CHAPTER 4

SEMICONDUCTORS AND
NANOTECHNOLOGY
 

 Semiconductor
- limits of two types of measurements:
(a) electrical resistance – ( 1 to Ω at the room temperature )
(b) the energy gap ( 1 to 2 eV )
Elemental Semiconductors
- Pure Silicon and Germanium ( the best examples of elemental
semiconductors )
- Classification (based on the electrical conductivity)
(1) Intrinsic semiconductors – very small amounts of impurities
into an extremely pure semiconductor
(2) Extrinsic semiconductors – lightly and moderately impurities
into an pure semiconductors
 (1) Intrinsic semiconductors
- pure Germanium (Ge) and silicon (Si) exhibit semiconducting
behaviour at above 0°K
- Forbidden energy gaps, Eg for Ge and Si = 1.0 and 2.0 eV
- Two approaches (the semiconducting behaviour of pure Ge & Si)

(a) Atomic lattice model

- A pair of electrons is shared in

the covalent bond between
each pair of silicon atoms.
 - At above 0K, some of the electrons are
thermally released from these bonds and
are free to wander through the crystal.
(conduction electrons)
- These electrons provide a mechanism for
electrical conductivity in the solid.
- The vacant position left behind in the
covalent bonds – positive hole or hole

- Successive jumps of valence electrons into

empty positions produce an opposite net
motion of the hole in the direction of the
electric field.
- Hole (a + charge) that the entity moves in
the field and in the opposite direction of
the net shift of the valence bond electrons

 The total conductivity of Si is due to the transport of both electrons and holes.

σ= ne( + ) a = the electron and hole mobilities

n = the total number of charge carriers n = = for intrinsic semiconductor
(b) Intrinsic semiconductance of pure elemental silicon in terms of
Band Theory

At 0°K, all the valence electrons of silicon atoms lie in a completely filled VB, while the
next higher conduction band is empty and therefore, the Si crystal behaves as an insulator.
At temperature above 0°K, thermal agitation will lift a predictable number of electrons
into higher conduction band, depending on the distribution of energy of allowed status
and the temperature.
The number of electrons promoted to conduction band in the silicon crystal for semi-
conduction
The thermally excited free electrons move in the conduction band, while an equal number
of ‘holes’ created in the VB moves in the opposite direction under the applied field.
 
The total semiconductivity of pure intrinsic silicon is due to both
electrons and holes at temperature above 0°K and the number of
electrons and holes increases with temperature.
n = exp ( ̶ E/2KT)
 
 Electrical Conductivity of an Intrinsic Semiconductor
- the “electrons and holes” contribute to the total conductivity of
an intrinsic semiconductor
- the conductivity of a semiconductor
σ= ne( + )
σ = conductivity ( )
n = density of charge carriers (concentration of e)
the number of charge carriers ( )
e = the charge carrier ( 1.602 x C )
μ = the mobility of charge carriers ( / V s (or) )

Ω = V s/C
 
Q. 1 The electron and hole mobilities of silicon are 1900 and
500 respectively. Calculate the number of charge
carriers for silicon at 290°K.
( e = 1.602 x C , σ = 5 x )

= 1900 = 500
e = 1.602 x C , σ=5x
σ= ne( + )
n=
=
= 1.302 x
 
Q. 2. The electron and hole mobilities of germanium at 298 K are
3350 and 1855 respectively. Calculate the number of
charge carriers, given the conductivity of Ge = 2.08 x
and electronic charge = 1.602 x C )
2.45 x

Q. 3. Calculate the electrical conductivity of Ge, if the conduction

electron density is 2 x , the electron and the hole
mobilities are 3600 and 1700 respectively.
Given: e = 1.602 x C
1.69 x
(2) Extrinsic semiconductors
- chemical impurities and lattice defects determine the electrical
conductivity of semiconductors, which exhibit a conductivity that
increases rapidly with temperature over certain ranges.
- all the pure elemental semiconductors (Si & Ge) – intrinsic type
- the addition of impurities atoms (dopants) – altered the
conductivity of intrinsic type.

 
Host lattice Impurities

p – type semiconductor Si & Ge B, Ga, In & Al (trivalent)

n – type semiconductor Si & Ge P, As,& Sb (pentavalent)

 n – type Extrinsic Semiconductor
- If majority of charge carriers are electrons in an extrinsic type
semiconductor ( n- type )
- If “pentavalent atoms” are doped into an elemental Si or Ge
semiconductor, the dopants create a large number of electrons as
charge carriers. (n-type semiconductors)

(a) Atomic lattice Model

-  Silicon atom in its crystal lattice is hybridized and
forms 4 covalent bonds with the neighbouring Si
atoms and crystallize in diamond cubic structure .
- When dopant atoms such as As is added into the
lattice, they substitute few of the normal sites.
- As is pentavalent and forms 4 covalent bonds with the
surrounding 4 atoms of Si; its 5th valence electron
remains loosely bound to the donor atom itself.
- The presence of the excess electron on the donor
atom causes electronic defects in the host lattice
- They are available for conduction as free
electrons and enhances the conductivity of the
host Si lattice.
- As a result of As doping, majority of charge
carriers obtained are electrons and provide a
mechanism for electrical conductivity in solids.

  n-type semiconductor, majority of charge

In
carriers are electrons, the number of electrons
exceeds the number of holes ( > )
The conductivity of n-type semiconductor is
σ= e
= the density of the added donor impurity
(dopant) atoms
=
 
(b) Band Model

 According to the band model,

the substitution of Si atoms by
donor As atoms (excess electron
in the non-bonded molecular
orbital , NBMO) results in the
creation of a new energy levels
( donor energy levels) below the
conduction band = 0.01 eV

the energy difference between the donor and conduction band energy level – narrow
(0.01 – 0.05 eV) , the donor electrons can be easily to the conduction band. (n-type
semiconductor)
 The conductivity of n-type semiconductor is
 σ= e
 = the density of the added donor impurity (dopant) atoms
 = = the energy gap between the conduction band and the
donor energy level
 p – type Extrinsic Semiconductor
If majority of charge carriers are holes in an extrinsic type
semiconductor ( p- type )
When host Si or Ge lattice is doped with trivalent impurities
(B,Ga,In , etc), the majority of the charge carriers are holes.( p-type)

(a) Atomic lattice Model

 - Silicon atom in its crystal lattice is hybridized

and forms 4 covalent bonds with the
neighbouring Si atoms and crystallize in
diamond cubic structure .
- The addition of trivalent dopants (Group III)
such as B, Ga,In produce a number of holes in
the semiconductor.
- These trivalent impurities - acceptors ( the
holes created by them can accept electrons
from the lattice)
 
- All the three valence electrons of the
aceeptor boron forms 3 covalent bonds with
the surrounding Si atom in the host crystal
lattice (resulting in the forming +ve charge
(hole) in Si )
- These holes created by the impurity
acceptor atoms in the lattice Si, accounts for
the conductivity in p-type semiconductor.

- During the conduction process, a hole travels to an adjacent atom by acquiring an

electron and re-establishing a new covalent bond, by breaking an existing covalent
bond in the adjacent silicon atom and create bond in the adjacent silicon atom and
creating a new ‘ hole’ at the site.
 The conductivity of p-type semiconductor is
 σ= e
 = the density of the acceptor atoms or holes
 = mobility of holes
(b) Band Model
-  Si in its crystalline lattice - s
hybridized and forms 4 covalent
bonds with the neighbouring Si
atoms.
- When trivalent B atoms
substitute tetravalent Si atoms of
the host Si lattice, a +ve charge(a
hole) is left behind
uncompensated at the B atom
site.
- 3 valence electrons of B atom
overlaps with 3 s orbitals of Si.
-  A deficiency of electron (+ve charge) is created.
- The formation of 3 covalent bonds between B and Si atoms results in the formation
of the conduction band (ABMO) and the valence band (BMO) energy levels and both
are separated by narrow (1.1 eV).
- A new acceptor energy level is created little above the VB due to the uncompensated
+ve charge at the B atom site (NBMO, non-bonded molecular orbital)
- The energy difference between the acceptor energy level and VB is extremely small
(0.01 – 0.05 eV) and with little thermal energy, electrons from VB can be easily
promoted to the acceptor energy level and leaves behind holes in the VB.
- Holes can moved in the applied field and exhibit p-type semiconductor.
Acceptor Impurity = N
 EFFECT
  OF TEMPERATURE ON n- OR p-TYPE EXTRINSIC ELEMENT
SEMICONDUCTORS
the semi-conductivity of doped materials - σ= ne
σ is dependent on : - the density of the charge carriers, n
- the mobility of charge carriers,
Both factors are dependent on temperature.
(a) Effect of temperature on the mobility of charge carriers, μ
- the mobility of electrons and holes is influenced by scattering.
- the chief source of scattering ina semiconductor are photons and
ionized impurity atoms (donors or acceptors)
- at low temperature, μ in a semiconductor varies .
- at high temperature, the converse holds.
- ionic scattering (due to dopants) tends to dominate in extrinsic
semiconductors at low temperature and photon scattering at high
temperature.
(b)  Effect of temperature on carrier density and conductivity
- the carrier density (n) of the semiconductor is sensitive to
temperature (conduction electrons and holes are provided by
thermal excitation) n = exp ( ̶ E/2KT)
- For Ge based extrinsic materials, the energy gap for intrinsic
conduction = 0.72 eV and upper limit for extrinsic conduction is 100°C
- For Si based extrinsic materials, the gap is 1.1 eV and extrinsic
conduction up to 200°C possible.
 Non-Elemental Semiconductors
- A host of non-elementals too exhibit semiconductivity above 0K
( non-elemental or compound semmiconductors)
- Classification – 1. Stoichiometric semiconductors
2. Non-stoichiometric semiconductors
1. Stoichiometric semiconductors
- stoichiometric intermetallic compounds such as GaAs, GaP, InSb,
CdTe, CdSe are synthesised by combining the elements of (group
IIIand V )or (group II and VI) in 1:1 ratio, they are stoichiometric
semiconductors.
- the crystal lattice structures of these stoichiometric intermetallic
resemble the crystal structure lattice of pure Si and Ge.
( 4 covalent bonds with 4 neighbouring elements and crystallise in
diamond structure)
 
- the mechanism of electrical conductivity – similar to intrinsic
semiconductivity of pure Si or Ge crystal but these intemetallics have
different forbidden energy , , depending on the nature of
constituents and values ranging from 0.5 eV to 2.3 ev
- these compounds - extensive application in electronics because of
their wide range of values
- these compounds can also be doped to get n-type or p-type
extrinsic semiconductors .
 2. Non-stoichiometric Semiconductors
- many oxides of metals, especially transition metal oxides (3d-
transition metal oxide), are non-stoichiometric semiconductors at
temperature above 0K that show a wide variety of electrical
properties because of variable oxidation states of metal ions and
defect lattice structures.
- metal oxides, non-stoichiometric showing either excess or
deficient metal ions, compared to what one would expect from the
chemical formula.
- the types of imperfections or lattice defects present in ionic solids
rise to two types of semiconductivity in materials
(i) n-type and (ii) p-type semiconductors.
 (i) non-stoichiometric p-type semiconductor
- a cation deficient lattice – p-type semiconductivity in ionic solids
eg. FeO
FeO is a p-type non-stoichiometric semiconductor because of
‘cation deficient’ lattice structure above 0°C.
In FeO lattice, few cation sites are vacant due to missing of Fe2+
ions, the excess (-)ve charges of anions of lattice are compensated by
the neighbouring Fe2+ ions acquiring Fe3+ state.
Since Fe3+ ion is deficient of one electron with respect to Fe2+ ion
in the lattice of FeO can be considered as a ‘hole’.
The mechanism of conduction in such materials are due to
hopping of holes between equivalent Fe2+ sites of the FeO lattice
under the applied field.
 
(ii) non-stoichiometric n-type semiconductor
- Non-stoichiometric ionic solids having either oxygen vacant or
cation interstitial lattices because the charge carriers are electrons
- Eg . ZnO
-ZnO is non-stoichiometric n-type semiconductor due to the
excess of ions in the lattice od ZnO.
- In ZnO, lattice defects occur with few ion occupying interstitial
sites of the lattice, and simultaneously, two electrons occupies in the
interstitial position to balance the excess +ve charge of the lattice.
- in this ion excess lattice, the electrons trapped at the interstitial
sites are available for conduction under the applied field.
This provides a mechanism for n-type semiconduction in ZnO lattice.
PREPARATION OF PURE GERMANIUM SEMICONDUCTORS BY
FRACTIONAL DISTILLATION METHOD

  layer of HCl is kept

A  
Heated in
over Ge Cgas Sent to
 
Ge  
Ge
(liquid) (vapor)
To remove Fractionati
impurities like As ng column

Treated  
Reduced in
with water atmosphere Pure Ge
 Pure Ge
GeO2
  (used as a
semiconductor)
Production of Solar grade Silicon from Quartz
Production of MG-Si from quartz
- The silica is reduced through a reaction with carbon in the
form of coal, charcoal and heating to 1500-2000°C in an
electrode arc furnace.
SiO2 + C → Si + CO2
- Liquid Si collects in the bottom of the furnace and is drained and
cooled.
- The resulting Si is metallurgical grade silicon (MG-Si) and is 98%
pure Si.

- A small amount of MG-Si is further refined for the semiconductor

industry.
Production of Polycrystalline Si from MG-Si
- Powdered MG-Si is reacted with anhydrous HCl at 300°C in a
fluidized bed reactor to form SiHCl3.
Si + 3HCl → SiHCl3 + H2
- Impurities such as Fe, Al, and B react to form their halides.
(FeCl3, AlCl3, BCl3)

- SiHCl3 has a low boiling point of 31.8°C and distillation is

used to purify the SiHCl3 form the impurity halides. The
resulting SiHCl3 has electrically active impurities(Al, P, B,
Fe, Cu or Au) of less than 1 ppba.

- The pure SiHCl3 is reacted with hydrogen at 1100°C

for ~ 200-300 hours to produce a very pure form of silicon.
SiHCl3 + H2 → Si + 3HCl
- The reaction takes place inside large vacuum chambers and
the silicon is deposited onto thin polysilicon rods to produce
high-purity polysilicon rods of diameter 150-200 mm. The
process is referred to as the Siemens process.
- Silicon produced from this and similar process is called
polycrytalline silicon (impurity levels of 1ppba and less)
Physical Methods
- In zone melting, the first silicon purification method to be
widely used industrially, rods of metallurgical grade silicon

was heated to melt at one end.

- The heater is slowly moved down the length of the rod,
keeping a small length of the rod molten as the silicon is
cooled and resolidified behind it.
- Most of the impurities tend to remain in the molten region
rather than resolidify, when the process was complete, most
of the impurities in the rod had been moved into the end that
was the last to be melted.
- This end was cut off and discarded, and the process repeated
if it still higher purity was desired.
(i) Single –Crystal Silicon
(a) Czochralski process
- A seed of single-crystal Si is dipped into a crucible on
molten silicon and withdrawn slowly, pulling a crystal single
crystal as the silicon crystallizes on the seed.
(b) Float-Zone process
- The float zone process produces purer crystals than the
Czochralski method, because they are not contaminated by
the crucible used in growing Czochralski crystals.
- In float zone process, a silicon rod is set atop a seed crystal
and then lowered through an electromagnetic coil.
- The coil’s magnetic field induces an electric field in the rod,
heating and melting the interface between the rod and the
seed.
- Single-crystal silicon forms at the interface, growing upward
as the coils are slowly raised.
Methods of doping of n-type semiconductor
- The most common method is to coat the top of a layer of
silicon with phosphorous and then heat the surface.
This allows the P atoms to diffuse into Si. The temperature
is then lowered so that the rate of diffusion drops to zero.
- Other methods of introducing P into Si include gaseous
diffusion, a liquid dopant spray-on process and a technique
in which P ions are driven precisely into the surface of the
silicon.
Doping of Boron – p-type silicon semiconductor
- n-type silicon cannot form the electric field by itself; it’s also
necessary to have some silicon altered to have the opposite electrical
properties.
- Boron is introduced during the silicon processing, where silicon is
purified for use in PV devices.
Doping of Boron – p-type silicon semiconductor
- n-type silicon cannot form the electric field by itself; it’s also
necessary to have some silicon altered to have the opposite electrical
properties.
- Boron which has three valence electrons, is used for doping p-type
silicon.
- Boron is introduced during the silicon processing, where silicon is
purified for use in PV devices.
- When a boron atom assumes a position in the crystal lattice formerly
occupied by a silicon atom, there is a bond missing an electron (an
extra hole) that is relatively free to move around the crystal.