Chapter 4.

The Semiconductor
in Equilibrium
Charge Carriers in Semiconductors
Dopant Atoms and Energy Levels
The Extrinsic Semiconductor
Statistics of Donors and Acceptors
Charge Neutrality
Position of Fermi Energy Level
Young-Hwan Lee
http://cafe.daum.net/lyh201circuit
E-mail : lyh201@hanyang.ac.kr
Mobile : 010-7178-1884
Hanyang University fall 2007 2
4.1 Charge Carriers in Semiconductors
Thermal equilibrium ; no external forces (electric fields,
magnetic fields, or temperature gradients)
Dopant atoms: the electrical properties of a semiconductor can
be altered in desirable ways by adding controlled amounts of
specific impurity atoms.
Current density in semiconductor
J = (drift current density: J
dri
) + (diffusion current density: J
dif
)
Electrical properties (current) : electron andhole
band
Density of states function andFermi-Diracdistribution
function
4.1.1 Equilibrium Distribution of Electrons and Holes
Hanyang University fall 2007 3
4.1 Charge Carriers in Semiconductors
) ( ) ( ) ( E f E g E n
F c
=
The distribution of holes as a function of energy in V.B
function y probabilit Dirac - Fermi : ) (E f
F
band conduction in the states quantum of density : ) (E g
c
The distribution of electrons as a function of energy in C.B.
[ ] ) ( 1 ) ( ) ( E f E g E p
F v
=
band valence in the states quantum of density : ) (E g
v
An ideal intrinsic semiconductor is a pure semiconductor
with no impurity atoms and no lattice defects in the crystal.
At T = 0 K,
all energy states in the valence band : filled with electrons
all energy states in the conduction band : empty of electrons
Hanyang University fall 2007 4
4.1 Charge Carriers in Semiconductors
Density of states functions, Fermi-Diracprobability function, and areas representing
electron and hole concentrations for the case when E
F
is near the midgapenergy
Hanyang University fall 2007 5
4.1.2 The n
0
and p
0
Equations
If E E
F
>>kT, then Fermi-DiracfunctionBoltzmannapproximation
N
c
:
(effective density of states function
in the conduction band)

=
T k
E E
N n
B
F c
c
) (
exp
0
The thermal-equilibrium concentration of electrons in the conduction band

+
=
T k
E E
T k
E E
E f
B
F
B
F
F
) (
exp
) (
exp 1
1
) (
2 / 3
2
*
2
2

=
h
T k m
N
B n
c

dE
T k
E E
E E
h
m
B
F
E
c
n
c

) (
exp
) 2 ( 4
3
2 3 *

= dE E f E g n
F c
) ( ) (
0
k
B
: 1.38066210
23
[J /K]
Boltzmannconstant
Hanyang University fall 2007 6
4.1.2 The n
0
and p
0
Equations
Example 4.1
Calculate the probability that a state in the conduction band isoccupied
by an electron and the thermal-equilibrium electron concentration in
silicon at T =300 K. Confer table 4.1. E
c
E
F
=0.25 eV.
T k
E E
T k
E E
E f
B
F
B
F
c F
)] ( [
exp
) (
exp 1
1
) (

+
=
5
10 43 . 6
0259 . 0
25 . 0
exp ) (

=

=
c F
E f
( )
5 19
0
10 43 . 6 ) 10 8 . 2 (
) (
exp

=

=
kT
E E
N n
F c
c
3 15
0
cm 10 8 . 1

= n
Hanyang University fall 2007 7
4.1.2 The n
0
and p
0
Equations
Thermal-equilibrium concentration of holes in the valence band

=
kT
E E
N p
v F
v
) (
exp
0
N
v
:
(effective density of states function
in the valence band)
Table 4.1 Effective density of states function and effective mass values (at T =300 K)
0.37 0.55 6.0 x 10
18
1.04 x 10
19
Ge
0.48 0.067 7.0 x 10
18
4.7 x 10
17
GaAs
0.56 1.08 1.04 x 10
19
2.8 x 10
19
Si
m
p
*
/m
0
m
n
*
/m
0
N
v
[cm
3
] N
c
[cm
3
]
2 / 3
2
*
2
2

=
h
kT m
N
p
v

k : 1.38066210
23
[J /K]
Boltzmannconstant
Hanyang University fall 2007 8
4.1.2 The n
0
and p
0
Equations
Example 4.2
Calculate the thermal-equilibrium hole concentration in silicon at
T =400 K. Fermi energy is 0.27 eV above the valence band
energy. Confer table 4.1.
3 19
2 / 3
19
cm 10 60 . 1
300
400
) 10 04 . 1 (

=

=
v
N
eV 03453 . 0
300
400
0259 . 0 =

= kT

=
03453 . 0
27 . 0
exp ) 10 6 . 1 (
) (
exp
19
0
kT
E E
N p
v F
v
3 15
0
cm 10 43 . 6

= p
Hanyang University fall 2007 9
4.1.3 IntrinsicCarrier Concentration
For an intrinsic semiconductor with no impurity atoms
p
0
= n
0
= n
i
, p
0
n
0
= n
i
2

= =
T k
E E
N n n
B
Fi c
c i
) (
exp
0

= = =
T k
E E
N n p p
B
v Fi
v i i
) (
exp
0

=
T k
E E
T k
E E
N N n
B
v Fi
B
Fi c
v c i
) (
exp
) (
exp
2

=
T k
E
N N
T k
E E
N N n
B
g
v c
B
v c
v c i
exp exp
2
Hanyang University fall 2007 10
4.1.3 IntrinsicCarrier Concentration
n
i
=2.4x10
13
cm
3
Ge
n
i
=1.8x10
6
cm
3
GaAs
n
i
=1.5x10
10
cm
3
Si
n
i

(Fermi energy )
Table 4.2Commonly accepted
values of n
i
at T =300 K
The intrinsic carrier concentration
of Ge, Si, and GaAsas a function
of temperature.
Hanyang University fall 2007 11
Example 4.3
Calculate the intrinsic carrier concentration in gallium arsenide at
T =300 K and T =450 K. The bandgapenergy of gallium
arsenide is 1.42 eV and does not vary with temperature over this
range. Confer table 4.1.
eV 03885 . 0
300
450
0259 . 0 =

= kT
12 18 17 2
10 09 . 5
0259 . 0
42 . 1
exp ) 10 0 . 7 )( 10 7 . 4 ( =

=
i
n
3 6
cm 10 26 . 2

=
i
n
at T = 300 K
at T = 450 K
21
3
18 17 2
10 48 . 1
03885 . 0
42 . 1
exp
300
450
) 10 0 . 7 )( 10 7 . 4 ( =

=
i
n
3 10
cm 10 85 . 3

=
i
n
4.1.3 IntrinsicCarrier Concentration
Hanyang University fall 2007 12
4.1.4 The Intrinsic Fermi-level Position
: E
midgap
= (E
c
+E
v
)/2
Intrinsic Semi.
E
Fi
density of states functionband .
If m
p
*
=m
n
*
, then E
Fi
: the center of the bandgap
m
p
*
<m
n
*
, then E
Fi
: slightly below the center of the bandgap
m
p
*
>m
n
*
, then E
Fi
: slightly above the center of the bandgap

kT
E E
N
kT
E E
N
v Fi
v
Fi c
c
) (
exp
) (
exp

+ + =
c
v
v c Fi
N
N
kT E E E ln
2
1
) (
2
1

+ + =
*
*
ln
4
3
) (
2
1
n
p
v c Fi
m
m
kT E E E
* *
when
p n
m m =
* *
when
p n
m m
Hanyang University fall 2007 13
4.2 Dopant Atoms and Energy Levels
Practical semiconductor devicesspecific dopant(or impurity)
atomsextrinsic(or impurity) semiconductor
.
impurity atoms<substitutional impurity>: dopant atoms
for Si, n-type: P, As, Sbetc. group V elements (donor atom)
p-type: B, Al, Ga, In etc. group III elements (acceptor atom)
extrinsic semiconductor: impurity atomsionization
carriers .
intrinsic semiconductor: electrons (in valence band)
conduction bandtransition
electron-hole pair carriers .
p
0
= n
0
Carrier generation in semiconductor
Hanyang University fall 2007 14
4.2.1 Qualitative Description
for n-type semiconductor (n
0
> p
0
)
The intrinsic silicon lattice.
The silicon lattice doped with a
phosphorusatom.
The discrete donor energy state.
The effect of a donor state being ionized.
Hanyang University fall 2007 15
4.2.1 Qualitative Description
for p-type semiconductor (n
0
< p
0
)
The ionization of the boronatom.
The discrete acceptor energy state.
The effect of an acceptor state being ionized.
The silicon lattice doped
with a boronatom.
Hanyang University fall 2007 16
4.2.2 Ionization Energy
Bohr Modeldonor
Bohr a
0

for Si, =11.7, m

*
/m
0
=0.26, r
1
/a
0
=45, r
1
=23.9
: Donor donor atombound .
n n
r
v m
r
e
2 *
2
2
4
=
o
h
A 53 . 0
4
2
0
2
0
0
= =
e m
a

h n v r m
n
=
*
2 *
2 2
4
e m
n
r
n
h
=

=
*
0
2
0
m
m
n
a
r
r
n

ionization energy : extrinsic semiconductorimpurity atoms

ionization energy
Hanyang University fall 2007 17
4.2.2 Ionization Energy
Boron
Phosphrous
0.0102 0.06 Aluminum
Ge Si
0.0104 0.045
Acceptors
0.0127 0.05 Arsenic
0.012 0.045
Donors
Ionization energy [eV]
Impurity
Table 4.3 Impurity ionization
energies in silicon and
germanium
Ionization Energyof hydrogen : E = 13.6 eV, Si : 25.8 meV <<E
g
V T E + = Total energy of orbital electron
Kinetic energy
2 2
4 *
2 *
) 4 ( ) ( 2 2
1
h n
e m
v m T = =
Potential energy
2 2
4 * 2
) 4 ( ) ( 4 h n
e m
r
e
V
n

=
2 2
4 *
) 4 ( ) ( 2 h n
e m
E

=
Hanyang University fall 2007 18
4.2.3 Group III-V Semiconductors
0.0404 Germanium
0.0345 Silicon
0.0307 Zinc
0.0061 Germanium
0.058 Tellurium
Beryllium
Selenium
0.0347 Cadium
0.028
Acceptors
0.058 Silicon
0.0059
Donors
Ionization energy [eV] Impurity
Table 4.4 Impurity ionization energies in gallium arsenide
Amphoteric:
GaAsSi, Ge
Hanyang University fall 2007 19
4.3 The Extrinsic Semiconductor
Extrinsic semi. :
electron, hole
intrinsic semi.
.
(carrier)
For n-type semi. E
F
>E
Fi
then n
0
> n
i
, p
0
< n
i
n
0
> p
0
For p-type semi. E
F
<E
Fi
then p
0
> n
i
, n
0
< n
i
p
0
> n
0

=
kT
E E
N n
F c
c
) (
exp
0

=
T k
E E
N p
B
v F
v
) (
exp
0

=
T k
E E
n n
B
Fi F
i
exp
0

=
T k
E E
n p
B
Fi F
i
) (
exp
0
Hanyang University fall 2007 20
4.3.2 The n
0
p
0
Product
The n
0
p
0
product is always a constant for a
given semiconductor material at a given
temperature.
The values of n
0
and p
0
are not necessarily
equal.
, extrinsic semiconductor
: The Boltzmannapproximation is valid.
n
0
p
0
product
2
0 0 i
n p n =

=
kT
E E
n n
Fi F
i
exp
0

=
T k
E E
n p
B
Fi F
i
) (
exp
0
4.3.3 Fermi-Dirac Integral

=
T k
E
N N p n
B
g
v c
exp
0 0
Hanyang University fall 2007 21
4.3.4 Degenerate and NondegenerageSemiconductors
at low impurity concentration : local energy statesEg,
impurity atoms()
, carrierMaxwell-Boltzmannstatistics.
at higher impurity concentration : impurity atom
.
electronwave functionsoverlap. (neighboring impurity
center) local energy level
impurity bands .
impurity atomsionization energy.
Hanyang University fall 2007 22
4.3.4 Degenerate and NondegenerageSemiconductors
high doping three major effects (degenerate semiconductors)
(1) The Fermi level is located within the allowed bands(C.B. or V.B.)
themselves. impurity atomsionization energy
insignificant.
(2) The impurity states broaden into bands.
(3) The intrinsic band gap is reduced. (so-called band-edge tailing)
impurity atoms(atomic spacing
), carriersFermi-Diracstatistics.
Hanyang University fall 2007 23
4.4 Statistics of Donors and Acceptors
N
i
g
i

spin
1/g
i

n
d
donor level
N
d
+
donor
p
a
acceptor level
N
a

acceptor
4.4.1 Probability Function

+
=
a a
a F
a
a
N N
kT
E E
g
N
p
exp
1
1

+
=
kT
E E
N
n
F d
d
d
exp
2
1
1
+
=
d d d
N N n

=
a a a
N N p
Hanyang University fall 2007 24
4.4.2 Complete Ionization and Freeze-Out
If (E
d
E
F
) >>k
B
T, then the Boltzmannapproximationis also valid.

=
kT
E E
N n
F c
c
) (
exp
0

+
=
+
kT
E E
N
N
n n
n
d c
d
c
d
d
) (
exp
2
1
1
0

kT
E E
N
kT
E E
N
n
F d
d
F d
d
d
exp 2
exp
2
1
E
c
E
d
: donor electronionization energy
The ratio of electrons in the donor state to the total number of
electrons in the conduction band plus donor state
Hanyang University fall 2007 25
4.4.2 Complete Ionization and Freeze-Out
At T =300 K : Complete ionization
10
16
cm
3
doping
At T =0 K : Freeze-Out
0 = =
a d
p n
0 or = =
+
d d d
N N n
0 exp =

kT
E E
F d

+
=
kT
E E
N
n
F d
d
d
exp
2
1
1
0 =

e
E
F
>E
d
fig 4.13
Energy-band diagrams showing complete
ionization (a) donor states and (b) acceptor states
Hanyang University fall 2007 26
4.4.2 Complete Ionization and Freeze-Out
Example 4.7
Determine the fraction of total electrons still in the donor
states at T = 300 K. Phosphorus doping in silicon, for T =
300 K, at a concentration of N
d
= 10
16
cm
3
.

+
=
+
0259 . 0
045 . 0
exp
) 10 ( 2
10 8 . 2
1
1
16
19
0 d
d
n n
n
% 41 . 0 0041 . 0 = =
Hanyang University fall 2007 27
4.5 Charge Neutrality
DonorAcceptor impurity atoms .
Device .
electronhole
In thermal equilibrium, the semiconductor crystal is electrically
neutral. The net charge density is zero.
The charge-neutrality condition is used to determine the thermal-
equilibrium electron and hole concentration as a function of the
impurity doping concentration.
An n-type compensated semiconductor ; N
d
>N
a
A p-type compensated semiconductor ; N
a
>N
d
A completely compensated semiconductor ; N
a
=N
d
4.5.1 Compensated Semiconductors
Hanyang University fall 2007 28
4.5.2 Equilibrium Electron and Hole Concentrations
n
0
+ N
a

= p
0
+ N
d
+
n
0
+ (N
a
p
a
) = p
0
+ (N
d
n
d
)
Complete ionization : n
d
= p
a
= 0
n
0
+ N
a
= p
0
+ N
d
4.5.2 Equilibrium Electron and Hole Concentrations
2
2
0
2 2
i
d a d a
n
N N N N
p +

=
0
2
0
2
0 0
/ n n p n p n
i i
= =
2
2
0
2 2
i
a d a d
n
N N N N
n +

=
Charge Neutrality Condition
density of negative charge = density of positive charge (fig. 4.14)
n-type (N
d
>N
a
) p-type (N
d
<N
a
)
Hanyang University fall 2007 29
4.5.2 Equilibrium Electron and Hole Concentrations
Determine the thermal equilibrium electron and hole
concentration for a given doping concentration.
N
d
=10
16
cm
-3
, N
a
=0, n
i
=1.5 x 10
10
cm
-3
.
Example 4.9
n
0
10
16
cm
3
, p
0
2.25 x 10
4
cm
3
3 4
16
2 10
0
2
0
cm 10 25 . 2
10
) 10 5 . 1 (

=

= =
n
n
p
i
2
2
0
2 2
i
a d a d
n
N N N N
n +

=
3 16 2 10
2
16 16
cm 10 ) 10 5 . 1 (
2
0 10
2
0 10

+

=
Hanyang University fall 2007 30
E
V
E
C
E
Fi
Intrinsic Semi.
Extrinsic Semi.
E
d
E
V
E
Fi
E
C
4.5.2 Equilibrium Electron and Hole Concentrations
A few donor electrons annihilate
some intrinsic holes.
Cf) Fig 4.16 Electron concentration versus temperature
showing the three regions.
Hanyang University fall 2007 31
Example 4.10
Calculate the thermal-equilibrium electron and hole concentration
in a germanium sample for a given doping density.
N
d
= 5x10
13
cm
-3
, N
a
=0, n
i
=2.4 x 10
13
cm
-3
.
2
2
0
2 2
i
a d a d
n
N N N N
n +

=
4.5.2 Equilibrium Electron and Hole Concentrations
n
0
6 x10
13
cm
-3
, p
0
9.6 x 10
12
cm
-3
3 12
13
2 13
0
2
0
cm 10 6 . 9
10 6
) 10 4 . 2 (

=

= =
n
n
p
i
3 13 2 13
2
13 13
cm 10 6 ) 10 4 . 2 (
2
0 10 5
2
0 10 5

+

+

=
Hanyang University fall 2007 32
4.6 Position of Fermi Energy Level
for n-type semi. N
d
>>n
i
, then n
0
N
d
Compensated semi. : N
d
N
d
N
a

=
i
B Fi F
n
n
T k E E
0
ln

=
d
C
B F C
N
N
T k E E ln

=
0
ln
n
N
T k E E
C
B F C
The position of Fermi level as a function of the doping
concentrations and as a function of temperature.
4.6.1 Mathematical Derivation

=
kT
E E
N n
F c
c
) (
exp
0

=
T k
E E
n n
B
Fi F
i
exp
0
Hanyang University fall 2007 33
4.6 Position of Fermi Energy Level
Determine the required donor impurity concentration to obtain a
specified Fermi energy. Silicon at T =300 K contains an acceptor
impurity concentration of N
a
=10
16
cm
3
. Silicon is n-type and the
Fermi energy is 0.2 eV below the conduction band edge.
Example 4.13

=
a d
C
B F C
N N
N
T k E E ln

=
T k
E E
N N N
B
F C
C a d
) (
exp
3 16 19
cm 10 24 . 1
0259 . 0
2 . 0
exp 10 8 . 2

=

=
a d
N N
3 16 16
cm 10 24 . 2 10 24 . 1

= + =
a d
N N
Hanyang University fall 2007 34
4.6.1 Mathematical Derivation
For a p-type semiconductor,
N
a
>>n
i
, thenp
0
N
a
Compensated semiconductor : N
a
N
a
N
d

=
i
B F Fi
n
p
T k E E
0
ln

=
kT
E E
N p
v F
v
) (
exp
0

=
0
ln
p
N
T k E E
v
B v F

=
a
v
B v F
N
N
T k E E ln

=
T k
E E
n p
B
Fi F
i
) (
exp
0
n-type
E
F
E
V
E
C
E
Fi
p-type
E
F
E
V
E
C
E
Fi
Hanyang University fall 2007 35
4.6.2 Variation of E
F
with Doping Concentration & Temp.
n
i
(intrinsic carrier concentration) : strong function of
temperature
E
F
(Fermi energy level): function of temperature
At high temperature : E
F
E
Fi
, intrinsic semiconductor
.
At the very low temperature (Freeze-out):
.
Boltzmannapproximation is no longer valid.
n-type : E
F
> E
d
p-type : E
F
< E
a
Hanyang University fall 2007 36
4.6.2 Variation of E
F
with Doping Concentration & Temp.
Position of Fermi level as a function
of temperature for various doping
concentrations.
Position of Fermi level as a function
of donor concentration (n type) and
acceptor concentration (p type).
Hanyang University fall 2007 37
4.6.2 Variation of E
F
with Doping Concentration & Temp.
Example 4.14
Table 4.3 Boronionization energy : 0.045 eV
Si E
Fi
band gap
4.68 E
Fi
E
F
=E
g
/2 +E
v
E
F
=E
g
/2 (E
a
E
v
) (E
F
E
a
)
=1.12 eV/2 0.045 eV 3*(1/0.0259 eV)
=k
B
T ln(N
a
/n
i
) =0.437 eV
N
a
=n
i
exp (0.437/0.0259)
=1.5 x 10
10
exp (0.437/0.0259) 3.2 x 10
17
cm
-3
Determine the Fermi level and the maximum doping at which the
Boltzmannapproximation is still valid. Consider p-type Si, at T =
300 K, doped with boron. , E
F
E
a
=3k
B
T Boltzmann
.
Hanyang University fall 2007 38
4.6.3 Relevance of the Fermi Energy
:
In thermal-equilibrium, theFermi
energy level is a constant
throughout a system.
(a) Electrons are more energetic in Mo, so
they tunnel to the surface of Pt.
(b) Equilibrium is reached when the Fermi
levels are lined up.
When two metals are brought together,
there is a contact potential V.