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Classification of Solids

 Key material for most electronic devices such as diodes,

transistors, FETs, LEDs, detectors etc

Metals Semiconductors Insulator

(Conductors) ρ ≈ 10-3 – 103 Ω cm ρ > 107 Ω cm
ρ ≈ 10-6 Ω cm
 A semiconductor, therefore, is a material that has a
conductivity level somewhere between the extremes of an
insulator and a conductor
 For metals, ρ increases with temperature (+ve temp. coeff.)
 For semiconductors, ρ decreases with temperature ( -ve temp.
S. Kal, IIT-Kharagpur 2
Atomic Structure – Silicon and Germanium

Atomic Structure: Covalent bonding of the

Germanium Silicon atom
S. Kal, IIT-Kharagpur

Atomic Structure and Energy Levels

Energy Levels : The more distant the electron from the

nucleus, the higher the energy state, and any electron that
has left its parent atom has a higher energy state than any
electron in the atomic structure.

Energy Bands : If we consider a large number of Si or Ge

atoms which gradually come closer to one another and
finally form a solid by arranging themselves in a regular
three – dimensional array ( called “crystal” ), the energy
levels no longer remains “discrete”. They become energy
“bands”. Each band really consists of a very large number
of discrete energy levels which are very closely spaced. So
these bands may be thought of as continuous.
S. Kal, IIT-Kharagpur

Energy bands in conductor, semiconductor and insulator
Energy Bands : These energy bands ( called allowed bands )
are separated by forbidden energy gaps. i.e. no electron can
have any energy value within forbidden bands. In a solid crystal,
energy bands, called valency band, originated from the shells
occupied by valence electrons in single atoms (3s, 3p for Si and
4s, 4p for Ge), may or may not be separated from another higher
energy band, called conduction band, which extends up to zero
electron energy corresponding to that outside the solid.

S. Kal, IIT-Kharagpur

Electrons and Holes in a Semiconductor
At low temperatures ( close to 0 K ), the valence band is
completely filled up with electrons and the conduction band is
perfectly empty. If temp is raised , the average thermal energy
increases. At T = 300 K ( room temp ), kT= 0.026 eV. [ k = 8.62 x
10-5 eV/K ] This is average energy. Some electrons will have
energies more than 0.026 eV, while some will have much less.
Those, which will have energies more than Eg, will enter the C.B.,
creating an equal number of vacancies or empty states in V.B.
These vacancies in V.B. may be treated as positively charged
particles, called “holes”, having the same quantity of positive
charge as an electron.
The electron in the C.B. and the holes in the V.B. are “free”,
because they may be excited to higher energies by a small
electric field or thermal energy. The electrons “move” from
higher electron energies to lower energy combine with holes or
fill up vacancies, subsequently creating new vacancies or holes.
These free charge carriers ( electron in C.B. and holes in V.B. )
carry electrical current.
S. Kal, IIT-Kharagpur
Metals , Insulators and Semiconductors
For metals, the C.B. and the V.B overlap each other ( Eg=0). So
the large no of valency band electrons ( ≈1022 per cm3) are
available for conduction. Metals are, therefore, very
conducting. Increasing temp., electrons face more obstacle to
their movement because of increased atomic vibrations.

For insulators, Eg >>> kT ( ~ 4 - 8 eV), very few electron-hole

pairs (EHPs) may be created by thermal process. Thus,
insulators or dielectrics are extremely poor conductors of

For semiconductors in pure, crystalline form, Eg lies in the

range 0.1 – 3.0 eV. Thus, appreciable number of EHPs are
created by thermal process. Increasing temperature causes
creation of more EHPs, hence resistivity falls. S. Kal, IIT-Kharagpur

Intrinsic Semiconductor
The number of electrons in C.B. or holes in V.B. per unit
volume in a pure semiconductor crystal is called intrinsic
carrier concentration.
Material Band Gap ( eV) Intrinsic conc.,300 K
Germanium 0.67 ~ 1013 per cm3
Silicon 1.1 ~ 1010 per cm3
GaAs 1.4 ~ 107 per cm3

Please note that the energy associated with each electron is

measured in electron volts ( eV). This is appropriate, as we know
W = QV
Q is the charge associated with an electron ( 1.6 x 10-19 Coulomb ).
Since the energy is also measured in Joules,
W = QV = (1.6 x 10-19 C) (1V) or, 1 eV = 1.6 X 10-19 J
S. Kal, IIT-Kharagpur

Extrinsic Semiconductors: (n- and p- type)
 A semiconductor material that has been subjected to the doping
process is called an extrinsic material.

 Impurities at a very low level ( 0.01 – 1000 p.p.m.) can alter the
band structure sufficiently to totally change the electrical
properties of the material

There are two class of extrinsic semiconductor materials of

importance to semiconductor device fabrication : n-type and p-

n-Type Extrinsic Semiconductor

Doping of Si and Ge by penta-valent impurity atoms like P, As,

Sb, etc. create excess unbound electrons in C.B. The penta-
valent impurity atoms introduce energy levels near the edge of
C.B. inside the band-gap.
S. Kal, IIT-Kharagpur

n-Type Extrinsic Semiconductor

C.B. (nearly empty) EC Majority carriers

Donor levels (ED) + + + + + + + + + + +


V.B. (nearly filled) EV

Minority carriers

Thus at room temp., almost all the impurity atoms donate their
loosely bound “excess” valence electrons to the C.B. As a
result these atoms become positively ionized but remain
immobile, while the donated electrons in the C.B. are “free”.
S. Kal, IIT-Kharagpur

Antimony and Boron Doped Extrinsic Semiconductor

Antimony impurity in n-type Boron impurity in p-type

material material
S. Kal, IIT-Kharagpur

p-Type Extrinsic Semiconductor
Doping of Si and Ge by trivalent impurity atoms like B, Al, Ga, etc.
create excess unbound holes in V.B. The trivalent impurity atoms
introduce energy levels near the edge of V.B. inside the band-gap.

Thus at room temp., shortage of electrons at the outer orbit of

dopant atoms will be filled from the V.B. host atoms and as a
result, vacancies (“holes”) are created in V.B. The dopant atoms
become negatively ionised and remain immobile, while the
excess holes in V.B. are “free”.
S. Kal, IIT-Kharagpur
Doped Semiconductor
Thus, in an extrinsic semiconductor, there will be a large no. of
majority carriers ( electrons in C.B. for n-type and holes in V.B. for
p-type) approximately equal to the no. of impurity atoms, and a
very few minority carriers ( holes in V.B. for n-type and electrons
in C.B. for p-type) produced by thermal excitation (intrinsic
process )
For lightly and moderately doped semiconductors ( up to ~ 10
p.p.m )
n . p = ni2

where, n = electron density in C.B., p = hole density in V.B.

ni = pi = intrinsic concentration = 1010 per cm3 for Si

For n-type Si, if ND = donor density = 1016 per cm3

tnen, n ≈ ND = 1016 per cm3
and p = ni2 /n = 1020 / 1016 = 104 per cm 3
S. Kal, IIT-Kharagpur

Conduction in Semiconductors
If an electric field, E is applied in a semiconductor, the electrons
move opposite to the field, while the holes move along the field

Thus the total current density due to electrons and holes is

J = Jn + Jp = q n vn + q p vp

Now, vn = µ n E and vp = µ pE

where µ n and µ p are electron and hole mobilities (cm2 / V-sec)

J = q ( n µn + p µp ) E = σ E

where σ is the electrical conductivity of the semiconductor.

Therefore, the resistivity, ρ is given by
ρ = 1/σ = 1 / [ q ( n µ n + p µ p ) ]
For Si, µ n = 1200 cm2 / V-sec, µ p = 500 cm2 / V-sec
S. Kal, IIT-Kharagpur