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Polymers for photovoltaics
PHY652B
3. Op9cal proper9es of organic semiconductors
Gilles Horowitz

gilles.horowitz@polytechnique.edu

Polymers for photovoltaics 2016

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)

Polymers for photovoltaics 2016

Interac9on of light with molecules


Light is an electromagne9c wave that exerts electric and
magne9c forces on charges par9cles (electrons and nuclei) and
magne9c dipoles (spins)
A light wave generates a 9me-dependent force eld similar to
that generated by an oscilla9ng electric dipole
Electrons in molecules and solids may be set into mo9on by
the oscilla9ng electric eld of light
The interac9on of light and molecules can be viewed as a
process in which energy is exchanged between a radia9on eld
and a collec9on of oscilla9ng dipoles
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Dipole

An electric dipole is a pair of electric charges of equal


magnitude q but opposite sign, separated by a distance a
The dipole moment is dened as a vector poin9ng from the
nega9ve to the posi9ve charge with a magnitude equal to the
electric charge 9mes the distance between the two charges
= qa

Some molecules have a permanent dipole moment

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Oscilla9ng dipole generates light

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Light makes dipoles to oscillate

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Transi9on dipole
gravity centre of
the molecule

light

r
r

electron

= er

=h

i|

er|

fi

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Oscillator strength

In the classical theory, the oscillator strength f is a sta9s9cal


weight indica9ng the rela9ve number of oscillators bound to a
resonant frequency
In quantum mechanics, f measures the rela9ve strength of an
electronic transi9on within an atomic or molecular system

Polymers for photovoltaics 2016

Rela9on between f and


4m 2
f=
||
2
3~e

is the resonant frequency related to the energy


dierence E between the ini9al and nal states by
E = h

Polymers for photovoltaics 2016

Beer-Lamberts law
I0

cuveNe

T = I/I0 , OD = log10 (1/T )

Absorbance: A = log10(I0 / I) Also known as Op9cal Density (OD)


Assump9on 1: A c (concentra9on of the solu9on)
Assump9on 2: A d
A = dc, molar ex9nc9on coecient
Unit: L.mol-1.cm-1 or m2.mol-1
Note that the absorbance uses decimal logarithms

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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

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Energy

Energy (E) vs. wavelength () vs. wavenumber ()


E = h ( = frequency)
= c / (c = light speed)
= 1/; (cm1) = 10,000 / (m)
E = hc / ; E (eV) = 1.24 / (m); E (eV) = (1.24 x 104) (cm1)

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The oscillator strength can be es9mated by integra9ng the


molar ex9nc9on coecient over the whole energy range:
f = 4.3 10

"d

Note that here the energy is expressed in terms of


wavenumber (unit: cm-1)

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Vibra9onal structure
absorp9on

emission

atom: Sharp line


absorp9on and emission
molecule:
Vibra9onal
structure
emission absorp9on

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In a molecule, one has to consider the mo9ons of the nuclei


rela9ve to one another (vibra9ons, rota9ons, collisions)
The absorp9on and emission spectra involve transi9ons over a
range of energy, so that the sharp line broadens into a set of
closely spaces lines
In some cases (e.g., molecules in solu9on) the absorp9on and
emission lines appear as unresolved broad features

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Vibra9onal energy

In a diatomic molecules, nuclei have an equilibrium spacing R0


If this distance is slightly changed (R = R0 + x) the respec9ve
poten9al energy can be developed in a Taylor series:
V (x) = V (0) + x

dV
dx

x
+
2
x=0

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d V
dx2

x
+
6
x=0

d V
dx3

+ ...
x=0

Polymers for photovoltaics 2016

Not interested in absolute poten9al, so we can set V(x) = 0

dV
x = 0 corresponds to equilibrium, so
dx

=0
x=0

The lowest approxima9on is the harmonic oscillator


The energy of the quantum mechanical harmonic oscillator is
quan9zed and limited to the values
En =

n is an integer

1
n+
2

~!, ! =

17

k
m

1/2

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Harmonic oscillator

n = 5
n = 4
n = 3
n = 2
n = 1
n = 0

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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
~

Hn(y) is the Hermite polynomial of degree n


n
d
Hn (y) = ( 1)n ey
e
n
dx
2

y2

Eigen energy
En =

1
n+
2
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~!
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Hermite polynomials

H0 (y) = 1
H1 (y) = 2y
H2 (y) = 4y 2

H3 (y) = 8y 3

12y

H4 (y) = 16y 4

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48y 2 + 12

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Wave func9on

Probability density

n=4
n=3
n=2
n=1
n=0

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Franck-Condon principle

The mass of electrons is much lower than that of nuclei


Electronic transi9on occur in a sta9onary nuclear framework

Nuclei remain unchanged during an electronic transi9on. then


re-adjust aWer electrons have adopted their nal distribu9on
In most cases, excited states have a more an9-bonding
character than ground states. so equilibrium bond length
increases

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rst excited state

Absorp9on

Here. 01 is the most probable


Franck-Condon transi9on

ground state

R0 R0*
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Absorp9on - emission

When light is absorbed. molecules are in the lowest vibra9onal


level of the ground-state
When light is emiNed. the excited state decays from the lowest
vibra9onal level
In the ideal case, the ground and rst excited states have
iden9cal harmonic poten9al, so absorp9on is the mirror image
of emission

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rst excited state

Emission

ground state

01 the most probable


Franck-Condon transi9on

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Absorp9on and emission spectra


absorp9on

emission

atom: sharp line

absorp9on and emission


molecule:
vibra9onal
structure

emissionabsorp9on
emission is the mirror image of absorp9on
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Excitons

An exciton is a Coulombically bound combina9on of an


electron and a hole
Equivalent to liWing an electron from the HOMO to the LUMO
level

Excitons can be formed by absorp9on of an energe9c photon


(photoluminescence) or direct recombina9on of an electron
and a hole (electroluminescence)

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Exciton binding energy


M+ + M M* + M

LUMO

energy gap

op9cal gap

HOMO
electron
polaron

hole
polaron

exciton

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neutral
molecule

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Frenkel vs Wannier exciton

(a) Frenkel exciton


(b) Wannier exciton

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Frenkel exciton: Large binding energy (> kT), small extension


(localised on a single molecule)
Wannier exciton: Small binding energy (< kT), extends over
several lawce parameters
2
e
Exciton binding energy Eb
4 k 0 R
energy is inversely propor9onal to size R
energy is inversely propor9onal to dielectric constant k

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The dielectric constant in solids measures the screening of the


Coulomb force by the charges (electrons and nuclei). The
higher the dielectric constant. the more ecient the screening
Organic materials have low dielectric constants (k = 3 - 5). The
interac9on between the electron and the hole that cons9tute
the exciton is high, so the size of the exciton is small (Frenkel
exciton). The binding energy of a Frenkel exciton in in the range
0.1 to 1 eV. and its size compares with that of a unit cell
Inorganic semiconductors have large dielectric constants (k >
10). The binding energy of the exciton is lower than kT, so it
spontaneously dissociates at room temperature. The Wannier
exciton extends over several unit cells.

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Exciton binding energy


energy gap

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

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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

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Spin wave func9on


Singlet (S = 0)

Triplet (S = 1)

Ms = 1, |

1
Ms = 0, (|
2

1
Ms = 0, (| + | )
2

| )

Ms =

An9-symmetric

1, |
Symmetric

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The overall quantum state of an electron (or a hole) is dened


by spa9al and spin coordinates

spatial

spin

As electrons and holes are Fermions. Paulis exclusion principle


dictates that the total wave func9on of a mul9-electron state is
an9-symmetric with respect to par9cle exchange
Thus. spa9al wave-func9ons must have opposite symmetry to
spin wave func9on

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Spa9al wave-func9on
singlet: symmetric

triplet: an9symmetric

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The spa9al wave func9on of a singlet state is symmetric. That


of a triplet state is an9-symmetric
Much smaller overlap of the electrons for the triplet state;
therefore, much smaller Coulomb repulsion between the
electrons
Energy of triplet excited state signicantly lower than that of the
singlet state
The dierence is termed exchange energy

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Luminescence yield
S2
S1

inter-system crossing

kisc
Fluorescence

Absorp9on
knf

kf

kp

T1

knp

Exchange
energy

Phosphorescence

S0
Singlet

Triplet
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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

Fluorescence quantum yield


kf
=
, 0
kf + knf
39

1
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According to classical theory, the radia9ve rate constant kf (per


unit 9me) is related to the molar ex9nc9on coecient by:
kf = 3 10

9 2
0

2
"d

= 0f

Here, 0 is the wavenumber of the maximum of absorp9on

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Case of polymers
Disordered molecular semiconductors

Recall we can describe a organic


semiconductor as having a Gaussian
distribution of states.
If an exciton is created on a molecule
(polymer chain), having a large energy
gap, it can undergo rapid energy
transfer to neighbouring sites of lower
Polymers are cons9tuted of
energy.

chains of various length


LUMO
(empty states)

The longer the chain. the


narrower the HOMO-LUMO
energy gap
Energy

poly(9.9-dioctyl-uorene)
Data from polymer
poly(9,9 dioctyl fluorene)

HOMO
(filled states)

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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

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short chains

long chains

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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)

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Energy transfer by dipole interac9on

di

LUMO

po
o
c9
ra
te
i n
le
n

HOMO
M1*

M2

M1

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M2*

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Energy transfer by electron exchange


electron exchange
LUMO

electron exchange
HOMO
M1*

M2

M1

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M2*

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The dipole interac9on is an ac9on at distance: each electron


stays in the same molecule before and aWer the energy
transfer. The interac9on occurs via the Coulomb force and does
not require physical contact of the molecules.
The exchange interac9on involves a double subs9tu9on
reac9on: An electron ini9ally on M1 jumps to M2
simultaneously with the jump of an electron from M2 to M1.
The interac9on requires physical contact between the
molecules.

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Exciton diusion

Excitons are uncharged species. They do not move under the


ac9on of an electric eld
They can diuse in a solid through the process of energy
transfer
Because the intermolecular distance in a solid is mainly
dictated by its crystal structure. the Frster (dipolar) process is
more likely than the Dexter (electron exchange) process

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