Excitons – Types, Energy Transfer

•Wannier exciton
•Charge-transfer exciton
•Frenkel exciton

•Exciton Diffusion
•Exciton Energy Transfer (Förster, 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
Excitons Frenkel exciton
(typical of inorganic (bound (typical of organic
semiconductors) electron-hole materials)
pairs)

treat excitons
as chargeless
particles
capable of
diffusion,

also view
SEMICONDUCTOR PICTURE them as MOLECULAR PICTURE
CONDUCTION excited states
BAND
of the S1
molecule

S0

VALENCE
BAND

GROUND STATE WANNIER EXCITON Charge Transfer (CT) GROUND STATE FRENKEL EXCITON

Exciton
binding energy ~10meV binding energy ~1eV
(typical of organic
radius ~100Å materials)
radius ~10Å
Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg 3
 Wannier-Mott Excitons

n = ∞ ----------
Columbic interaction between
the hole and the electron is given by
EEX = -e2/∈r

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 µ/m∈

µ– reduced mass = memh / (me+mh)

Adapted from Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg 4
An Example of Wannier-Mott Excitons

exciton progression
fits the expression

ν[cm-1] = 17,508 – 800/n2

corresponding to
µ = 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

5
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.

6
 Crystalline Organic Films
PTCDA
PTCDA

CHARGED CARRIER MOBILITY

INCREASES WITH INCREASED
π−π ORBITAL OVERLAP
11.96 Å
GOOD CARRIER MOBILITY
IN THE STACKING DIRECTION
17.34 Å
µ = 0.1 cm2/Vs – stacking direction
µ = 10-5 cm2/Vs – in-plane direction

z 3.21Å
Highest mobilities obtained on
single crystal

pentacene µ = 10 5 cm2/Vs at 10K y

tetracene µ = 10 4 cm2/Vs at 10K
(Schön, et al., Science 2000).
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

8
PTCDA Solution (~ 2µM in DMSO)

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

S1 [0-1]
CT [0-F]

S1 [0-2]
CT [0-ST]

S1 [0-3]
Fluorescence Absorption
S1 [0-1]

1.5 2.0 2.5 3.0 3.5

Energy [eV]
9
 CT [ST-3]

1.5
Fluorescence
CT [ST-2]

CT [ST-1]

2.0
PTCDA Thin Film

CT [0-ST]
CT [0-F]

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

2.5
Energy [eV]
S1 [0-2]

S1 [0-3]
3.0
Absorption

3.5

10
PTCDA Solution PTCDA Thin Film
(~ 2µM in DMSO)

0.6 eV
Fluorescence Absorption

1.5 2.0 2.5 3.0 3.5

Energy [eV]
11
Solution Absorption

PTCDA in DMSO
6
AGGREGATE 2 µM
State AGGREGATE
1.6 µM STATE
. ABSORPTION
Absorption [a.u.]

.
. increases with
4
PTCDA solution
0.25 µM concentration

0
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
r = 0.53 ± 0.02
S 1 [0-0]: 2.39 eV
1
Relative Oscillator Strength

r = 0.73 ± 0.02

S 1 [0-2]: 2.74 eV

CT [0-ST]: 2.23 eV

Measurement
6
Fit
0.1 r = 1.00 ± 0.02 [k] = 0.8 µ M
4
Absorption [a.u.]
2

0
r = 1.75 ± 0.02
2.0 2.4 2.8
0.01 Energy [eV]

0.5 1 2 4
PTCDA Concentration in DMSO [ µ M]
13
Solution Luminescence

6 Integrated Fluorescence 4
2 µM
Intensity [a.u.]
3
.
2
I ∝ [k] 0.65
.
Fluorescence [a.u.]

4 1
.
0
0 1 2 0.25 µ M
Solution Concentration
[k] [µ M]
2

1.8 2.0 2.2 2.4

Energy [eV]
14
 Monomer and Aggregate Concentration in Solution
[µM]
1 MONOMER
[km] ∝ [k] 0.65 Monomer and
Aggregate
Monomer concentrations
are derived from
Concentration integrated solution
[km] fluorescence
AGGREGATE efficiency by

[ka] ∝ [k] 1.75

0.1 assuming that
the 2.3 eV solution
fluorescence is due
to monomers and
Aggregate that the most dilute
Concentration rate of rise solution primarily
[ka] r = 1.75 contains monomers.

0.01
0.5 1 2 [µM]
Nominal Solution Concentration [k]
15
 PTCDA Electron Energy Structure

S1 S1
2 2
1 1
0 0
CT F CT F
CT ST CT ST

1.55 eV
2.74 eV

1.70 eV
2.55 eV

1.85 eV
2.39 eV

2.17 eV
2.20 eV

2.32 eV
2.12 eV

S0 S0
3 3
2 2
1 1
0 0

MONOMER THIN FILM MONOMER THIN FILM

TRANSITIONS TRANSITIONS TRANSITIONS TRANSITIONS

Absorption Luminescence

16
PTCDA Solution PTCDA Thin Film
(~ 2µM in DMSO)

0.6 eV
Fluorescence Absorption

1.5 2.0 2.5 3.0 3.5

Energy [eV]
17
 Solution and Thin Film Fluorescence

FLUORESCENCE LIFETIME

Normalized Counts
* Thin film 10
3
Thin Film
fluorescence is 1.0 τ = 10.8 ± 0.5 ns
red-shifted by 10
2

0.60 eV from
Fluorescence [a.u.] 0.8
solution 10
1
Solution
fluorescence τ = 4.0± 0.5 ns
0.6 0 20 40 60
* Minimal Time [ns]
fluorescence
broadening due 0.4
Thin Film
to aggregation
(E + 0.60 eV) 0.25 µM
0.2
* Fluorescence 2.0 µM Solution
lifetime is longer
in thin films 0.0

1.8 2.0 2.2 2.4

Energy [eV]
18
 Thin Film Excitation Fluorescence

S1

CT [0-ST]
CT [0-F]
T1

S1 [0-1]

S1 [0-3]
S1 [0-2]
S1 [0-0]
CT

Integrated Fluorescence [a.u.]

30

650 nm PTCDA
S0
20 Thin Film

* Fluorescence energy
and shape is not 10
affected by the change
in excitation energy
0
* Fluorescence
efficiency increases
when exciting directly 2.0 2.4 2.8 3.2 3.6
into CT state Excitation Energy [eV]

19
 Exciton Quantum Confinement in Multi Quantum Wells

So and Forrest, Phys. Rev. Lett. 66, 2649 (1991). Exciton radius = 13 Å
Shen and Forrest, Phys. Rev. B 55, 10578 (1997).

mh, ⊥ = 0.18 mo
∆E LUMO
30

mh, ⊥ = 0.16 mo ∆E HOMO

∆ E 1s [meV]

20
d
mh, ⊥ = 0.14 mo
10

NTCDA

NTCDA
PTCDA

PTCDA
PTCDA
0

10 100 1000
d [Å]

20
 (a) Delocalized CT Exciton (b) Localized CT Exciton
Bandwidth >> VPSEUDO Bandwidth << VPSEUDO

ϕ∗ϕ ϕ∗ϕ
1 1

0 0
r r
V [eV]
V [eV]

-1 -1

-2 -2

-3 -3
21
 Electronic Processes in Molecules

density of available JABLONSKI DIAGRAM

S and T states on
surrounding molecules 10 ps

CONVERSION
Energy

INTERNAL
INTERSYSTEM
FÖRSTER, DEXTER CROSSING
or RADIATIVE
ENERGY TRANSFER 1-10 ns
S1
T1

PHOSPHORESCENCE
FLUORESCENCE
ABSORPTION
S: spin=0 (singlet) states >100 ns
T: spin=1 (triplet) states
S0

22
Effect of Dopants on the Luminescence Spectrum

1.0 N
O

Alq3
Normalized EL Intensity

0.8
NC CN
DCM2:Alq3
N
0.6 Al PtOEP:Alq3
O
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. Förster transfer

3. Dexter transfer
24