UNIT- II

SEMICONDUCTING
MATERIALS
 Introduction
Semiconducting material has the
electrical conductivity between that of a
good conductor and a perfect insulator. It
is a special class of material, very small in
size and sensitive to heat, light and
electricity.
The resistivity of a semiconductor is
lesser than an insulator but more than
that of a conductor. It is in the order of
10-4 to 0.5 ohm metre.
A semiconductor has nearly empty
conduction band and almost filled
valence band with a very small energy
gap (≈ 1 eV).

Germanium and silicon are the

important semiconductors.
 Properties
The resistivity of a semi-conductor is less than an
insulator, but more than a conductor

Semi conductor have –ve temp coefficient of

resistance ( (i.e. the resistance of a semi –
conductor deceases with increase in temp & vice-
versa
When suitable metallic impurities e.g. As , In
are added to a semiconductor its current
conducting properties changes appreciably.
 Bond in semi Conductor

• In semiconductor, bonds are

formed by sharing of valence
electron such bonds are called
covalent bonds. In the formation of
covalent bond, each atom
contributes equal no of valence
electron and the contributed
electron are shared by atoms
engaged in the formation of the
bond. Eg. Germanium
 Classification of Semiconductors

Semiconductors

Elemental Compound
Semiconductors Semiconductors

Elemental Semiconductors:
These semiconductors are made from a single element of
fourth group elements of the periodic table.
They are also known as indirect band gap semiconductors
Compound semiconductors:
Semiconductors which are formed by combining third and fifth
group elements or second and sixth group elements in the
periodic table are known as compound semiconductors. These
compound semiconductors are also called Direct Band gap
.Semiconductors
S.No. Group Compound semiconductor
1. Combination of third and fifth Gallium Phosphide (GaP)
group elements (III and V) Gallium Arsenide (GaAs)
Indium Phosphide (InP)
Indium Arsenide (InAs)
2. Combination of second and sixth Magnesium oxide (MgO)
group elements (II and VI) Magnesium silicon (MgSi)
Zinc oxide (ZnO)
Zinc sulphide (ZnS)
Uses: These compound semiconductors are used in photovoltaic
materials, photoconductive cell, laser materials, LEDs [Light
Emitting Diode] and Laser diodes
Types of Semiconductors
Semiconductors

Intrinsic Extrinsic
Semiconductor Semiconductor

A semiconductor in extremely pure form, without

the addition of impurities is known as an intrinsic
semiconductor.
Its electrical conductivity can be changed due to
thermal excitation.
Carrier Concentration of Intrinsic semiconductor

We know that in intrinsic semiconductor the charge

carriers are electron in the conduction band and holes
in the valence band

These charge carriers are generated due to breaking

of covalent bonds, we have equal no of holes and
electrons

At 0K, all bonds are intact, the semiconductor acts as

an insulator.

With increase of thermal energy the covalent bonds

are broken and electron and holes pairs are created.
Our aim is calculated the carrier concentration No of
electron in the conduction band per unit volume and No of
holes in valence band per unit volume of the materials

Calculation of density of electron

Let dn be the no of electron available between energy
interval E and E +dE in conduction band

dn = Z (E) F(E) dE … (1)

The mobility of electron

m= 
Ec
Z(E )F (E )dE...(2)
. Hence the density of electron

The density state of electron is given by

4 3 1
Z(E )dE = 3 (2m)2 E 2 dE..(3)
h
Since the electron is moving in a
periodic potential its mass has to be
*
replaced by its effective mass m
e
Hence the density of electron

4 * 2
3 1
Z(E )dE = 3 (2me ) E 2 dE..(4)
h
Hence the energy E starts from bottom of conduction band

4 * 2
3 1
Z(E )dE = 3 (2me ) (E − Ec )2 dE...(5)
h

Fermi function

1
F (E ) = ...(6)
 E − EF 
1 + exp  
 kT 
For E- EF >> kT
−1
  E − EF 
F (E ) = 1 + exp    ...(7)
  kT 
 Expanding the series
 E − EF 
F (E ) = exp−   ....(8)
 kT 
 EF − E 
F (E ) = exp  
 kT 
Then the density state of electron is


4 3 1  EF − E 

* 2
n= 3
(2me ) (E − Ec ) dE exp 
2

Ec
h  kT 
 
4 3  EF  1  −E 

* 2
n = 3 (2me ) exp  (E − E c ) 2
dE exp  kT  ...(9)
h  kT  Ec  

Put E-Ec= x E-Ec x

E= x+Ec Ec 0

 
dE =dx


4 3  EF  1  − x − Ec 

* 2
n = 3 (2me ) exp   ( x )2
exp   dx
h  kT  0  kT 


4 3  E F − Ec  1  −x 

* 2
n = 3 (2me ) exp   ( x ) 2
exp   dx...(10)
h  kT  0  kT 

1
4 * 2
3  E F − Ec  3  2

n = 3 (2me ) exp   x(kT )2

...(11)
h  kT  2
 3
 2 me*kT   E F − Ec 
2
n = 2 2  exp   ...(12)
 h   kT 
Calculation of density of holes
Let dp be the no of holes available between energy
interval E and E +dE in valence band

dp = Z (E)(1- F(E)) dE … (13)

Where Z (E) dE is the density of states in the energy
interval E and E+dE and (1-F(E)) is the probability of
existence of holes (since F(E) is the prob. Of electron
accompany)
 Fermi function
1
1 − F (E ) = 1 − ...(14)
 E − EF 
1 + exp  
 kT 
−1
  E − EF 
1 − F (E ) = 1 − 1 + exp    ...(15)
  kT 

For EF –E >> kT
Expanding the series
 E − EF 
1 − F (E ) = exp   ...(16)
 kT 
Then the density state of holes in the valence band

4 * 2
3 1
Z(E )dE = 3 (2mh ) E 2 dE...(17)
h
Energy E starts from top of valence band

4 * 2
3 1
Z(E )dE = 3 (2mh ) (Ev − E )2 dE...(18)
h

No. of holes available per unit volume is given by

Ev

p=  Z(E ){1 − F (E )}dE...(19)

−
 Ev
4 3 1  E − EF 
p =  3 (2mh ) (Ev − E ) dE exp 
* 2 2
 ...(20)
−
h  kT 
Ev
4 3  −EF  1 E 

* 2
p = 3 (2mh ) exp   (Ev − E ) exp   dE...(21)
2

h  kT  −  kT 

Put EV –E = x Ev-E x
E= Ev-x EV 0
dE =-dx - 

0
4 −
 F
3 E 1  Ev − x 

*
p = 3 (2mh ) exp  2
 (x) exp 
2
 (−dx)...(22)
h  kT    kT 
 
4 3 E
 v − E F 
1  −x 

*
p = 3 (2mh ) exp 
2
 (x) exp   dx...(23)
2

h  kT  0  kT 
This is a Gamma function

1
4 * 2
3  Ev − EF  3 
2

p = 3 (2mh ) exp   x(kT ) 2 ...(24)

2

h  kT 

3
 2 mh*kT   Ev − EF
2

p = 2 2  exp   ....(25)
 h   kT 
Intrinsic carrier concentration
In intrinsic semiconductor n=p

Therefore multiplying equation (12) and (25) we get

3
 2 kT   Ev − Ec 
( )
3
2
ni = np = 4  2  me*mh* 2
exp   ...(26)
 h   kT 

3
 2 kT   −E g 
( )
3
* * 2
= 4 2  me mh exp   ...(27)
 h   kT 
Where (Ec –Ev) = Eg is the forbidden energy gap.

3
 2 kT  2  −E g 
(m m )
3
* * 4
ni = 2  2  e h exp   ...(28)
 h   2kT 

Fermi level and its variation with temperature

3 3
 2 m kT 
* 2
 EF − Ec   2 m kT  *
 Ev − EF
2

2 e
2  exp   = 2  exp 
h
2  ..(29)
 h   kT   h   kT 
 3 3
* 2  E F − Ec   Ev − EF 
* 2
(m ) exp 
e  = (m ) exp h 
 kT   kT 
OR
3
 2EF   mh*   Ev + Ec 
2
exp   =  *  exp   .....(30)
 kT   me   kT 
Taking logarithms on both sides

2EF 3  mh   Ev + Ec
*

= log  *  +   ...(31)
kT 2  me   kT 
 3kT  mh   Ev + Ec
*

EF = log  *  +   ...(32)
4  me   2 
If we assume that

* *
m = m since log 1 =0
e h

 Ev + Ec 
EF =   .....(33)
 2 
Thus Fermi level is located half way between the valence
and conduction bands its position is independent of
temperature.
Since mh*  me*
EF is just above the middle and rises slightly with
increasing temperature as shown fig below
 Charge mobility and electrical conductivity

The electrical conductivity is given by

 = (nee + peh )...(34)

Where e and H are the mobility of electron and holes
respectively. Mobility is the velocity acquired by the electron or hole
under unit potential gradient.

Since n= p = ni

 = ni e(e + h )....(35)
 3
 2 kT  2  −E g 
( )
3
 = (e + h )2e  2  *
mm
e
*
h
4
exp   ....(36)
 h   2kT 
The electrical conductivity depends upon the negative exponential
of the forbidden energy gap between the valence and conduction
band and on the mobilities of both holes and electrons. The
mobilities are determined by the interaction of the electron or hole
with lattice wave or phonons.

 −E g 
 i = A exp   ...(37)
 2kT 
 Eg
l og  i = log A − ....(38)
2kT

A graph drawn between (1/T) and log  i

is shown in fig. From the graph we understand that conductivity

increases with temp

Band gap determination

 −E g 
 i = A exp   ....(39)
 2kT 
Therefore the resistivity of the intrinsic semiconductor

1  Eg 
i = exp   ....(40)
A  2kT 
Ri a 1  Eg 
= exp   (since = Ra/L)...(41)
L A  2kT 

L  Eg 
( Ri ) = aA exp  2kT  ....(42)
 
  Eg  L
Ri = c exp   where c= ...(43)
 2kT  aA
Taking logarithms on both sides

 Eg 
log Ri = log c +   ....(44)
 2kT 
From the above equation (44) we understand that by
measuring the resistance of intrinsic semiconductor at
different temperature, we can measure the forbidden energy
gap Eg. Fig shows the plot of a curve between (1/T) and log
Ri. The slop of the curve gives the value of ( Eg
/2k)
Determination of Band Gap
Hal effect : When a conductor (metal or semiconductor ) carrying current (I) is
placed in a magnetic field (B) perpendicular to this current, a potential
difference (electric field) is developed inside the conductor in a direction of
both current and magnetic field.

This phenomenon is known as Hall effect and the voltage thus generated is
called Hall voltage.

Hall effect in n-type semiconductor: Let us consider a n-type semiconducting

material in the dorm of rectangular slab. In such a material, the current flows in
X-direction, magnetic field B is applied in Z-direction. As a result, Hall voltage
is developed along Y direction as shown in fig.

The current flow is entirely due to the flow of electrons moving from right to
left along X-direction as shown in fig. When a magnetic field (B) is applied in Z-
direction, the electrons moving with velocity v will experience a downward
force.
Downward force experienced by the electron =Bev ………(1)
where e is the charge of electron

This downward force deflects the electrons in downward direction and therefore,
there is an accumulation of negatively charged electrons on the bottom face of the
slab as shown in fig.
This causes the bottom face to be more negative with respect to the top face.

EH = Bv

Therefore, a potential difference is developed between the top and the bottom of the
specimen. This potential difference causes an electric field EH called Hall field in
negative Y-direction. This electric field develops a force which is acting in the
upward direction on each electron.
Upward force acting on each electron =eEH …………..(2)

At equilibrium, the downward force Bev will balance the upward force eEH
 Bev = eEH

EH = Bv ………………..(3)
The current density (Jx) acting along the X-direction is related to the velocity v as
J x= −nev
Where n is the concentration of current carriers (electrons).

− Jx ………………………..(4)
v=
ne
Substituting equation (4) in equation (3), we have

− BJ x ……………………….(5)
EH =
ne
EH = RH J x B ……………………..(6)

Or
EH
RH =
JxB
1
RH = −
ne

RH is a constant and it is known as Hall coefficient.

The negative sign indicates that the electric field is developed in the negative
Y-direction.
Hall effect in P-type semiconductor:

Consider a rectangular slab of p-type semiconducting material and the current

flow in this case is entirely due to the flow of positive holes from left to right as
shown in fig.

The current flow is along X-direction and the magnetic field is applied in the Z-
direction. Due to applied magnetic field, the holes are accumulated in the bottom
of the slab and thus produce a potential difference.

Similar to N-type semiconductor, we can write

EH = RH J x B
where Hall coefficient (RH) is written as

1
RH = +
pe
where p is the concentration of current carriers (holes).

The positive sign indicates that the electrical field (Hall field) is developed in the
positive Y-direction.
Hall coefficient in terms of Hall Voltage: If t is the thickness of the sample and VH
the voltage developed (Hall voltage), then

VH = EH t ……………………………(8)

where EH is Hall field.

Substituting equation (6) in equation (8), we have

VH = RH J x Bt …………………………(9)

If b is the breadth of the sample, then

Area of the sample (A) = Breadth (b) x Thickness (t)
Ix I
Currentdensity , J x = = x ………………………..(10)
Areaofthesample( A) bt

Substituting equation (10) in equation (9) we have

RH I x Bt
VH =
bt
Or
RH I x B
VH =
b
VH b
Hallcoffic ient , RH =
IxB
MOBILITY OF CHARGE CARRIERS:
We know that Hall coefficient,

1
RH = −
ne
This expression correct only when the charge carriers are free from any type of
attractive forces in the energy band and they are moving with a constant drift
velocity v. However, this is not true in the case of semiconductors.

Considering the average speed, we can show that

1.18
RH = − for electrons
ne
1.18
Or ne = ne = − ……………………………. (1)
RH
1.18
and RH = for holes
pe
1.18
or pe = − ………………………………(2)
RH
Electrical conductivity of a n-type semiconductor

 e = nee
Where e is the mobility of electrons

Or e …………………………(3)
e =
ne
Substituting the eqn (1) in the eqn (3), we have

e
e =
1.18
−
RH
 e RH
Mobility of electron e = − ……………………(4)
1.18

Electrical conductivity of a p-type material,

 h = neh
h
Or h = ……………………………….(5)
pe
Substituting eqn (2) in (5) , we have
h
h =  h RH
−
1.18 Mobility of the hole h = −
RH 1.18
DETERMINATION OF HALL COEFFICIENT:
The experimental set up for the measurement of Hall – coefficient is shown in fig:

A semiconducting material is taken in the form of rectangular slab of thickness t

and breadth b. A suitable current Ix ampere is passed through this sample along
X – axis by connecting it to a battery.

This sample is placed in between two poles of an electromagnet such that the
magnetic field is applied along Z – axis. i,e ., Perpendicular to the plane of paper.

Due to Hall effect, Hall voltage (VH) is developed in the sample. This voltage is
measured by fixing two probes at the centres of the bottom and top faces of the
sample.

By measuring Hall voltage, Hall coefficient is determined from the formula

VH b
RH =
IxB

For Hall coefficient, carrier concentration and mobility can be determined

APPLICATIONS OF HALL EFFECT:

(i) Determination of Semi-conductors

For a n – type semiconductor, Hall coefficient is negative whereas for a p – type
semi-conductor it is positive. Thus, the sign of the Hall coefficient is used to
determine whether a given semiconductor is n – type or p – type.

(ii) Calculation of carrier concentration

By measuring Hall coefficient RH’ carrier concentration is obtained from the
Relation.

1
n=
eRH
(iii) Determination of mobility
We know that electrical conductivity,  = nee
e
 =
ne

or e =  e RH

Thus, by measuring electrical conductivity and Hall coefficient of a sample, the

mobility of charge carriers can be calculated
(iv) Magnetic field meter
The Hall voltage VH for a given current is proportional to B. Hence, VH measures
the magnetic field B.

(v) Hall effect multiplier

This instrument can give an output proportional to the product of two signals.
Thus, if current I is made proportional to one input and if B is proportional to the
second input, then Hall voltage VH is proportional to the product of two inputs.

IMPORTANCE OF HALL EFFECT:

The study of Hall effect gives the following important information.

1. It can be used to decide whether a material is a metal, semiconductor or an

insulator.
2. The sign of current carrying charges can be determined.

3. From the magnitude of Hall coefficient, the number of charge carriers per unit
volume can be calculated.

4. The mobility can be measured directly.