Organic Electroluminescence

Dieter Neher
University of Potsdam, Institute of Physics
Am Neuen Palais 10, 14469 Potsdam
www.pled.de

Utilizing molecules with delocalized π orbitals

Dieter Neher Organic Electroluminescence 1

 Overview

Introduction into LEDs

Some basic considerations and equations
The real device
cathode-quenching
recombination
singlet-triplet ratio
Outcoupling of light
external efficiencies
microcavity effects
luminance and luminous efficiencies
Phosphorescent LEDs

Dieter Neher Organic Electroluminescence 2

 Organic Light-Emitting Diodes

counter electrode
e. g. Ca or Al

electron transport layer

-V emission layer
−
hole transport layer
e− hν
transparent electrode

glass substrate −
∆T

+
j h+

Typical active layer thickness: 100-250 nm

+
Dieter Neher Organic Electroluminescence 3
 Organic Light-Emitting Diodes (OLEDs)

Thin layer devices from organic dyes or conjugated polymers

N
First demonstration of efficient LED from organic dye O O
(layers prepared by thermal evaporation) Al N

C.W. Tang, S.A. Vanslyke, Appl. Phys. Lett. 51 (1987) 913 N O

Alq3

First demonstration of electroluminescence from a conjugated polymer

(layers prepared by spincoating)
J.H. Burroughes et al., Nature 347 (1990) 539
n

Poly(p-Phenylen-Vinylen)

Dieter Neher Organic Electroluminescence 4

 Basic Mechanisms in Electroluminescence

j + -

2
2
e- 1
1 h+
+ -
3

4
∆T

hν

1 Charge injection 2 Charge diffusion and recombination

3 Exciton diffusion 4 Exciton recombination and photon emission

Dieter Neher Organic Electroluminescence 5

 Internal EL Efficiency

# generated photons
Internal EL-efficiency defined as
#charges flowing through the device

η int ( EL)= φ rφ R

φR probability that charges recombine to excitons

φr probability that exciton decays radiatively

triplet singlet
↑↑
↑ ↑
h+ + e-
1
2
( ↑↓ + ↓↑ ) 1
2
( ↑↓ − ↓↑ )
↓ ↓
↓↓

Dieter Neher Organic Electroluminescence 6

 Radiative Recombination

simple spin statistic: φS : φT = 1 : 3

φS φT pure hydrocarbon materials:
η(ph) <<1
η ( fl )
Simplification: η(fl) = η(PL)
? η ( ph)
fluorescence quantum efficiency

Radiative recombination efficiency:

φ r =φ Sη ( fl ) + φTη ( ph) η int ( EL) = 0.25 × φ R × η ( PL)

Dieter Neher Organic Electroluminescence 7

 Charge Carrier Balance

jminor
LUMO Ca 2,9 eV Simplifications:

Al 4,3 eV injection limited currents

Polymer
determined by barrier heights
Au 5,2 eV
electrons are minority carriers
ITO 4,7 eV
HOMO

jmajor
r jmin or jmin or
φR = r =1
→
(1 − r ) jmin or + jmajor jmajor

Dieter Neher Organic Electroluminescence 8

 Tuning of Color and Electronic Properties

Variation of the electronic structure by the defined control of the chemical

composition

n k
O

PPP PPV
R
R
O
O

n O
O n
R
R

M. Remmers, D. Neher, R.H. Friend, J. Warman,

J.-L. Bredas, Macromolecules 29 (1996) 7432

Dieter Neher Organic Electroluminescence 9

 Efficiency of Charge Recombination
R R
O O

Compare η(PL) with η(EL)

n O
O n

η int ( EL) = 0.25 × φ R × η ( PL)

R R

PPP PPV
PPP P3A P3V P2VMEH-PPV
100
0

Recombination Probablity [%]

-1 10

-2
Energy [eV]

-
e
1

-3 Ca
0.1
-4

-5
+
ITO 0.01
h

Dieter Neher Organic Electroluminescence 10

 The Real Device

Questions:

is the spin statistics: φS : φT = 1:3 correct

is recombination and emission homogenous throughout the layer
under which conditions do all electrons recombine with holes (or vice versa)
is it correct to assume η(fl) = η(PL)
how many photons leave the device

the following sheets will give some answers!!!!

Dieter Neher Organic Electroluminescence 11

 Determination of the Emission Zone

Detection of the polarization of emitted light from a supramolecular stack of

molecules

light output

ITO

100 - n monolayers
Spreading of perpendicular O
orientation

O n
n monolayers
of parallel
orientation

Aluminium

Transfer

Dieter Neher Organic Electroluminescence 12

 Recombination and Quenching
Dis ta nc e from Al-e le c trode [nm]
0 20 40 60 80 100 120

quenching
Pe rc e nta ge of light e mitte d p e r
60%
at cathode exponential
10 monola ye rs (12 nm)
50% decay

40%

30%

20%

Que nc hing 10%

0%

Al PPP e mis s ion Zone ITO

J. Grüner, M. Remmers, D. Neher, Adv. Mater. 9 (1997) 964

Dieter Neher Organic Electroluminescence 13

 Effect of Metal Cathodes on Radiative Emission

kr
η ( PL) =
k r + k nr
light
Laser

CN-PPV

SiO2 spacer

Metal layer

Quartz substrate H. Becker, S.E. Burns, R.H. Friend,

PRB 56 (1997) 1893

Dieter Neher Organic Electroluminescence 14

 Quenching at Metal Cathodes

Thin (ca. 2-3 nm) metal layer Thick (ca. 35 nm) metal layer

energy transfer self-

to metal, interference,
affects knr affects kr

Dieter Neher Organic Electroluminescence 15

 Langevin Recombination

e2
Coulomb radius rc: = kT
E
-
4πε oεrc
Electron current towards countercharge:

- -
ie = ene v e Ac
rc +
4πrc2
- (µ e + µ h )F ( r = rc )
F(rc)

Recombination current per cation iR: i R = ie = ene

(µ e + µ h )e = en γ
ε oε
e

γ=
(µ e + µ h )e
ε oε
Dieter Neher Organic Electroluminescence 16
 Recombination Cross Section

+ - jh µ e + µ h
α=
j

ε oεE 2 µ e µ h
+
h+ e- -
x 30

σR 25

Efficiency [cd/A]
20
current density of electrons towards cations
15
electron “absorption coefficient” α
10
dne
= − αne 5

dx
µe + µh
0
~ e 0 2 4 6 8

α = nhσ R = nh 2
Current density [mA/cm ]
ε oεE µ e
Dieter Neher Organic Electroluminescence 17
 Recombination Considerations

jh ( x ) µ e + µ h
α ( x) =
ε o εE 2 ( x ) µ e µ h

injection limited currents space charge limited currents

constant nh, constant E nh(x), E(x)
x [nm]
0 20 40 60 80 100

exponential recombination profile

E [a.u.]
nh [a.u.]
small jj, α < d-1
inefficient recombination

large, α > d-1

anode cathode
recombination close to cathode
largest α close to anode
ideal recombination conditions

Dieter Neher Organic Electroluminescence 18

 Multi-Layer Devices
counter electrode
e. g. Ca or Al

electron transport layer

emission layer
Cathode
-V
hole transport layer

transparent electrode

glass substrate

Large carrier density at interface

efficient recombination Anode
Electron-
Emission Transporting-
Recombination zone far from cathode Layer Layer
no quenching of excitons

Dieter Neher Organic Electroluminescence 19

 The Singlet-Triplet Branching Ratio

↑↑
↑ ↑
h+ + e-
1
2
(
↑↓ + ↓↑ ) 1
2
(↑↓ − ↓↑ )
↓ ↓
↓↓

spin statistics: φS : φT = 1 : 3, if
singlet and triplet excitons have
same formation cross-section: σS : σT

M. Wohlgenannt, S. Mazumdar, Z.V. Vardeny et al.

Nature 409 (2001) 494

Dieter Neher Organic Electroluminescence 20

 Few Remarks on the Quantum Efficiency of Emission

Is η(fl) = η(PL)?

In comparison with PL experiments, emission in a LED is in the presence of

an electric field and charge carriers

singlet excitons (and triplet excitons) can be quenching in the presence

of an electric field (exciton dissociation)

Singlet excitons are quenching by charges (via energy transfer)

M. Deussen, M. Schneidler, H. Bässler, Synth. Met. 73 (1995) 123.

K.E. Ziemelis,D. D. C. Bradley, R. Friend, J. Rühe, G. Wegner, Phys. Rev. Lett. 66 (1991) 2231.
D. Fichou, F. Charra, Synth. Met. 76 (1996) 11.

Dieter Neher Organic Electroluminescence 21

 External Efficiencies

External quantum efficiency:

only fraction of generated photons leave LED

LED is a Lambert emitter

Cathode

ηint ( EL)
ηext ( EL) =
Emitter
2
Anode 2n
Substrate
ideal fluorescent emitter
ideal recombination conditions
n = 1.7:
ηext ( EL) = 5%
N.C. Greenham et al., Adv. Mater 6 (1994) 491

Dieter Neher Organic Electroluminescence 22

 Microcavity Effects
Z
de < lc

de
self-interference of emitted
photons by multiple reflections

ϑ λ I(ϑ ,λ)

because of energy conservation and Fermi’s Golden Rule, photons can only
be emitted under conditions of constructive interference

Spectral Tuning: I(λ) at fixed angle ϑ

Angular Tuning: I(ϑ) at fixed wavelength λ
Efficiency Tuning Avoid emission into leaky modes

Dieter Neher Organic Electroluminescence 23

 Microcavity – Color Tuning
H R R' H R R'

1.0
n
R' H R R'

Normalized Intensity
4 0.8
Absorption coefficient α(107 m-1)

Emission Intensity (arb. unit)

0.6
3 LPPP
0.4
2

0.2
1

0.0 glass/Au/LPPP/Al
0
400 500 600 700 800
200 300 400 500 600 700 800
W avelength λ (nm)
W avele ngth λ (nm )

Blue (λ = 460 nm) for d = 60 nm

V. Cimrova, U. Scherf, D. Neher,
Green (λ = 565 nm) for d = 250 nm
Appl. Phys. Lett. 69 (1996) 608
Red (λ = 695 nm) for d = 150 nm
Dieter Neher Organic Electroluminescence 24
 Microcavity – Field Distribution

25 nm Aluminium
O
(a)
4 layers SPPP
n + 114 layers

230nm
O
Polyglutamate

NH CH CO NH CH CO 25 nm Aluminium
CH2 CH2
(b) 0.2
CH2 CH2
m=2 mode
~387nm

Intensity of on axis emission

COOCH3 COOC18H37
0.7 0.3 0.15

Simulation
Experiment 0.1
Intensity of on-axis

FWHM
~20nm
0.05
emission

0
360 370 380 390 400 410 420 430 440
0 50 100 150 200 250 Wavelength (nm)
Distance into sample, nm S. E. Burns, D. Neher, et al., Adv. Mater. 9 (1997) 395

Dieter Neher Organic Electroluminescence 25

 Microcavity – Optimization of Efficiency

top-emitting microcavity diodes 12

ZnSe
10 0 nm
30 nm
40 nm

Intensity [ a.u. ]
8 50 nm
60 nm
100 nm
6
solid: exp
dashed: sim
4

0
450 500 550 600 650
Wavelength [ nm ]

dielectric layer: ZnSe

cathode: Ca/Mg
anode Al/Ni H. Riel, S. Karg, T. Beierlein, W. Rieß, K. Neyts, JAP in press

Dieter Neher Organic Electroluminescence 26

 Luminance and Luminous Efficiencies

Power efficiency: φE ω
light power versus electrical power
η p ( EL) = = η ext ( EL)
eU eU
≤ η ext ( EL)

Luminous flux φV λmax= 555 nm

680

φV [lumen ]= Vλ (λ )[lm / W ] × φ E [W ]

Vλ (lm/W)
Luminous efficiency:
luminous flux versus electrical power

ηV [lm / W ]= Vλ (λ ) × η P
400 500 600 700
Wavelength (nm)

Dieter Neher Organic Electroluminescence 27

 Limits of Luminous Efficiency

Luminous efficiency: 120 100

luminous flux versus electrical power Singlet
100 Triplet n = 1.7
ηV [lm / W ]= Vλ (λ ) × η P
80

ηV [lm/W]

ηL [cd/A]
80
60
60
Luminance efficiency: 40
40
luminance (brightness) versus current
20
η L [cd / A]= ηV [lm / W ]×
U 20

π 0
400 500 600
0
700

λ [nm]
What is needed?
Computer display, 100 cd/m2, 1 mA/cm2 (10 cd/A)
blue: ηext > 7 %
difficult to achieve with
green: ηext > 2.6 % fluorescent materials
red: ηext > 6.4 %
Dieter Neher Organic Electroluminescence 28
 Phosphorescent Emitters

Increase phosphorescent rate by addition of heavy metal atoms

Pt(II) Octaethylporphine, N

ππ* transition in ligand N Pt N

PtOEP
N

Ir-complexes,
ligand-to metal transition
F
1.0 Firpic
F CH3 Ir(ppy)3

Intensity (a.u)
F H3C CH3
N N
N O 0.8 btp2ir(acac)
Ir
Ir O Ir N
S O
O
F N N N
CH3 0.6

H3 C 0.4

Firpic Ir(mppy)3 btp2ir(acac) 0.2

0.0
M. A. Baldo, S. Sibley, M. E. Thompson, 400 500 600 700
S. R. Forrest et al. Nature 395 (1998) 151. Wavelength (nm)

Dieter Neher Organic Electroluminescence 29

 Guest-Host Systems

Pure phosphorescent dyes can not be used due to triplet-triplet annihilation

Host Guest
e-
LUMO LUMO
S1
S1
T1
T1

HOMO
HOMO
h+
3 major processes: charge transfer to guest
Dexter and Förster transfer for singlet excitons
Dexter transfer of triplet excitons

Dieter Neher Organic Electroluminescence 30

 Selection of Host

Guest T1 energy must be below host T1 level!!

HOMO-LUMO (single particle) gap versus S1 energy
S1 gap versus T1 energy

T1 = (1.13 S1 – 1.45 eV)

e.g. green emitting guest

requires large-bandgap host

A.P. Monkman, A.D. Burrows et al.,

PRL 86 (2001) 1358

Dieter Neher Organic Electroluminescence 31

 Charge and Energy Transfer

Variation of polymer matrix: Phosphor.-quenching

Exciton- Hole- Electron- Exciton-
transfer trapping transfer transfer

V. Cleave, N. Tessler et al.,

Adv. Mater 13 (2001) 44

Dieter Neher Organic Electroluminescence 32

 Charge Carrier Trapping on Guest

n
N Pt N

PFO PtOEP

EL spectrum dominated by guest

already at very low concentration

Increase in driving voltage with

increasing guest concentration

ηext = 3.5 % ηV > 0.2 lm/W

P.A. Lane et al., PRB 63 (2001)235206

Dieter Neher Organic Electroluminescence 33

 PVK-based Green Phosphorescent Diode

doped into PVK-PBD (40 wt.%) ITO/PEDOT/Emitter/Ca/Al

X. Gong, D. Moses, A.J. Heeger et al., Adv. Mater, 14 (2002) 581

Dieter Neher Organic Electroluminescence 34
 Device with Improved Carrier Injection
Use 70 nm PEDOT layer, CsF/Al cathode
80 30
(a) (b) 15

Luminance efficiency [cd/A]

Current density (mA/cm )
2

15000

Brightness (cd/m )
25

2
60
20

PCE [lm/W]
10
10000
40 15

10 5
20 5000
5

0 0 0 0
0 2 4 6 8 10 12 0 20 40 60 80 100
Voltage (V) 2
Current density (mA/cm )

improved electron injection: compensation of positive space charge

Peak luminance efficiency: 27 cd/A, EQE 7.6 % at 610 cd/m2
Peak PCE: 14 lm/W at 170 cd/m2 X. Yang, D. Neher
Adv. Mater.

Dieter Neher Organic Electroluminescence 35

 The Efficiency Record

Ir(ppy)3 in TCTA

70 lm/W @ 65 cd/A, ηext = 19 % M. Ikai et al., APL 79 (2001) 156

Dieter Neher Organic Electroluminescence 36

 Doped Injection Layers

Problem:
depending on treatment, ITO has a work function of 4.3-4.9 eV
inefficient hole injection into many organic semiconductors

One solution:
chemical or electrochemical
doping of semiconductor

One example:
PEDOT:PSS
work function ca. 5.2 eV
not soluble in organic solvents
quite transparent
hole-injection layer

Dieter Neher Organic Electroluminescence 37

 Control of Workfunction

Electrochemical doping of
polythiophene hole-injection layer

M. Gross, U. Scherf, D. Neher, K. Meerholz,

Nature 405 (2000) 661-665.

Dieter Neher Organic Electroluminescence 38

 Efficiency of Light-Emitting Diodes

Small molecule OLED

Polymer OLED

Dieter Neher Organic Electroluminescence 39

 eMagin 0.6‘‘ Microdisplay Kodak Camera

Thanks to:

Heike Riel (IBM)

Andreas Elschner (HC Starck)

Sony 13‘‘
Dieter Neher Organic Electroluminescence 40