Excitons

1
ECE 407 Spring 2009 Farhan Rana Cornell University

Review Handout
Excitons and Optical Absorption Spectra
Electromagnetic Wave Basics
Consider an electromagnetic wave passing through a solid with electric field
given by:
( ) ( ) t r q E n t r E
o
e =

. sin ,
The vector potential associated with the field is:
( )
( )
t
t r A
t r E
c
c
=
,
,
( ) ( )
( ) t r q A n
t r q
E
n t r A
o
o
e
e
e
=
=

. cos
. cos ,
The power per unit area or the Intensity of the field is given by the Poynting vector:
( ) ( ) ( )
q
e
q 2
2
, , ,
2 2 2
o o
A
q
E
q t r H t r E t r S I = = = =

n
o o
q
c
q = =
The photon flux per unit area is:

q
e
e 2
2
o
A
I
F = =
E
The divergence of the field is zero:

( ) ( ) 0 , . , . = V = V t r A t r E

2
Two-Band Model for Non-interacting Electrons
Consider optical absorption in a semiconductor described by a two-band model:
e
The initial state of ALL the electrons is
the many-body state in which all the
valence band is full and the conduction
band is empty:
0
initial
=
After absorption of a photon, the final
many-body state is the one in which there
is one electron in the conduction band
and one empty space (or hole) in the
valence band:
0
final
k
k
b c

+
=
Where and are the destruction and creation operators for conduction
band states, and and are the destruction and creation operators for
the valence band states
k
c
+
k
c
k
b
+
k
b
matter) not (does ??

initial
= E
( ) ( ) e

= + = =
r
g v c
m
k
E k E k E E E
2
2 2
initial final
k

Optical Transition Rate
The transition rate (per unit volume per second) is given by the Fermis golden rule:
( ) e o
t

=
| | initial final
2
initial final
states
final ll
1 2
E E V
V
R
A
The perturbation due to the radiation field is approximately (neglecting the
photon wavevector in comparison to the electron wavevector) :
= =
+
+
+
|
k
k k
vc
o
k
k k
cv
o
c b n P
m
A e
V b c n P
m
A e
V

n P
m
A e
b c n P
m
A e
c b
b c n P
m
A e
c b V
cv
o
k k
cv
o
k k
k
k k
cv
o
k k
.
2

0 .
2
0
0 .
2
0
'
' '
final final

=
=
=
+ +
+ +
|

The optical matrix element is then:
( ) ( ) ( ) e o
t

|
.
|
\
|
=
|
k E k E
V
n P
m
A e
R
v c
k
cv
o
2
.
2
2
2
2
Also added a
factor of 2 for
the spin
3
Two-Band Model for Interacting Electrons
e
The Hamiltonian is now assumed to include coulomb interaction between electrons:
( ) ( ) ( )
( ) ( ) + +
+ + =
+
+
+
+
+
+
+
+
+
+ +
q k k
k k q k q k
q k k
k k q k q k
q k k
k k q k q k k k
k
v
k k
k
c
b b b b q V
V
c c c c q V
V
c b b c q V
V
b b k E c c k E H

, ' ,
' '
, ' ,
' '
, ' ,
' '
2
1
2
1

1
( ) = =
2
2
q
e
q V
s
c
Fourier transform of the repulsive coulomb potential between electrons

The last two terms describe coulomb interaction between
conduction electrons only and between valence electrons
only, respectively, and both terms can be ignored here
(since the conduction band is empty and the valence band
is full)
We keep only the term that describes the coulomb
interaction between the conduction and valence electrons:
( ) ( ) ( ) + + =
+
+
+
+ +
q k k
k k q k q k k k
k
v
k k
k
c
c b b c q V
V
b b k E c c k E H

, ' ,
' '
1

e
Problem:
In the presence of coulomb interaction between electrons,
the assumed final state:
is not an eigenstate of the Hamiltonian:
0
final
k
k
b c

+
=
final final final
E H =
( ) ( ) ( ) + + =
+
+
+
+ +
q k k
k k q k q k k k
k
v
k k
k
c
c b b c q V
V
b b k E c c k E H

, ' ,
' '
1
Lets make sure:

( ) ( ) | | ( )
final final initial final
0
1
+ =
+
+
+
q
q k q k
v c
b c q V
V
k E k E E H

So what do we do??
Two-Band Model for Interacting Electrons
4
e
( ) ( ) ( ) + + =
+
+
+
+ +
q k k
k k q k q k k k
k
v
k k
k
c
c b b c q V
V
b b k E c c k E H

, ' ,
' '
1
( ) =
+
k
k k
b c k A
V

0
1
final
The Exciton State

We try a different final state that could be an eigenstate:
It is a superposition of electron-hole states with different momenta!
( ) ( ) ( ) | | ( ) ( ) + =
+ +
q k
k k
k
k k
v c
b c q V q k A
V
b c k E k E E k A H

,
initial final
0
1
0

Lets see if this could be an eigenstate:
If we want the above to equal:
( ) = =
+
k
k k
b c k A
V
E E H

0
1
final final final final

then we must have:
( ) ( ) ( ) | | ( ) ( ) ( ) = +
q
v c
k A E q V q k A
V
k E k E E k A

final initial
1
( ) 1
1
1
2
final final
= =
k
k A
V

Superposition
The Exciton State
( ) ( ) | |
r
g v c
m
k
E k E k E
2
2 2

+ =
Note that:
The easiest way to solve the above equation is to inverse Fourier transform it:
( ) ( ) ( ) ( ) r A E E E r A r V
m
g r
r

=
(
V
initial final
2
2
2
( )
r
e
r V
s
tc 4
2
=
The above equation looks like the Schrodinger equation of a hydrogen atom (in
relative coordinates) with an attractive coulomb potential. The bound solutions are
hydrogenic wavefunctions and the corresponding energies are:
{ ..... 3 , 2 , 1
2
initial final
= + = n
n
E
E E E
o
g
2
2
2
4
2
|
|
.
|
\
|
=
s
r
o
e m
E
tc
Lowest excited state (with the smallest E

final
) has:
( ) ( )
o
a r
o
s m n
e
a
r r A

= = =
= =
3
1 0 , 0 , 1
1
t
|

r
s
o
m
e
a
2
2
4
|
.
|
\
|
=
tc
o g
E E E E + =
initial final
( ) ( ) ( ) | | ( ) ( ) ( ) = +
q
v c
k A E q V q k A
V
k E k E E k A

final initial
1
5
The Exciton State
The final state:
( ) =
+
k
k k
b c k A
V

0
1
final
is a superposition of electron-hole states with different momenta

This superposition ensures that the hole state in the valence band is localized in real
space near the electron and the electron state is localized in real space near the hole
The electron and hole form a bound hydrogen-atom-like state and the function (or the
wavefunction) describes their relative positions (i.e. ) ( ) r A

e h
r r r

=
{ ..... 3 , 2 , 1
2
initial final
= + = n
n
E
E E E
o
g
To illustrate the last point, we will take the exciton state and try to destroy the
electron in the conduction band at location and create an electron in the
valence band at location and see if we are successful in doing so, and with
what probability
The real-space destruction and creation operators for electrons in the conduction
and valence bands are:
e
r
h
r
( ) ( )
( ) ( ) = =
= =
+
+
+
+
k
k
r k i
v
k
k
r k i
v
k
k
r k i
c
k
k
r k i
c
b
V
e
r b
V
e
r
c
V
e
r c
V
e
r

. .
. .

The Exciton State
The probability with which we can destroy and electron in the conduction band at
location and create an electron in the valence band at location is given by
the expression:
e
r
h
r
( ) ( )
( )
V
r r A
r r
e h
e c h v
2
2
final
0

=
+

The above result shows that the conduction band electron and the valence band hole
in real space are localized near each other and their relative positions are described by
the wavefunction ( ) r A

( ) =
+
k
k k
b c k A
V

0
1
final
Interaction
Superposition
In real space
(semi-classical picture)
Electron (-)
Hole (+)
In k-space
6
Optical Transition Rate for the Exciton States
( ) e o
t

=
| | initial final
2
initial final
states
final ll
1 2
E E V
V
R
A
Where as before:
= =
+
+
+
|
k
k k
vc
o
k
k k
cv
o
c b n P
m
A e
V b c n P
m
A e
V

( )
( )
( ) =
=
=
+ +
+ +
|
k
cv
o
k k
cv
o
k k
k
k
k k
cv
o
k
k k
k A
V
n P
m
A e
b c n P
m
A e
c b k A
V
b c n P
m
A e
c b k A
V
V

*
*
'
' '
*
final final
1
.
2

0 .
2
0
1

0 .
2
'
1
0

( ) =
|
k
cv
o
k A
V
n P
m
A e
V

*
final final
1
.

The optical matrix element is:
We get:
( ) ( )
( )
2
2
2
2
final final
* *
final final
0 .
0 .
2
1
.
A V n P
m
A e
V
r A V n P
m
A e
k A
V
n P
m
A e
V
cv
o
cv
o
k
cv
o
|
.
|
\
|
=
= = =
|
|

( )
|
.
|
\
|
|
.
|
\
|
=
=
=
|
e o
t

2
2
, ,
1
0 1
2
2
0 2 .
2
2
n
E
E A n P
m
A e
R
o
g m n
m
n
n
cv
o
{ ..... 3 , 2 , 1
2
initial final
= + = n
n
E
E E E
o
g
All final exciton states can be labeled by the hydrogen atom indices n, , m :
( ) =
+
k
k k
m n
b c k A
V

0
1
, , final
So the transition rate (per unit volume per second) becomes:

Also added a factor
of 2 for the spin
7
( )
|
.
|
\
|
|
.
|
\
|
=
=
=
|
e o
t

2
2
, ,
1
0 1
2
2
0 2 .
2
2
n
E
E A n P
m
A e
R
o
g m n
m
n
n
cv
o
The transition rate (per unit volume per second) is:
In the hydrogen atom, only the s-orbitals have non-zero probability at the center
Therefore:
( )
|
.
|
\
|
|
.
|
\
|
=

=
|
e o
t

2
2
0 , 0 ,
1
2
2
0 2 .
2
2
n
E
E A n P
m
A e
R
o
g n
n
cv
o
The delta function is usually replaced by a Lorentzian whose width is related to the
exciton (bound electron-hole pair) lifetime:
( )
2
2
2
2
0 , 0 ,
1
2
2
0 2 .
2
2
I + |
.
|
\
|

I
|
.
|
\
|
=

=
|
e
t t
n
E
E
A n P
m
A e
R
o
g
n
n
cv
o
The exciton absorption spectrum consists of sharp lines below the bandgap energy
e
( ) e
|
R
g
E
Complete Optical Absorption Spectrum
( ) ( ) ( ) ( ) e o
t
e

|
.
|
\
|
=
|
k E k E
V
n P
m
A e
R
v c
k
cv
o
2
.
2
2
2
2
( ) ( )
2
2
2
2
0 , 0 ,
1
2
2
0 2 .
2
2
I + |
.
|
\
|

I
|
.
|
\
|
=

=
|
e
t t
e
n
E
E
A n P
m
A e
R
o
g
n
n
cv
o
Exciton lines
n=1
n=2
n=3
n=4
This part can be also obtained by
considering the non-bound
solutions of the attractive Coulomb
potential
8
Moving Excitons
( ) =
+
k
k k
b c k A
V

0
1
The state:
describes a stationary exciton (with no momentum)
We can construct a state with a non-zero momentum as well
Consider the state:
In k-space
(Superposition)
( ) =
+
+
+
k
Q k Q k
b c Q Q k A
V

0 , ,
1
2 1
2 1
( ) ( ) ( ) | |
( ) ( )
+ + + =
+
+
+
+
+
+
q k
Q k Q k
k
Q k Q k
v c
b c q V q k A
V
b c Q k E Q k E E Q Q k A H

,
2 1 initial 2 1
0
1

0 , ,
2 1
2 1
Lets see if this is an eigenstate of the Hamiltonian:

It is an eigenstate provided:
( ) ( ) ( ) | |
( ) ( ) ( )
2 1 final
,
2 1
2 1 initial 2 1
, , , ,
1

, ,
Q Q k A E q V Q Q q k A
V
Q k E Q k E E Q Q k A
q k
v c

=
+ + +
Moving Excitons
( ) ( )
h e h e r
g v c
m
Q
m
Q
m
Q k
m
Q k
m
k
E Q k E Q k E
2 2
. .
2
2
2
2 2
1
2
2
2
1
2 2 2
2 1

+ + + + + = + +
Note that:
The equation to be solved is:
( ) ( ) ( ) | |
( ) ( ) ( )
2 1 final
,
2 1
2 1 initial 2 1
, , , ,
1

, ,
Q Q k A E q V Q Q q k A
V
Q k E Q k E E Q Q k A
q k
v c

=
+ + +
A bound solution is possible only if:
Q
m
m
Q Q
m
m
Q
m
Q k
m
Q k
e
r
h
r
h e

= = = +
2 1
2
2
1
2
0
. .
( ) ( ) =
+
+ k Q
m
m
k Q
m
m
k
e
r
h
r
b c Q k A
V
Q

0 ,
1
( ) ( ) ( )
( )
( ) Q r A
m m
Q
E E Q E Q r A r V
m
h e
g r
r

,
2
,
2
2 2
initial final
2
2
|
|
.
|
\
|
+
=
(
V
Upon inverse Fourier transforming:
9
Moving Excitons
The equation:
( ) ( ) ( )
( )
( ) Q r A
m m
Q
E E Q E Q r A r V
m
h e
g r
r

,
2
,
2
2 2
initial final
2
2
|
|
.
|
\
|
+
=
(
V
is identical to the previous one except that the solutions now will have an extra
kinetic energy term:
( )
( )
{ ..... 3 , 2 , 1
2
2 2
2
initial final
=
+
+ + = n
m m
Q
n
E
E E Q E
h e
o
g

The extra term stands for the kinetic energy of the moving exciton which is moving
with a velocity:
( ) ( )
( )
h e
Q
m m
Q
Q E Q v
+
= V =

final exciton
1
The state:
( ) ( ) =
+
+ k Q
m
m
k Q
m
m
k
e
r
h
r
b c Q k A
V
Q

0 ,
1
therefore describes an exciton with a momentum equal to Q

Interaction of Moving Excitons with Radiation
( ) e o
t

=
| | initial final
2
initial final
states
final ll
1 2
E E V
V
R
A
Where as before: = =
+
+
+
|
k
k k
vc
o
k
k k
cv
o
c b n P
m
A e
V b c n P
m
A e
V

( ) ( )
0
0 .
2
, '
1
0
' ' '

*
final final
=
=
+
+
+
|
k
k k
cv
o
k Q
m
m
k Q
m
m
k
b c n P
m
A e
c b Q k A
V
V Q
h
r
e
r

unless: 0 = Q
Radiation only interacts with zero momentum excitons!

If photon momentum is not ignored than: q
= =
+
+
+
+
+
|
k
q k k
vc
o
k
k q k
cv
o
c b n P
m
A e
V b c n P
m
A e
V

( ) 0
final final
=
|
V Q

unless: q Q

=
The momentum of the absorbed photon is the momentum of the photogenerated
exciton!
10
The Exciton Gas and BEC
Consider the exciton dispersion relation:
( )
( )
{ ..... 3 , 2 , 1
2
2 2
2
initial
=
+
+ + = n
m m
Q
n
E
E E Q E
h e
o
g

A large exciton population generated by light (or by any other mechanism) quickly
acquires a thermal (Bose-Einstein) distribution with a non-zero Fermi level:
( ) Q E

( )
( ) ( )
1
1
=
KT E Q E
f
e
Q n
But only excitons near interact with radiation

Bose-Einstein Condensation of Excitons:
At low enough temperatures and high enough exciton densities, one can achieve
a macroscopic population of excitons in the lowest state and all excitons
in this state will interact with radiation! This BEC of excitons has been achieved
experimentally in semiconductor quantum wells!
0 = Q
0 = Q

Excitons

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Excitons

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1

ECE 407 Spring 2009 Farhan Rana Cornell University

The divergence of the field is zero:

matter) not (does ??

ECE 407 Spring 2009 Farhan Rana Cornell University

Fourier transform of the repulsive coulomb potential between electrons

ECE 407 Spring 2009 Farhan Rana Cornell University

Lets make sure:

The Exciton State

final final final final

Lowest excited state (with the smallest E

is a superposition of electron-hole states with different momenta

So the transition rate (per unit volume per second) becomes:

Lets see if this is an eigenstate of the Hamiltonian:

therefore describes an exciton with a momentum equal to Q

ECE 407 Spring 2009 Farhan Rana Cornell University

' ' '

Radiation only interacts with zero momentum excitons!

The optical matrix element is then:

But only excitons near interact with radiation

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