Organic light-emitting diodes

Introduction
Fang-Chung Chen Department of Photonics and Display Institute National Chiao Tung University

Organic light-emitting diodes --The emerging technology

OLED Displays

Pull out travel guide

OLED Revenue Forecast by Application

r !! Sta re utu

http://www.displaysearch.com/press/2003/122303.htm

Seiko Epson: The largest OLED Display using IJP

Screen size 40-inch diagonal Number of pixels 1280 x RGB x 768dots (W-XGA) Driving method Active matrix Pixels per inch 38 No. of colors 260,000 Main Specifications Screen size 40-inch diagonal Number of pixels 1280 x RGB x 768dots (W-XGA)

commercialization in 2007

http://www.epson.co.jp/e/newsroom/news_2004_05_18.htm

Efficiencies of LEDs

Performance (lm/W)

OLEDs

s D LE P

Candle
year
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History of organic light-emitting devices (OLEDs)

1963 --- First organic electroluminescent (EL) based on anthracene single crystal; (Pope et al.) Problem: low quantum efficiency and high operating voltage (>100V) 1987 --- First organic electroluminescent (EL) based on amorphous organic molecules; (Kodak; C. W. Tang et al.) high quantum efficiency (~1%); low driving voltage bi-layer structure; thin amorphous organic films 1990 --- First organic electroluminescent (EL) based on polymer; (Cambridge University; Burroughes et al. polymer light-emitting diodes (PLEDs)
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Device structure of OLEDs

Mg Ag

Alq3

Diamine ITO Glass

Devices were fabricated by thermal evaporation Drive voltage ~5V QE: ~1%; 3 cd/A (green) Fast response time (<1 sec)
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Operating mechanism of OLEDs

Mg Ag Alq3

Diamine ITO Glass

Mechanism involves: 1: Charge injection 2: Charge transport

diamine (hole-transporting layer)

HTL ITO + anode + +

Mg/Ag cathode

3: Charge recombination (Exciton formation)

ETL

Electrical field: >105 V/cm 100 nm; @~1V

Alq3 electron-transporting layer

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Operating mechanism of PLEDs

MEH-PPV + Ca/Al MEH-PPV

PEDOT:PPS ITO
H3CO

glass PEDOT:PPS
O O S S O O S + O O O O S S n O O

Devices were fabricated by spin-coating Single emissive layer was used

SO3-

SO3H

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Device mechanism
Mechanism involves:
1 2 Cathode Polymer LUMO 3

1: Charge injection 2: Charge transport 3: Charge recombination

eLUMO * (2.8eV)

Anode

Polymer HOMO 1 2
4.7eV ITO

2.9eV Ca

(4.9eV) HOMO
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h+

I-V characteristics Diodes!!!

10
-3

10

-3

ITO/MEH-PPV/Ca Au/MEH-PPV/Ca
10
-5

10

-5

Radiance (W)

Current (A)

10

-7

10

-7

10

-9

10

-9

10

-11

-10

-5

10 10

-11

Voltage (V)
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Why PLEDs?

Easy and low-cost fabrication Solution processability Light weight and flexible Easy color tuning Spin-coating for mono-color display Ink Jet printing for multi-colors display

40-inch commercialized in 2007 http://www.nobel.se/chemistry/laureates/2000/illpres/7.html http://www.epson.co.jp/e/newsroom/news_2004_05_18.htm

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Family of light-emitting poly(thiophene)

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Molecular engineering of light-emitting polymers

PA PPP

n
Eg = 1.4 eV Eg = 3.0 eV

PPV

MEH-PPV

n
Eg = 2.4 eV

H3CO
Eg = 2.1 eV

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The merits of OLEDs over other display technologies

Flat and thin Wider viewing angle (> 160o) Saturated emissive color Wide operating temperature High contrast Flexible, Plastic can be used as substrates Light weight Fast response time (~s) Low temperature processing Low cost
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Comparison of O/PLED with other display technology

< 1sec

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OLED Displays

LCD

OLED

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OLED Displays

LCD

OLED

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OLED Displays

20

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OLED Displays

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OLED Displays AUO world first 4 a-Si AMOLED (2003)

Parameter Display Size Resolution Sub-Pixel Pitch Driving Method Color Number Brightness Power Cons. Substrate Contrast ratio Module thickness Emission Type Features 4-inch 160(RGB)234 171um264um 2-TFT Voltage Programming 262K (6 bits) 300 cd/m2 670 mW a-Si TFT >250 1.8 mm Bottom Emission
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Flexible OLEDs
OLED built on flexible substrates Flexibility Ultra-lightweight and Thin

http://www.universaldisplay.com/

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Organic light-emitting diodes

Chemical and electronic Structure of organic materials

Fang-Chung Chen Department of Photonics and Display Institute National Chiao Tung University

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Organic Materials
C HONS..

-NPD

Organic metallics Alq3CuPc..

25

Comparison of Bohr and wave-mechanical atom models

26

13

Atomic Orbitals

: one-electron wave function 2 : electron density

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Molecular Orbitals

Energy levels Anti-bonding

Bonding

: depends on the degree to which the orbitals occupy the same space or overlap

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14

Molecular Orbitals

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Electronic energy vs interatomic separation of an aggregate of 12 atoms

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15

Carbon atom bonding configurations

orbitals

single bond

double bond

triplet bond

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Orbital structure of benzene (Six Carbons)

32

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The -molecular orbitals and energy levels for benzene

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Chemical structures of common organic semiconductors

Eg1

Eg2

The lowest electronic transition (band gap, Eg) Ethylene (C2H4) : Eg1 = 6.9 eV Benzene (C6H6) : Eg2 = 4.6 eV More delocalized electrons, the lower the band gap energy
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17

Electron band structures in solids at 0 K

Metal (Cu) Metal (Mg) Insulator Empty conduction band Band gap Filled states Filled states Filled valence band (Eg >2 eV) Semiconductor

Empty band Band gap Empty states Ef Ef

Empty band

Empty conduction band Band gap Filled valence band

107 -1 cm-1

10-10 - 10-20 -1 cm-1

10-6 - 104 -1 cm-1

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Chemical structures of common organic semiconductors

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Conductivity domain of metals, semiconductors, and insulators

p-doped polyacetylene

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Organic (Molecular) Semiconductors

Weak bonding (van der Waals force) Low melting point Low conductivity 10-8 - 10-12 -1 cm-1
Small Molecules Functional Polymers
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Conjugation
A conjugated system is one having alternating single and double bonds

Conjugated Polymer Backbones: alternating single-double bonds Delocalized electron clouds

Eg = 3.0 eV

PPP

PA

n
Eg = 1.4 eV

PPV

n Eg = 2.4 eV

polyacetylene

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Polymer vs Small Molecular

Polymer, Macromolecules Historically, molecules larger than 10k (10000 g/mole) belong to this group Technically, all polymers are mixtures Polymers show isomers, and polymers having the same Chemical formula can show different properties
different
Regioregular - Polypropylene Random - Polypropylene
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Excitons in Organic Materials

Electronic excitation is considered as a quasi-particle, capable of migrating. This is termed as Exciton Excitons can be regarded as bounded electron-hole pairs. Also can be viewed as the excited states of molecules

lattice constant

Charge-transfer exciton

Wannier-Mott exciton

Frenkel exciton
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The Nature of Excitons in Organic Materials

organic molecules LUMO -

hv

Frenkel Exciton

HOMO

Coulombic interaction

q1 q2 r

(binding energy 0.2 - 1.0 eV Radius ~ 10)

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21

Ultraviolet-visible (UV-vis) Spectroscopy

E ground state excited state

+ h

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Ultraviolet-visible (UV-vis) Spectroscopy

~ 150 nm, * transition < 200 nm, vacuum ultraviolet, strongly absorbed by the oxygen = 200 - 400 nm, ultraviolet, = 400 - 750 nm, visible,

* transition

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 * transitions

The longer the chain of conjugation The longer the wavelength of the absorption band

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Ultraviolet-visible (UV-vis) Spectroscopy

monochromator Sample

h
Light source I0

h
I detector

A = - log (

I I0

)
n C8H17 C8H17

PF

UV-vis Spectroscopy of polyfluorene

46

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UV-vis Spectroscopy of polyfluorene -- another example

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Photoluminescence (PL)
h
Light source Sample

Monochromator & detector

48

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Typical energy levels and energy-transfer energyprocess of a molecule

Energy

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Vector representation of an electrons spin magnet moment electron

Only two spin states (, ) are stable

50

25

Single and Triplet

single excited state

S1

S1

triplet excited state

T1 S0 S0
S=0 ground state S=0 Fluorescent S=1 Phosphorescent

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Single and triplet states

up state down state

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Organic light-emitting diodes

Basic Device Physics

Fang-Chung Chen Department of Photonics and Display Institute National Chiao Tung University

Device structure of OLEDs

Mg Ag

Alq3

Diamine ITO Glass

Devices were fabricated by thermal evaporation Drive voltage ~5V QE: ~1%; 3 cd/A (green) Fast response time (<1 sec)

Operating mechanism of OLEDs

Mg Ag Alq3

Diamine ITO Glass

Mechanism involves: 1: Charge injection 2: Charge transport

diamine (hole-transporting layer)

HTL ITO + anode + +

Mg/Ag cathode

3: Charge recombination (Exciton formation)

ETL

Electrical field: >105 V/cm 100 nm; @~1V

Alq3 electron-transporting layer

Operating mechanism of OLEDs

LUMO (Conduction band)

h + + +

cathode

anode

HOMO (Valence band)

Typical multilayer-device structures

Metal Metal ETL EML HTL (EML) ITO HTL Metal

ETL ETL (EML) HTL ITO

ITO

ETL, electron-transport layer EML, emissive layer HTL, hole-transport layer

Operating mechanism of PLEDs

MEH-PPV + Ca/Al MEH-PPV

PEDOT:PPS ITO
H3CO

glass PEDOT:PPS
O O S S O O S + O O O O S S n O O

Devices were fabricated by spin-coating Single emissive layer was used

SO3-

SO3H

What is PEDOT:PSS?
PEDOT:PSS is a hole-transporting conductive polymer Deposited from an aqueous suspension ~ 1000 to 100000 -cm Work function ~ 5.00.2 eV
ITO work function depends on the surface treatment ITO surface is often full of spikes
SO3O O S S O O S + O O

PEDOT:PPS
O O S S n O O

SO3H

PEDOT:PSS (~ 100 nm) both planarizes the surface and stablizes the work function of the anode of the PLEDs It is one of the keys to reproducible devices

Single layer organic EL device

1 2 Cathode Polymer LUMO 3

Anode

Polymer HOMO 1 2

Very common for PLEDs The material should be bi-polar

Small molecule and Polymer OLEDs

Metal Metal

ETL EML HTL

Emitting polymer Hole-injection layer

ITO

ITO

smOLEDs: Evaporation of a multilayer stack of small organic molecules (Mw ~ several 100)

PLEDs: Spincoating/inkjet printing of polymers (Mw ~ 50,000 500,000)

I-V characteristics
Diodes!!!
10
-3

10

-3

ITO/MEH-PPV/Ca Au/MEH-PPV/Ca
10
-5

10

-5

Radiance (W)

Current (A)

10

-7

10

-7

10

-9

10

-9

10

-11

-10

-5

10 10

-11

Voltage (V)

Why PLEDs?

Easy and low-cost fabrication Solution processability Light weight and flexible Easy color tuning Spin-coating for mono-color display Ink Jet printing for multi-colors display

http://www.nobel.se/chemistry/laureates/2000/illpres/7.html http://www.toshiba.co.jp/about/press/2001_05/pr_j3001.htm

Efficiency of Organic EL Devices

ext = int p = r f p
~100% ~25% ~100% ~20%

Maximum external quantum efficiency is ~5% ext : external quantum efficiency int : internal quantum efficiency p : light out-coupling efficiency : charge carrier balance factor (e/h) r : efficiency of exciton production f : internal quantum efficiency of luminescence

p : light out-coupling efficiency

due to total internal reflection loss p = 1 / (2n2) n : reflection index of the emissive medium
If n ~ 1.5

p = 22%

Front view
n = 1.0 Organic layer n ~ 1.5

Mirror

: charge carrier balance factor (e/h)

Jh Je
ITO anode

Jh

Je
Metal cathod

= Jr / J J : circuit current Jr : current used for charge recombination J = Jh + Je = Je + Jh Jr = Jh - Jh = Je - Je

r : efficiency of exciton production

hole (+) electron (-) exciton (*)

+
s in

or

gl e

tri

ple

3 symmetric states Triplets

1/

1/

1 antisymmetric state Singlet

f : internal quantum efficiency of luminescence

kO other deactivation processes

S1
kF

kI

intersystem crossing

T1 X phosphorescent
kP

Thermal deactivation kT

fluorescence S0
kF kF + kI+ kT + kO

F =

Typical I-L-V curves of an Alq3-based OLED

75 nm NPD/75 nm Alq3

L. S. Hung and C. H. Chen, Mater. Sci. & Eng. R 39, 143 (2002)

Manufacture of OLEDs
Thermal evaporation
substrate Metal mask

Cathode material

Organics

Manufacture of PLEDs
Spin-coating or ink-jet printing

Ink-jet printing to pattern polymers

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Efficiency of organic EL Devices

Quantum efficiency: ext = int p = r f p
ext : external quantum efficiency int : internal quantum efficiency p : light out-coupling efficiency : charge carrier balance factor (e/h) r : efficiency of exciton production f : internal quantum efficiency luminescence

Power efficiency:

optical power output electrical power input

pow = ext EpU-1

Ep : the average energy of the emitted photons

U : the known values of the applied voltage

(lm/W), important for engineer and system design

Efficiency of organic EL Devices

Luminous efficiency: lum = pow S S : the eye sensitivity curves

Current efficiency (Cd/A), important for material evaluation

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Efficiency of organic EL Devices an Example

Device current density : 50 mA/cm2 at 10V Brightness : 3500 cd/m2

Current Efficiency : 3500 cd/m2 1 x 2 50 mA/cm 10

7 cd/A

Power Efficiency : 7 cd/A x = 10 V

2.2 lm/W

Definitions of Efficiencies of OLEDs

S. R. Forrest et al. Adv. Mat. 15, 1043 (2003)

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