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Polymers for photovoltaics
PHY652B
3. Op9cal proper9es of organic semiconductors
Gilles Horowitz
gilles.horowitz@polytechnique.edu
Books
hNp://plas9cphotovoltaics.org/lc
Organic Photovoltaics: Mechanisms, Materials, and Devices,
Sam-Shajing Sun & Niyazi Serdar SariciWci (Eds), CRC Press
(2005)
Organic Photovoltaics, Christoph Brabec, Vladimir Dyakonov,
Ullrich Scherf (Eds), Wiley-VCH (2009)
Polymer electronics, Mark Geoghegan & Georges
Hadziioannou, Oxford University Press (2013)
Dipole
Transi9on dipole
gravity centre of
the molecule
light
r
r
electron
= er
=h
i|
er|
fi
Oscillator strength
Beer-Lamberts law
I0
cuveNe
10
OD vs. transmiNance
T = I/I0 , OD = log10 (1/T )
Optical density
Transmittance
Transmittance (%)
100
0.1
0.79
79
0.25
0.56
56
0.5
0.32
32
0.75
0.18
18
0.9
0.13
13
0.1
10
0.01
0.001
0.1
11
Energy
12
"d
13
Vibra9onal structure
absorp9on
emission
14
15
Vibra9onal energy
dV
dx
x
+
2
x=0
16
d V
dx2
x
+
6
x=0
d V
dx3
+ ...
x=0
dV
x = 0 corresponds to equilibrium, so
dx
=0
x=0
n is an integer
1
n+
2
~!, ! =
17
k
m
1/2
Harmonic oscillator
n = 5
n = 4
n = 3
n = 2
n = 1
n = 0
18
Wave func9on
Time-independent Schrdinger equa9on
~2 d 2
1 2
+ kx
2
2m dx
2
=E
Wave func9on
1/4 1 1/2
Hn (y)e
n (x) =
n
2 n!
y 2 /2
m!
, =
, y = 1/2 x
~
y2
Eigen energy
En =
1
n+
2
19
~!
Polymers for photovoltaics 2016
Hermite polynomials
H0 (y) = 1
H1 (y) = 2y
H2 (y) = 4y 2
H3 (y) = 8y 3
12y
H4 (y) = 16y 4
20
48y 2 + 12
Wave func9on
Probability density
n=4
n=3
n=2
n=1
n=0
21
Franck-Condon principle
22
Absorp9on
ground state
R0 R0*
23
Absorp9on - emission
24
Emission
ground state
25
emission
emissionabsorp9on
emission is the mirror image of absorp9on
26
Excitons
27
LUMO
energy gap
op9cal gap
HOMO
electron
polaron
hole
polaron
exciton
28
neutral
molecule
29
30
31
op9cal gap
binding E (eV)
Cu-Pc
2.3
1.7
0.6
Zn-Pc
2.2
1.7
0.5
PTCDA
3.2
2.6
0.6
6T
3.4
0.4
pentacene
2.95
1.84
1.1
Alq3
4.6
3.2
1.4
32
Singlet vs triplet
Electrons and holes have an intrinsic angular momentum (spin)
s = 1/2. mz = 1/2
s = magnitude of spin. mz = projec9on of s on z-axis
spin can be up (ms = + 1/2) or down (ms = - 1/2)
Excitons combine two spin 1/2 par9cles. Their total spin can be
either S = 0 or S = 1
If S = 0, only one possible value of z-axis projec9on (Ms = 0). State
termed singlet
If S =1, Ms = - 1, 0 or + 1. This state is termed triplet
33
Triplet (S = 1)
Ms = 1, |
1
Ms = 0, (|
2
1
Ms = 0, (| + | )
2
| )
Ms =
An9-symmetric
1, |
Symmetric
34
spatial
spin
35
Spa9al wave-func9on
singlet: symmetric
triplet: an9symmetric
36
37
Luminescence yield
S2
S1
inter-system crossing
kisc
Fluorescence
Absorp9on
knf
kf
kp
T1
knp
Exchange
energy
Phosphorescence
S0
Singlet
Triplet
38
Time scales
Absorp9on 10-15 s
Vibra9onal decay 10-12 s
Fluorescence emission 10-9 s
Phosphorescence 10-6 to 10-3 s
The observed uorescence life 9me combines the radia9ve and
non radia9ve rates by
obs =
1
kobs
1
=
kf + knf
1
Polymers for photovoltaics 2016
9 2
0
2
"d
= 0f
40
Case of polymers
Disordered molecular semiconductors
poly(9.9-dioctyl-uorene)
Data from polymer
poly(9,9 dioctyl fluorene)
HOMO
(filled states)
41
Absorp9on
All the chains absorb light. Because of the distribu9on of chain
lengths, this results in a broad, featureless absorp9on spectrum
Emission
Excited electrons tend to migrate to the chains with lowest LUMO
energy level. Only those chains emit light, so the vibra9onal
structure is preserved
42
short chains
long chains
43
Exciton diusion
A Frenkel exciton can be viewed either as a localised electronhole pair or as an excited molecule
Exciton diusion occurs via energy transfer from one molecule
to a neighbouring molecule: M1* + M2 M1 + M2*
Two basic processes for energy transfer
Dipole-dipole coupling (Frster)
electron exchange (Dexter)
44
di
LUMO
po
o
c9
ra
te
i n
le
n
HOMO
M1*
M2
M1
45
M2*
electron exchange
HOMO
M1*
M2
M1
46
M2*
47
Exciton diusion
48