Properties of

Semiconductors
Diamond
In the diamond structure, the
carbon atoms are arranged
on an fcc-type lattice with a
total of 16 electrons per
primitive cell.

The valence band and 7 lower bands are full, leaving no
electrons in the conduction band.
Diamond
Electrons may be
thermally activated to
jump a gap. At room
temperature, k
B
T is only
0.026 eV. To jump the
energy gap, the
electron requires very
high temperatures. So,
diamond is an excellent
insulator.
= 10
18
O-m
Graphite
= 9 O-m
Silicon
Silicon has the diamond
structure.
There are 14 electrons per
primitive cell.
Gap is only 1.12 eV, however.
Now there is a small (but finite) chance for a few
electrons to be thermally excited from valence band to
conduction band.
Silicon
eV 12 . 1 }
Effective Mass Revisited
An electron moving in the solid under the
influence of the crystal potential is
subjected to an electric field.
We expect an external field to accelerate
the electron, increasing E and k and
change the electrons state.

Effective Mass Revisited
dt
dx
dx
dV
e
dt
dV
e
dt
d
eV
= =
=
c
c
and
dk
d
g
v
c

1
=
g
v
dx
dV
e
dt
dk
dk
d
=
c
dx
dV
e k
dt
d
g
v
dx
dV
e
dt
dk
g
v
=
=

eE k
dt
d
=
Effective Mass Revisited
dt
dk
dk
d
dk
d
dk
d
dt
d
dt
dv
a
g
|
.
|

\
|
=
|
.
|

\
|
= =
c c

1 1
|
.
|

\
|
|
|
.
|

\
|
=
|
.
|

\
|
k
dt
d
dk
d
dt
dk
dk
d

2
2
2 2
2
1 1 c c
eE = F
e
1
m
1
2
2
2
e
1

|
|
.
|

\
|
=
dk
d
m
c

Effective Mass Revisited

This relates the curvature of the band to the effective
mass.
One can show that a free electron band gives an effective
mass equal to the rest mass of an electron.
Electrons in a crystal are accelerated in response to an
external force just as though they were free electrons with
effective mass m
e
.
Usually , m
e
< m
0
.


Effective Mass Revisited
Effective Mass Revisited
Material Electron Effective Mass Hole Effective Mass
Si (4.2 K) 1.08 0.56
Ge 0.555 0.37
GaAs 0.067 0.45
InSb 0.013 0.60
ZnO 0.,19 1.21
ZnSe 0.17 1.44
Group IV
Groups III-IV
Groups II-VI
in multiples of the free electron mass
m
0
= 9.11 10
31
kg
Experimental Measurement

Traditionally effective masses were measured using cyclotron
resonance, a method in which microwave absorption of a
semiconductor immersed in a magnetic field goes through a
sharp peak when the microwave frequency equals the cyclotron
frequency.



In recent years effective masses have more commonly been
determined through measurement of band structures using
techniques such as angle-resolved photoemission or, most
directly, the de Haas-van Alphen effect.

Effective masses can also be estimated using the coefficient of
the linear term in the low-temperature electronic specific heat at
constant volume C
v
. The specific heat depends on the effective
mass through the density of states at the Fermi level and as such
is a measure of degeneracy as well as band curvature.
Electrons & Holes
In a semiconductor, there are two charge carriers:
Electrons (conduction band)
negative mass
negative charge
Holes (valence band)
positive mass,
positive charge
Electrons & Holes
For the electrons occupying the vacant
states,



(Negative!) and the electrons will move in
same direction as electric field (wrong
way!)
0
1
2
2
2
<
|
|
.
|

\
|
dk
d c

Carrier Concentration
To calculate the carrier concentrations in energy bands we
need to know the following parameters:
The distribution of energy states or levels as a function of
energy within the energy band, D(c).
The probability of each of these states being occupied by
an electron, f(c).

c
( ) ( ) n f D d
c
c c c

=
}
| |
1 ( ) ( )
v
p f D d
c
c c c

=
}
A band is shown for a one-dimensional crystal. The
square represents an initially empty state in an otherwise
filled band. When an electric field is applied, the states
represented by arrows successsively become empty as
electrons make transitions.
The band is completely filled except for a state marked by
a square. Except for the electron represented as a circle,
each electron can be paired with another, so the sum of
their crystal momentum vanishes. The total crystal
momentum for the band and the crystal momentum of the
hole are both k.
The empty state and the unpaired electron for two times
are shown when an electric field is applied. The change in
momentum is in the direction of the field.
Conduction Band Carrier
Concentration
0
( ) ( ) n f D d
c
c c c

=
=
}
For c >> c
F
, the Boltzmann distribution approximates the F-D
distribution:
T
B
k
F c
T
B
k
c
T
B
k
F
T
B
k
F
e e
e
e
f
/ ) ( / ) (
/ ) (
/ ) (

1
1
) (
c c c c
c c
c c
c

=
~
+
=
3/ 2
e
2 3
2 ( ) 1
( )
2
m dN
D
dE
c
c c
t
| |
= =
|
\ .
which is valid for the tail end of the distribution.
( )
/
( ) /
0
( )
c B
c F B
k T
k T
n e D e d
c c
c c
c
c c

=
=
}
2 / 3
2
e
2
2 |
.
|

\
|
=
t
T k m
N
B
C
( ) T k
C
B c F
e N n
/ c c
=
Conduction Band Carrier Concentration
Conduction Band
Carrier Concentration
Valence Band Carrier
Concentration
The hole distribution is related to the electron distribution,
since a hole is the absence of an electron.


( ) ( )
( )
) as long (as
1
1
1
1
1 1
/
/ /
T k e
e e
f f
B F
T
B
k
F
T
B
k
F
T
B
k
F
e h
>> ~
+
=
+
= =

c c
c c
c c c c
The holes near the top of the valence band behave like
particles with effective mass m
h
; and the density of states is


3/ 2
2 2
2 1
( )
2
h
v
m
D c c c
t
| |
=
|
\ .
| |
( )
3/ 2
/
2
1 ( ) ( ) 2
2
v
v F B
k T
h B
m k T
p f D d e
c
c c
c c c
t

| |
= =
|
\ .
}
Equilibrium Relation
Multiply n and p together:



The product is constant at a given temperature.
It is also independent of any impurity concentration at a given
temperature. This is because any impurity that adds electrons,
necessarily fills holes.
This is important in practice, since we could reduce the total
carrier concentration n + p in an impure crystal via the
controlled introduction of suitable impurities such reduction
is called compensation.
( )
( ) T
B
k
g
e h
B
e m m
T k
np
/
3/2
3
2

2
4
c
t

|
.
|

\
|
=

Intrinsic Semiconductors
i
n p n = =
( ) ( )
v F F c
v
c
B
T
B
k
F v
v
T
B
k
c F
c
N
N
T k
e N e N
c c c c
c c c c
+ =
|
|
.
|

\
|

=

ln
/ /
|
|
.
|

\
|

+
=
v
c
B
v c
F
N
N
T k ln
2
1
2
c c
c
c
F

c
c

c
v

Extrinsic Semiconductors
Extrinsic semiconductors: we can add impurities to
make a material semiconducting (or to change the
properties of the gap).
There are 2 types of extrinsic semiconductors:
p-type and n-type
These are materials which have mostly hole carriers
(p) or electron carriers (n).
These give you ways of modifying the band gap
energies (important for electronics, detectors, etc).
Extrinsic Semiconductors: n type
Add a small amount of phosporus (P:
3s
2
3p
3
) to Silicon (Si: 3s
2
3p
2
)
(generally, a group V element to a
group IV host) P replaces a Si atom
and it donates an electron to the
conduction band (P is called the donor
atom). The periodic potential is
disrupted and we get a localized energy
level, c
D
.

This is an n-type semiconductor more electrons around that
can be mobile; and the Fermi energy is closer to the
conduction band.
Extrinsic Semiconductors: n type
Phosphorus provides an extra electron.
c
C
c
D
= 45 meV
So, its easy for the donor electrons to enter
the conduction band at room temperature.

This means that at room temperature n ~ N
D
.
This is called complete ionization (only true if n
i

<< N
D
). Therefore, by doping Si crystal with
phosphorus, we increase the free electron
concentration.
At low temperature, these extra electrons get
trapped at the donor sites (no longer very mobile)
- the dopant is frozen out.
Next suppose Si atom is replaced with Boron (B: 2s
2
2p) to Silicon
(Si: 3s
2
3p
2
). Again, we have a perturbed lattice and
a localized E-level created.
Boron is missing an electron and accepts an
electron from valence band, creating a hole.
Therefore doping with B increases hole
concentration. We call this p-type doping,
the electron concentration n is reduced.
c
F
moves closer to c
V
.
Extrinsic Semiconductors: p type
c
F

c
c

c
v

c
A

Extrinsic Semiconductors
Extrinsic Semiconductors
Boron in Silicon
Mass Action Law
Valid for both intrinsic and extrinsic semiconductors.

It is important in devices to control n and p
concentrations and to suppress the influence of the
intrinsic concentration.

These equations are important in establishing upper
limits in semiconductor operating temperature.

We generally require n
i
<< (minimum doping density)
and, practically, this means we need doping
concentrations above 10
14
cm
3
.
Semiconductors