MODULE-4: Electrical Properties of Solids BPHYS102/202

CLASSICAL FREE ELECTRON THEORY:

A German physicist Paul Drude, proposed a theory to account for the electrical conductivity in
metals. According to his theory, metal consists of free electrons. Later Lorentz improved
Drude’s theory and it’s known as Lorentz- Drude theory or classical free electron theory.
Assumptions
1. Atoms in a metal are considered to be made up of ion cores
2. There are many free electrons in metal which are free to move anywhere inside the metal
3. The free electrons are treated equivalent to gas molecules and hence they obey the laws of
kinetic theory of gas. In the absence of field, the energy (Eth) associated with each electron
at a temperature T is given by 3/2 kT where, k is the Boltzmann constant. Therefore, the
kinetic energy of the electron, 1/2 mvth2 = 3/2kT, where, vth is the thermal velocity.
3. The effect of electric potential due to positive ions on the electrons is considered to be
constant and hence neglected.
4. The repulsion between the free electrons and attraction between ion core and electrons are
considered to be constant negligible and hence neglected.
Based on classical free electron theory, it can be shown that electrical conductivity
ne 2 τ
σ = m = = neµ, where n is the free electron concentration, e electron charge, τ is the
mean collision time, mass of the electron,µ is the mobility of electrons.

Drift velocity:
If no electric field is applied on a conductor, the free electrons move in random directions.
They collide with each other and also with the positive ions. Since the motion is completely
random, average velocity in any direction is zero. If a constant electric field is established inside
a conductor, the electrons experience a force F = -eE due to which they move in the direction
opposite to direction of the field. These electrons undergo frequent collisions with positive
ions. In each such collision, direction of motion of electrons undergoes random changes. As a
result, in addition to the random motion, the electrons are subjected to a very slow directional
motion. This motion is called drift and the average velocity of this motion is called drift velocity
vd.

The average velocity with which the free electrons drift in the presence of electric field is
called drift velocity vd.

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

eEτ
It can be shown that drift velocity vd = m where e is the charge of an electron, E is the
applied electric field, τ is the mean collision time and m is the mass of the electron.

Mean collision time and mean free path

Mean collision time (τ) is the average time that elapses between two consecutive collisions of
an electron with lattice ions.
Average distance traveled by the conduction electrons between two successive collisions with
the lattice ions is called mean free path (λ).
Relaxation time (τr)
The relaxation time τr , may be defined as the time taken for the drift velocity to decrease
1
 
to  e  times its value at the time when the electric field is turned off.

Mobility:
Mobility of a charge carrier is the ratio of the drift mobility to the electric field.
vd
µ= E m2/volt-sec
Electrical Conductivity:
To deal with electrical conductivity, it is necessary to learn about the related terminologies.
Current (I): It is the rate of flow of charge through the given cross sectional area of the
conductor.
Current density (J): It is the current per unit area of cross sectional area of a current
carrying conductor.
I
i.e, J= A
Resistivity (  ): It is the measure of the opposition offered by the material during a current
flow in it. If R is the resistance of a conductor of length L with cross sectional area A,
RA
Resistivity  = L
Conductivity (  ): It is a measure of the ability of the material to allow charge carriers to
flow through it. It is given by inverse of resistivity. Based on classical free electron theory, it
ne 2 τ
can be shown that electrical conductivity σ = m = = neµ
where ‘n’ is the concentration of electrons.

Failures of classical free electron theory

1. Temperature dependence of electrical resistivity
According to kinetic theory of gases,
Kinetic energy of electron is given by

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

1 3
mv 2  kT
2 2
3kT
v 
m
or, v  T
ne 2 τ
But electrical conductivity σ = m and mean free path, λ = vτ,
ne 2 λ
∴ σ = mv
Since v  T
1
σ
T
or ρ  T
But experimental observation is ρ ∝ T
Thus in this case, classical free electron theory is not agreeing with the experimental
observations.

2. Specific heat capacity

The theoretically predicted value of specific heat capacity (Cv = 3/2 R) of a metal does not agree
with the experimentally obtained value (10-4 RT). Experimentally observed value of specific
heat is far lower than expected value.

3. Dependence of electrical conductivity on electron concentration

ne 2 τ
As per the classical free electron theory, σ = m or, σ ∝ n .i.e, monovalent metals should
have lesser electrical conductivity compared to the divalent and trivalent metals. This contrary
to the experimental observation that silver and cooper (monovalents) are more conducting than
zinc (divalent) and aluminium(trivalent).

Quantum free electron theory (Sommerfeld model)

Classical free electron theory could not explain many physical properties. In classical free
electron theory, we use Maxwell-Boltzmann statistics which permits all the free electrons to
gain energy. In 1928, Sommerfeld developed a new theory, in which he retained some of the
features of classical free electron theory and included quantum mechanical concepts and Fermi-
Dirac statistics to the free electrons in the metal. This theory is called quantum free electron
theory.
The main assumptions of Quantum free electron theory are:
1. The energy values of conduction electrons are quantized and are realized in terms of a set
of energy levels. The distribution of energy of free electrons in a metal must obey Fermi-
Dirac quantum statistics
2. In a metal every level is filled in correspondence with Pauli’s exclusion principle i.e, an
energy level can accommodate maximum of two electrons.
3. The electrons move in a constant potential inside the metal and are confined within defined
boundaries.

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

4. The attraction between the electrons and the lattice ions and the repulsion between the
electrons themselves are ignored.

Density of states:
The density of states g(E) can be defined as the number of available energy states per unit
volume per unit energy range. The expression for g(E) in an energy range between E and E +
dE for the electrons in a 3- dimensional solid of unit volume is given by

3
8√2𝜋𝑚2 1
𝑔(𝐸)𝑑𝐸 = [ 3
] 𝐸2 𝑑𝐸
ℎ

For a given energy range, the g(E) (number of energy per unit energy range) will increase
parabolically with increase in energy, that can be shown as

Density
of states
(g(E))

Energy

Fermi energy:
At absolute zero, electrons occupy energy levels in pairs starting from the bottom of the band
to an upper level designated as EF. Fermi level can be therefore, defined as the uppermost
filled energy level in a conductor at 0K.
Fermi energy is defined as maximum energy that a free electron can have in a conductor
at 0K.

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

Energy Vacant
Energy levels

Filled Energy
EF levels

Fermi-Dirac statistics
Fermi-Dirac statistics is applicable to the assembly of particles which obey Pauli’s exclusion
principle. They must also be identical particles of spin ½ and are indistinguishable. Since
electrons satisfy these conditions they obey Fermi-Dirac statistics. The particles which obey F-
D statistics are called fermions. According to Fermi-Dirac statistics, the probability that an
electron occupies an energy level E at steady temperature T is given by,

where EF is called Fermi energy.

Fermi factor:
The existence of electron in a particular energy level can be explained by Fermi-Dirac statistics.
According to it the probability f(E) of existence of electron in an energy state E at steady
temperature T is given by,

where f(E) is called Fermi factor and EF is the Fermi energy.

Fermi factor is the probability of occupation of a given energy state for a material in
thermal equilibrium.

Effect of temperature on Fermi factor (or Dependence of Fermi factor on temperature and effect
on occupancy)
Fermi factor is given by,

where EF is the Fermi energy, k is Boltzmann constant , E is the energy level at which
probability occupancy measured at temperature T

(i) Probability of occupation for E<EF at T = 0K

When T = 0K and E<EF , E-EF is negative quantity.

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

1 1


Therefore, f(E) = 1  e 1 0 = 1
f(E) = 1 indicates that all the energy levels lying below EF are occupied.

(ii) Probability of occupation for E> EF at T = 0K

1 1


f(E) = 1  e  =0
Therefore, at T =0K all the levels above Fermi level are vacant.

(iii) Probability of occupation at T>0K

At ordinary temperature, though the value of probability remains 1 for E<<E F it starts
decreasing from 1 as the values of E become closer to EF.
1 1 1
 
0
11 2
Let the energy level E =EF then f(E) = 1  e kT
Thus Fermi level at T>0K is that
level which has the probability of occupation of electron equal to half.
Further, for E> EF, the probability value falls off to zero rapidly.

Variation of f(E) with E :

Merits of quantum free electron theory:

1. Temperature dependence of electrical resistivity/conductivity

According to Quantum free electron theory, electrical conductivity of a metal is given by,

n e2 τ F 
σ= where m * is the effectivemass of the elcton But τ F  F
m* vF
n e 2 F
or σ 
m * vF

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

Here, where vF is the Fermi velocity which is the velocity of electrons occupying Fermi level
and F the mean free path.
1
EF = m * v 2F
2
1
 2E F  2
or, v F =  
 m* 

Now electrical conductivity can be expressed as,

ne 2 λF
σ=      1
m * vF

Here vF is independent of temperature but λ is temperature dependent. As the temperature

increases, the lattice ions start vibrating with larger amplitudes and offer scattering of the
electrons which results in the reduction in the value of mean free path of the electrons.
1
λF 
i.e., T

But from equation (1), σ ∝ λF

1
σ
∴ T and ρ ∝ T
This result is in accordance with experimental observation.

2. Specific heat
According to classical free electron theory, specific heat Cv = 3/2 R. But experimentally
observed value is around 10-4 RT which is very low. According to classical free electron theory,
all electrons are capable of absorbing heat energy. Thus the theory predicts a large value of
specific heat. But according to quantum free electron theory, only those electrons which occupy
energy levels close to Fermi level EF absorb heat energy. Such electrons constitute a very small
percentage of the total number of free electrons. Hence specific heat value becomes very small.
 2k 
 RT
Further, it is shown on the basis of quantum free electron theory that Cv =  E F  .
 2k 
 
If EF = 5eV, we get  E F  = 10-4 Therefore
Cv = 10-4RT, which is conformity with experimentally observed values.

3. Electrical conductivity and electron concentration:

The discrepancy in the electrical conductivity of metals of different valences could not be
explained by the classical theory.
According to Quantum free electron theory, electrical conductivity of a metal is given by,

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

n e 2 F
σ
m * vF
As per quantum free electron theory, it is observed that all valence electrons are not conduction
electrons and only those valence electrons having energy equal to or greater than the Fermi
energy will take part in conduction. From the above equation it is clear that, the value of σ
F
depends on n, the ratio v F .If we compare the cases of copper and aluminium, the value of n
F
is 2.13 times higher than that of copper. But the value of v F for copper is about 3.73 times
higher than that of aluminum. Thus the conductivity of copper exceeds that of aluminium.

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

Semiconductors
A semiconductor is one whose electrical conductivity lies in between those of insulators and
conductors. In terms of energy bands, semiconductors have an almost empty conduction band
and almost filled valence band with a small energy gap separating the two.

Two types of semiconductors:

1) Intrinsic semiconductor
2) Extrinsic semicomductor

Intrinsic semiconductors
Chemically pure semiconductors are known as intrinsic semiconductors. Pure silicon and
germanium are examples for intrinsic semiconductors.
Consider a silicon crystal. There are four valence electrons. Each of the valence electron of the
neighboring atom as shown in fig(a). At 0K, none of the valence electrons are available for
conduction. In other words, At 0K, the valence band of an intrinsic semiconductor is
completely filled and the conduction band which is separated by a distance Eg from the valence
band is empty. Hence it behaves as an insulator and has zero conductivity. However, when
thermal energy is supplied some of these covalent bonds break up causing the release of free
electrons inside the crystal. With rise in temperature more covalent bonds get ruptured
releasing more free electrons. In other words, as temperature increases, the electrons in the
valence band gain thermal energy and surmount the forbidden energy gap and move into the
conduction band. The excitation of electrons from valence band to conduction band leaves an
equal number of vacancies (called holes) in the valence band. Both electrons and holes
contribute to the electrical conductivity.

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

Extrinsic semiconductors
When impurities are added to the crystal of an intrinsic semiconductor then it is called extrinsic
semiconductor. The process of adding impurity is called doping and the impurity added is
called dopant. There are two types of extrinsic semiconductors namely, n-type and p-type.

n-Type semiconductor :
Addition of a pentavalent impurity atom to a crystal of intrinsic semiconductor like germanium
or silicon gives an n-type semiconductor. The pentavalent impurities added are generally
phosphorous, arsenic, antimony or bismuth. The impurity atom being pentavalent only four of
its valence electrons are used in covalent bonding with the surrounding four Si atoms (fig. )
The fifth electrons being loosely bound to the atom is available for conduction. Hence there is
large number of free electrons in such a semiconductor since each impurity atom donates one
electron for conduction. So the impurity atoms are called donors.
When the temperature is increased some of the covalent bonds are broken and electrons set
free. These electrons leave behind vacancies called holes which serve as positive charge
carriers. Thus number of free electrons is greater than the number of holes. Hence in n-type
semiconductors electrons are majority carriers and holes are minority carriers.

p-Type semiconductor:

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 MODULE-4: Electrical Properties of Solids BPHYS102/202

Addition of a trivalent impurity atom to a crystal of intrinsic semiconductor like germanium or

silicon gives an p-type semiconductor. The trivalent impurities added are generally boron,
gallium, indium or aluminum. The impurity atom being trivalent only three of its valence
electrons are used in covalent bonding with the surrounding four Si atoms(fig. ). However the
fourth covalent bond will be incomplete because of the deficiency of an electron. Thus a hole
is formed in the structure which is in a position to accept an electron from the neighboring Si
atoms. The addition of each impurity atom thus gives rise to a hole which is available for
conduction. So the impurity atom is called donors.
When the temperature is increased some of the covalent bonds are broken and electrons are set
free. These electrons leave behind vacancies called holes. Thus number of holes is greater than
the number of electrons. Hence in p-type semiconductors holes are majority carriers and
electrons are minority carriers.

Relation between Fermi energy & Energy gap in intrinsic semiconductors

Expression for concentration of electrons in conduction band:

The electron density or electron concentration (n) in the conduction band is given by
3
∗
2𝜋𝑚𝑒 𝑘𝑇 2 −(𝐸𝑐 −𝐸𝐹 )
𝑛= 2[ 2
] 𝑒 𝑘𝑇
ℎ
where, Ec is the energy of corresponding to bottom edge of the conduction band, EF is the Fermi
energy, k is the Boltzmann constant, h is the Planck’s constant, T is the absolute temperature,

𝑚𝑒∗ is the effective mass of the electron.

Expression for concentration of holes in valence band:

The hole density or hole concentration (p) in the valence band is given by
3
∗
2𝜋𝑚ℎ 𝑘𝑇 2 −(𝐸𝐹 −𝐸𝑣)
𝑝= 2[ 2
] 𝑒 𝑘𝑇
ℎ
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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

Where, Ev is the energy of corresponding to top edge of the valence band, EF is the Fermi
energy, k is the Boltzmann constant, h is the Planck’s constant, T is the absolute temperature,

𝑚ℎ∗ is the effective mass of the hole.

Relation between Fermi energy & Energy gap in intrinsic semiconductors

For an intrinsic semiconductor, the number of holes/unit volume in valence band is equal to
number of electron/unit volume in conduction band.

∴ 𝑝=𝑛

Substituting value of p and n

3 3
2𝜋𝑚ℎ∗ 𝑘𝑇 2 −(𝐸𝐹 −𝐸𝑣 ) 2𝜋𝑚𝑒∗ 𝑘𝑇 2 −(𝐸𝑐 −𝐸𝐹 )
2[ ] 𝑒 𝑘𝑇 = 2[ ] 𝑒 𝑘𝑇
ℎ2 ℎ2

3
2𝜋𝑚ℎ∗ 𝑘𝑇 2 𝐸 −𝐸
2[ ] −( 𝑐 𝐹 )
ℎ2 𝑒 𝑘𝑇
3 = 𝐸 −𝐸
−( 𝐹 𝑣 )
2𝜋𝑚𝑒∗ 𝑘𝑇 2 𝑒 𝑘𝑇
2[ ]
ℎ2

3
𝑚ℎ∗ 2 𝐸 −𝐸 𝐸 −𝐸
−( 𝑐 𝐹 )+( 𝐹 𝑣 )
[ ∗] = 𝑒 𝑘𝑇 𝑘𝑇
𝑚𝑒
3
𝑚ℎ∗ 2 −𝐸𝑐 +2𝐸𝐹 −𝐸𝑣
[ ∗] = 𝑒 𝑘𝑇
𝑚𝑒
3
𝑚ℎ∗ 2 (
2𝐸𝐹 −𝐸𝑔
)
[ ∗ ] = 𝑒 𝑘𝑇
𝑚𝑒
Taking natural logarithm on both sides

3 𝑚ℎ∗ 2𝐸𝐹 − 𝐸𝑔
𝑙𝑛 [ ∗ ] = ( )
2 𝑚𝑒 𝑘𝑇
Under practical condition 𝑚ℎ∗ ≈ 𝑚𝑒∗
2𝐸𝐹 − 𝐸𝑔
0=( )
𝑘𝑇
0 = 2𝐸𝐹 − 𝐸𝑔
𝐸𝑔
∴ 𝐸𝐹 =
2
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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

Law of mass action (Intrinsic carrier concentration) :

Expression for concentration of electrons in conduction band:
The electron density or electron concentration (n) in the conduction band is given by
3
∗ 𝐸 −𝐸
2𝜋𝑚𝑒 𝑘𝑇 2 −( 𝑐 𝐹)
𝑛 = 2[ ] 𝑒 𝑘𝑇 ---------- (1)
ℎ2

where, Ec is the energy of corresponding to bottom edge of the conduction band, EF is the
Fermi energy, k is the Boltzmann constant, h is the Planck’s constant, T is the absolute
∗
temperature, 𝑚𝑒 is the effective mass of the electron.

Expression for concentration of holes in valence band:

The hole density or hole concentration (p) in the valence band is given by
3
∗ 𝐸 −𝐸
2𝜋𝑚ℎ 𝑘𝑇 2 −( 𝐹 𝑣 )
𝑝 = 2[ ] 𝑒 𝑘𝑇 --------------- (2)
ℎ2

where, Ev is the energy of corresponding to top edge of the valence band, EF is the Fermi
energy, k is the Boltzmann constant, h is the Planck’s constant, T is the absolute temperature,
𝑚ℎ∗ is the effective mass of the hole.
We know that at 0K intrinsic SC behave like insulator because all free electrons are involved
in the bond formation with other atom. But as temperature increases, breaking of bond takes
places and it leads to generation of an electron-hole pair. At any temperature T, the number
of electrons generated will be equal to the number of holes generated per unit. Thus,
n= p = ni
We can write that
𝑛𝑖2 = 𝑛𝑝
3 3
∗ ∗
2𝜋𝑚𝑒 𝑘𝑇 2 −(𝐸𝑐 −𝐸𝐹 ) 2𝜋𝑚ℎ 𝑘𝑇 2 −(𝐸𝐹 −𝐸𝑣)
= [2 [ ] 𝑒 𝑘𝑇 ] [2 [ ] 𝑒 𝑘𝑇 ]
ℎ2 ℎ2

2𝜋𝑘𝑇 3 3 𝐸 −𝐸 𝐸 −𝐸
−( 𝑐 𝐹)−( 𝐹 𝑣)
=4 [ ] (𝑚𝑒∗ 𝑚ℎ∗ )2 𝑒 𝑘𝑇 𝑘𝑇
ℎ2
2𝜋𝑘𝑇 3 3 −𝐸𝑐 +𝐸𝐹 −𝐸𝐹 +𝐸𝑣
( )
=4 [ ] (𝑚𝑒∗ 𝑚ℎ∗ )2 𝑒 𝑘𝑇
ℎ2

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

2𝜋𝑘𝑇 3 3 𝐸 −𝐸
−( 𝑐 𝑣 )
=4 [ ] (𝑚𝑒∗ 𝑚ℎ∗ )2 𝑒 𝑘𝑇 ------ (3)
ℎ2

The term (Ec – Ev) is the difference in energy between the top level of valence band and the
bottom level of conduction b and, which is the band gap or forbidden energy gap Eg.
i.e., Ec – Ev = Eg ------------------------------------------- (4)
Substitute (4) in (3), we get
𝐸𝑔
2𝜋𝑘𝑇 3 3
−( )
𝑛𝑖2 = 𝑛𝑝 = 4 [ ] (𝑚𝑒∗ 𝑚ℎ∗ )2 𝑒 𝑘𝑇 ------------ (5)
ℎ2
This is the expression for intrinsic carrier concentration. Thus equation (5) shows that the
product of hole and electron concentrations, for a given material, is a constant at a given
temperature. The relation (5) is also called as law of mass action.

Intrinsic conductivity:
A single event of bond breaking in intrinsic semiconductor leads to generation of an electron-
hole pair. At any temperature T, the number of electrons generated will be equal to the number
of holes generated per unit volume. As the two charge carrier concentrations are equal, they
are denoted by a common symbol ni, which is called intrinsic concentration. Thus, n = p = ni .
When a potential difference is applied across a semiconductor, the direction of electron flow
and hole flow are show in fig. The net movement of electrons and holes is called drift.

The current density due to electrons is given by Je = neµeE

The current density due to holes is given by Jh = peµh E
Comparing the above exressions with Ohm’s law J = σ E
We get electronic conductivity σe = neµe
Hole conductivity σh = peµh
Total current density J= Je + Jh = (neµe + peµh)E
Therefore, the intrinsic conductivity is given by σ = neµe + peµh
As n = p = ni in intrinsic concentration, the intrinsic conductivity σ = nie(µe + µh)

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

Hall Effect:
If a rectangular metal or semiconductor slab carrying a current density J is placed in transverse
magnetic field B, a potential difference is produced in a direction perpendicular to both the
current density and magnetic field directions. This phenomenon is called the Hall Effect. The
generated voltage is called the Hall voltage.
Assume that the material is n-type semiconductor; the current flow almost entirely consists of
electrons. Consider a slab of n-type semiconductor subjected to an external electric field Ex
along the x-direction and a magnetic field B along the z-direction as shown in fig. Under the
influence of magnetic field, the electron will subject to a Lorentz force such that upper surface
collects a positive charge while lower surface collects’ negative charge. The accumulation
charge on the specimen continuous until the force on moving charges due to developed electric
field along y-direction large enough to cancel the force exerted by the magnetic field. Hence,
a potential difference VH is established along y-direction.

This potential difference causes a electric field Ey = EH.

The downward force acting on each electron due to magnetic field = Bev
The upward force acting on each electron due to electric field E y is = eEH where e is the
charge of the electron.
At equilibrium condition, Bev = eEH
Or EH = Bv ------------------ (1)
If Jx is the current density along x-direction, then

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri
 MODULE-4: Electrical Properties of Solids BPHYS102/202

Jx = nev where n is the concentration of electrons

Jx
or v =             ( 2 )
ne
substitute( 2 ) in ( 1 ) weget Hall field E H i.e.,
BJ x
EH =              ( 3 )
ne
or E H = RH BJ x          ( 4 )
1
where RH = is called Hall coefficient
ne

1
RH 
In n-type semiconductor ne negative sign is due to EH is developed along negative
y-direction. Hall voltage is given by
VH
EH =
w
VH  E H w  RH BJ x w
1
RH 
For p-type semiconductor Hall coefficient is given by pe
where p is the concentration of positive charge carriers.

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Dr. Ramamprasad A T, Department of Engineering Physics-AIET-Moodbidri