Semiconductor Physics I

SC-Phys-I_Schweizer-2010
1
Semiconductor Physics
Semiconductor Physics I
Chap. 1 Introduction
1. Literature
2. semiconductor properties
3. basic parameters
Chap. 2 Crystal Structure
1. real lattice
2. Reciprocal lattice
3. Brillouin zone
Chap. 3 Band structure Calculations
1. Symmetries
2. Kronig-Penny
3. Brillouin/Bloch Approx.
4. LCAO/APW/OPW/Pseudo pot.
5. kp-method
Chap. 4 Experimental determination
band structure
1. Methods
2. Results
Chap. 5 Impurity States
1. Exp. observation
2. eff. Mass / deeps levels
Chap. 6 Statistics
1. equilibrium TD
2. Distribution functions
Chap. 7 Non-equilibrium
1. Field effect
2. Currents
3. Recombination/relaxation
Chap. 8 Transport
1. Boltzmann equation
2. Scattering mechanisms/mobility
3. ..
Chap. 9 Opt. Properties Semiconductors
1. Opt. transition/ Dirac perturbation
2. Absorption/Emission
3. Exciton, impurity-band transition
2
Semiconductor Physics
Semiconductor Physics II
Chap. 10 Device technology
1. Crystal growth
2. Doping technology
3. Pattern technology
(lithography, etching)
Chap. 11 Bipolar technique
1.1. pn transition
1.2. Diode characteristics
1.3. Diode capacitance
1.4. Diode structures
2.1. Hetero semiconductor
2.2. Hetero/bipolar junctions
2.3. Quantum size effect / band gap
engineering
3.1. Bipolar transistor
4.1. Bipolar integration
Chap. 12 Unipolar technology
1.1. Schottky diode
2.1. Field effect transistor (FET)
2.2. JFET
2.3. MOSFET
2.4. Si-MOSFET
3.1. Switching speed and power
3.2. Noise in semiconductors
Chap. 13 Optoelectronic
1. LEDs
2. Detectors / solar cells
3. Semiconductor lasers
4. Modulators
3
4.Physikalisches Institut
Universitt Stuttgart
Heinz Schweizer
Micro/Nano-Structure-Lab. (MSL)
Semiconductor Physics I / II
SC-Phys I
Wed. 15.10.2010
08.00 - 09.30
V 57.06
4
Chap.6 Statistics
6.1. Density of states (05-18)
1. Density of states k-space
2. Density of states D(E) E-space
3. D(E) anisotropic bands
4. D(E) VB
5. D(E) low dimensions
6.2 Distribution Functions. (19-35)
1. Fermi-Dirac and Bose
2. Fermi-Dirac
3. Bose
4. Boltzmann
5. Graphs
6.3 Charge carrier concentrations in a band (36-43)
1. Construction / examples
6.4 Statistics of defect states . (44-57)
Bragg scattering/ methods / X-ray sources/Laue method/Rotating
crystal/Debye-Scherrer
6.5 Appendix statistics (58-81)
Partition functions and thermo dynamics
TD of e-h-plasma
5
Chap.6.1 Density of States
Outline
6.1. Density of States (D(E)) (6.1/05-18)
6.1.1 Density of states in k-space (05-08)
6.1.2 Density of states in E-space (09-11)
6.1.3 Anisotropic bands (12-13)
6.1.4 Valence bands (14-14)
6.1.5 Lower dimensions (15-18)
6
Chap.6.1.1 Density of states (k-space)
Density of states and band model
Starting point energy band model for semiconductors
Energy levels are dense for large periodic atomic system
Question: How much states N in a given energy interval and a given volume ?
- - - - - - - - - - -
a
L
semiconductor crystal subdivided in an area L occupied by N atoms (Eq. 1)
translational invariance in L and also in whole crystal
properties of electron (wave function) can not depend on L (L is arbitrary) (Eq.2)
) ( ) ( ) 2 . 6 ) ( ) 0 ( ) 2 . 6
) 1 . 6
Na x x b L a
a N L
+ + = + + = +
=
7
boundary conditions for electron in L
o periodic boundary conditions in L
o only 1 electron in L (Eq.6.3)
o wave function has Bloch form ((Eq.6.4)
from Eq. 6.4 we find condition for possible
k-values
) 13 . 1 . 3 . ( 1 ) 4 . 6
1 * ) 3 . 6
2 /
2 /
Eq see e
dx
a N k i
L
L
=
= + +

+
}
( ) integer n n
a N
n
a N
k
o o n
=
=
t t 2 2
) 5 . 6
restriction of k
n
on first Brillouin zone
possible (number of states is N (Eq. 6.6))
n
o
= 0, 1, .., N/2
momentum difference between neighboured
states Ak = 2t/L = 2t/(Na)
( )
N
a N
a
state one size
states all size
Z
states number
=
= =
/ 2
/ 2
) 6 . 6
t
t
-t/a
+t/a
k
E
a N L
=
t t 2 2
a
t 2
8
3D analogous to 1D
momenta Eq. 6.7a
number of states N
3
values
size all states Eq. 6.7b
size one state Eq.6.7c
3 3
3
2 2
) 7 . 6
2
) 7 . 6
, , ;
2
) 7 . 6
|
.
|
\
|
=
|
.
|
\
|
=
|
.
|
\
|
=
=
=
L a N
k c
a
k b
z y x i n
a N
k a
one
tot
i i
t t
t
t
Density of states (k) in k-space
1 state V
k
= 2t/L
number of states dZ in dk
(Eq. 6.8a)
relation to basic area L dZ*
and gives (k) (Eq. 6.8b,c)
(k) for 3D Eq. 6.8d
( )
3
) 3 (
2
1
) ( ) 8 . 6
2
1
) ( ) 8 . 6
) ( * ) 8 . 6
2
) 8 . 6
|
.
|
\
|
=
=
= =
= =
t
t
k d
k c
dk k
L
dZ
dZ b
L
dk
V
dk
dZ a
D
k
9
Chap.6.1.2 Densities of states (E-space)
Density of states in energy space D(E)
defined as number of states per
energy interval (Eq. 6.9a)
can be calculated if dispersion
relation E(k) is known
number of states in E-/k- space
identical (Eq. 6.9b)
D(E) volume integral in k-space
}
A +
A
=
=
=
A
A
=
E E
E
k d k
E
E D c
dE E D k d k dZ b
dE
dZ
E
Z
E D a
3
3
) (
1
) ( ) 9 . 6
) ( ) ( ) 9 . 6
: ) ( ) 9 . 6
E
k
Qualitative discussion density of states for
given dispersion relation E(k):
chain rule: D(E)=dZ/dE =dZ/dk (dk/dE)
or D(E) = (k) /(dE/dk)
D(E) large for shallow bands (m* large)
D(E) small for steep bands (M* small)
D(E) volume integral in k-space
L
t 2
large
D(E)
small
D(E)
10
Decomposition formula of differential
volume in k-space according Eq. 6.10a
(E-coordinate radius in k-space)
Reformulation Eq. 6.9c (Eq.6.10b)
From Eq.6.10b one obtains
integral formula for D(E) (Eq. 6.10d)
dA
k
can be a Cartesian or any other
curvilinear coordinate system
|
|
.
|
\
|
c
c
= =
V
|
.
|
\
|
=
V A
|
.
|
\
|
=
V A
|
.
|
\
|
=
V
= =
}
} }
}
=
A +
=
A +
) , (
) , (
2
1
) ( ) 10 . 6
1
2
1
) ( ) 10 . 6
1
2
1
) ( ) 10 . 6
) 10 . 6
.
3
.
3
3
3
y x
y x k
const E k
k
E E
E const E k
k
E E
E k
k
k
k k
k k
k k
dk dk dA
E
dA
E D d
dE
E
dA
E
E D c
E
dE
dA
E
E D b
E
dE
dA dk dA k d a
_
t
t
t
AE
11
Density of states for isotrope parabolic bands
( ) ( )
( )
CB
const E CB
k
const E
k CB k
z y x k CB z y x
E E m
h
E E
m
dA E D d
spherical k dA d E E
m
k
m
E c
k k k
m
k E b E k k k
m
k E a
=
|
.
|
\
|
=
= = = V
+ + = V + + + =
}
}
=
=
2 / 3
3
.
3
2
.
2
2
2 2 2
2
* 2
2 1
2
*
2
1
) ( ) 11 . 6
) ( 4 ) 11 . 6
*
2
*
) 11 . 6
*
) ( ) 11 . 6
* 2
) ( ) 11 . 6
t
t
t

( )
( ) E E m
h
E D b
E E m
h
E D a
VB h
VB
CB e
CB
=
=
2 / 3
*
3
) (
2 / 3
*
3
) (
2
4
) ( ) 12 . 6
2
4
) ( ) 12 . 6
t
t
Density of states for CB and VB with spin (D(E) =2 D
without
(E) )
12
Chap.6.1.3 Densities of states (anisotropic)
Density of states for anisotropic elliptic bands
( )
( )
( )
( ) | | ( )
3 / 1
* * * *
2 / 3
*
3
2 2 2
*
2
2 / 1
*
*
2 / 1
*
*
2 / 1
*
*
*
2
*
2
*
2
2
; 2
4
) ( ) 13 . 6
* 2
) ( ) 13 . 6
2
) ( ) 13 . 6
z y x d CB d
z y x
d
z
z
d
z
y
y
d
y
x o
x
d
x
CB
z
z
y
y
x
x o
m m m m E E m
h
E D c
k k k
m
k E b
k
m
m
k
k
m
m
k
k k
m
m
k
tion transforma
E
m
k
m
k
m
k k
k E a
= =
+ + =
|
|
.
|
\
|
=
|
|
.
|
\
|
=
|
|
.
|
\
|
=
+
|
|
.
|
\
|
+ +
=
t
13
Chap.6.1.3 Densities of states (anisotropic)
specialization for Si and Ge
Si
CB-min in [100] (X-point)
m
x
= m
l
, m
y
=m
z
=m
t
6 equivalent minimaM
e
=6
( )
| | 6 ) 14 . 6 ) 14 . 6
2
4
) ( ) 14 . 6
3 / 1
2 * * *
2 / 3
*
3
= =
=
e t l d
CB d e
M c m m m b
E E m M
h
E D a
t
Ge
CB-min in [111] (L-point)
m
x
= m
l
, m
y
=m
z
=m
t
4 equivalent minima
M
e
=4 (at the edge of the BZ)
( )
| | 4 ) 15 . 6 ) 15 . 6
2
4
) ( ) 15 . 6
3 / 1
2 * * *
2 / 3
*
3
= =
=
e t l d
CB d e
M c m m m b
E E m M
h
E D a
t
Effective density of state mass
m*
d, eff
* 3 / 2 *
,
: ) 16 . 6
d e eff d
m M m =
14
Chap.6.1.4 Densities of states (VB)
Valence bands
Neglecting warping
Neglecting band interaction
(kp-interaction of tightly separated bands, spin-orbit interaction)
Charge carrier densities linearly summed
Density of states lin. sum.

( )
| |
3 / 2
2 / 3 *
2 / 3
* *
,
2 / 3
*
,
3
) 17 . 6
2
4
) ( ) ( ) ( ) 17 . 6
lh hh h d
VB h d
lh hh total
m m m b
E E m
h
E D E D E D a
+ =
=
+ =
t
15
Chap.6.1.5 Densities of states (low dimension)
Specialization on films and wires
Film is 2D system
film of thickness L
z

energy values in z-direction
quantized (Eq.6.18a)
D(E) calculation of area in
k-space (k
x
, k
y
)
(with Eq. 6.10d)
( ) ( )
}

|
.
|
\
|
= = V
+ = =
|
|
.
|
\
|
=
dk du E D d k
m
k E c
k k
m
E k E b n n
L m
E a
k
y x
k
y x
y x
n z CB
z z
n z CB
2
*
,
2
2 2
*
,
2
, ,
2
*
2
, ,
2
1
) ( ) 18 . 6 ) ( ) 18 . 6
2
) ( ) 18 . 6 , 2 , 1 ;
2
) 18 . 6
t
t
k
y
k
x
dk
d
k
k
z
|
|
.
|
\
|
z
L
t
(according Eq. 6.10d)
16
D(E) according Eq. 6.18d
( )
( )
=
=
=
V
|
.
|
\
|
=
V
|
.
|
\
|
=
}
=
) ( ) .(
2
) ( ) .( *
2
) ( ) 18 . 6
18 . 6 .
2
2
1
2
1
) ( ) 18 . 6
2 / 1
* *
2
2
) 2 (
2
.
2
c anisotropi E const m m
isotropic E const m
E D f
c Eq with
E
k
E
d k
E D e
y x
D
k const E k
t
t
t
t
t
k
y
k
x
dk
d
k
Eq. 6.18f valid for each quantized state n=1,2,.. total density of states is a sum over
all quantized states D
tot
= E
n=1,2,..
D
(2D)
H(E-E
n
) H=Heaviside function E
n
Eq.6.18a)
17
wire 1D system
wire of thickness L
y
, L
z

energy values in y,z-direction
quantized (Eq.6.19a)
D(E) calculation of length in
k-space (k
x
) (Eq. 6.19d)
( )
( ) ) 0 , 0 , ( ) ( ) 19 . 6
2
) ( ) 19 . 6
2 2
) 19 . 6
*
2
2
*
2
, , 3 ,
2
*
2
2
*
2
, ,
k k k
m
k E c
k
m
E E k E b
m
L m
n
L m
E a
x
k
x
x
y z CB D CB
y y z z
y z CB
= = V
=
|
|
.
|
\
|
+
|
|
.
|
\
|
=
t t
( )
E
h
m
E D f
dE
E m d
E
E m E E m
E D e
E
E E
k
E
dk k
E
E D d
x D
x x x
E E
E
1
2
2
) ( ) 19 . 6
2
1
2 2
1
2
1
) ( ) 19 . 6
1
2
1
) (
1
) ( ) 19 . 6
*
) 1 (
* * *
=

A
A +
=
A +
A
=
A
=
}
A +
t
t
18
Summary for different dimensions
) ( ) ( ) 20 . 6 : 1
1
) ( ) 20 . 6 : 1
. ) ( ) 20 . 6 : 2
) ( ) 20 . 6 : 3
) 0 (
) 1 (
) 2 (
) 3 (
E E D d D
E
E D c D
const E D b D
E E D a D
D
D
D
D
o
19
Chap.6.2 Distribution Functions
Outline
6.2.1. Distribution functions (1.1/06-47)
6.2.1 Fermi- and Dirac statistics (30-29)
6.2.1 Fermi-Dirac (30-39)
6.2.3 Bose (xx-xx)
6.2.4 Boltzmann (xx-xx)
6.2.5 Graph of distribution functions (xx-xx)
20
Chap. 6.2.1 Fermi- and Bose statistics
Description subchapter 6.2:
we start with a classical description of thermodynamical potentials and the possibility
to describe with their help the interaction between a small system o
(I)
with its environment
then we discuss the relation between quantum mechanics and classical statistics
(Appendix)
at the end we derive some single particle distribution functions for Bose- and
Fermi- statistics
and discuss the role of the chemical potential / Fermi energy
21
P
dN
d
kT
E
b
m equilibriu TD for and P
dN
d
kT E a
E
dN
dE
E N E d
dN
dS
T
dN
dE
c
P P k S b dN pdV TdS dE a
i
i
i
i
i i
i
i
i
i i
i i
i
B
i
i i
ln ) 22 . 6
... : ln ) 22 . 6
; ) 21 . 6 ; ) 21 . 6
) ( ; ln ) 21 . 6 ; ) 21 . 6
1
=
= = = =
= = =
E = + =
Single particle distribution function / chemical potential : ( Toda, Kubo,Saito, Statistical Physics I, Solid
State Sciences 30 Springer Series 1992, Kubo,Toda Hashitsume Statistical Physics II Solid State Sciences 31 Springer Series
1992 )
We start with the 1
st
fundamental theorem of TD and the entropy given in Appendix Eq. 17a):
Equation 29b will be the basis to calculate the single particle distribution function f(E)
from the occupation probability P which corresponds to the phase space volume E
22
Calculation of occupation function P :
Properties of particles with Fermi and Bose statistics. The fundamental relation between
Symmetry of states and properties with respect to permutations as well as particle spin was
proofed by Pauli 1940. He founds:
Fermions: - particle spin S is a multiple of . S= n (1/2) h, n= 1,3,5,
- particles of one sort are identical
- number of places for each energy state E
i
: N
i
=2
- total state function + antisymmetrical
Bosons: - particle spin S is a multiple of an integer S= n h, n= 0,1,2
- particles of one sort are identical
i
: N
i
oo
- total state function + symmetrical
Classical: - spin S without meaning.
(Boltzmann) - particles of one sort are identical
i
: N
i
oo
The numbers of the spins are based on the physics of the angular momentum. From general
discussion of the angular momentum one finds the solely possible values of J to be:
J=0, 1/2, 1, 3/2, 2 , 5/2, 3,
23
Chap. 6.2.2 Fermi- Dirac
Cell energy No. places No. particles
1 E
1
Z
1
N
1
* * * *
i E
i
Z
i
N
i
* * * *
* * * *
* * * *
* * * *
Ansatz for calc. P (Fermions) :
decompose whole system o
(I,II)
in
cells according found energy
values E
i
and number of places Z
i
from H.
group electrons in numbers N
i
.
Here N
i
</= 2
)! (
!
)) 1 ( ( ) 1 ( ) 23 . 6
i i
i
i i i i i
N Z
Z
N Z Z Z P
=
Calc. of occupation probability for
not identical particles:
1. part.
Z
i
places
2. part.
Z
i
1 places
N
i
. part.
Z
i
(N
i
-1) places
Pauli:
24
Now we assume that particles are identical correction in occupation probability P
i
1. particle N
i
possibilities for exchange
2. particle N
i
1 possibilities for exchange

N. particle 1 possibility for exchange N! possibilities if particles are identical.
By this amount P
i
will be reduced.
*)
! )! (
!
) 24 . 6
N N Z
Z
P a
i i
i
FD
i

=
The total probability is a product of the P
i
of all cells as entropies are additive. We get:
[ [
=

=
i
i
i
i i
i
FD
P
N N Z
Z
P b
! )! (
!
) 24 . 6
*) Permutation problem: Given Z
i
Elements. Combina-
tion of N
i
elements without repetition of same elements
without taking into account the arrangement
! )! (
!
N N Z
Z
N
Z
K
i i
i
i
i
n combinatio

=
(
=
25
Calculation of Fermi-Dirac occupation function:
We get for Eq. 6.22b with Eq. 6.24b and Stirling formula :
|
|
.
|
\
|
=
1 ln ) 25 . 6
i
i i
N
Z
kT
E
The occupation probability f =N
i
/Z
i
of level E
i
can now be calculated as (with Eq. 6.25) :
1
1
: ) ( ) 26 . 6
) (
+
= =

kT
E
i
i
i
FD
i
e
Z
N
E f
) ln ! ln ln ! (ln A A
dA
d
A A A A = ~
Eq. 6.26 is valid for all energy levels E
i
therefore we can also write:
1
1
) ( ) 26 . 6
) (
+
=

kT
E
FD
e
E f
Fermi-Dirac occupation function
26
Chap. 6.2.3 Bose
Calculation of the Bose occupation function :
1 E
1
Z
1
N
1
* * * *
i E
i
Z
i
N
i
* * * *
* * * *
* * * *
* * * *
Ansatz for calc. P (Bosons) :
(I,II)
in
values E
i
i
from H.
group particles in numbers N
i
.
Here N
i
01,23.
)! 1 ( ) 27 . 6 + =
i i i
N Z P
Calc. of occupation probability not
identical particles (number of possible
permutations:
27
Chap. 6.2.3 Bose
Calculation of Bose occupation function :
Now we assume that particles are identical correction in occupation probability P
i
Therefore N
i
!(Z
i
-1)! needs not to be carried out.
*)
! )! 1 (
)! 1 (
) 28 . 6
N Z
N Z
P a
i
i i
B
i

+
=
i
of all cells (entropies are additive). We get:
[ [
=

+
=
i
i
i
i
i i
B
P
N Z
N Z
P b
! )! 1 (
)! 1 (
) 28 . 6
i
different Elements. Combination of N
i
elements with
repetition of same elements without taking into account arrangement
Bronstein p. 163f (Eq.2.19)
! )! 1 (
)! 1 (
1
N Z
N Z
N
N Z
ns Combinatio of Number
i
i i
i
i i

+
=
(
+
=
28
Chap. 6.2.3 Bose
Calculation of the Bose occupation function:
|
|
.
|
\
|
+ =
1 ln ) 29 . 6
i
i i
N
Z
kT
E
i
/Z
i
of level E
i
can now calculated as (with Eq. 6.29) :
1
1
: ) ( ) 30 . 6
) (
= =

kT
E
i
i
i
B
i
e
Z
N
E f
dA
d
A A A A = ~
i
therefore we can also write:
1
1
) ( ) 31 . 6
) (
=

kT
E
B
e
E f
Bose occupation function
29
Chap. 6.2.4 Boltzmann
Calculation of the Boltzmann occupation function :
1 E
1
Z
1
N
1
* * * *
i E
i
Z
i
N
i
* * * *
* * * *
* * * *
* * * *
Ansatz for calc. P (Boltzmann) :
(I,II)
in
values E
i
i
from H.
group electrons in numbers N
i
.
Here N
i
oo
i
N
i i i i
BM
i
Z Z Z Z P = ) 32 . 6
Calc. of occupation probability not
Identical particles:
1. part.
Z
i
places
2. part.
Z
i
places
N
i
. part.
Z
i
places
No
Pauli:
30
Again we assume that the particles are identical correction in occupation probability P
i
And we get again a correction factor of N! :
*)
!
) 33 . 6
N
Z
P a
i
N
i
BM
i
=
i
of all cells (entropies are additive). We get:
[ [
= =
i
i
i
N
i
BM
W
N
Z
P b
i
!
) 33 . 6
i
Elements. Combination of N
i
elements with repetition and
with taking into account the arrangement :
i
N
i
Z K ns Kombinatio of Number =
31
Calculation of the Boltzmann occupation function :
|
|
.
|
\
|
=
i
i i
N
Z
kT
E
ln ) 34 . 6
i
/Z
i
of level E
i
can now calculated as (with Eq. 6.34) :
dA
d
A A A A = ~
kT
E
i
i
i
BM
i
e
Z
N
E f
) (
: ) ( ) 35 . 6

= =
i
therefore we can write:
kT
E
Boltzmann
e E f
) (
) ( ) 36 . 6

=
Boltzmann occupation function
32
P
B
Chap. 6.2.5 Graph of occupation functions
Properties of the occupation functions P
B
:
T(K)
E(meV)
P
B
macroscopic occupation number for Ei Bose-Einstein condensation
for Ei >> P
B
~ P
BM
~ P
BM
33
Chap. 6.2.5 Properties of occupation functions
Properties of the occupation functions (P
FD
):
P
FD
T(K)
E(meV)
occupation at chemical potential ( = E
F
)
efficient particle redistribution only for energies E
i
E
F
or higher temperatures
for E
i
>> P
FD
~ P
BM
P
FD
~P
BM
34

FD
, and 1- P
FD
):
occupation at chemical potential ( = E
F
) for P
FD
, and 1- P
FD
efficient particle redistribution only for energies E
i
E
F
or higher temperatures
for E
i
>> P
FD
~ P
BM
for E
i
<< 1-P
FD
~ P
BM
1-P
FD
defect electron (hole) distribution function
P
FD
1-P
FD
~P
BM
~P
BM
35
E(meV)
T(K)
P
BM
Nano-Physics I Schweizer 2002
BM
):
class. occupation function. Limiting occupation function for P
B
and P
FD
max. occupation near
steeper for smaller temperatures
36
Chap. 6.3 Charge carrier densities in a band
Outline
6.3 Charge carrier densities in a band (6.2/36-xx)
6.2.1 Fermi- and Dirac statistics (30-29)
6.2.1 Fermi-Dirac (30-39)
6.2.3 Bose (xx-xx)
6.2.4 Boltzmann (xx-xx)
6.2.5 Graph of distribution functions (xx-xx)
37
Carrier densities for a system with known D(E):
Based on the single particle occupation function and the density of states one can calculate
the carrier density in the conduction and valence band of a crystal
} }
=
=
= =
E
E
l
k
l
E f E D dE k k d n
0 0
) ( ) ( ) ( : ) 37 . 6
max
( )
( )
( )
|
.
|
\
|

=
+
=

=
|
.
|
\
|

=
|
|
.
|
\
|
=

=
|
.
|
\
|

=
|
|
.
|
\
|
=
}
}
kT
E E
e
x
dx F f
h
kT m
N e
kT
E E
F N p d
cm T
m
m
h
kT m
N c
kT
E E
F N E E f dE
m
n b
F VB
x
h
V
F VB
V
e e
L
CB F
L
q q
t
t
t
t
t
t
q
;
1
) 38 . 6
2
2 ) 38 . 6
2
) 38 . 6
) ( 10 871 . 4
2
2 ) 38 . 6
2
) (
2
) 2 (
2
2 ) 38 . 6
0
2 / 1
2 / 1
3
2 / 3
*
2 / 1
) 3 (
3 2 / 3
2 / 3
0
*
15
3
2 / 3
*
2 / 1
2 / 1
0
2 / 3
2
*
3
) 3 (
for l=3 (other dim see 6.1.5)

38
Summary for e and h:
( )
( )
( )
( )
|
.
|
\
|

=
+
=
+ =

=
|
.
|
\
|

=
=

=
|
.
|
\
|

=
}
kT
E E
e
x
dx F e
m m m dd bands hh and lh with
h
kT m
N d
kT
E E
F N p c
m M m bb bands c anisotropi with
h
kT m
N b
kT
E E
F N n a
F VB
x
lh hh dh
h
V
F VB
V
D
de e e
e
L
CB F
L
D
q q
t
t
t
t
q
;
1
) 39 . 6
) 39 . 6 ) (
2
2 ) 39 . 6
2
) 39 . 6
) 39 . 6 ) (
2
2 ) 39 . 6 ;
2
) 39 . 6
0
2 / 1
2 / 1
3 / 2
2 / 3 * 2 / 3 * *
3
2 / 3
*
2 / 1
) 3 (
* 3 / 2 *
3
2 / 3
*
2 / 1
) 3 (
39
Physics and Technology of Nano-Systems
Carrier densities (Boltzmann approximation) :
For single carrier energies far away from the chemical potential the Boltzmann approx.
applies
kT
E E
v
D
n p
kT
E E
L
D
x x
kT
E E
L
F VB
CB F
CB F
e N p c
f f with holes and e N n b
dx e x dx e x e N n a
=
= =
|
|
.
|
\
|
= I = ~
} }
) 3 (
) 3 (
0
2 / 1
0
2 / 1 ) 3 (
) 40 . 6
1 ) 40 . 6
2
) 2 / 3 ( ;
2
) 40 . 6
t
t
Mass interaction law :
kT
E
v L i
kT
E
v L i
i
kT
E
v L
gap gap
gap
e N N n e N N n b
n p n conduction rinsic int e N N p n a
2
2
) 41 . 6
) : ( ) 41 . 6

= =
= = =
40
Carrier densities (Boltzmann approximation) :
Fermi energy and carrier densities in the for the intrinsic case n=p=n
i
|
|
.
|
\
|
+
+
|
|
.
|
\
|
+
+
=
= =

*
*
,
ln
4
3
2
ln
2
) 42 . 6
) 42 . 6
, ,
e
h VB CB
L
v VB CB
i F
n
kT
E E
v
kT
E E
L
m
m
kT
E E
N
N
kT
E E
E b
e N e N p n for a
i F VB CB i F
Introduction of u =E
F
- E
i
(E
i
=(E
CB
+E
VB
)/2) np=n
2
i
:
kT
i
kT
i
e n p b and e n n a
| |
= = ) 43 . 6 ) 43 . 6 different cases of u :
doping type n
n p
n n
E E c
doping type p
n p
n n
E E b
conduction rinsic
n p
n n
E E a
i
i
i F
i
i
i F
i
i
i F

)
`
<
>
> >

)
`
>
<
< <
)
`
=
=
= =
: 0 ) 44 . 6
: 0 ) 44 . 6
int : 0 ) 44 . 6
|
|
|
E
CB
E
VB
E
i
E
F
(n)
E
F
(p)
41
Case of degeneracy:
(E
F
-E
CB
)/kT >>1 E
F
deep in bands approx. Eq.6.45,46 for n,p
( )
( )
( )
+
|
|
.
|
\
|

|
.
|
\
|
=
+
|
|
.
|
\
|

|
.
|
\
|
=

=
|
.
|
\
|

=

=
|
.
|
\
|

=
= ~
>
<
~
} }
VB
V
Fh
CB
L
Fe
h
V
F VB
V
e
L
CB F
L
E
E
CB e de
E
E
D
F
F
e
E kT
N
p
E
E kT
N
n
E
a
h
kT m
N bb
kT
E E
N p
h
kT m
N ba
kT
E E
N n
b
E E dE M m
h
E f E D dE n a
E E if
E E if
E f
F
CB
F
CB
3 / 2
3 / 1
3 / 2
3 / 2
3 / 1
3 / 2
3
2 / 3
*
2 / 3
3
2 / 3
*
2 / 3
2 / 3
3 / 2 *
3
) 3 (
4
3
4
3
) 47 . 6
;
2
2 ) 46 . 6
3
4
2
2 ) 46 . 6
3
4
) 46 . 6
2
4
) ( ) ( ) 46 . 6
0
1
) ( ) 45 . 6
t
t
t
t
t
t
t
42
Case of degeneracy:
example Si
( )
3 20
3 19
3
2 / 3
*
10 3 . 2
300
) 49 . 6
10 75 . 2
2
2 ) 49 . 6
5
5
: . ) 48 . 6
=
=
=
=
>
>
cm
K T
n b
cm
h
m
N a
kT
E E
kT
E E
for valied approx degeneracy
e
L
F VB
CB F
t
the degenerated semiconductor is characterized by densities n > N
L
degenerated semiconductors show metallic properties
43
Summary degeneracy:
Boltzmann / Fermi-Dirac / degeneracy
(E
F
-E
CB
)/kT
ln(n/N
L
)
0 5 -3
-1
-0.5
+0.5
+1
Boltzmann
< 2%
Degeneracy
< 5%
no approx.
valid
kT E E for e N n
CB F
kT
E E
L
D
CB F
3
) 3 (
> =

kT E E for
kT
E E N
n
CB F
CB F L D
5
3
4
2 / 3
) 3 (
>
|
.
|
\
|

=
t
|
.
|
\
|
=
kT
E E
F N n
CB F
L
D
2 / 1
) 3 (
2
t
44
Chap. 6.4 Statistics of defect states
Donors:
problem: no simple F-D-statistic
possible
reason: properties of ionized
donors / acceptors
| |
! )! (
!
! / )) 1 ( ( ) 1 ( ) 51 . 6
) 51 . 6
0 0
0 0
0
D D D
D
D D D D D
D
N N N
N
N N N N N P b
e D D a

=
+
+
+

1. part.
N
D
sites
2. part.
,
N
D
1 sites
N
D
. part.
N
D
(N
0
D
1) sites
Pauli:
) ( 1 ) 50 . 6
, 2 ) 50 . 6
0
0
repulsion Coulomb site N N b
spin to due sites N N a
D D
D D
+ |
+
+
number of ionized donors N
+
D
number of N
0
D
electrons can be distributed to N
D
+ +

E
CB
E
D
N
+
D
N
0
D
N
D
45
Donors:
modification of Eq 6.51b by
spin:
for N
0
D
1 unpaired e
/ donor
spin can be up / down
modification P
donor
(Eq. 6.52a)
! )! (
!
2 ) 52 . 6
51 . 6 . 2 ) 52 . 6
0 0
0
0
D D D
D
N
D
N
spin
N N N
N
P b
b Eq for P a
D
D

=
=
+
+ +

E
CB
E
D
N
+
D
N
0
D
N
D
46
Acceptors:
problem: no simple F-D-statistic
possible
reason: properties of ionized
donors / acceptors
with spin N
0
A
= N
A
N
A
unpaired
electrons modification 6.53b
Eq. 6.54b
! )! (
!
! )! (
!
) 53 . 6
) 53 . 6
0 0
0

=
+ +
A A A
A
A A A
A
A
N N N
N
N N N
N
P b
e A A a

+
E
VB
E
A
N
A
N
0
A
N
A
+
! )! (
!
2 ) 54 . 6
2 2 ) 54 . 6
0

=
=
A A A
A
N N
A
N N N
spin
N N N
N
P b
P a
A A
A A A
47
Total occupation probability:
electrons P
CB
as in intrinsic case
total probability by and relation
of P
donor
P
acceptor
P
CB
Eq. 6.55a and 6.55b CB A D total
P P P P a = ) 55 . 6
(
|
|
.
|
\
|

|
|
.
|
\
|

=
[

i
i i i
i
A A A
A
N N
D D D
D
N
total
N N Z
Z
N N N
N
N N N
N
P b
A A D
! )! (
!
! )! (
!
2
! )! (
!
2 ) 55 . 6
0 0
0
calculation of distribution function from TD-relations 6.56a,b and caloric relations Eq.6.56c
and 6.57
( )
( )

+ + + = + +
+ + = =
+ + + =
A D i F tot A A D D i i
A A D D i i tot
A D i F
dN dN dN E P kT dN E dN E dN E
c a with dN E dN E dN E dE c P k S b
dN dN dN E pdV TdS dE a
0 0
0
0
ln ) 57 . 6
) 56 , 56 . 6 ( ) 56 . 6 ; ln ) 56 . 6
) 56 . 6
48
from Eq. 6.57 we obtain by derivation according N
i
,
N
0
D
, and N
A
the distribution functions for electrons
on Z
i
, N
D
, N
A
.
|
|
.
|
\
|

=
|
|
.
|
\
|

=
|
|
.
|
\
|

=

! )! (
!
2 ln : ) 58 . 6
! )! (
!
2 ln : ) 58 . 6
! )! (
!
ln : ) 58 . 6
0 0 0
0
0
A A A
A
N N
A
F A
A
D D D
D
N
D
F D
D
i i i
i
i
F i
i
N N N
N
dN
d
kT
E E
N according dervation c
N N N
N
dN
d
kT
E E
N according dervation b
N N Z
Z
dN
d
kT
E E
N according dervation a
A A
D
49
Eq. 6.58a-c must be fulfilled simultaneously probability functions
( )
( )
( )
( )
A
A
A
kT
E E
A
D
D
D
kT
E E
D
N on e number
N
N
e
P c from c
N on e number
N
N
e
P b from b
Dirac Fermi a from a
F A
F D
=
+
=
=
+
=
2 1
1
: ) 58 . 6 ( ) 59 . 6
2
1
1
1
: ) 58 . 6 ( ) 59 . 6
: ) 58 . 6 ( ) 59 . 6
0
0
factor 1/g
i
before exp. function in P
D
/ P
A
is called degeneracy factor
Donor: e
on non-ionized N
D
can have 2 spin positions g
i
=2
Acceptor: e
on ionized N
A
have 1 spin position g
i
=1/2
50
probability function of emitted carriers to CB and VB:
Probability function of emitted electrons (Eq. 6.60a)
( )
( ) CB in e number
N
N
e
N P N P a
D
D
kT
E E
D D D D
F D
+

+
=
+
= =
2 1
1
) ( 1 ) ( ) 60 . 6
0
( )
( ) VB on h number
N
N
e
N P b
A
A
kT
E E
A A
F A
=
+
=
2 1
1
) ( ) 60 . 6
Probability function of emitted holes (Eq. 6.60b)
51
Density of states and charge carrier densities on occupied defect states:
D(E) defect state is o-function (Eq. 6.61a)
( )
t t t
E E N E D a = o ) ( ) 61 . 6
( ) ( )
( )
( )
( )
( )
( ) VB to h emitted of number
e
N
N P N p b
acceptor
CB to e emitted of number
e
N
N P N n a
donor
A D t E f N dE E f E E N n b
kT
E E
A
A A A A
kT
E E
D
D D D
D
t t t
E
E
t t t t
F A
F D
t
t
+
+
= =
+
= =
= =
=
+
}
2 1
) ( ) 62 . 6
:
2 1
) ( 1 ) 62 . 6
:
, ); ( ) ( lim ) 61 . 6
0
0
c
c
c
o
occupation (Eq. 6.61b)
52
Neutrality condition and position of Fermi level :
ionized donors / acceptors show charge separation
in hole semiconductor, however, neutrality
with N p p N n n b
or N p N n a
D A i A D i
D A
+
+
+ + = + +
+ = +
) 64 . 6
) 64 . 6
( ) ( )
kT
E E
A
A A
kT
E E
D
D D
kT
i
kT
i
F A F D
i i
e
N
N n c
e
N
N n c
e n p b e n n a

+
+
+
= =
+
= =
= =
2 1
) 65 . 6 ;
2 1
) 65 . 6
) 65 . 6 ; ) 65 . 6
/ / | |
Fermi level from neutrality (Eq.6.64a)
low temperatures for n-type semiconductor
N
A
~ 0; p~0; (with Eq.6.64a) n ~ N
+
D
|
|
.
|
\
|
+
+
=
=

L
D CB D
F
kT
E E
L
N
N kT E E
E
c Eq and e N n with
CB F
2
ln
2 2
) 66 . 6
65 . 6 .
E
T
T
max
dE
F
/dT= 0 T
max
T
max
~ N
D
~ 1/m
53
Fermi level from neutrality (Eq.6.64a) at low temperatures for n-type semiconductor
N
A
~ 0; p~0; (with Eq.6.64a) n ~ N
+
D
T 0
2
) 67 . 6
CB D
F
E E
E
+
=
E
T
T
max
dE
F
/dT= 0 T
max
54
high temperatures (saturation doping centres)
all N
D
ionized N
+
D
~N
D
neutrality n ~ p + N
D
with MWG np ~ n
i
2
( )
( )
(
=
(
+ ~
(
(
(
|
|
|
.
|
\
|
|
|
.
|
\
|
+ + + =
(
+
= =
|
|
|
.
|
\
|
|
|
.
|
\
|
+ + =
=
>>
+
V
A
VB Fp
L
D
CB
n N
D
i
L
D
CB Fn
kT E E
D
D
kT E E
L
D
i
L
D
i D
N
N
kT E E
analogues acceptors
N
N
kT E
N
n
N
N
kT E E
e
N
N e N n with
N
n
N
N
n b
n n N n a
i D
D F
F CB
ln ) 70 . 6
: ) (
ln
2
1 1
2
ln ) 69 . 6
2 1
;
2
1 1
2
) 68 . 6
0 ) 68 . 6
2
2
2 2
55
Summary
Fermi energies in a semiconductor for different doping situations
( )
( )
( )
( )
A
V
A
VB Fp
D
L
D
CB Fn
V
A A VB
Fp
L
D D CB
Fn
N saturation
N
N
kT E E d
N saturation
N
N
kT E E c
tor semiconduc type p
N
N kT E E
E b
tor semiconduc type n
N
N kT E E
E a
(
=
(
+ =
+
=
+
+
=
ln ) 71 . 6
ln ) 71 . 6
2
ln
2 2
) 71 . 6
2
ln
2 2
) 71 . 6
56
Band charge density and neutrality, Fermi energy level, n-doping
X=( E
F
E
CB
)/ k T
|
|
.
|
\
|
+
L
D
N
N
ln
X
N
n
L
=
|
|
.
|
\
|
ln
X
N
n
L
2
3
3
4
ln ln +
|
|
.
|
\
|
~
|
|
.
|
\
|
t
|
|
.
|
\
|
+
|
|
.
|
\
|
=
|
|
.
|
\
|
}
0
2 / 1
ln
2
ln ln
X
L
e
d
N
n
q
q
q
t
ln[n/N
eff
]
E
D
E
F_1,2,3
1
n=N
eff
+
+
+ =
~
D D D
D
N N N
N n
) 0 (
E
CB
saturation
donors
N
D1
N
D2
N
D3
N
D1
: charge reserve
N
D3
: saturation range
57
Band charge density and neutrality, Fermi energy level, p-doping
|
|
.
|
\
|

V
eff
A
N
N
ln
|
|
.
|
\
|
+
|
|
.
|
\
|
=
|
|
.
|
\
|
}
0
2 / 1
ln
2
ln ln
X
V
e
d
N
p
q
q
q
t
X
N
p
V
=
|
|
.
|
\
|
ln
X
N
p
V
2
3
3
4
ln ln +
|
|
.
|
\
|
~
|
|
.
|
\
|
t
X=( E
F
E
V
)/ k T
ln[p/N
V
eff
]
E
A
1
p=N
eff
+ =
~
A A A
A
N N N
N p
) 0 (
E
V
N
A1
N
A2
N
A3
saturation
acceptors
N
A1
: charge reserve
N
A3
: saturation range
E
F_1,2,3
58
Law of mass action in doping case :
Donors:
chem. rate equation
( ) kT E E
L
D
D
D
D
D CB
e
N
N
N n
c or const
N
N n
b
e D D a

+ +
+
=
+
2
) 72 . 6 . ) 72 . 6
) 72 . 6
0 0
0
+ +

E
CB
E
D
N
+
D
N
0
D
N
D
discussion Eq. 6.72c for low temperatures N
0
D
~ N
D
; N
+
D
~ n
( ) ( ) kT E E
L D
kT E E
L
D
D CB D CB
e
N N
n b e
N
N
n
a

= =
2
0
2
2
) 73 . 6
2
) 73 . 6
behaviour of doped semiconductors at low T similar as intrinsic semiconductor
relevant gap energy, however, smaller AE=E
CB
-E
D
instead AE=E
CB
-E
CV
59
Chap. 6.5 Appendix Statistics
Description Appendix 6.5:
we start with a classical description of thermodynamical potentials and the possibility
to describe with their help the interaction between a small system o
(I)
with its environment
then we discuss the relation between quantum mechanics and classical statistics
at the end we derive some single particle distribution functions for Bose- and
Fermi- statistics
and discuss the role of the chemical potential / Fermi energy
60
Thermodynamic equilibrium and contacts (class. relation):
o
I
o
II
o
0
Some definitions:
o
(0)
total system of particles (gas, solid, crystal,)
o
(I)
subsystem, o
(II)
bath (any combinations, e.g. solid / gas,
dot / crystal matrix, molecule / matrix, )
o
I
<< o
II
1
st
fund. Theorem TD: dE=dQ+dA or dS=dE/T-dA/T
entropies S
(0)
=S
(I)
+ S
(II)
virtual shifts oS
(0)
=0
; 0 ) 2 ; 0 ) 2 ; 0 ) 2
: ) , , ( ) (
1 1
) 2
) ( ) 1
) ( ) ( ) 0 ( ) ( ) ( ) 0 ( ) ( ) ( ) 0 (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) (
) 0 (
) ( ) ( ) 0 (
= + = + = +
+ + + =
+ =
II I II I II I
II
II
II
I
I
I
II
II
II
I
I
I
II
II
I
I
II I
E E E d V V V c N N N b
E energies V volums N particles of shifts virtual BCs conditions boundary
N
T
N
T
V
T
p
V
T
p
E
T
E
T
S a
sheet next see potentials other additive is entropy S S S a
o o o o o o o o o
o
o o o o o
) ( ) ( ) ( ) ( ) ( ) (
) ( ) ( ) ( ) ( ) ( ) (
; ; ) 3
; ; ) 3 :
II I II I II I
II I II I II I
p p T T b and
N N V V E E a BCs from

o o o o o o
= = =
= = =
equilibrium condition
61
Example canonical contact between I,II : (exchange only energy oE
(I)
=-oE
(II),
keep
constant Volume V, and particles N (class. relations). )

= + + =
=
= + =
= = = = =
) (
) (
) ( ) ( ) (
) (
) (
) (
) (
) (
) (
) (
) 0 (
) (
) (
.
) (
) ( ) ( ) ( ) ( ) ( ) ( ) ( ) (
) ( ) ( ) ( ) ( ) ( ) (
1
) 4
) (
1
) 4
) 4 :
0 ) 4 ; ) 4
I
II
I II I
II
I
II
I
I
II
II
II
II
rev
II
II I I II I II I I
II I II I II I
F
T
b
S T E
T
S
T
E
S
T
Q
S a
T
Q
S and
Q Q N V p Q E c on conservati energy with
N N V V b E E a
o
o o
o
o
o
o
o
o
o o o o o o
o o o o o o
virtual variation of oS
(0)
corresponds to variation oF
(I)
For other contacts given in Tab.1 oS
(0)
corresponds to variations of other potentials
oA
(I)
. A
(I)
is called general TD-potential of subsystem o
(I)
. These examples see in the
exercises and further below.
62
Contacts between subsystems I and II , Tab.1 : Here we give classical thermodynamic potentials as
function of certain observable variables as energy E, volume x, general force K (e.g. pressure p), particle
number N,entropy S, chem. Pot. , Also interactions between subsystems e.g. exchange between o
(I)
, o
(II)
is
given for some cases. E, S describe an isolated system, F describes energy exchange., Y describes energy
and particle exchange.
Potential Diff. Derivations exchange const.
E(S,x,N) dE=TdS+Kdx+dN T=oE/oS, K=oE/ox,
=oE/oN
-- E,x,N
S(E,x,N) dS=1/T(dE-Kdx-dN) 1/T=oS/oE, K/T=oS/ox,
/T=oS/oN
-- E,x,N
F(T,x,N)=
E-TS
Free Energy
dF=-SdT+Kdx+dN S=-oF/oT, K=oF/ox,
=oF/oN
E N,x
Y(T,p,N)
Grand
Canonical Pot.
dY=-SdT+Kdx-Nd -S=oY/oT, -N=oY/o,
K=oY/ox
E,N x
63
Quantum mechanics and statistics: ( Toda, Kubo,Saito, Statistical Physics I, Solid State Sciences 30 Springer
Series 1992, Kubo,Toda Hashitsume Statistical Physics II Solid State Sciences 31 Springer Series 1992 )
k k L b and k E k H a
k k
A = = ) 5 ) 5
Given is a Hamiltonian H and its eigen states |k> of the system o
(I)
After state preparation we assume the state |u > of the system o
(I)
as known
. ) 6 op projection P P k k a
k
k
k
k
= u u = u

If we have the state |u > we can determine averages of observables of system o
(I)
Average of observable L (L can be pressure, number of particles, energy, etc.):
{ }
u
u u u u = u u =

LP tr aa
k L k L k k L L a
k k
) 7
) 7
(L being any observable of the system)
64
|u > < u | represents a state projector therefore it represents at all times the physical
behaviour of system o
(I)
. With the energy eigen states we find for the matrix of |u><u| :
| |
2
2
,
,
) ( ) ( ) 9
) ( ) , (
) 9 ); 7 , 7 ) ( ) 9
0 , ) 9
k k w b
or k k j j k
k j Lj k L c aa a with k w L b
H L assume we k k L a
k
k
k j
j
k j
k
k
k
u =
A u u u A =
u u = A =
= A =

o
k j j k k k j j
k j k j
u u = u u u u

) ( ) ( ) 8
,
*
,
Probability of measurement value A of observable L
65
Physics and Technology of Nano-Systems
In larger systems (see below Chap. 4.2) there could be a mixture of states, which need not to
be orthogonal to each other
1 ) 10
0
, , , , , 2 , 1
) 10
1
) (
) ( ) ( ) 1 ( ) 1 ( ) (
=
u u = u
= u
=
=
f
p assume we b
p p and f
a
o
o
o
o o o
o
A u u u A =
u u =

o
o o o o o
o
o o
o
o o o o
o
o
o
,
) (
2
) ( ) ( ) ( ) (
, ,
) ( ) (
) ( ) ( ) ( ) ( ) (
) ( ) , (
) 11
k
k
k j
j k p k j j k p
L p L p L
Average of L:
Compound probability
P
tot
= P
mix
x P
QM
for measurement value A
(o)
k
66
{ } L tr L b
P p a
o
o
o
=
=
u
) 12
) 12
) (
) (
Quantum mechanics and statistics (statistical operator): ( Toda, Kubo,Saito, Statistical Physics I, Solid
State Sciences 30 Springer Series 1992, Kubo,Toda Hashitsume Statistical Physics II Solid State Sciences 31 Springer
Series 1992 )
is called density matrix. According to the interaction of subsystems o
(I)
, o
(II)
the probability weights p
(a)
are given by boundary conditions o
(0)
= o
(I)
+ o
(II)
.
And the |u
(o)
|
2
are due to the Hamiltonians in systems o
(I)
, o
(II)
.
How we can get in the case of larger mixed systems?
The concept of phase space and entropy:
Motivation for definition of operator (statistical operator)
(compound probability mixed states / QM):
67
with E = phase space (PS) volume and O = surface in PS for E=E
0
. Simplest case (sphere with
radius E
0
). Eq. 13 is also called partition formula for PS volume. If the interaction between
subsystems I and II contain besides energy also particle and volume exchange we get for Eq.13:
Quantum mechanics and statistics: (Concept of phase space and entropy)
dE E E d ) ( ) ( ) 13 O = E
Eq. 16 motivates the definition of the entropy S:
Investigation of the phase space volumes (all moments, all positions of a particle in the class.
Case) (dimension of the Hilbert space of e.g. Hamiltonian H in the QM case) gives us the
relation:
j
j
j j
j
j
dx K dE
x E
E d
a or dx K dE x E x E d

=
O
E
)
`
O = E
) , (
) (
) 14 ) , ( ) , ( ) 14
With the 1
st
fundamental law of thermodynamics (energy conservation) and x
j
=V,N
dN pdV dE dQ TdS + = > ) 15 we get TdS
x E
E d
=
O
E
) , (
) (
) 16
68
Entropy and partition function:
16 . ) 17
1 1
) 17
) ln( ln : ) 17
Eq of result TdS
d
c
T
E
E
S
d
dS
b
E k k S a
B B
=
O
E
O

E c
c
c
c
=
E
O ~ E = o
Definition of Entropy
With differential relations Tab.1
(Maxwell relations) 1/T = oS/oE
From definition 17a we see that the entropy of a given system (o
(I)
, o
(II)
) is a measure of the
systems phase space volume.
S
k
S
k
B B
e E and e

~ O = E
1 1
) 18 o
69
Entropy and partition function:( Toda, Kubo,Saito, Statistical Physics I, Solid State Sciences 30 Springer
For interacting systems I, II and o
(I)
<< o
(II)
we can decompose the phase space volume
under the assumption that o
(I)
and o
(II)
is additive E
(0)
=E
(I)
+E
(II)
, x
j
(0)
=x
j
(I)
+x
j
(II)
:
using the entropies and
Development of S
(II)
at E
(0)
together with Tab.1 we get
( )
) (
0
) ( ) (
1
) ( ) (
1
) 0 ( ) ( ) ( ) (
) (
) 0 ( ) ( ) 0 ( ) (
) ( ) 19
I
E
I I
x K E
T k
E S E S
k
dE E e e b
j
I
j
I
j
I
I
B
II o
B
}
O
= + =
|
|
.
|
\
|
) (
0
) ( ) ( ) ( ) 0 ( ) ( ) 0 ( ) 0 (
) 0 (
) ( ) ( ) , ( ) 19
I
E
I I I II
dE E E E x E a
}
O E = E
Expression 19b is called partition function. In the case of quantum mechanics (the energies in
the subsystems dont change continously) the integral in Eq. 19b becomes a sum over energies,
particles,.:
( )
|
|
.
|
\
|

= + =
) 0 ( ) 0 (
) ( ) ( ) (
) (
) 0 ( ) ( ) 0 ( ) ( ,
,
1
) ( ) (
1
) 20
j a
j a
x K E
T k
E S E S
k j
I
j
I
j
I
a
I
B
II o
B
e e
classical
QM
70
Entropy and partition function form for given H:
Using a representation based on the eigenstates |k> of the Hamiltonian H :
k k E f H f c
k k E H b k E k H a
k
k
k
k k
=
= =
) ( ) ( ) 21
) 21 ) 21
we get for the partition function + :

= +
= +
k j
I
k j
I
j
I
k
B
j
I
j
I
j
I
B
x K E
T k
b
x K H
T k
tr a
) (
1
exp ) 22
) (
1
exp ) 22
) (
,
) (
) (
) ( ) ( ) (
and K
j
x
j
corresponds to pV, N
71
+
(

=
+
(

= =

k j
I
k j
I
k j k
B
j
I
j
I
j
B
k
k
k k x K E
T k
x K H
T k
b k k w a
) (
1
exp
) (
1
exp
) 24 ) 24
) (
,
) (
,
) ( ) (

Density matrix and averages of observables - relation to partition function:
As + represents the phase space or the dimension of the Hilbert space of system o
(I)
we get
the probability w
k
to find o (I) in the state with values E
(I)
, p
(I)
, T
(I)
,
(I)
, :
+
(

=

) (
1
exp
) 23
) (
,
) (
) (
j
I
k j
I
j
I
k
B
k
x K E
T k
w
The density matrix therefore reads:
According to Eq. 12b averages of observables are given by
{ } L tr L = ) 25
72
General TD-potential and averages of observables:
=
= + =
0
) 26 ) ) 22 ( ln ) 26
j
j j
TS x K A b b and kT A a
Definition of a general TD-potential A together with Eq. 22b):
Using x
0
=E, K
0
=1, x
1
=p, K
1
=V, x
2
= K
2
=N, we get explicitly for 26b :
TS N pV E A c + = ) 26
) ( ) ( ) ( ) (
) (
) (
) ( ) (
) (
1
, : .
:
: ) 27
:
, , : .
:
: ) 27
:
I I II I
II
I
I I
F S T E
T
A
N V const
E exchange
C b
canonical
S A
N V E const
exchange
MC a
canonical micro
= =

A describes the contacts given in Eqs. 1,2
73
) ( ) ( ) ( ) ( ) ( ) (
) (
) (
) ( ) ( ) ( ) ( ) ( ) (
) (
) (
) (
1
: .
, :
: ) 27
) (
1
: .
, :
: ) 27
I I II I II I
II
I
I I II I II I
II
I
Y S T N E
T
A
V const
N E exchange
GC d
canonical grande
G S T V p E
T
A
N const
V E exchange
Gibbs c
Gibbs
= =
= + =
74
=
c
c
= =
c
c
c
c
=

=
n j
K
A
E x j
K
A
K
T
A
T A
x a
I
j
I
j
I
j
I
I
j
I
I
I I
A
j
,... 3 , 2 , 1 ;
; 0 ;
) 28
) (
) (
0
1
) (
) (
) (
) (
) (
) ( ) (
With A also averages of observables can be calculated (according Tab. 1) :
For the canonical conjugated variables P to the const. Variables z we get :
)
1 1
( ;
) ln(
) 28
) ( ) (
) (
0
) (
) (
) (
0
) (
) (
) ( ) (
0
II I
I
I
l
I
I
I
l
I
A
I
l
I
kT kT z
A
z
P b =
c
c
=
c
+ c
= | | |
75
General TD-potential and density matrix: ( Toda, Kubo,Saito, Statistical Physics I, Solid State Sciences 30
Springer Series 1992, Kubo,Toda Hashitsume Statistical Physics II Solid State Sciences 31 Springer Series 1992 )
( )
( )
( )
( )
( )
( )
+
=
|
.
|
\
|

=
+
=
|
.
|
\
|
+
=
+
=
|
.
|
\
|
=
+
|
|
.
|
\
|
=

+ +

=
) (
1 1
) (
1 1
) (
1 1
1
1
:
1
:
1
:
) 28 ;
1
exp
) 28
GC
N H
kT
N H
kT
GC
G
pV H
kT
pV H
kT
G
C
H
kT
H
kT
C
j
j j
e
N H
kT
tr
e
GC
e
pV H
kT
tr
e
Gibbs
e
H
kT
tr
e
C
b
x K H
kT
a

The different potentials also give the form of the density matrices for the different contacts:
76
Chap. 6.5.1 Appendix e-h-plasma
Thermodynamic of a low dimensional plasma: ( Chow, Koch, Sargent III, Semiconductor-Laser
Physics, (Chap. 3,4,5) Springer-Verlag, Berlin Heidelberg 1994 )
In the following we discuss the relations to understand the thermodynamic properties
of a plasma consisting of electrons and holes
furthermore we give some important definitions to describe the plasma in different
dimensions
the observables which describe the plasma are the particle number N, the volume V, and the
the temperature T
Definition of carrier densities
) ( : ) 1 ( ) 89
) ( : ) 2 ( ) 89
) ( : ) 3 ( ) 89
3
2 2
3 3
=
= =
= =
cm
L
N
n D c
L A cm
A
N
n D b
L V cm
V
N
n D a
Densities are obtained by summation over
all states in k-space
3 , 2 , 1
) 2 (
1
) 90
: ) 90
0
0
= ~
=
O
=
}
}

=
=
=
=
d k d b
by replace
N
n a
F
F
k k
k
d
d
k k
k
t
77
Fermi momentum from Eq. 90a,b
) ( ) ( : ) 1 ( ) 91
) ( ) 2 (
2
: ) 2 ( ) 91
) ( ) 3 (
3
: ) 3 ( ) 91
1
1 2 / 1
2
2
1 3 / 1 2
2
3
= =
O
=
= =
O
=
= =
O
=
cm n k
k N
n D c
cm n k
k N
n D b
cm n k
k N
n D a
F
F
F
F
F
F
t
t
t
t
t
t
78
The internal energy of a plasma splits in an ideal kinetic part plus an part due to exchange
and correlation mechanisms.
) , ( ) , , ( ) 92 V N H T V N H H a
xc id tot
+ =
One finds that H
xc
depends only weakly on T and the index v of the single particle
energies and therefore a constant value E
xc
can be taken out from the sums. We get:
| |
| | { }
| |
| | { }
) (
) (
) (
) (
) (
) (
1
1
exp
) ( exp
exp
) ( exp
) ( ) 93
) 93
) , ( ) , , ( ) 93
) , ( ) , , ( ) 93
id
E
id
id
tot
tot
id
xc id
xc id
e
H tr
E H
tr
H tr
E H
tr E w d
S S c
V N E T V N F F b
V N E T V N E E a
+
=
)
`
)
`
=
=
+ =
+ =
|
|
o |
|
o |
79
Proof for 93 a:
) , ( ) , , ( ) 94
1 ) 94
V N E T V N E E aa
E H n H n H n H n E a
xc id
xc id xc id tot
+ =
+ = + = =

v
v v
v
v v
v
v v
v
v v
Canonical partition function and free energy according Eq. 26, 27
| | { } | | { } | |
| |
xc id
N N
xc id tot
N
E Z Z bb
kT
E H tr H tr Z b
|
| | | |
exp ) 94
1
exp exp exp ) 94
=
= = =
Proof for 93 b:
( ) ( )
xc id
xc id
N
tot
N
E F F cc
E Z kT Z kT F c
+ =
+ = =
) 94
ln ln ) 94
80
Proof for 93 c: (entropy according Eq. 27b and with Eq. 94b)
( ) ( )
( )
T
E
Z k S S dd
T
E
T
E
T
E
Z k
T
E
Z k S d
id
id
N
id
xc id xc
id
N
tot
N
+ =
+ + = + =
ln ) 94
ln ln ) 94
Proof for 93 d: in exercises
81
derivative of a thermodynamical potential with respect to particle number:
according Eq. 89a-c one gets for all dimensions for a arbitrary potential P
) 1 3 ( ) , , ( ) , ( ) 95
) (
) 95
1
, ,
D D N T V N P T n p b
n
np
N
P
a
V T V T
=
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c

(p=P/N represents a thermodynamical potential per particle)
chemical potential of a plasma from free energy f=F/N
} }
=
=
= =
c
c
+ =
|
.
|
\
|
c
c
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E f E D dE k k d n
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) ( ) ( ) ( : ) 96
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max
c
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82
sketch of the different energies in a plasma with renormalization of ist energy levels as
function of carrier density.
xc
h
xc
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xc
g
xc xc id
xc id
E E
holes and electrons for
different ation renormaliz
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gap band ed renormaliz
plasma the of
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+ =
= =
+ =
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)
( ) 97
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xc
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E
xc
h
id
h
id
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Semiconductor Physics I

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Semiconductor Physics I

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SC-Phys-I_Schweizer-2010

Density of states lin. sum.

for l=3 (other dim see 6.1.5)

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