SS12 PhysEngII 1 PDF

M. Sc.
Polymer Science A joint program by FU, HU, TU, and UP

First year, fourth quarter

Dr. Frank Jaiser / Prof. Dr. Dieter Neher*
Sahika Inal, M.Sc.
Physical and Engineering Properies II:
Opto-electrical Properties of Polymers
2 Physical & Engineering Properties II 2012
Contents
VII Polymers for Optical Data
Communication
Polymer optical waveguides and fibres
Integrated optics with polymers

VIII Conjugated Polymers
t-electron conjugated systems
Molecular orbital approaches
Excited states and charges on polymer
chains

IX Emission from Conjugated Polymers
Fluorescence and phosphorescence
Fluorescence quantum yield and
fluorescence lifetime
Polymer Lasers
X Charges in Polymers
Mechanism of charge transport in
polymers
Conducting polymers
Field-effect transistors
Electroluminescence
Photogeneration of charges and solar
cells
Literature
Electrical Properties of Polymers
T. Blythe and D. Bloor
Cambridge University Press 2005
hardcover ISBN 0521552192, 87 ; paperback ISBN 0521558387, 46 ;
university library

Polymers and Light Fundamentals and Technical Applications
W. Schnabel
Wiley-VCH 2007
ISBN 3527318666, 179
VII Polymers for
Optical Data Communication
Fiber Optics
Polymers are suitable for data transmission, manipulation and storage.
Depending on the materials, this can be done optically or electrically.
Why not use electrical wires (and signals)?
capacity and resistivity of wire cause losses at
high signal rates
emission of electromagnetic waves can be
monitored
noise due to other EM sources
Optical Data Transmission and Processing
80 Mbps optical link for plastic optical fiber
optical data transmission
Early examples: divergent, spectrally broad & slow
Greece, about 1000 BC: sun light & mirrors
Today: small, monochromatic light sources with low divergence
1960 Ruby laser
1961 HeNe laser
1963 GaAs laser
Snells law of refraction:
for n
2
< n
1
,
2
will approach 90 for large
1
, i.e. no refraction
total reflection at interface
enclose medium 1 by medium 2:
light can not leave medium 1
total internal reflection

19
th
century, John Tyndall : guide light inside a water stream
1950s: use glass fibers for illumination
1960s: invention of LASER, use for data transmission
Nobel prize 2009 Charles Kuen Kao for groundbreaking
achievements concerning the transmission of light in fibers
for optical communication
Total (Internal) Reflection
2 2 1 1
sin sin n n =
1
n
1
n
2
< n
1
2
Guided Wave Optics
total internal reflection for
propagation angle
transmission velocity along a waveguide
acceptance angle & numerical aperture
typically, n = n
1
-n
2
0.02-0.1
1
2
sin
n
n
>
u = 90
2
1
2
0
1
2
1 1 1 1
sin cos
n
n
c
n
n
c c c v = = = = u
o o ~ ~ =
2
2
2
1
sin n n n NA
air
c
1
v
1
n
1
n
2
< n
1
Transmission Modes
light propagation:
light at points A and C needs to be in phase
such that AC is one wave front

consider
reflections at A and B introduce phase
changes (0 for loose ends, n
2
< n
1
)
path length AB+BC
( )
u
u
u u
u u
u
sin 2
2 cos
sin sin
2 cos 2 180 cos
sin
b
b b
BC AB
AB AB BC
AB b
=
= +
= =
=
t
|
u
2
2
sin 2
1 1
+ = b N
( )
vacuum
n =
1
need minimal thickness b for propagation
thicker waveguides allow multiple modes
|
n
1
n
2
< n
1
A
B
C
D
b

Planar Waveguides
F.G. Smith & T.A. King, Optics and Photonics (Wiley 2000) ISBN 978-0-471-48924-7
Transmission Modes in Cylindrical
Waveguides
Meridional Rays
Skew Rays
Mode Patterns
Single and Multi Mode Fibers
M. Donhowe in R.G. Hunsperger (ed.), Photonic Devices and Systems (Marcel Dekker 1994) ISBN 978-0-824-79243-2
Refractive index n = 1.491
T
g
= 110C
Refractive index n = 1.590
T
g
=110C
must be transparent for transmission wavelength
no optical absorption at visible wavelength
mostly used : amorphous polymers (no scattering)
PMMA PS
C C
H
H H
n

n

C C
C
O
H
CH
3
H
CH
3
O
Polymers for Optical Fibers
for most materials,
r
1
n defined via
c
0
= 2.997910
8
m/s vacuum speed of light
0
= 8.8610
-12
As/Vm vacuum permittivity
0
= 1.12510
-6
Vs/Am vacuum permeability
r
relative permittivity
r
relative permeability
n refractive index

r
n c =
Origin of
r
: field-induced polarization
at frequency of light (f 10
15
Hz)
E
+
_
+
_
( )E P 1
0
= c c
two contributions:
1. reorientation of dipoles (at low frequencies)
2. polarization of atoms/ molecules
Tuning the Refractive Index of Polymers
( )
n
c
medium c
r r r r
0
0 0 0 0
1 1 1
= = =
c c c c
p dipole moment [Asm]
polarizability [Asm
2
/V]
E electric field
E p o =
assembly of molecules of density
p
p
p
E
results in electric polarization
E E
V
N
p
V
N
P
) 1 (
0
_ c o = = =
dielectric susceptibility
) 1 (
_
0
) 1 (
c
o
_
V
N
=
Nucleus (+) Electron
cloud (-)
no field: charge centers coincide
Electron cloud
charge center (-)
Nucleus (+)
E
Microscopic Origin of n
V
N
Relation between n and P
simplistic approach
( ) E E E E P E D
r
c c _ c _ c c c
0
) 1 (
0
) 1 (
0 0 0
1 + = + = + =
0
2
1
c
o
c
V
N
n
r
+ = =
charge displacement
0
) 1 (
c
o
_
V
N
=
i.e.,
) 1 ( 2
1 _ c + = = n
r
1
) 1 (
=
r
c _
or
and ( ) E E P
r
) 1 (
0 0
1 _ c c c = = with
So, if P (and thus ) are known,
r
is known
0
3c
P
E E
ext loc
+ =
local field in a polarizable medium
o
t
c
o
c
c
~
3
4
3 2
1
0
V
N
V
N
r
r
=
=
+
with polarizability volume

0
4
~
tc
o
o =
m
L
A
A
r
r
V
R
N
V
N N
V
N
= = =
+
o
t
o
t
c
c
~
3
4 /
~
3
4
2
1

R
L
molar refraction [m
3
/mol]
Local Field and
Clausius-Mosotti Equation
in molar units
( )
( )
( )
ext r ext
r
ext loc
ext r
E E
P
E E p
p
V
N
E P
2
3 3
1
1
3
1
0
0
+ =
|
.
|
\
|

+ =
|
|
.
|
\
|
+ = =
= =
c
o c
o
c
o o
c c
polarization and dipole moment
due to local field
mol per volume
= inverse molar volume
Polymers used for optical waveguides:
non-conjugated bonds all subunits contribute individually to
r

M V
m
=
1
V
m
molar volume
mass density
M molar mass
I total number of different substructures
K
i
number of identical substructures in repeat unit
R
i
molar refraction of substructures
M
R
molar mass of repeat unit
m
L
V
R
=
+
2
1
c
c
= = = =
+
=
+
=
i i
i i
m
i i
I
i
i i
R
L
R
V K
R K
V
R K
R K
M
R
M n
n
1
2
2
2
1
2
1
c
c
C C
R1
R2 n

Tuning n by Chemical Structure
and
Tuning n by density is difficult for dense polymers, 1g/cm
3
molar refractions:
CH
2
4.5
C-CH
3
7.9
COO 6.3
CH
3
5.9
24.6 cm
3
/mol
PMMA: M
R
= 100.12 g/mol, = 1.17 g/mol
Calculation of n:
49 . 1
21 . 2
mol
cm
6 . 24
2
1
2
3
2
2
~
~
=
+
n
n
M n
n
R
Compare to experimental results:

n = 1.49 (!)
n tuning: Example PMMA
C H
2
C
CH
3
C
O
CH
3
O
n
W. Groh & A. Zimmermann, Macromolecules 24, 6660 (1991)
Molar Refractions
Quantifying Losses
i.e., a specific attenuation of 10 dB/km translates to 10% transmission through
a fiber of 1 km length
or at 100 dB/km, 10% transmission after 100 m
Lambert-Beer law of absorption ( )
A l
I I l I

= = 10 10
0 0
o
I
I
A
0
lg dB 10 ] dB [ n attenuatio total =
absorption coefficient
l length
A optical density
I
I
0
lg
km
dB
10
km
dB
n attenuatio specific =
(
o
measure losses:
)
`
=
dB 10
] dB [
0
10
A
I
I
)
`

=
] km [
dB 10
] dB/km [
0
10
l
I
I
o
Losses in Polymer Fibers and Waveguides
PMMA core POFs
PS core POFs
*
*
O O
n
*
*
n
T. Kaino in L.A. Hornak (ed.), Polymers for Lightwave and Integrated Optics (Marcel Dekker 1992) ISBN 978-0-824-78697-1
UV electronic absorption,
e
C-H vibrational absorption,
v
Rayleigh scattering at impurities
and permanent fluctuations of density
Rayleigh scattering at thermally induced
density fluctuations
Vibrational Absorption
*
D
2
C C
*
CD
3
C
O
CD
3
O
n
T. Kaino in L.A. Hornak (ed.), Polymers for Lightwave and Integrated Optics (Marcel Dekker 1992) ISBN 978-0-824-78697-1
t
v
K
2
1
=
2 1
2 1
m m
m m
+
=
replace H by D
almost doubles
shifts to lower frequency
(higher wavelength)
K spring constant of bond
reduced mass
most severe:
v

solution: change vibrational frequency
Rf : Perfluoroalkyl
d-MMA d-FMA
d-MMA-d-FMA copolymer: n 1.3631.484
Optical loss: < 0.1 dB/cm @1.3 m
> 1.5 dB/cm @1.55 m
R. Yoshimura, M. Hikita, S. Tomaru and S. Imamura, J. Lightwave Technol. 14 (1998) 2338
H. Ma et al., Adv. Mater. 14 (2002) 1339
D
2
C C CD
3
C O
O
CD
3
D
2
C C CD
3
C O
O
Rf
Tuning Losses in Polymer Waveguides
Approaches to Reduce Vibrational Losses
typical values for loss L [dB/km]
GaAlAs
= 650 nm
GaAs
= 768 nm
standard
PMMA
100
deuterated
PMMA
10 15
fluorinated
PMMA
60 320
Note that F substitution reduces also n:
PMMA, n = 1.495 PMMA-F
50%
, n = 1.401
used as cladding material
compare to SiO
2
:

[nm] 900 1000 1300 1500
L [dB/km] 1 0.8 0.25 0.12
H. Ma et al., Adv. Mater. 14 (2002) 1339
Polymers are bad to guide light over large distances, but no problem over
centimeters, i.e. integrated optics, e.g. distributors, splitters etc.
Integrated Optics
Planar waveguide is not very useful for integrated optics (in-plane spread)
channel waveguide
n
2
n
1
n
3
Application: eg. 41 coupler/splitter 1 input / 4 output or vice versa
Channel waveguide
Integrated Optics
light is confined in one dimension
need to control refractive index on m scale
Patterning Waveguides
Lithography and reactive ion etching
Photocrosslinking
Microcontact printing
Photopolymers
14 channel shuffle PI ridge waveguide
B.L. Booth in L.A. Hornak (ed.), Polymers for Lightwave and Integrated Optics (Marcel Dekker 1992) ISBN 978-0-824-78697-1
Light- induced change of refractive index via
photocrosslinking
photosolubilization
photoinitiated polymerization

Concept: blend of inert binder
monomers
photoinitiator
Refractive index grating is created by polymerization and diffusion of monomers
Light-induced polymerisation of monomers
in illuminated regions
a) consumes monomers and
b) induces diffusion of additional monomers
into illuminated region, i.e. change of n
light
Photopolymers
Photoninitiated Polymerization
C
H
C
H
O
(CH
3
CH
2
)
2
N N(CH
2
CH
3
)
2
Photoinitiator: DEAW
2,5-bis[[(4-diethylamino)phenyl]methylene]cyclopentanone
B.M. Monroe, W.K. Smothers in L.A. Hornak (ed.), Polymers for Lightwave and Integrated Optics (Marcel Dekker 1992) ISBN 978-0-824-78697-1
Mach-Zehnder Interferometer
L
manipulate n in arm 1
optical path difference, phase propagation: L n L n
2
0
2 1
0
1
2
,
2
t
|
t
| = =
= A = A
ion transmiss low ,
mission high trans , 0
2
0
t
t
| nL
L
n
2
0
= A need
POCKELS effect
( ) E n n E n
1 0
+ =
( ) ( ) ...
2 ) 2 ( ) 1 (
0
+ + = E E E P _ _ c
( ) ( )
( ) ( )
( )E E
E E
E E P E D
r
c c
_ _ c
_ _ c c
0
) 2 ( ) 1 (
0
2 ) 2 ( ) 1 (
0 0
... 1
... 1
=
+ + + =
+ + + = + =
( ) ( )
... 1
2
) 2 ( ) 1 (
2 2
1 1 0
2
0
2
+ + + =
+ + = =
E
E n E n n n E n E
r
_ _
c
0
) 2 (
1
2n
n
_
=
want
use nonlinear polarization

so, two expressions for
r
:
( )
4
0
) 2 (
3
0 0
2
1
n
r
E rn n E n
_
=
=
also used: POCKELS coefficient r
Nonlinear Optical Chromophores
N
C H
3
C H
3
NO
2
P.J. Skabara in T.H. Richardson, Functional Organic and Polymeric Materials (Wiley 2000) ISBN 978-0-471-98724-7
DANS
4-Dimethylamino-4'-nitrostilbene
Molecules with Large Hyperpolarizabilities
T. Blythe and D. Bloor, Electrical Properties of Polymers (Cambridge University Press
2005) ISBN 978-0-521-55219-2
0
0
4tc
|
| =
Polymer Poling
T
T
G
E
t
t
Orienting Dipoles
electric field E orients dipoles by torque M to minimize potential energy E
pot
random fluctuations due to thermal energy E
therm
= k
B
T prohibit perfect orientation
T k
E
E E E M
B
g
g pot g
5
cos , cos , sin = = = u u u
E
z
E
,,
E
m
o
l
e
c
u
l
a
r

a
x
i
s
NL
non-linear polarization due to a partially oriented
non-linear dipole moment:
3
2
2
2 2
||
cos cos , cos u | u u | |
z NL z z NL
E E E = = = =
3
2
cosu |
z z NL
E
V
N
V
N
P = =
T k
E
f
V
N
B
g
5
3
0
) 2 (
c
|
_ =
NLO Polymer
Chia-Cheng Chang et al., Polymer Reviews 45, 125 (2005)
= 60 ... 150 pm/V
Low-Voltage Optical Modulator
dispersed in PMMA
Yongqiang Shi et al., Science 288, 119 (2000)
push-pull poling and operation
Y-Type Directional Coupler
crosslinked polyurethane with FTC
Dechang An et al., Applied Physics Letters 76, 1972 (2000)
Broadband Electro-Optic Modulator
Mark Lee et al., Science 298, 1401 (2002)
DR1 in PMMA
limited by (electrical)
contact resistance!
VIII Conjugated Polymers
Semiconductors Typical Applications:
light-emitting diodes
solar cells and photodiodes
field-effect transistors, integrated circuits
Polymers Typical Properties:
flexibility
mechanical toughness
chemical variability
layer forming properties
E
0
Metals, Semiconductors, Insulators
metal
(conductor)
no gap
semiconductor

small gap
insulator

large gap
occupied states
empty states
vacuum level
energy gap
E
F
work function
ionization potential
electron affinity
CB
VB
E
F
Fermi energy
CB conduction band
VB valance band
Band diagram: allowed energies for electrons in a solid
Inorganic Devices: Crystals
H. Ibach, H. Lth, Festkrperphysik: Einfhrung in die Grundlagen, Springer 2009 (ISBN 9783540857945) Fig. 2.12
diamond structure
made of two fcc lattices displaced (, , )
typical for group IV elements

zinc blende structure for III-V combinations
Band Gaps of Inorganic Semiconductors
III-V semiconductors (LEDs):
AlGaAs
GaP
GaN

CIGS solar cells:
Cu(In,Ga)
x
(S,Se)
y
de.wikipedia.org/wiki/III-V-Verbindungshalbleiter
experimentalchemie.de
Inorganic Devices
GaAlAs
InGaAlP
GaP
GaN
Advantages:
high charge carrier motilities
all emission colors
well-known technology
Disadvantages:
sensitive to crystal defects
no large area devices
low flexibility
Organic Devices
Montage
Fraunhofer IAP
Uni Potsdam
Dai Nippon Printing
Physical & Engineering Properties II 2012
Nobel Prize in Chemistry 2000
for the discovery and development of conductive polymers
Alan J. Heeger
University of California
* 1936
Alan G. MacDiarmid
University of Pennsylvania
* 1927
2007
Hideki Shirakawa
University of Tsukuba
* 1936
49
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2000/
Classes of Conjugated Polymers
a) Hydrocarbon Polymers
Polyacetylene PAc
Polydiacetylene PDAc
Poly(para-phenylene vinylene) PPV
Polyfluorene PF
Poly(para-phenylene) PPP
red
blue
*
C
H
C
H
*
n
*
C
H
C
H
*
n
*
*
R2
R1
n
*
*
R1 R2
n
* *
n
R1
R2
b) Heteroatomic Polymers
Poly(3-alkylthiophene) P3AT
Polyaniline PAni
S
*
*
R
n
N
H
N
H
N
*
*
x y
N
n

c) conjugated Polymers
Silanes
Germanes
Carbon Hybrid Orbitals
http://wps.prenhall.com/wps/media/objects/724/741576/chapter_01.html
sp
3
hybridization single bonds
sp
2
hybridization double bonds
sp hybridization triple bonds
ethane
ethylene
ethene
acetylene
ethyne
Molecular Orbital Description of Ethylene
52
Molecular Orbitals of Ethene and Butadiene
53
Molecular Orbitals of Hexatriene
Pentacene SPM Images
STM constant current on Cu/NaCl:
HOMO & LUMO levels
AFM constant height with CO modified tip:
carbon atoms & C-H bonds
J. Repp et al., Phys. Rev. Lett. 94, 026803 (2005) L. Gross et al., Science 325, 1110 (2009)
http://dx.doi.org/10.1103/PhysRevLett.94.026803 http://dx.doi.org/10.1126/science.1176210
conjugated system
= box for electron to move in
box length determined by number of carbon
atoms N and bond length L
allowed states have defined energies
standing waves
lowest N/2 states are filled energy gap

Gap decreases with number of carbon atoms!

Particle in a Box
N L m
n h
E
e
n
1
8
2 2
=
N L m
h
E
e
1
16
2
2
= A
E
n
E( =6) N
n
NL
*
*
n
Energy Level Evolution
red = occupied
?
Oligothiophenes
T. Izumi, S. Kobashi, K. Takimiya, Y. Aso & T. Otsubo, J. Am. Chem. Soc. 125, 5286 (2003)
http://dx.doi.org/10.1021/ja034333i
Oligo-para-phenylene-vinylenes
J. Gierschner, H.-G. Mack, L. Ler & D. Oelkrug, J. Chem. Phys. 116, 8596 (2002)
J. Gierschner, J. Cornil & H.J. Egelhaaf, Adv. Mater. 19, 173 (2007)
59
http://dx.doi.org/10.1063/1.1469612 http://dx.doi.org/10.1002/adma.200600277
Final Band Gap for infinite Polymers
a) potential has no flat bottom bond length alternation
b) polymer consists of subunits chromophores with finite length (random coil)
conjugation length limited (and random)
G.D. Scholes & G. Rumbles, Nature Materials 5, 683 (2006)
C=CC=C C=C C=C
E
c) self trapping of excitons or charges:
molecular geometry change needs energy
Revised Energy Evolution
*
*
n
Counting Chromophores
single molecule spectroscopy on LPPP oligomers
of defined length
above a certain length, a single chain emits at
several frequencies.
Chain consists of several chromophores.
F. Schindler et al., Angew. Chemie Int. Ed. 44, 1520 (2005)
C
6
H
13
H
13
C
6
C
10
H
21
H
21
C
10
C H
3
CH
3
C
6
H
13
H
13
C
6
H
13
C
6
C
6
H
13
n

conjugated polymers = chains of chromophores
optical properties can be described in molecular picture
absorption and emission typically between singlet states
strong allowed transitions in visible spectrum
oscillator strength increases with number of electons
conjugation length
strong absorption coefficients
in solution
m
10
5
/mol/cm
in thin film 10
5
/cm
fast and efficient emission

f
1 ns
in solution up to 100%
in thin films up to 60%
IX Emission from Conjugated Polymers
Configurations, States, Polarons
S
0
P
-
P
+
S
1
T
1
*
E
excited state =
combination of different configurations
charging or excitation: higher lying orbitals are (partially) occupied
and/or lower lying orbitals are (partially) emptied
position of atomic cores will be redistributed (vibrations!) to reduce energy of new
state
[roughly, charging or excitation of a chromophore weakens its bonds]
coupling between state and geometry = polaron
Ground and first excited state of hexatriene
Occupation of LUMO leads
to weaker bonding between
central carbon atoms
HOMO becomes partially
emptied and the bond
between the outer carbon
atoms and also between
the central carbon atoms
becomes weaker
Molecular Excitations: Jablonski Diagram
V
i
b
r
o
n
i
c

R
e
l
a
x
a
t
i
o
n

I
n
t
e
r
n
a
l

C
o
n
v
e
r
s
i
o
n
+
V
R

F
l
u
o
r
e
s
c
e
n
c
e

ISC
ISC
L
i
g
h
t

A
b
s
o
r
p
t
i
o
n

P
h
o
s
p
h
o
r
e
s
c
e
n
c
e

66
Frack-Condon Principle
Potential energy curves
with vibrational probability functions
Atoms vibrate in an effective potential, whose shape is
determined by the spatial distribution of electrons.

Potentials can be different in ground and excited state.

Upon excitation of an electron, the atom cores do not move.
Therefore, a transition from the ground to a higher excited
state is only possible, if this state has a finite probability to
find the atoms at the same positions as in the ground state
(vertical transition).

Shape of absorption (and emission) spectra depends on
the potential energy curves in the ground and excited state.
M. Pope, C.E. Swenberg, Electronic Processes in Organic Crystals and Polymers,
Oxford University Press 1999 (ISBN 0195129636)
Different Absorption Spectra
W. Demtrder, Experimentalphysik III, Springer 2010
nach H. Haken, H.C. Wolf, Moleklphysik und Quantenchemie, Springer 2006
Einstein Coefficients
http://www.thespectroscopynet.com/Index.html?/Atomic_Structure_1.html
absorption
0 01
0
N B
dt
dN
=
1 10
1
N A
dt
dN
=
1 10
1
N B
dt
dN
=
spontaneous
emission
stimulated
emission
N
0
number of atoms in ground state
B
01
Einstein coefficient of absorption
spectral energy density of incident
light
N
1
number of atoms in excited state
A
10
Einstein coefficient of spontenous
emission
B
10
Einstein coefficient of stimulated
emission
Einstein Coefficients and Oscillator Strength
It can be shown that
10 01
B B =
10
3
3
10
8
B
c
h
A
u t
=
u h
B
01
is related to the oscillator strength f of the particular transition,
01
2
0
4
B
e
h m
f
e
u c
=
which can be calculated from the spectrum of the molar extinction coefficient
}
= u u c
~
)
~
( 10 39 . 4
9
d f
m
wavenumber in units of cm
-1
u
1
~
=
On the other hand, A
10
is proportional to the radiative decay rate of spontaneous
emission,
r
r
k A
t
1
10
= =
and the Einstein coefficients are related to the transition dipole moment via
2
10
3
0
3 3
10
3
16
c
u t
hc
A =
2
10
2
2
3
8
u t
he
m
f
e
=
transition energy
2
10
2
0
2
10
6
4
c
t
h
B =
Example: Oligofluorenes
*
*
R1 R2
n
R=
C. Chi, C. Im, G. Wegner, J. Chem. Phys. 124, 024907 (2006)
S
1
S
0
N
1
molecules in excited S
1
state
consider radiative decay back to S
0
state
( )
( ) =
1 10
1
t N A
dt
t dN
A
10
Einstein coefficient of spontaneous emission
k
r
radiative rate
r
radiative lifetime of S
1
Fluorescence Lifetime
( ) ( )
( )
( )
r
r
t
t k
t A
e N
e N
e t N t N
t

=
=
= =
0
0
0
1
1
1 1
10
( )
| | ( ) | | ( )
( ) ( )
( )t k k
nr r ISC IC r
nr r
e N t N
t N k k t N k k k
dt
t dN
+
=
+ = + + + =
0
...
1 1
1 1
1
number of photons N
ph
emitted per time unit:
( )
( ) ( )
( )t k k
r r
ph
nr r
e N k t N k
dt
t dN
I
+
= = = 0
1 1
fluorescence lifetime:
k
nr
increases
f
decreases
=
+
=
k k k
nr r
f
1 1
t
k
nr
= 0
k
nr
> 0
consider additional non-radiative decay channels
Nonradiative Decay Channels
S
1
S
0
r
t
I
Total number of emitted photons
( )
( )
( )
nr r
r
t k k
r
ph
ph
k k
k
t N
t e N k t
dt
t dN
N
nr r
+
= =
= =
} }

+
) 0 (
d 0 d
1
0
1
0
Fluorescence quantum yield:
( )
photons absorbed of number
photons emitted of number
state excited in molecules of number
photons emitted of number
= = PL q
( )
( )
r
f
nr r
r
ph
k k
k
N
N
PL
t
t
q
=
<
+
= = 1
0
1
Quantum Efficiency
PL Efficiencies of Polymers
M. Pope, C.E. Swenberg, Electronic Processes in Organic Crystals and Polymers,
Oxford University Press 1999 (ISBN 0195129636)
formation of exciplex states
exciton migration to traps
(exciton diffusion range ca.10 nm)
electron transfer
(good for solar cells)
exciton exciton annihilation
photoisomerization
photooxidation

Exciton Quenching in Solid State
M M
*
k
1
k
-1
M M
*
http://www.ks.uiuc.edu/images/ofmonth/2003-07/fullsize.jpg
J.B. Birks & L.G. Christophorou, Spectrochimica Acta 19, 401 (1963)
Excimer Emission
Fluorescence spectra of pyrene at various concentrations
conc.
Photooxidation of Polyfluorenes
E.J.W. List et al., Adv. Mater. 14, 374 (2002)
E. Zojer et al., J. Chem. Phys. 117, 6794 (2002)
400 450 500 550 600
0
50
100
150
200
250
300
P
L

I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Wavelength [nm]
photooxidation time
0 s
266 s
532 s
798 s
1064 s
decrease of PF
emission
appearance of
new emission
photo-oxidation of PF in air
strong decrease of PF emission
intensity
formation of keto defects, which
acts as trap for excitons and
electrons
*
* n
*
O
* x y
h
polymer laser: photograph of a red emitting
two-dimensional distributed feedback laser
What do you need?
population inversion
light amplification (gain medium) feedback (resonator)
Why polymeric (organic) materials?
intense transitions
contains 4 level systems
inversion guaranteed
Level 4 is always empty
polymer photonic crystal microcavity
Feedback e.g. Microcavity resonator
or Bragg grating
Polymer Lasers
S
0
S
1
4
1
2
3
remember Einstein coefficients:
stimulated emission is inverse to absorption with B
10
= B
01
L
gL
I
L I
+
=10
) (
0
V
N
g
SE
3
=o
for typical polymers, need
3
19 18
3
3 2
cm
10 10
cm
10 10
~ ~
V
N
g
Stimulated Emission & Lasers
I
0
I(L)

2 16
10 cm
SE

~ o
with gain
and cross section
i.e., only 1 out of 100 or 1000 chromophores needs to be excited
L N
R
P
abs SE 1
3
0
ln
o o
t
~
S
0
S
1
4
1
2
3
lasing threshold:
3
lifetime of state 3
R reflectivity of cavity
SE
cross section of stimulated emission
abs
absorption cross section
N
1
number of chromophores in state 1 total number
L length of gain medium
Organic Semiconductors 2012
ASE (Amplified Spontaneous Emission)
energy
pump
stimulated
emission
configuration coordinate
1
4
2
3
N
1

N
4

N
3

N
2

81
F. Hide, M.A. Daz-Garca, B.J. Schwartz, M.R. Andersson, Q. Pei & A.J. Heeger, Science 273, 1833 (1996)
http://dx.doi.org/10.1126/science.273.5283.1833

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M. Sc.

Polymer Science A joint program by FU, HU, TU, and UP

10 Physical & Engineering Properties II 2012

with polarizability volume

Compare to experimental results:

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