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EE-606: Solid State Devices

Lecture 11: Equilibrium Statistics
Muhammad Ashraful Alam
alam@purdue.edu

Alam ECE-606 S09 1

Outline

1) Law of mass-action & intrinsic concentration

2) Statistics of donors and acceptor levels
3) Conclusion

Reference: Vol. 6, Ch. 4 (pages 110-120)

Alam ECE-606 S09 2

Fermi-Level for Intrinsic Semiconductors

n= p= ni
− β Eg
n = N C NV e
2
i
EF
− β Eg 2
ni = N C NV e
EF ≡ Ei

n=
p ⇒ NC e
− β ( Ec − Ei )
NV e ( v
=
+ β E − Ei ) E
3
EG 1 NV
=
Ei + ln
2 2β NC 2
k
Alam ECE-606 S09 3
However …

Intrinsic concentration too small ..

We need to do something to
increase carrier concentration or
conductivity of semiconductors

This is done by doping.

Alam ECE-606 S09 4

Looking ahead: Carrier-Density w/Doping

A bulk material must be charge neutral over all …

∫
 
+ −
p − n + N D − N A dV =0

Further if the material is spatially homogenous

p − n + N D+ − N A− =0

ND NA
NV e −( EF − EV ) / kBT − N C e −( EC − EF ) / kBT + ( EF − ED ) / k B T
− ( E A − EF ) / k B T
=
0
1 + 2e 1 + 4e

Let us see how the formula come about …

Alam ECE-606 S09 5
Outline

1) Law of mass-action and intrinsic concentration

2) Statistics of donor and acceptor levels
3) Conclusion

Alam ECE-606 S09 6

Characteristics of Donor Atoms

r0

(D)

ET

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Localized vs. Delocalized States

2N states/per-band (with spin)

2N-2 states/per-band (with spin)

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 Statistics of Donor Levels

e −( Ei − Ni EF ) / kBT e −( Ei − Ni EF ) / kBT
=Pi ≡
∑e −( Ei − Ni EF ) / k BT

i
Z

u/d Ei Ni Pi
0/ 0 0 0 1/ Z
( Ei − EF )
−
k BT
1/ 0 1 1 e Z
( Ei − EF )
−
k BT
0/1 1 1 e Z

1/1 x x x Coulomb interaction

forbids this configuration

Alam ECE-606 S09 9

 Statistics of Donor Levels
u/d Ei Ni Pi
0/ 0 0 0 1/ Z
( Ei − EF )
−
k BT
0/1 1 1 e Z
( Ei − EF )
−
k BT
1/ 0 1 1 e Z

Prob. that the donor

= f 00 =
P00 1/ Z
=
1
is empty (charged) P00 + P01 + P10 1 / Z + 2e −( E − E ) / k T / Z 1 + 2e( E − E ) / k T
i F B F i B

Prob. that the donor 1 1

is filled with at least 1 − f 00 =−
1 =
one electron (neutral)
1 + 2e( EF − Ei ) / kBT 1
1 + e( Ei − EF ) / kBT
2
Note the extra factor ….
Alam ECE-606 S09 10
 Coulomb Exclusion for Band Electrons?

−( Ei − Ni EF ) / k BT −( Ei − Ni EF ) / k BT
E=4 e e
=Pi ≡
E=2
E=0
∑e
i
−( Ei − Ni EF ) / k BT
Z

state Ei Ni Pi
Ei 0 0 0 1/ Z
( Ei − EF )
−
kB T
1 1 1 e Z

Alam ECE-606 S09 11

Localized vs. Band Electrons

E6 ← 12π/Lx Two electrons (even with

E5 ← 10π/Lx opposite spin) can not
E4 ← 8π/Lx be at the same position
E3 ← 6π/Lx and same energy because
E2 ← 4π/Lx of electrostatic repulsion
E1 ← 2π/Lx

Lx
Band electrons (with
E3’ ← 6π/(Lx/2) opposite spin) need not
E2’ ← 4π/(Lx/2) be at the same position,
so they can share occupy
E1’ ← 2p/(Lx/2) same energy level.

When we divide space by a factor of 2, the

Lx/2 Lx/2 number of states (e.g. 6 here) does not change.
12
Acceptor Atoms

State [1] …. Hole present … N-1 charges

State [0] … Hole filled …. N charges

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 Statistics of Acceptor Levels in Si and Ge
1. Each atom contributes 2 states (up & down spin)
EC to a band, therefore a band has 2N states.

2. Every time a host atom is replaced by a impurity

from lh atom, 2 states are disappear per a band and
from hh appear as localized states (sort of).
EV
3. Therefore an acceptor atom close to hh and lh
bands removes four states from those bands.

4. Because of Coulomb interaction only 1 hole can

seat in these 4 states: the states are
0000, 0001, 0010, 0100, 1000.

5. One now uses Pi to compute the occupation of

acceptors.
14
 Number and Energy Considerations …

0000 1000 0100 0010 0001 4N-4 States

In HH/LH bands

1) [0000] is the charged state as it has N electrons, but N-1 protons.

2) Single hole configuration [0001] is uncharged, as we have N-1
electrons, and N-1 protons … same is true for [0010], [0100], [1000]
states.
3) Going from [0000] to [0001] states, the number of electrons goes
down by 1 (Ni=-1).
4) Going from [0000] to [0001] states energy goes down by –EA,
because one electron is no longer occupying the high energy level at
EA.
Alam ECE-606 S09 15
Statistics of Acceptor Levels

0000 1000 0100 0010 0001

−( 0 − 0 xEF ) / k BT
e 1
P0000 ≡
∑ e
i
−( Ei − Ni EF ) / k BT
Z Steps 3 & 4

e −( − EA −( −1 )EF ) / kBT e( EA − EF ) / kBT

P= P= P= P= ≡
∑e −( Ei − Ni EF ) / k BT
0001 0010 0100 1000
Z
i

P0000 1
f 0000 = ( E A − EF ) / k B T
P1000 + P0100 + P0010 + P0001 1 + 4e

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 Filled and empty Donor/Acceptor Levels

2N-2 states
1
00 10 01 N empty
≡=
N D+ N=
D f 00 ND
D
1 + 2e( EF − Ei ) / kBT

0000 1000 0100 0010 0001 1

N filled
N A [ f 0000 ] = N A
≡N = −
A A
1 + 4e( EA − EF ) / kBT
4N-4 States
In HH/LH bands
(Two holes can not seat together)

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Distributions are physical ….

ND
fD = ( EF − ED ) / k B T
1 + gDe

Degeneracy factor …

ND ND
fD = ε k B T ( EF − ED ) / k B T
1+ e e 1+ e( EF − ED' ) / k BT

Effective donor level

Alam ECE-606 S09 18

 Summary …

A bulk material must be charge neutral over all …

∫
 
+ −
p − n + N D + N A dV =0

Further if the material is spatially homogenous

p − n + N D+ + N A− =0

ND NA
NV e −( EF − EV ) / kB T − N Ae −( EC − EF ) / kBT + ( EF − ED ) / k B T
− ( E A − EF ) / k B T
=
0
1 + 2e 1 + 4e

Alam ECE-606 S09 19

Conclusions

Intrinsic concentration of electrons in a semiconductor is

relatively small.

The statistics of dopant levels are different because they are

close to the conduction band and because they are localized.
Influenced by pair-wise coulomb repulsion.

The statistics of donor and acceptor atoms are also different,

because donor levels couple with single conduction band,
while acceptor levels couple with two valence bands.

Alam ECE-606 S09 20