parameters or

quantum numbers n, l, ml and ms , respectively. Here n denotes the principal quantum
number, l is the angular momentum quantum number and it can take any integer
values from 0 to n − 1. Similarly values of ml and ms are restricted to [−l, l] and
[−1/2, +1/2], respectively.

• The electrons are only allowed to occupy certain discrete energy levels which we label
using the quantum numbers n and l since energy of an electron does not depend on

5
 ml and ms . l = 0 represents s orbital, l = 1 corresponds to p, l = 2 corresponds to d,
l = 3 corresponds to f, and so on.

• The occupancy of these levels is determined by the Pauli’s exclusion principle which
states that each electron must possess a unique set of quantum numbers. For example,
if we take Na11 atom, its occupancy can be written as 1s2 2s2 2p6 3s1 . There is only
one electron in 3s level.

In a solid, the atoms are not isolated. Infact they are in close proximity to a large number
of other atoms. What happens in this case? Let us first consider two Sodium atoms.

• When the atoms are far apart, they behave like isolated atoms. But as we move them
close together, the outer electrons begin to interact. That means the 3s electrons
from both Sodium atoms will interact with each other. This affects the energies of
the electrons. At the equilibrium separation a0 between the atom, we have two states:
one with a lower energy than the 3s state in the isolated atom and the other one is at
higher energy than the 3s state in the isolated atom.

• The energy levels can no longer be considered to belong to a specific atom. They are
property of the pair of atoms considered as a whole.

• The picture does not imply that the 3s electron attached to one atom has a higher
energy than the other. In fact, since there are two allowed values of ms , for each state,
both electrons can occupy the lowest level.

If we extend this same argument to a system of N Sodium atoms, we should get N discrete
3s energy levels.

• In a macroscopic crystal, the number of atoms are of the order of Avogadro’s number,
i.e, N = 1034 .

• Energy levels span a range of only few eV .

• Consequently, the spacing between adjacent levels is so small that we effectively have
a continuous band of energies.

6
• Similar interaction between 1s, 2s and 2p electrons also occur but the interactions
are much weaker because these electrons are closer to their respective nuclei. So
corresponding bands cover a smaller range of energies.

• Although, the quantum states in a solid are so closely spaced that we can treat them
as continuous band, we still need to be aware of the existence of the discrete energy
levels when we consider how many electrons can occupy each band. For example,

1s band contains N discrete states so that 2N electrons can occupy these states
2s band contains N discrete states so that 2N electrons can occupy these states
2p band contains 3N discrete states so that 6N electrons can occupy these states

For Sodium, all these energy levels are fully occupied. In the 3s band, however, there
are only N electrons available to occupy the 2N levels. So the 3s band is partially
occupied.

Now let us consider Carbon atom. There are 2 electrons in n = 1 shell (1s2 ) and
four electrons in n = 2 shell (2s2 2p2 ). In an isolated free atom, six electron states
have been filled and the remaining four states in the n = 2 shell are empty. As the
interatomic distance is decreased, the discrete energy levels broaden out into bands and
eventually the bands corresponding to the subshell of n = 2 overlap. As the interatomic
distance is further decreased, a split occurs between the upper four states and the
lower four states. At the equilibrium spacing the two bands are widely separated.
The upper band is called conduction band and the lower band is called the valence
band. The gap between the two bands is known as the forbidden energy gap (Eg ). For
diamond, Eg = 6 eV. At room temperature, i.e, at T = 300K, the thermal energy is
kB T = 0.025 eV. Thus diamond with very few electron in the conduction band is an
extremely good insulator at room temperature.

The concept of energy bands can be used to differentiate between the three kinds
of solids, namely, insulators, semiconductors and metals. Semiconductor differ from
insulators only in the width of the forbidden energy band. An insulator has a forbidden
gap which is so wide that a very few electrons can cross it at room temperature. A
semiconductor, on the other hand, possesses a narrow gap which allows a considerable
amount of electrons into the conduction band. The forbidden energy gap Eg is 1 eV

7
 for Silicon and 0.7 eV for Germanium. These are classified as semiconductors because
at room temperature there are enough electrons excited across the forbidden gap to
make both electron and hole concentration in the conduction and the valence band.
These cause conductivity.

FIG. 1:

D. Free electron model

The free electron model is the quantum mechanical analogue to the Drude’s classical
model. The objective is to obtain a simple description of metals assuming that the electrons

8
are free. They do not interact with the ions or with each other. It is basically the free
particle in a box. We have to solve the time independent Schrodinger’s equation
~2 2
− ∇ ψ(x, y, z) + V (x, y, z) ψ(x, y, z) = E ψ(x, y, z) , (10)
2m
where

V (x, y, z) = 0, 0 ≤ x ≤ a ,
= 0, 0 ≤ y ≤ a ,

= 0, 0 ≤ z ≤ a ,
= ∞, elsewhere . (11)

We know that outside the box, the wavefunction ψ will vanish. Inside the box, we need to
solve the following equation
~2 2
− ∇ ψ(x, y, z) = E ψ(x, y, z) ,
2m
2mE
∇2 ψ + ψ = 0,
~2
∂2 ∂2 ∂2 2mE
( 2 + 2 + 2 )ψ(x, y, z) + ψ(x, y, z) = 0 . (12)
∂x ∂y ∂z ~2
Let us consider that ψ(x, y, z) = X(x) Y (y) Z(z). With this, the time independent
SE (Eq. 12) takes the following form
d2 X d2 Y d2 Z 2 m E
Y (y) Z(z) + X(x) Z(z) + X(x) Y (y) + X(x) Y (y) Z(z) = 0 . (13)
dx2 dy 2 dz 2 ~2
Now dividing Eq. 13 by X(x) Y (y) Z(z), we get
1 d2 X 1 d2 Y 1 d2 Z 2 m E
+ + + = 0. (14)
X dx2 Y dy 2 Z dz 2 ~2
The first, 2nd, and the third tirm must all be constants. Let us assume that
1 d2 X
2
= −kx2 ,
X dx
1 d2 Y
= −ky2 ,
Y dy 2
1 d2 Z
= −kz2 , (15)
Z dz 2
so that
2mE
kx2 + ky2 + kz2 = . (16)
~2

9
Now the solution of Eq. 15 can be written as

X(x) = Ax sin kx x + Bx cos kx x ,

Y (y) = Ay sin ky y + By cos ky y ,
Z(z) = Az sin kz z + Bz cos kz z , (17)

where Ax,y,z and Bx,y,z can be determined from the boundary conditions. The boundary
conditions are
at x = 0, ψ = 0 which implies that X(0) = 0
at x = a, ψ = 0 which implies that X(a) = 0
at y = 0, ψ = 0 which implies that Y (0) = 0
at y = a, ψ = 0 which implies that Y (a) = 0
at z = 0, ψ = 0 which implies that Z(0) = 0
at z = a, ψ = 0 which implies that Z(a) = 0
Using these boundary conditions, we get Bx,y,z = 0 and
nx π ny π nz π
kx = , ky = , kz = , (18)
a a a
where nx,y,z = 1, 2, 3, ........ So the solutions are

X(x) = Ax sin kx x ,

Y (y) = Ay sin ky y ,
Z(z) = Az sin kz z , (19)

Using the normalization condition, we get

r
2
X(x) = sin kx x ,
a
r
2
Y (y) = sin ky y ,
a
r
2
Z(z) = sin kz z , (20)
a
So ψ(x, y, z) can be written as
r 2 3 nx π x ny π y nz π z
ψ(x, y, z) = sin sin sin . (21)
a a a a
Similarly E can be written as
~2  2  ~2 π 2 h 2 i h2 h 2 i
E= kx + ky2 + kz2 = n + n 2
+ n 2
= n + n2
+ n 2
z . (22)
2m 2 m a2 x y z
8 m a2 x y

10
Let us assume that the metal is in the form of a cube of side a. Wavefunction of the
stationary states are given by
r 2 3 nx π x ny π y nz π z
ψnx ,ny ,nz = sin sin sin . (23)
a a a a

within the metal and outside it is zero with energy

h2 h 2 2 2
i
Enx ,ny ,nz = n + n + nz . (24)
8 m a2 x y

• According to Pauli’s exclusion principle, not more than two electrons may occupy any
state.

• At absolute zero temperature, two electrons will be in the ground state, two will be
in each state of next higher energy and so on untill all the electrons are attached to
states of lowest possible energy.

• For a macroscopic dimension, say a centimeter cube, the energy of the ground state is
of the order of 10−15 eV and hence may be taken as zero. Also the maximum spacing
between consecutive energy levels is less than 01−6 eV, so that the distribution of
energy may be regarded as almost continuous.

Now the question is: How the electrons of a real metal are distributed among those available
energy states. First, we can represent the probability of occupying a given state by a
continuous distribution function. The probability F (E) of an electron occupying a given
energy level is given by

1
F (E) = h i, (25)
1 + exp E−E
kB T
F

where F (E) is the Fermi function, E is the energy of the level whose occupancy is being
considered, and EF is the Fermi energy. At T = 0K,

F (E) = 1 for E < EF ,

= 0 for E > EF . (26)

Below EF , all the energy levels are occupied, however, above EF , all the energy levels are
empty.

11
 E. Density of states

• F (E) gives us the probability of occupation of an energy state by a single electron.

• Difference between two energy levels is small (10−6 eV). Hence, in a macroscopically
small energy interval dE, there are still many discrete energy levels.

• To know the actual number of electrons with a given energy, we must know the number
of states in the system which have the energy under consideration.

• Multiplying the number of states by the probability of occupation will give us the
actual number of electrons.

Let us assume that N (E) is the number of electrons in a system that have energy E and
Z(E) is the number of states at that energy, Then

N (E) dE = Z(E) dE F (E) . (27)

From the expression of energy, we get

8 m a2
n2x + n2y + n2z = E = n2 . (28)
h2
q
2
This is a equation of a sphere with radius n = 8 mha2 E . A radius vector n from the origin
may be drawn to a point (nx , ny , nz ) in this space. All points on the surface of a sphere of
radius n have the same energy. In this space, every integer specifies a state. A unit cube

FIG. 2:

12
contains exactly one state. Henec, number of available states within a sphere of radius n is
1 4  1
Nn = π n = π n3 .
3
(29)
8 3 6
Similarly, number of available states within a sphere of radius n + dn is
1
Nn+dn = π (n + dn)3 . (30)
6
It should be mentioned that the 1/8 factor accounts for the fact that only positive integers
of (nx , ny , nz ) are allowed. Hence, number of available energy states having energy values
lying between E and E + dE is
1 1
Z(E) dE = π (n + dn)3 − π n3 ,
6 h 6
π 3 i
= n + 3 n dn − n3 ,
2
6
π 2
= n dn , (31)
2
here we have neglected the higher order terms containing dn2 and dn3 . Again from Eq. 28,
we have
4 m a2
n dn = dE . (32)
h2
Putting value of n and n dn in Eq. 31, we get
π  8 m a2 3/2 1/2
Z(E) dE = E dE . (33)
4 h2
Pauli’s exclusion principle permits two electrons in each state. So the number of energy
levels actually available are
π  8 m a2 3/2 1/2
Z(E) dE = E dE . (34)
2 h2
Density of states is defined as the number of energy states present in unit volume having
energy values lying between E and E + dE, i.e,
π  8 m 3/2 1/2
Z 0 (E) dE = E dE . (35)
2 h2
Number of electrons

N (E) dE = Z(E) dE F (E) ,

π  8 m a2 3/2 1/2 dE
= 2
E h i. (36)
2 h 1 + exp E−E F
kB T

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At absolute zero temperature T = 0K,
π  8 m a2 3/2 1/2
N (E) dE = E dE . (37)
2 h2
So, total number of electrons
EF
π  8 m a2 3/2 3/2
Z
N= N (E) dE = EF . (38)
0 2 h2
Hence, number of electrons per unit volume or density of electrons is
N N π  8 m 3/2 3/2
n= = 3 = EF . (39)
V a 2 h2

F. Behaviour of Fermi function F (E) with Temperature T

At T = 0K, all the energy levels are occupied up to E = EF , however, above EF , all the
energy levels are empty. When T 6= 0, then at E = EF , we get F (E) = 1/2. Now let us
calculate F (E) at E = EF + kB T .
1 1 1 1
F (E) = = = ≡ = 0.25 . (40)
1+e 1 + 2.7 3.7 4
Similarly, at E − EF = −kB T , we get
1 e 2.7 3
F (E) = −1
= = ≡ = 0.75 . (41)
1+e 1+e 3.7 4
So, at T = 0K, EF is the maximum energy of the occupied state. As T increases, an electron
may get energy of the order of kB T and go to higher vacant state, so the Fermi function
h i
E−EF E−EF
falls. But if EF − E >> kB T or kB T << −1, then exp kB T → 0 and hence F (E) → 1.
h i
Similarly, if E − EF >> kB T , i.e, E−E
kB T
F
>> 1 then exp E−EF
kB T
→ ∞ and hence F (E) → 0.
So F (E) begins to fall only in the neighbourhood of EF . Graphically it is shown in Fig. 3.

G. Semiconductor

In general, there are two types of semiconductors: Intrinsic and extrinsic. In case of
intrinsic semiconductor, the current carrier electrons or holes are produced by thermal acti-
vation. Pure Germanium and Silicon are such type of semiconductors. However, in case of
extrinsic semiconductors, electrons or holes are produced by the addition of small quantities
of elements of group III and group V of the periodic table. The elements added are called
impurities.

14
 FIG. 3: F (E) as a function of temperature.

1. Intrinsic semiconductor

FIG. 4: Silicon crystal

Silicon and Germanium are elements of the fourth column of the periodic table. A pure
Germanium atom has 32 electrons. Out of these, 28 are tightly bound to the nucleus, whereas
the remaining four revolve in the outermost level and are called valence electrons. Similarly
for silicon, there are 4 valence electrons. Hence, in a Germanium or Silicon crystal, two
electrons are shared by two atoms. At absolute zero temperature, pure Silicon or Germanium
is a non conductor of electricity as there are no free mobile electrons. Conduction occurs
in an intrinsic semiconductor by thermal activation of electrons from the valence to the
conduction band. As a result of thermal activation, an individual electron from a covalent
bond acquires sufficient energy to break the bond and becomes free. These electrons move
freely in the crystal in a random way. But when an external electric field is applied, this

15
random motion experiences a drift towards the positive electrode. This represents the flow
of current. When the electron escapes from the covalent bond, then the empty space left
behind is called hole. Due to the tendency to form a pair, the remaining electron from the
covalent bond steals one electron from the adjacent pair. Thus the previous hole is now
shifted to another place from which the electron is stolen. Thus once a hole is created, it
moves about in the crystal in a random way. In the presence of the electric field, they drift
towards the negative electrode. This costitutes flow of current.

2. Extrinsic semiconductor

• Pure semiconductors are usually of interest only from a theoretical point of view. In
pure semiconductors, the carrier concentration of both electrons and holes at normal
temperature is very low and hence for an appreciable current density, the applied
electric field must be very large.

• Electrical conductivity of a semiconductor is very much dependent on purity and

imperfections in the lattice. One way to improve the conductivity is to add a controlled
amount of certain impurities. Conductivity of Silicon is increased 1000 times by the
addition of small amount of Boron. The conduction is called impurity conduction.
The impurities added are called dopants.

• The impurities employed for Ge and Si are elements of Group III and Group V of the
periodic tabel. Boron, Galliuum, Indium are some Group III elements and Phosphorus,
Arsenic, Antimony are some Group V elements.

• Four of the valence electrons of the pentavalent impurity atom form valence band with
adjacent Silicon atoms. But the fifth one occupies a state which lies 0.045 eV below
the conduction band. Since the ionization energy for Phosphorus is much smaller
than the energy Eg , the phosphorus atoms will donate these fifth electrons to the
conduction band even at much lower temperature. An impurity of this kind is called
donors since it donates conduction electrons without producing holes in the valance
band. Thus, due to the pentavalent impurities, electrons are added to the conduction
band, outnumbering the holes in the valence band. The electrons then becomes the

16
 majority carriers and holes the minority carriers. These type of semiconductors are
called n type semiconductors.

• If, on the other hand, a trivalent impurity say Boron is added then the three valence
electrons enter into covalent bonding but a region of stress exists where the fourth
band ought to exist. So any electron in the vicinity can be trapped by the impurity
center which then becomes negatively charged. The region from which the electron
came is positively charged. In effect the trivalent impurity has injected a hole into the
crystal. Such an impurity is called an acceptor impurity since it accepts electrons into
the impurity center. Si or Ge doped in this way has many holes as charge carriers and
therefore termed as p type semiconductors. In p type, holes are the majority charge
carriers and thermally generated electrons are the minority carriers.

H. Electron concentration for intrinsic semiconductor

We have to claculate the number of electrons excited into the conduction band at ant
temperature T . It will be assumed that the electrons in the conduction band will behave
as free electrons with effective mass m∗e . The energy will be measured from the top of the
valence band. Number of electrons per unit volume having energy in the range E and E +dE
in the conduction band is

N (E) dE = Z 0 (E)dE F (E) , (42)

where
1
F (E) = h i,
1 + exp E−E
kB T
F

π 8 m∗e i3/2
h
Z 0 (E)dE = (E − Ec )1/2 dE . (43)
2 h2
Here we have used (E − Ec )1/2 because E starts at the bottom of the conduction band.
Fermi level for an intrinsic semiconductor must lie well within the forbidden energy region,
i.e, Ec − EF >> KB T since kB T << Eg . Since, E starts at the bottom of the conduction
band, so E − EF >> KB T will be satisfied automatically (look at Fig 5). So,
1 1 hE − E i
F (E) = h i= h i = exp F (44)
1 + exp E−E F
exp E−E F kB T
kB T kB T

17
So the number of electrons per unit volume is
Z ∞
π h 8 m∗e i3/2 ∞ hE − E i
Z
1/2 F
N= N (E) dE = 2
(E − Ec ) exp dE . (45)
Ec 2 h Ec kBT

Now let us assume that E − Ec = x. This implies that dE = dx. So substituting these
values in Eq. 45, we get

π h 8 m∗e i3/2 ∞ 1/2 hE − E − xi

Z
F c
N = 2
x exp dx ,
2 h 0 kB T
π h 8 m∗e i3/2 hE − E i Z ∞
F c
= 2
exp x1/2 e−(x/kB T ) dx . (46)
2 h kB T 0

x
Let us again assume that kB T
= y. This implies that dx = kB T dy. Putting this in Eq. 46,
we get

π h 8 m∗e i3/2 hE − E i Z ∞
F c
N = exp (kB T y)1/2 e−y kB T dy ,
2 h2 kB T 0
Z ∞
π h 8 m∗e i3/2 hE − E i
F c
= exp (kB T ) 3/2
y 1/2 e−y dy ,
2 h2 kB T
√0
π h 8 m∗e i3/2 hE − E i
F c 3/2 π
= exp (kB T ) ,
2 h2 kB T 2
 2 π m∗ k T 3/2 hE − E i
e B F c
=2 2
exp ,
h kB T
hE − E i
F c
= Nc exp . (47)
kB T

FIG. 5:

18
 I. Hole concentration

Number of holes can be found in a similar manner. Presence of holes can be regarded
as the absence of electron. Hence the Fermi function for hole will be of the form FP (E) =
1 − F (E). So
1 1
FP (E) = 1 − F (E) = 1 − h i= h i, (48)
EF −E
1 + exp E−E
kB T
F
1 + exp kB T

where FP (E) denotes the probability that a hole will be associated with a quantum state of
energy E. Again we know that the Fermi energy EF is several kB T units above the top of
the valence band. So EF − Ev >> kB T is satisfied. Since E will have maximum energy Ev ,
we get EF − E >> kB T . Number of holes per unit volume having energy in the range E
and Ed E in the valence band is

P (E) dE = Z 0 (E)dE FP (E) , (49)

where

0 π h 8 m∗p i3/2
Z (E)dE = 2
(Ev − E)1/2 dE . (50)
2 h
Since EF − E >> kB T , we get
1 1 h E − Ei
FP (E) = h i = h i = exp − F (51)
1 + exp EkFB−E exp EkFB−E kB T
T T

Hence
π h 8 m∗p i3/2 Ev hE − E i
Z
1/2 F
P = 2
(Ev − E) exp dE . (52)
2 h −∞ kB T
Now using Ev − E = x and solving the above equation we get,
 2 π m∗ kB T 3/2 hE − E i
p v F
P = 2 exp ,
h2 kB T
hE − E i
v F
= Nv exp . (53)
kB T
For intrinsic semiconductor, we know that N = P . So, we get
hE − E i hE − E i
F c v F
(m∗e )3/2
exp ∗ 3/2
= (mp ) exp ,
kB T kB T
Ec + Ev 3 kB T  m∗ 
p
EF = + ln . (54)
2 4 m∗e

19
If m∗e = m∗p , we get EF = Ec +Ev
2
. Normally m∗p is greater than m∗e . So, the Fermi level or EF
is just above the middle and rises slightly with increasing temperature. Now let us calculate
the following quantity.
hE − E i hE − E i
F c v F
N P = Nc Nv exp exp ,
kB T kB T
h E −E i
2 c v
N = Nc Nv exp − ,
kB T
h Eg i
N 2 = Nc Nv exp − ,
kB T
1/2
h Eg i
N = (Nc Nv ) exp − . (55)
2 kB T
 3/2
If m∗e = m∗p = m, then Nc = Nv = 2 2 π mh2kB T . So
 2 π m k T 3/2 h Eg i
B
N = 2 exp − ,
h2 2 kB T
h Eg i
= C T 3/2 exp − , (56)
2 kB T
 3/2
2 π m kB
where C = 2 h2
= 4.83 × 1021 . If Eg = 1 eV and T = 300K then N ≡ 1017 m−3 .
Number of atoms per cubic meter may be order of 1034 . So the number of electrons in
the conduction band or holes in the valence band for intrinsic semiconductor is very small
compared to the total number of atoms.

II. HALL EFFECT

If a conducting material is placed in a uniform magnetic field and current is passed

along the length of the conductor, a voltage is found to develop at right angles to both
the direction of current flow and that of the magnetic field. This voltage is known as Hall
voltage. Consider a specimen in the form of a rectangular cross section carrying a current Ix
in the x direction. If a uniform magnetic field Bz is applied along the z axis, it is found that
an emf develops along the y axis, i.e, in the direction perpendicular to Ix and Bz . Let us first
consider the situation before the magnetic field is introduced. There is an electric current
flowing in the x direction. Which means the conduction electrons are drifting with a velocity
vx in the negative x direction. When the magnetic field Bz is applied along the z direction,
the Lorentz force F~ = q(~v × B)
~ = q vx Bz (−x̂ × ẑ) = iq vx Bz ŷ causes the electrons to bend

upward. As a result, electrons accumulate on the upper surface producing a net negative

20
 FIG. 6: Hall effect for positive charge carriers (left) and negative charge carriers (right).

charge. Simultaneously, a net positive charge appears in the lower surface because of the
deficiency of electrons there. This combination of positive and negative surface charges
create a upward electric field. This is called Hall field. The field created by the surface
charges produce a force that opposes this Lorentz force at equilibrium, i.e,

q Ey = q EH = q vv Bz ,
EH = vx Bz , (57)

where EH is the Hall field. We know that the current density is given by the charge density
multiplied by the drift velocity, i.e, Jx = n q vx . So
EH Bz
= ,
Jx nq
 1 
EH = Jx Bz . (58)
nq
We see that the Hall field is directly proportional to the current density and the applied
magnetic field, i.e, EH ∝ Jx and EH ∝ Bz . The proportionality constant is given by
EH  1 
= = RH , (59)
Jx Bz nq
where RH is called the Hall coefficient. It is the ratio of the electric field produced per unit
current density to the transverse magnetic field. Measurement of Hall coefficient helps to
determine

• Sign of current carrying charges as RH depends on the sign of charge q. Negative value
of RH corresponds to negative charge carriers and positive value of RH corresponds
to positive charge carriers

21
• Number of charge carriers per unit volume, i.e, charge carrier concentration n.

22