Phys 590B-2009-04-01

Organic Light-Emitting Devices (OLEDs):

A Brief Overview

Joe Shinar

jshinar@iastate.edu

Support, mostly by DOE, gratefully acknowledged

Support by NASA, NSF, & NIH also gratefully acknowledged
Current Issues in the Science & Technology of OLEDs:

 Internal quantum efficiency, at low & high current densities

 Outcoupling or extraction efficiency.

 Power efficiency, at low & high current densities.

 Stability & degradation mechanisms: Oxidation (by water),

crystallization, delamination, atomic In, Na, etc. (electro)migration.

 Is an organic injection laser (i.e., an organic diode laser) feasible?

Basic Nature of p-Conjugated Materials
A carbon-based (small) molecule or polymer with alternating R'

single (s) and double (s & p) bonds. Examples:

R
C6H13

n
n
R R n
C6H13
poly(p-phenylene) vinylene (PPV) Polyfluorene (PFO)
R

methyl-bridged ladder-type poly(p-phenylene ) (m-LPPP) R'

N
O O
Al N
N O

4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl
tris(8-hydroxy quinoline) Al (Alq3) (DPVBi)
 Basic Nature of p-Conjugated Materials (cont.)
pz

 Consider ethylene (C2H4):

 sp2 hybridization: three sp2

orbitals 120o to each other, pz
orbital perpendicular to the
sp2 plane.

 In benzene (C6H6) ring:

ψ2 and ψ3 are HOMO –
Valence band
ψ4*, ψ5* are LUMO –
Conduction band
Basic Nature of p-Conjugated Materials (cont.)

 PPV:

 Electrons in p orbitals have higher energy than those in s orbitals.

 The energy gap between
the highest occupied molecular orbital (HOMO)
(analogous to the top of the valence band in inorganic semiconductors)
& the lowest unoccupied molecular orbital (LUMO)
(analogous to the bottom of the conduction band in inorganic semiconductors
is 1.5 – 3.5 eV, i.e., it covers the whole visible range.
 Basic structure of some (blue) OLEDs
-
Low-Workfunction Cathode DPVBi

+ Electron-Transporting &
Emitting layer (ETL)

Hole-Transporting Layer
: N N

(HTL)

Transparent Conducting Anode Pe:CBP

[indium tin oxide (ITO)]

Glass or Plastic Substrate a-NPD

N N

4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl (DPVBi), Perylene:4,4'-bis(9-carbazolyl)biphenyl (Pe:CBP)

N,N’-diphenyl-N,N’-bis(1-naphthyl phenyl)-1,1’-biphenyl-4,4’-diamine (a-NPD)
 Basic Operation, forward bias

Lowest
unoccupied
molecular orbital
e- Metal cathode
(LUMO)
Energy e- EF

ITO Anode ETL

HTL

EF

h+
Highest occupied
molecular orbital
(HOMO)

Position (from ITO anode bottom to methal cathode top

The state-of-the-art in OLEDs

• Numerous red-to-blue small-molecular- and polymer-OLEDs

• Fluorescent Green, yellow & red small molecular OLEDs with
continuous lifetimes > 300,000 hours (> 12,000 days > 33 yrs),
hext ~ 4%, power efficiency ~2%, at brightness of ~150 Cd/m2
• Blue small molecular OLEDs with
continuous lifetimes ~100,000 hours (> 4000 days > 12 yrs),
hext ~ 3%, power efficiency hP ~ 1.5%.
• Electrophosphorescent Red, green, & blue OLEDs, i.e.,
emission is from Triplet (Excitons), so efficiency can be very high --
hext ~ 18%, 19%, & 7%, hP ~ 9%, 9.5%, 3%, respectively.
Cd/m2 ????

• 1 Cd/m2 = 1 lumen/steradian = 1 lm/str = [1.46 mW @ 555 nm]/str

• For Lambertian source, 1 lm/str  total of p lm
• Typical values:
TV or computer monitor, 100 – 300 Cd/m2.
60 W incandescent light bulb, 840 lumens.
Power efficiency hP = [840 lm]/[60 W] = 14 lm/W
 [1.20 W light]/[60 W electrical] = 2%
Fluorescent tubes, 40  hP  60 lm/W, i.e., 6  hP  9 %
OLED Efficiencies

 Internal quantum efficiency IQE of fluorescent OLEDs

hint  0.25
Why? Can it be improved?

 Outcoupling or extraction efficiency hout  0.33

Why? Can it be improved?

 [Photon energy (in V)]/[Applied Voltage] = Vg / Vappl < 0.50

Why? Can it be improved?

Note: 0.250.330.50 ~ 0.04

Internal Quantum Efficiency: Carrier injection into a
luminescent p-conjugated molecule or polymer
The most basic process in all light-emitting diodes (LEDs):

Bottom of conduction band, inorganic semiconductor

LUMO, organic semiconductor
Electron e- from cathode
e- e-
h+ & e- meet to form an exciton on a
molecule or same conjugated
segment of polymer
Photon emission

h+ h+

Hole h+ from anode HOMO, organic semiconductor

Top of valence band, inorganic semiconductor
How many distinct SE & TE quantum states?

+ = TE, Spin 1, Sz = +1

+ = TE, Spin 1, Sz = 0
How many distinct SE & TE quantum states (cont.)?

+ TE, Spin 1, Sz = -1
=

SE, Spin Sz = 0
+ = 0
In summary:

 3 TE states (S = 1): () (Sz = +1), ( + )/2 (Sz = 0), () (Sz = -1).
 1 SE state (S = 0): ( - )/2 (S = 0).
 In fluorescent organic materials, only the SE decays radiatively,
to yield the photoluminescence (PL) or electroluminescence (EL).
A Fiercely Debated Question:
 Given an e- - h+ pair (i.e., a radical anion – radical cation pair)
at a given distance from each other, is
the cross section of a pair in the singlet configuration to form a SE (sSE)
equal to
the cross section of a pair in the triplet configuration to form a TE (sTE)?
 If sTE = sSE max internal quantum efficiency IQEmax of fluorescent OLEDs is 25%.

So, is sSE = sTE ?

 After ~8 years, jury is still out; i.e., there are two schools on it…
 Interestingly, the most powerful technique to explore this issue has turned
out to be optically detected magnetic resonance (ODMR), whose application
to p-conjugated polymers and OLEDs we pioneered in the late 80s.
Claiming sSE > sTE so IQEmax > 25%
1. Wohlgenannt , Vardeny, Mazumdar, et al., using ODMR [Nature
409, 494 (2001); PRL 88, 197401 (2002); PRB 66, 241201(R) (2002)]

2. Friend, Greenham, et al., using “standard” optical spectroscopy

[JAP 88, 1073 (2000); Nature 413, 828 (2001); CPL 360, 195 (2002)]

Claiming sSE ≈sTE so IQEmax ≈ 25%

1. Baldo & Forrest, using “standard” PL and EL measurements

[PRB 60, 14422 (1999); 68, 075211 (2003)]

2. Shinar, Baldo, Soos, et al., using ODMR and double-modulation ODMR

[PRL 94, 137403 (2005); PRB 71, 245201 (2005)]

Claiming spin-flip rates are very low
so sSE & sTE do not matter & IQEmax ≈ 25%

Lupton et al., using “standard” spectroscopy & time-resolved EDMR

[Nat Mat 4, 340 (2005); Nat Mat 7, xxx (2008)]
Outcoupling Efficiency Issue

 Due to total internal reflections at the various interfaces,

and resulting waveguiding of the light towards the edges of the OLED,

hout ~ 1/(2n2), where n is the organic index of refraction

[Kim et al., JAP 88, 1073 (2000)]

 So what do we do?

 Solution 1. Textured surfaces (even sandblasting helps by 20 – 100%).

 Solution 2. Microlens arrays.

 Solution 3. Top-emitting devices.

 Vg / Vappl Issue

 Need to minimize voltage for given current & brightness,

in order to maximize power efficiency for that given quantum efficiency.

 Solution: Minimize voltage drop across HTL & ETL,

by maximizing their conductivity. How?

 Solution: p-dope the HTL (e.g., F4-TCNQ-doped NPB) &

n-dope the ETL (e.g., Li-, Na-, etc., doped ETL).

Conclusion on Efficiency & Outlook

 With electrophosphorescent devices, IQE max > 90%

 With textured surfaces, microlens arrays, or top-emitting devices,

outcoupling efficiency may be ~ 0.60.

 With optimized p-doped HTL & n-doped ETL, Vg / Vappl ~ 0.80.

 Then power efficiency will be ~ 0.43

 We’ll get there…

Summary of Degradation Mechanisms

 Oxidation (by water & oxygen)

Solution: Barrier coatings.
 Crystallization of amorphous layers.
Solution: Use high glass-transition temp materials.
Or fabricate cystalline layers?
 Delamination of metal cathode (leads to “black spot”)
Solution: Better organic/cathode buffer layers &
better cathode fabrication procedures.
 Atomic In, Na, etc. (electro)migration.
Solution: Use Na-free glass substrate, fabricate ITO/organic buffer layer.
But what happens at high brightness
(needed for using OLEDs for general lighting)?

 High brightness (~2000 Cd/m2) means high current density.

 High current density means high SE, polaron, & TE densities.

 High SE, polaron, & TE densities means much higher

SE-SE annihilation & quenching of SEs by polarons & TEs.

 In electrophosphorescent OLEDs, it means much higher TE-TE

annihilation to SEs.

 What can we do about these quenching processes?

 Answer: Stacked tandem OLEDs.

Stacked tandem OLEDs

Glass
Transparent anode
Organic layers
Charge generation layer
Organic layers
Charge generation layer
Etc.
Metal cathode

This way, we can get more than 1 photon per e-

(But we pay with higher V for lower J)
Last but not least: Is an organic injection laser feasible?

 Realized only in the fraudulent mind of J. Hendrik Schoen.

 We can observe spectrally narrowed edge emission, but no clear evidence

for optical gain [Gan et al. APL (2007)].

 Current hopes are for LED- or OLED-pumped polymer lasers

The state-of-the-art in OLEDs (cont.)

• They are appearing increasingly in commercial products (see below)

• Investment & activity growing rapidly

Cambridge Display Technology (CDT), Dow Chemical, Dupont,

Eastman Kodak, General Electric, Idemitsu Kosan, IBM,

LG, 3M, Osram-Sylvania, Philips, Samsung,

Seiko-Epson, Siemens, Sanyo, Sharp, Sony, Tohoku Pioneer,

Toshiba, Toyota, Universal Display Corp.

Actual and potential applications of OLEDs

• 7-segment alphanumeric displays for, e.g., cell phones (already obsolete).

• Displays for car stereos (Pioneer-Toyota, 1st commercial product).
• Displays for MP3 players (currently > 40% of new MP3 players).
• Full-color microdisplays (eMagin-IBM, actual).
• Full-size flat panel TVs and computer screens
(demos, up to 40” diagonal, by Sony, Samsung, etc.; )
• Light sources for fluorescent chemical & biological sensors (potential)
• Ultimate application: White OLEDs (WOLEDs) & other OLEDs for
general purpose light-sources (Solid State Lighting Initiative) (potential)
• Current OLED sales > ~$1B/yr & growing exponentially.
First commercial product:
Display for car stereo by Pioneer/Toyota (1998)
Microdisplays by eMagin-IBM joint venture (2002)
(very expensive)
Sony 11” OLED TV, commercialized in Dec 2007.
Power consumption 45 W. MSRP ~ $2,000
Contrast 1,000,000:1
Ultimate application: White & multicolor OLEDs for gen’l lighting.
• Inorganic LEDs already shining in traffic lighting, rear vehicular
lighting, flashlights.
• OLEDs, however, must perform with higher efficiency and longer
life at high brightness (> 1000 Cd/m2).

30 cm x 30 cm White OLED (WOLED) Panels,

~20 lm/W @ 1000 Cd/m2, by Kido et al. (Science 310, 1762 (2005))
Combinatorial arrays of UV-violet OLEDs; among shortest
wavelengths OLEDs

L. Zou et al., Appl. Phys. Lett.

79, 2282 (2001).
Mapping of Radiance of Devices w/CsF/Al Cathode
Extremely bright white OLEDs [Lmax > 50,000 Cd/m2);
K.-O. Cheon & J. Shinar, Appl. Phys. Lett. (2002)]

2
10
F (MV/cm)
0.5 1.0 1.5
J (mA/cm )

0
2

10 10
4

2
L (cd/m )

10
2

-2
10
0
10

-4
10
0.4 0.8 1.2 1.6 2.0
F (MV/cm)
In same OLEDs
[K.-O. Cheon & J. Shinar, Appl. Phys. Lett 83, 2073 (2003)]

…[35 nm a-NPD]/x nm 5% DCM2:a-NPD/[40 nm DPVBi/[10 nm Alq3]…

When x increases from 0 to 3.5 nm, emission changes from blue to red!
Even brighter white OLEDs [Lmax ~ 74,000 Cd/m2)];
[G. Li & J. Shinar, Appl. Phys. Lett. 83, 5359 (2003) ]

1400
Device
5
1200 #1
#2
4

log10L (Cd/m )
1000

2
#3
3
J (mA/cm )
2

#4
800 #5
#6
2
600 1
400 0
200 -1
0 -2
0 2 4 6 8 10 12 14
Bias (V)
 Next time:
The most recent application of OLEDs:
Structurally-integrated OLED-based luminescent
chemical & biological sensors

Ruth Shinar
Microelectronics Research Center & ECpE Dept, ISU
Integrated Sensor Technologies, Inc. (ISTI)
Joseph Shinar
All of the aforementioned & ISTI

Support by DOE, NASA, NSF, & NIH also gratefully acknowledged