Semiconductor Materials

Dr. Adnan Daud Khan

Associate Professor

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Electronic Materials
• The goal of electronic materials is to generate and control
the flow of an electrical current.
• Electronic materials include:
• Conductors
• Insulators
• Semiconductors

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Conductors
• Conductors have low resistance which
allows electrical current flow i.e.,
material that easily conducts electrical
current.
• The best conductors are single-element
material (e.g copper, silver, gold,
aluminum).
• The atomic structure of good conductors
usually includes only one electron in
their outer shell.
• It is called a valence electron.
• It is easily striped from the atom, producing
current flow. Copper Atom
Insulators
• Insulators have high resistance which
suppresses electrical current flow i.e.,
material does not conduct electrical
current.
• Valence electron are tightly bound to the
atom – very few free electron.
• Good insulators include:
• Glass, ceramic, plastics, & wood
• Most insulators are compounds of several A good insulator has more
elements. than 4 electrons in the
valence band.
• It contains 5 to 8 electrons in the outer orbit.

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 Semiconductors
• Semiconductors are materials that
essentially can be conditioned to act as
good conductors, or good insulators, or
any thing in between.
• Common elements such as carbon,
silicon, and germanium are
semiconductors, which contains 4 valence
electrons. The main characteristic of a
• Silicon is the best and most widely used semiconductor element is that
it has four electrons in its outer
semiconductor. or valence orbit.

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Valence and Conduction bands
• Valence band:
• Valence band is a band, which consists of valence electrons i.e., the
outermost energy level where the valence electrons are residing is known as
valence band.
• Conduction band:
• Any band above the valence band is called conduction band.

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Energy band diagram
If electrons are present in the conduction
band then those electrons are called
conduction electrons or free electrons.

On the basis of this Energy

band diagram, we can
differentiate between
conductor, semiconductor
and insulator.

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 Distinction on the basis of energy band concept
Eg < 3 eV

• Require small amount

of energy.
• Without supplying
Eg > 3 eV energy, this material
will act as an insulator
Eg ≈ 0 eV
• The gap is
huge. • Here, the
• The electrons conduction and
will never valence bands
reach the are overlapping.
conduction • We really don’t
band, so they need any
always behave external energy
as an in this case.
insulator.

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Elements and compounds
• If the atomic number is increased or the
size of the atom increase then the
• Elements: bandgap reduces.
• Si, Ge etc • For example, if you have smaller atom,
then the electrons are tightly bound, so it
• Compounds: requires more energy to break them up
e.g., carbon, which has very high
• GaAs, InP, AlGaAs, InGaAsP etc bandgap, so it is an insulator.
• Group IV Elements:
Atomic number Bandgap Resistivity
Carbon (C) 6 5.3 eV 1014 Ωcm
Silicon (Si) 14 1.12 eV 103 Ωcm
Germanium (Ge) 32 0.67 eV 102 Ωcm
Tin (Sn) 50 0.08 eV 10-4 Ωcm
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Crystal
• When certain atoms combine to form a solid material, they arrange themselves in
a fixed pattern called a crystal.
• A crystal contains large number of atoms and all of them are arranged in a
periodic fashion i.e., the distance between each atom is fixed.

Crystal structure of a
single Si

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Covalent bonding
Covalent bonding – holding atoms together by sharing
1-3 Covalent Bonding
valence electrons

Sharing of To form Si crystal

valence electron
produce the
covalent bond

The atom within the crystal structure are

held together by covalent bonds, which
are created by the interaction of the
valence electrons of the atoms.
Types of Semiconductor
• Intrinsic Semiconductor
• Extrinsic semiconductor

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Intrinsic Semiconductor
• Intrinsic semiconductor is a pure semiconductor.
• For example, Si atom has got 4 electrons in the
outermost shell. When we have many Si atoms and
arrange them in a specific pattern like in a crystal,
covalent bonds (sharing of electrons) will be
formed.
• If you look at the Si as a whole, it has got 8
electrons. So it becomes stable. Here all the
electrons are involved in the bond formation.
• Here, we don’t have any free electrons to conduct
electricity.
• So this means that a pure semiconductor or
intrinsic semiconductor is an insulator because it
does not have any free electrons.

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Intrinsic Semiconductor
• But if we supply some external
energy i.e., increase the
temperature, then the bonds
will start breaking due to which
the electrons will become free
and this electron will be
available for conduction of
electricity.
• When the electron become free,
it will left a hole.

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 Now, look at the energy band diagram of intrinsic semiconductor.

If you do not change or increase the temperature,

then in this case the conduction band will be
empty and the valence band will have electrons.

Free electrons mean that some of the electrons will

jump from the valence band to the conduction band
due to which holes will be created in the valence
band.

So pure semiconductor will act as a conductor only

if you supply some external.

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In pure semiconductor, the number of electrons are equal to the
number of holes i.e.,

ni = ne = nh

The total current in an intrinsic semiconductor is the current due to

electrons and the current due to holes i.e.,

I = Ie + Ih

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 Electron and Hole Current

• When a voltage is applied across a piece of intrinsic silicon,

the thermally generated free electrons in the conduction
band, which are free to move randomly in the crystal
structure, are now easily attracted toward the positive end.
• This movement of free electrons is one type of current in a
semiconductor material and is called electron current.
• A valence electron can move into a nearby hole, with little
change in its energy level, thus leaving another hole where it
came from.
• Effectively the hole has moved from one place to another in
the crystal structure. This is called hold current.
Processes involved in an intrinsic SC
• Thermal generation:
• Here, the conduction electrons and holes are generated thermally when we supply some
thermal energy, the bonds broke as a result, the free electrons are emitted due to which
holes are created in the valence band. This mean, we are generating e-h pairs thermally.

Concentration of electrons in the

Ec conduction band is “n”
G
Ef
Concentration of hole in the valence
Ev
band is “p”
Electron in the valence band due to thermal
fluctuations will move to the conduction band and
will leave a hole in the valence band.
This is generation process.

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Recombination of electrons and holes:

The electron after releasing the energy will drop to the valence band again and recombine with the
hole.

Ec
G R
Ef
Ev

In equilibrium, rate of generation is equal to rate of recombination.

G=R

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• So intrinsic SC behaves like an insulator at absolute zero temperature
i.e., T=0K
• But at T > 0k, the thermally generated e-h pairs produce a current in
the semiconductor.
• The electron density in the conduction band is given by
   Ec  EF  
n  N c exp 
 kT 
where Nc is the effective density of states in the conduction band.
At room temperature (300k),
Nc for Silicon is 2.86x1019cm-3.
Nc for GaAs is 4.7x1017cm-3.

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EF is the fermi energy level.
Now, what is fermi energy level?
It is that energy level in which 50% probability of occupation (presence) by an electron
at any temperature.

So the occupation by electrons at any temperature

could be here
or could be here etc

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Fermi level of intrinsic SC
• In intrinsic SC, the number of electrons in the conduction band are equal to the number of holes
in the valence band.
• So the probability of electrons in the conduction (Pc(e)) is equal to the probability of holes in the
valence band (Pv(h)) i.e.,
Pc(e) = Pv(h)
• Hence, the fermi level will be in the middle of valence and conduction band i.e., it will lie at the
bandgap energy as shown in the figure.

Eg
Fermi level

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So, again, lets see the equation

   Ec  EF  
n  N c exp 
 kT 

Nc is the effective density of states in the conduction band.

EF is the fermi energy level.

Ec is the conduction band energy

k is the Boltzmann constant. Its value is 1.38 × 10-23 m2 kg s-2 K-1
T is the temperature in kelvin

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Similarly, the hole density “p” in the valence band can be written as

   EF  Ev  
p  N v exp 
 kT 

Nv is the effective density of states in the valence band.

At room temperature,
Nv for Si is 2.66x1019cm-3.
Nv for GaAs is 7.0x1018cm-3.

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As for intrinsic SC, the number of electrons in the conduction band is
equal to the number of holes in the valence band.
n=p
Put the expressions of both n and p here.

 EF  Ec   Ev  EF 
N c exp    N v exp  
 kT   kT 

Now, solve this expression for the Fermi energy level.

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  E  Ec 
exp  F
 kT   N v
2𝐸 − 𝐸 − 𝐸 𝑁
ln exp = ln
𝑘𝑇 𝑁
 E  EF  N c
exp  v 2𝐸 − 𝐸 − 𝐸 𝑁
 kT 
= ln
𝑘𝑇 𝑁
𝑁
 E  Ec  Ev  EF  N v 2𝐸 − 𝐸 − 𝐸 = 𝑘𝑇ln
exp  F   𝑁
 kT  Nc 𝑁
2𝐸 = 𝐸 + 𝐸 + 𝑘𝑇ln
 2 E  Ec  Ev  N v 𝑁
exp  F   𝐸 +𝐸 𝑘𝑇 𝑁
 kT  Nc 𝐸 =
2
+
2
ln
𝑁
take ln on both sides

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 𝐸 +𝐸 𝑘𝑇 𝑁
𝐸 = + ln
2 2 𝑁

This expression contains two terms.

The first term is temperature independent and is the average value between the conduction band edge and
valence band edge.

The 2nd term is a linear function of temperature.

Here, the 2nd term is much smaller than the 1st term.
At room temperature, the 2nd term will almost be negligible.

So, we will only left with the first term, which indicates that the fermi level is approximately in the middle
for intrinsic semiconductor.
𝐸 +𝐸
𝐸 ≈
2
Ec
EF
Ev 27
Since, in intrinsic SC, n = p = ni
where ni is the intrinsic carrier concentration or intrinsic carrier density.

So if we multiply n and p i.e.,

n x p = ni2

This is called Mass action law.

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 n x p = ni2
Put the expressions of n and p in the above equation.

   Ec  EF      EF  Ev  
n  N c exp  p  N v exp 
kT   kT 


   Ec  EF      EF  Ev  
N c exp   N exp  ni 2

 kT  v 
 kT 
  E  EF  EF  Ev 
N c N v exp  c   ni 2

 kT 
  Ec  Ev 
N c N v exp    ni 2

 kT 
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 As Eg  Ec  Ev
or Eg  -  Ev  Ec 
or  Eg  Ev  Ec
So the above equation becomes

  Eg 
N c N v exp    ni 2

 kT 
  Eg 
ni  N c N v exp 
 kT 

The larger the bandgap, the smaller the intrinsic carrier concentration.

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Extrinsic semiconductor
• Semiconductor with small amount of suitable impurity added to it.
• The purpose of adding impurity is that, it conducts electricity without
external energy.
• So extrinsic semiconductor will always be in conducting state.
• Impurity is added in extremely small amount say a few parts per
million i.e., we add 1 impurity out of 106 atoms.
• Impurity is added to increase conductivity.

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Doping
• The process of adding impurity is known as doping. The impurities are
called dopants.
• Therefore, extrinsic semiconductor is also known as Doped SC.
• Doping increase conductivity and reduce resistivity.
• Since, Si crystal contains thousand of Si atoms arranged in a periodic
fashion.
• By adding impurity to the crystal should not effect the arrangement of the
Si atoms.
• We will add impurity by removing one of the Si atoms.
• The size of the impurity always matters. For instance, if the size of the
impurity is much larger or smaller then the Si atom, then it will disturb the
arrangement of all the Si atoms in a crystal.

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• Doping agents are:
• Pentavalent (group-5):
• Trivalent (Group-3):

Trivalent Impurities: Pentavalent Impurites:

• Aluminum (Al) • Phosphorus (P)
• Gallium (Ga) • Arsenic (As)
• Boron (B) • Antimony (Sb)
• Indium (In) • Bismuth (Bi)

• If we doped a Semiconductor by group-5 impurity then this type of SC is known

as n-type.
• If we doped a Semiconductor by group-3 impurity then this type of SC is known
as p-type.
• So n-type and p-type are the types of extrinsic SC.
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 P-type SC
• Trivalent impurities are added to Si or Ge, the result is an increase of
free electrons.
• For example, we want to add Al so Si crystal.
• The electronic configuration of Al is: 1S2, 2S2, 2P6, 3S2, 3P1.

+4 +4 +4 Outermost shell has 3 electrons.

Si crystal +4 +4 +4

+4 +4 +4

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Now, we will add Al to Si crystal.
Al has a shortage of one electron to complete the
+4 +4 +4 bond. So this means that it has a hole.

One electron from the neighboring atom jumps

to this hole or you can say Al atom snatches
one electron from the neighboring atom to fill
+4 +3 +4 this hole.

The shifted electron will also create a hole.

e-
+4 +4 +4 So another electron will come to fill this hole.

In this way, the hole is moving in the lattice,

which will create a current.

So, in this case, we have additional holes

because the impurities gives rise to hole here.

Here, the impurities are known as acceptor

impurities.
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 Since, Al has taken the electron, so it will become a –ive ion.

+4 +4 +4

+4 +3
- +4

+4 +4 +4

Since, Al is involved in the covalent bonding, therefore it cannot move. It will become immobile i.e., fixed at
one place due to bond formation on all the sides.
All this happen at room temperature i.e., holes are generated at room temperature.

If we provide small amount of thermal energy or increase the temperature, then the same e-h pair generation will
takes place just like in intrinsic semiconductor.
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So, in p-type SC, we have extra holes i.e., some of the holes will come
from adding impurity and some will arise from providing thermal energy,
therefore, if we consider a large Si crystal then the number of holes will
be greater then the number of electrons.

nh >> ne

Here, the majority carriers are holes and the minority carriers are
electrons.

So in this case, the conduction mainly happens due to holes.

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 Energy band diagram of p-type SC
In p-type, the probability of occupation of electrons in the conduction (Pc(e)) are less than the probability of holes
in the valence band (Pv(h)) i.e.,
Pc(e) < Pv(h)
or the number of holes are much greater then the number of electrons.

So in this case, the fermi level will move down form the middle position i.e., it will be closed to valence band.

Concentration of electrons in the

Ec conduction band is “n”

Intrinsic fermi Ei
level
Ef Concentration of hole in the valence
Ev
band is “p”

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N-type SC
• Here, we add pentavalent (group 5) impurities or donor impurities to
SC materials. For example P, As etc.
• Let us add phosphorus atom to Si crystal.
• The electronic configuration of P atom is: 1S2, 2S2, 2P6, 3S2, 3P3.

+4 +4 +4 Outermost shell has 5 electrons.

Si crystal +4 +4 +4

+4 +4 +4
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Now, we will add P to Si crystal.

Here, 4 electrons of P will form covalent bond with Si

+4 +4 +4 atoms.

But one extra electron will be left.

This extra electron is loosely bound to the nucleus.

+4 +5 +4
If we apply a small amount of energy, the 1st electron
to come out would be this extra electron.
+4 +4 +4 So the amount of energy, which is required by this
extra electron is even lesser than what we need incase
of intrinsic SC.
So we don’t even need to increase the temperature. At
room temperature itself, this extra electron will come
out and will help in the conduction.

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Since, in this process, the extra electron will be donated to nearby atom and will result in a +ive charge on P atom.

So, in n-type SC, a +ive ion is produced which is immobile because all the electrons are participated in bond
formation.

+4 +4 +4

+
+4 +5 +4

+4 +4 +4

Since, the conduction begin at room temperature, however, by increasing the temperature, thermal generation
will also takes place i.e., more extra electrons will come out, and more e-h pairs will be generated (as in case of
intrinsic SC).

So, in this case, we will observe that the number of electrons are much greater than the number of holes.

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 ne >> nh

So, the majority carriers are electrons and minority carriers are holes.

In this case, the conduction mainly happens due to electrons.

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 Energy band diagram of n-type SC
In p-type, the probability of occupation of electrons in the conduction (Pc(e)) are more than the probability of holes
in the valence band (Pv(h)) i.e.,
Pc(e) > Pv(h)
or the number of holes are much smaller then the number of electrons.

So in this case, the fermi level will move up form the middle position i.e., it will be closed to conduction band.

Concentration of electrons in the

Ef Ec conduction band is “n”

Intrinsic fermi Ei
level
Concentration of hole in the valence
Ev
band is “p”

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 Law of mass action

The law of mass action states that the product of number of electrons in the
conduction band and the number of holes in the valence band is constant at a fixed
temperature and is independent of amount of donor and acceptor impurity added.

Mathematically it is represented as
np = ni2 = constant

where ni is the intrinsic carrier concentration

n is number of electrons in conduction band
p is number of holes in valence band

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 Law of mass action for extrinsic semiconductor

The law of mass action is applied for both intrinsic and extrinsic semiconductors. For extrinsic
semiconductor the law of mass action states that the product of majority carriers and minority carriers is
constant at fixed temperature and is independent of amount of donor and acceptor impurity added.

The law of mass action for n-type semiconductor is mathematically written as

nn pn = ni2 = constant

Where nn= number of electrons in n-type semiconductor

pn = number of holes in n-type semiconductor

The electrons are the majority carriers and holes are the minority carriers in n-type semiconductor.

In n-type semiconductor, as the number of electrons (majority) in the conduction band increases the
number of holes (minority) in the valence band decreases.
Therefore, the product of electrons (majority) and holes (minority) remains constant at fixed temperature.

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 Law of mass action for p-type semiconductor

The law of mass action for p-type semiconductor is mathematically written as

pp np = ni2 = constant

Where pp = number of holes in p-type semiconductor

np = number of electrons in p-type semiconductor

The holes are the majority carriers and electrons are the minority carriers in p-type semiconductor.

In p-type semiconductor, as the number of holes (majority) in the valence band increases the number of
electrons in the conduction band (minority) decreases. Therefore, the product of holes (majority) and
electrons (minority) remains constant at fixed temperature.

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Ionization
• Ionized particles are the particles that carry a +ive or –ive charge.
• This is due to the loss or gain of electrons.
• Losing an electron will cause a particle to become more positively
charged, while gaining an electron will cause a particle to become
more negatively charged.

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Complete ionization
The condition when all donor atoms are positively charged by giving up their donor
electrons and all acceptor atoms are negatively charged by accepting electrons.

p ≈ Na

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For donors n = Nd (where Nd is the donor concentration) Similarly for acceptors: p = Na (where Na is the
acceptor concentration)
   Ec  EF  
As n  N c exp 
kT     EF  Ev  
 As p  N v exp 
 kT 
So put n = Nd in the above equation.
 Nv 
EF  Ev  kT ln  
   Ec  EF    Na 
Nd  N c exp 
 kT 
 E  EF  N c Here, for higher acceptor concentration,
exp  c  the fermi level will move closer to the
 kT  Nd
top of the valence band.
take ln
Ec  EF N 
 ln  c 
kT  Nd  Form this equation, we can see that the higher
the donor concentration, the smaller the
N 
Ec  EF  kT ln  c  energy difference (Ec - Ef) will be i.e., the fermi
 Nd  level will move closer to the bottom of the
conduction band.
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 It is useful to express electrons and hole densities in terms of the intrinsic carrier concentration ni and the intrinsic
fermi level Ei.

So consider n-type SC.

   Ec  EF  
n  N c exp 
 kT 

Add and subtract Ei in the equation

   Ec  EF  Ei   Ei      Ec  Ei  
n  N c exp  ni  N c exp 
 kT  where 
 kT 
   Ec  Ei     EF  Ei  
n  N c exp    exp  
 kT   kT 
  E  Ei  
n  ni exp  F 
 kT 
  E  EF  
Similarly p  ni exp  i 
 kT 
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 What will happen if we add donor and acceptor impurities simultaneously?

The impurity that is present in greater concentration determines the type of SC.

If only donor impurities are added than under complete ionization condition, n = Nd
And if acceptor impurities are added than p = Na

If both the impurities are added than we will check which impurity concentration is more. For example:

If donor impurity concentration is more compared to acceptor than the SC will act as n-type. In this case,
the concentrations can be written as

n = Nd – Na if Nd > Na

or Nd < Na than the SC will be p-type i.e., p = Na - Nd

If both types of impurities are equal than the SC will become intrinsic and under complete ionization
condition, we can write

n + Na = p + Nd if Na = Nd

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