Excitons Types, Energy Transfer

Wannier exciton
Charge-transfer exciton
Frenkel exciton
Exciton Diffusion
Exciton Energy Transfer (Frster, Dexter)
Handout (for Recitation Discusssion):
J.-S. Yang and T.M. Swager, J. Am. Chem. Soc. 120, 5321 (1998)
Q. Zhou and T.M. Swager, J. Am. Chem. Soc. 117, 12593 (1995)

@ MIT

February 27, 2003 Organic Optoelectronics - Lecture 7

1

Exciton
In some applications it is useful to consider electronic excitation as if a
quasi-principle, capable of migrating, were involved. This is termed as
exciton. In organic materials two models are used: the band or wave model
(low temperature, high crystalline order) and the hopping model (higher
temperature, low crystalline order or amorphous state). Energy transfer in
the hopping limit is identical with energy migration.

Caption from IUPAC Compendium of Chemical Terminology

compiled by Alan D. McNaught and Andrew Wilkinson
(Royal Society of Chemistry, Cambridge, UK).
2

Wannier exciton
(typical of inorganic
semiconductors)

Excitons

Frenkel exciton

(bound
electron-hole
pairs)

(typical of organic
materials)

treat excitons
as chargeless
particles
capable of
diffusion,
SEMICONDUCTOR PICTURE
CONDUCTION
BAND

also view
them as
excited states
of the
molecule

MOLECULAR PICTURE
S1

S0
VALENCE
BAND

GROUND STATE

WANNIER EXCITON

binding energy ~10meV

radius ~100

Charge Transfer (CT)

Exciton
(typical of organic
materials)

GROUND STATE

FRENKEL EXCITON

binding energy ~1eV

radius ~10

Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg

Wannier-Mott Excitons
Columbic interaction between
the hole and the electron is given by
EEX = -e2/r

n = ----------

The exciton energy is then

E = EION EEX/n2 , n = 1,2,
EION energy required to ionize the molecule
n exciton energy level
EEX = 13.6 eV /m
reduced mass = memh / (me+mh)

Adapted from Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg

An Example of Wannier-Mott Excitons

exciton progression
fits the expression
[cm-1] = 17,508 800/n2
corresponding to
= 0.7 and = 10
The absorption spectrum of Cu2O
at 77 K, showing the exciton lines
corresponding to several values
of the quantum number n. (From
Baumeister 1961).
Quoted from Figure I.D.28.
Electronic Processes in Organic
Crystals and Polymers by M. Pope
and C.E. Swenberg

Charge Transfer Excitons

The lowest CT exciton state
in the ab plane of an
anthracene crystal with two
inequivalent molecules per
unit cell; the plus and minus
signs refer to the center of
gravity of charge distribution.
The Frenkel exciton obtains
when both (+) and () occupy
essentially the same
molecular site.

Crystalline Organic Films

PTCDA
PTCDA

CHARGED CARRIER MOBILITY

INCREASES WITH INCREASED
ORBITAL OVERLAP

11.96

GOOD CARRIER MOBILITY

IN THE STACKING DIRECTION
17.34

= 0.1 cm2/Vs stacking direction

= 10-5 cm2/Vs in-plane direction

3.21

Highest mobilities obtained on

single crystal
pentacene = 10 5 cm2/Vs at 10K
tetracene = 10 4 cm2/Vs at 10K
(Schn, et al., Science 2000).

y
x

substrate
7

Organic Semiconducting Materials

Van der Waals-BONDED
ORGANIC CRYSTALS
(and amorphous films)

PTCDA monolayer on HOPG

(STM scan)

HOMO of
3,4,9,10- perylene tetracarboxylic dianhydride

S1 [0-3]

S1 [0-2]

S1 [0-1]

CT [0-F]

CT [0-ST]

S1 [0-0]
S1 [0-0]

PTCDA Solution (~ 2M in DMSO)

S1 [0-1]

Fluorescence

1.5

2.0

2.5

3.0

Absorption

3.5

Energy [eV]
9

1.5
CT [0-ST]

2.0
2.5

S1 [0-3]

S1 [0-2]

S1 [0-0]
S1 [0-1]

CT [0-F]

CT [ST-2]

Fluorescence

CT [ST-1]

CT [ST-3]

PTCDA Thin Film

Absorption

3.0
3.5

Energy [eV]
10

PTCDA Solution

PTCDA Thin Film

(~ 2M in DMSO)
0.6 eV

Fluorescence

1.5

2.0

Absorption

2.5

3.0

3.5

Energy [eV]
11

Solution Absorption
PTCDA in DMSO
6

2 M

Absorption [a.u.]

AGGREGATE
State

1.6 M
.
.
.

0.25 M

AGGREGATE
STATE
ABSORPTION
increases with
PTCDA solution
concentration

1.8

2.0

2.2

2.4

2.6

2.8

3.0

Energy [eV]
12

Absorption of Vibronic Transitions

Change with Solution Concentration
S 1 [0-1]: 2.55 eV

S 1 [0-0]: 2.39 eV

r = 0.73 0.02
S 1 [0-2]: 2.74 eV
CT [0-ST]: 2.23 eV
6

0.1

r = 1.00 0.02

Absorption [a.u.]

Relative Oscillator Strength

r = 0.53 0.02

Measurement
Fit

[k] = 0.8 M

r = 1.75 0.02

2.0

0.01
0.5

2.4
Energy [eV]

2.8

PTCDA Concentration in DMSO [ M]

13

Fluorescence [a.u.]

Integrated Fluorescence
Intensity [a.u.]

Solution Luminescence

2 M

4
3

I [k] 0.65

0
0

0.25 M

1
2
Solution Concentration
[k] [ M]

0
1.8

2.0

2.2

2.4

Energy [eV]
14

Monomer and Aggregate Concentration in Solution

[M]
1

MONOMER
[km] [k] 0.65

Monomer
Concentration

[km]
0.1

Aggregate
Concentration

[ka]

AGGREGATE
[ka] [k] 1.75

rate of rise
r = 1.75

Monomer and
Aggregate
concentrations
are derived from
integrated solution
fluorescence
efficiency by
assuming that
the 2.3 eV solution
fluorescence is due
to monomers and
that the most dilute
solution primarily
contains monomers.

0.01
1
0.5
Nominal Solution Concentration [k]

2 [M]
15

PTCDA Electron Energy Structure

S1

S1
2

2
1

1
0

CT F

3
2

S0

2.32 eV
2.17 eV
1.85 eV
1.70 eV
1.55 eV

2.74 eV
2.55 eV
2.39 eV
2.20 eV
2.12 eV

CT ST

CT F
CT ST

3
2

S0

1
0

MONOMER THIN FILM

TRANSITIONS TRANSITIONS

Absorption

0
MONOMER THIN FILM
TRANSITIONS TRANSITIONS

Luminescence
16

PTCDA Solution

PTCDA Thin Film

(~ 2M in DMSO)
0.6 eV

Fluorescence

1.5

2.0

Absorption

2.5

3.0

3.5

Energy [eV]
17

Solution and Thin Film Fluorescence

* Minimal
fluorescence
broadening due
to aggregation
* Fluorescence
lifetime is longer
in thin films

1.0
Fluorescence [a.u.]

* Thin film
fluorescence is
red-shifted by
0.60 eV from
solution
fluorescence

0.8
0.6

Normalized Counts

FLUORESCENCE LIFETIME
10

10

10

Thin Film
= 10.8 0.5 ns

Solution
= 4.0 0.5 ns
0

20

40

60

Time [ns]

0.4
0.2

Thin Film
(E + 0.60 eV)

0.25 M
2.0 M Solution

0.0
1.8

2.0

2.2

2.4

Energy [eV]
18

S0

* Fluorescence energy
and shape is not
affected by the change
in excitation energy
* Fluorescence
efficiency increases
when exciting directly
into CT state

S1 [0-3]

S1 [0-2]

S1 [0-1]

S1 [0-0]

T1

Integrated Fluorescence [a.u.]

CT

CT [0-ST]

S1

CT [0-F]

Thin Film Excitation Fluorescence

30
650 nm PTCDA
Thin Film

20

10

0
2.0

2.4

2.8

3.2

3.6

Excitation Energy [eV]

19

Exciton Quantum Confinement in Multi Quantum Wells

Exciton radius = 13

So and Forrest, Phys. Rev. Lett. 66, 2649 (1991).

Shen and Forrest, Phys. Rev. B 55, 10578 (1997).

mh, = 0.18 mo

E LUMO

E HOMO

mh, = 0.16 mo
20

mh, = 0.14 mo
PTCDA

NTCDA

PTCDA

NTCDA

10

PTCDA

E 1s [meV]

30

0
10

100

1000

d []
20

(a)

Delocalized CT Exciton

(b)

Bandwidth >> VPSEUDO

Bandwidth << VPSEUDO

r
V [eV]

V [eV]

r
-1

Localized CT Exciton

-1

-2

-2

-3

-3
21

Electronic Processes in Molecules

JABLONSKI DIAGRAM

INTERNAL
CONVERSION

10 ps

FRSTER, DEXTER
or RADIATIVE
ENERGY TRANSFER

INTERSYSTEM
CROSSING

1-10 ns
PHOSPHORESCENCE

S: spin=0 (singlet) states

T: spin=1 (triplet) states

FLUORESCENCE

S1
ABSORPTION

Energy

density of available
S and T states on
surrounding molecules

T1

>100 ns

S0

22

Effect of Dopants on the Luminescence Spectrum

1.0

Normalized EL Intensity

Alq3

0.8
0.6

Al

NC

N
O

CN

DCM2:Alq3
PtOEP:Alq3
3

0.4

N
N

Pt

N
N

0.2
0.0
400

500

600

700

800

Wavelength [nm]
23

Nonradiative Energy Transfer

dopant molecules
(generate luminescence)
host molecules

How does an exciton in the host transfer to the dopant?

Energy transfer processes:
1. Radiative transfer
2. Frster transfer
3. Dexter transfer
24