Haldi Andreas 200812 PHD

PATTERNABLE ELECTROPHOSPHORESCENT ORGANIC
LIGHT-EMITTING DIODES WITH SOLUTION-PROCESSED

ORGANIC LAYERS

A Dissertation
Presented to
The Academic Faculty

By

Andreas Haldi

In Partial Fulfillment
Of the Requirements for the Degree
Doctor of Philosophy in the
School of Electrical and Computer Engineering

Georgia Institute of Technology

December 2008

PATTERNABLE ELECTROPHOSPHORESCENT ORGANIC
LIGHT-EMITTING DIODES WITH SOLUTION-PROCESSED
ORGANIC LAYERS

Approved by:

Prof. Bernard Kippelen, Advisor
School of Electrical and Computer
Engineering
Prof. Glenn S. Smith
Engineering

Prof. Russell D. Dupuis
Engineering
Prof. Jean-Luc Brdas
School of Chemistry and Biochemistry

Prof. Oliver Brand
Engineering

Date Approved: August 1, 2008

iii
ACKNOWLEDGMENTS

Many people deserve a thank you for their support during my Ph.D. program, and
I already apologize to whomever I am forgetting in the following list. First, I would like
to thank my advisor, Prof. Bernard Kippelen, for accepting me as a graduate student in
his group and for letting me work on whichever project I wanted to work on. Then, I have
to thank Dr. Benoit Domercq for leading me to and on the OLED project towards where I
knew enough about it that I could take on that research by myself. Further thanks go to
my reading and oral defense committee, Prof. Russell D. Dupuis, Prof. Oliver Brand,
Prof. Glenn Smith, and Prof. Jean-Luc Brdas for their availability as a committee
member and for their helpful input towards additional chapters in this thesis when I
proposed my Ph.D. work.
It goes without saying that my program would have lasted a lot longer if it had not
been for the support of many students and postdocs in the Kippelen Research Group.
There are too many to name them all, but the following have to be mentioned separately:
Dr. Joshua N. Haddock for helping me out anywhere inside and outside of the lab during
the first two years of my Ph.D. program, Prof. Seunghyup Yoo for his help on the
vacuum deposition system and his insight into organic electronics, Dr. Canek Fuentes for
any support I needed when optics came into play, William J. Potscavage for any kind of
help and company during many years, and Dr. Asha Sharma for some of the device
fabrication that was helpful to me, too.
Since many OLEDs in this dissertation were fabricated with newly synthesized
materials, it is also necessary to mention the chemists that provided me with these
iv
materials: Alpay Kimyonok in the group of Prof. Marcus Weck made all the
phosphorescent copolymers that are used in chapter 4 and 5 of this thesis. The synthesis
of hole-transport and electron-transport polymers was done by Yadong Zhang, as well as
several other graduate students and postdocs in the group of Prof. Seth Marder.
And last but not least, special thanks go to my family and Erica who have
supported me for a long time and were always proud of my Ph.D. program regardless of
whether they saw any progress in my work or not.
The financial support for this work came in part from Solvay SA, from the STC
Program of the National Science Foundation under Agreement Number DMR-0120967,
and from the Office of Naval Research.

v
TABLE OF CONTENTS

Acknowledgments ............................................................................................................ iii
List of Tables .................................................................................................................. viii
List of Figures................................................................................................................... ix
Summary......................................................................................................................... xiv
Chapter 1 Introduction............................................................................................... 1
1.1 Organic Light-Emitting Diodes .......................................................................... 1
1.2 Advantages of OLEDs ........................................................................................ 2
1.3 History of OLED Technology ............................................................................ 4
1.4 Organic Compounds: Small Molecules and Polymers ....................................... 5
1.5 Figures of Merit .................................................................................................. 6
1.6 Goal and Structure of the Dissertation................................................................ 8
Chapter 2 Background on Organic Semiconductors and Organic Light-Emitting
Diodes....................................................................................................... 10
2.1 Organic Semiconductors................................................................................... 10
2.1.1 Atomic Orbitals ............................................................................................ 11
2.1.2 Chemical bonds ............................................................................................ 12
2.1.3 Molecular Energy Levels and Energy Bands ............................................... 14
2.2 Principle of Operation of OLEDs ..................................................................... 16
2.2.1 Charge Injection............................................................................................ 17
2.2.2 Charge Mobility............................................................................................ 18
2.2.3 Space-Charge-Limited Current..................................................................... 21
2.2.4 Langevin Recombination.............................................................................. 22
2.2.5 Singlet and Triplet Excited States................................................................. 24
2.2.6 Light Emission.............................................................................................. 25
2.2.7 Energy Transfer from Host to Guest ............................................................ 28
2.3 OLED Efficiency.............................................................................................. 30
2.3.1 OLED Device Architecture .......................................................................... 32
2.3.2 Light Outcoupling......................................................................................... 33
Chapter 3 Experimental Methods ........................................................................... 36
3.1 OLED Test Setup.............................................................................................. 36
vi
3.2 Electroluminescence Spectra Measurements.................................................... 37
3.3 CIE Spectral Coordinates.................................................................................. 37
3.4 Luminance Calculation..................................................................................... 40
3.5 OLED Efficiency Calculation........................................................................... 41
Chapter 4 Hybrid Electrophosphorescent OLEDs with a Solution-Processed
Hole-Transport Layer ............................................................................ 43
4.1 State-of-the-Art High-Efficiency OLEDs......................................................... 43
4.2 Ionization Potential Study................................................................................. 45
4.3 Simplification of the Device Architecture........................................................ 50
Chapter 5 Hybrid Electrophosphorescent OLEDs with Solution-Processed Hole-
Transport and Emissive Layers............................................................. 54
5.1 Introduction....................................................................................................... 54
5.1.1 Solution-Processed Multilayer Stacks and Crosslinking.............................. 55
5.1.2 Molecularly Doped OLEDs.......................................................................... 56
5.1.3 Dendrimers ................................................................................................... 58
5.1.4 Emissive Layers from Copolymers .............................................................. 59
5.2 Experimental Results ........................................................................................ 61
5.2.1 Iridium Complex Variation........................................................................... 63
5.2.2 Optimization Rationale................................................................................. 66
5.2.3 Molecular Weight and Iridium Content Variation........................................ 68
5.2.4 Spacer Variation ........................................................................................... 72
Chapter 6 Solution-Processed Electrophosphorescent Multilayer OLEDs......... 74
6.1 Introduction....................................................................................................... 74
6.1.1 State of the Art.............................................................................................. 74
6.1.2 Crosslinking of the Emissive Layer.............................................................. 76
6.1.3 Electron-Transport/Hole-Blocking Polymer ................................................ 77
6.2 Experimental Results ........................................................................................ 80
6.2.1 OLEDs with a Crosslinkable Emissive Layer .............................................. 80
6.2.2 Solution-Processed Multilayer OLEDs ........................................................ 82
6.2.3 Photopatterned OLEDs................................................................................. 85
Chapter 7 Modeling the Charge Injection into OLEDs ........................................ 88
7.1 Introduction....................................................................................................... 88
7.2 Theory and Model............................................................................................. 90
7.3 Experiment........................................................................................................ 91
7.4 Results and Discussion ..................................................................................... 93
vii
Chapter 8 Conclusions and Outlook ..................................................................... 104
8.1 Conclusions..................................................................................................... 104
8.2 Outlook ........................................................................................................... 107
8.3 List of Publications ......................................................................................... 109
Appendix - Device Fabrication.................................................................................... 110
References...................................................................................................................... 113

viii
LIST OF TABLES

Table 4.1. Ionization potentials I
p
, mobility, and triplet energy values of different hole-
transport materials (HTM) and device performance at 100 cd/m
2
of OLEDs with device
structure ITO/HTM (25-35 nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (6 nm)/Alq
3
(20 nm)/LiF
(1 nm)/Al........................................................................................................................... 47
Table 5.1. Characterization of copolymers with peak maxima of solid-state
photoluminescence
max,PL
and electroluminescence spectra
max,EL
, plus external quantum
efficiencies and luminous efficiencies at 100 cd/m
2
for devices based on phosphorescent
copolymers with various molecular weights, various iridium concentrations, and different
linkers between the side groups and the polymer backbone. The device structure was
ITO/P3 (35 nm)/P(8-10)(a-c)(2-40) (20-25 nm)/BCP (40 nm)/LiF (1 nm)/Al. ............... 69
Table 7.1. Saturation current density J
0
, ideality factor n, parallel resistance R
p
, zero-field
mobility
0
, and mobility field-dependence factor , all resulting from fits of the model to
electrical characteristics at room temperature for -NPD diodes with different thicknesses
L. ....................................................................................................................................... 95
0
p
, zero-field
mobility
0
electrical characteristics at room temperature for organic diodes with thickness L. For
pentacene and C
60
diodes, the series resistance R
s
is noted instead of any mobility. The
effective Richardson constant A* and the injection barrier
B
were extrapolated from
current measurements at different temperatures. .............................................................. 99

ix
LIST OF FIGURES

Figure 1.1. Sony XEL-1 OLED TV. .................................................................................. 2
Figure 1.2. Increase of the power efficiency of OLEDs over time. ................................... 5
Figure 2.1. Illustration of the 2s- (a), the 2p- (b), and the hybrid (c) orbitals for a carbon
atom [23]. .......................................................................................................................... 12
Figure 2.2. Illustration of an ethylene molecule (C
2
H
4
) with a - and a -bond between
the carbon atoms (top), and part of a conjugated polymer with overlapping p-orbitals
(bottom) [23]. .................................................................................................................... 13
Figure 2.3. Illustration of the interaction between the p-orbitals of N ethylene (C
2
H
4
)
molecules with band formation in the case of an infinite number of molecules stacked on
top of each other. The two p-orbitals on the carbon atoms are shown with the different
phases of the wavefunction. Arrows indicate the presence of electrons in a certain energy
level with the direction of the arrow denoting the direction of the spin (modified from
[25])................................................................................................................................... 15
Figure 2.4. Principle of operation of an organic light-emitting diode with charge injection
(1), charge transport (2), electron-hole pair creation (3) and its migration (4), followed by
recombination resulting in an excited state of a molecule, which relaxes radiatively (5).
E
F
denotes the Fermi energy level of the metal electrode. ............................................... 16
Figure 2.5. Metal-to-organic semiconductor interface in the Schottky-Mott limit where
the vacuum level is assumed to be constant for hole injection (left) and electron injection
(right) with the Fermi energy E
F
and the work function W of the metals, the HOMO and
LUMO levels of the organic semiconductor, the ionization potential I
p
, the electron
affinity , and the injection barrier
B
. ............................................................................. 18
Figure 2.6. Representation of the reorganization energy for a hopping process
according to Marcus theory. The two parabolas represent the potential energies of
reactants and products....................................................................................................... 19
Figure 2.7. Jablonski diagram of electronic singlet and triplet states and possible
transitions between these states. Solid arrows represent radiative transitions, curvy lines
show nonradiative transitions from higher excited states to the lowest excited state
(internal conversions, IC) and the nonradiative transition from the lowest singlet to the
lowest triplet state (intersystem crossing, ISC)................................................................. 27
Figure 2.8. Frster (top) and Dexter (bottom) energy transfer in a host-guest system. The
arrows denote electrons with the direction of their spin. .................................................. 30
x
Figure 2.9. Single-layer (left) and multilayer (right) OLED device architecture with
electron-blocking layer (EBL), hole-transport layer (HTL), emissive layer (EL), hole-
blocking layer (HBL), and electron-transport layer (ETL)............................................... 33
Figure 2.10. Bottom-emitting (left) and top-emitting (right) OLEDs. Small arrows in the
bottom-emitting OLED represent light that is waveguided in the ITO or in the glass. .... 35
Figure 3.1. Illustration of the current-voltage test setup. ................................................. 37
Figure 3.2. Color-matching functions x , y , and z as a function of the wavelength. .... 38
Figure 3.3. CIE 1931 chromaticity diagram. The outer curved boundary is delimited by
monochrome light with the according wavelengths in nanometers. The corners of the
triangle represent the RGB primary colors, and E marks the equal energy point
corresponding to a constant energy distribution in the visible wavelength range. ........... 39
Figure 3.4. Photopic (S
ph
) and detector (S
det
) response as a function of the wavelength in
the visible range. ............................................................................................................... 41
Figure 4.1. Chemical structures of -NPD, CBP, BCP, Ir(ppy)
3
, and Alq
3
(top), and the
device structure of the first efficient devices reported by Baldo et al. [53] (bottom)....... 44
Figure 4.2. Structure of crosslinkable TPD-based copolymers. ...................................... 46
Figure 4.3. External quantum efficiencies as a function of the current density for OLEDs
with device structure ITO/HTM (25-35 nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (6 nm)/Alq
3

(20 nm)/LiF (1 nm)/Al. ..................................................................................................... 48
Figure 4.4. Current density as a function of the applied voltage for devices with the
3
(6%, 20 nm)/Al. ...................................... 49
Figure 4.5. Luminance (solid shapes) and external quantum efficiency (empty shapes) as
a function of the applied voltage for a device with 4 organic layers (device A, squares):
ITO/PVK (25 nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (6 nm)/Alq
3
(20 nm)/LiF (1 nm)/Al,
and for a device with 3 organic layers (device B, circles): ITO/PVK (25
nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al. The bottom part of the
figure illustrates the different device architectures. .......................................................... 51
a function of the applied voltage for device B (circles): ITO/PVK (25 nm)/CBP:Ir(ppy)
3

(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al, for device C (diamonds): ITO/PVK (35
nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al, and for device D (triangles):.
3
(6%, 20 nm)/BCP (40 nm)/LiF (2.5 nm)/Al. ............... 53
Figure 5.1. Chemical structure of Ir(mppy)
3
, PBD, and the dendrimer reported by Lo et
al. [108]............................................................................................................................. 57
xi
Figure 5.2. Electrophosphorescent copolymers with an iridium complex in the polymer
backbone as described in [114] with m:n = 1:99 (a), and with an iridium complex in a
side-chain of the polymer as reported in [112] with x:y:z = 18:79:3 (b).......................... 60
Figure 5.3. Chemical structures of carbazolyl-fluorene based copolymers with different
iridium complexes where the ratio m:n is 9:1................................................................... 62
Figure 5.4. Electroluminescence spectra for devices with the structure ITO/P1 (35
nm)/P(5-8) (25 nm)/BCP (6 nm)/AlQ
3
(20 nm)/LiF (1 nm)/Al and the corresponding CIE
1931 coordinates. .............................................................................................................. 64
Figure 5.5. Current density (solid symbols, top), luminance (empty symbols, bottom),
and external quantum efficiency (solid symbols, bottom) as a function of the applied
voltage for devices with the structure ITO/P1 (35 nm)/(P7 or P8) (25 nm)/BCP (6
nm)/AlQ3 (20 nm)/LiF (1 nm)/Al..................................................................................... 65
Figure 5.6. Chemical structure of orange copolymers with different linker groups. ....... 67
Figure 5.7. Device structure of OLEDs based on copolymers with different colors (a) and
device structure for optimization of the orange-emitting copolymer P8 (b). ................... 68
Figure 5.8. External quantum efficiencies as a function of the loading level of the iridium
complex in the copolymer for OLEDs with device configuration ITO/P3 (35 nm)/P8a(2-
40) (20-25 nm)/BCP (40 nm)/LiF (1 nm)/Al. ................................................................... 70
Figure 5.9. Electroluminescence spectra for OLED devices using copolymers P8a(2, 10,
20, 40) with increasing iridium complex content as emitting layer.................................. 71
Figure 5.10. Current density (solid symbols, top), luminance (solid symbols, bottom),
and external quantum efficiency (empty symbols, bottom) as a function of the applied
voltage for a device with structure ITO/P3 (35 nm)/P10a(5) (25 nm)/BCP (40 nm)/LiF (1
nm)/Al. .............................................................................................................................. 73
Figure 6.1. Crosslinkable electrophosphorescent copolymer based on polymer P10a(5)
with a charge-transport moiety (left), a phosphorescent orange-emitting complex (center),
and a crosslinkable cinnamate based group (right) with m:n:o = 70:5:25. ....................... 77
Figure 6.2. Chemical structures of solution-processable electron-transport materials used
in the literature [128, 158, 162]. Whereas PFN and TPBI are examples of a polymer and a
small molecule, respectively, that are soluble in organic solvents, t-Bu-PBD-SO
3
Na is
soluble in ethanol. ............................................................................................................. 78
Figure 6.3. Chemical structures of electron-transport polymers based on a silole small-
molecule (P12) and based on a bisoxadiazole small-molecule (P13). ............................. 79
Figure 6.4. Absorption spectrum of the monomer of the hole-transport moiety in
copolymer P11. ................................................................................................................. 81
xii
voltage for devices with the structure ITO/P3 (35 nm)/P11 (17 nm)/BCP (40 nm)/LiF
(2.5 nm)/Al with (circles) and without (square) 1250 mJ/cm
2
UV exposure of P11. ...... 82
voltage for devices with the structure ITO/P3 (35 nm)/P11 (17 nm)/ETL (35-40 nm)/LiF
(2.5 nm)/Al where the electron-transport layer (ETL) consisted of BCP (squares), P12
(circles), or P13 (triangles). .............................................................................................. 83
Figure 6.7. Absorption spectra of P12 (solid line) and P13 (dashed line). ...................... 84
Figure 6.8. Schematic of interdigitated electrodes with photopatterned emissive layers
(left), and a micrograph of the electrodes with a photopatterned layer of P3 (right). ...... 86
Figure 6.9. Photograph of photopatterned OLEDs with orange electrophosphorescent and
blue electrofluorescent lines with linewidths of 110 m. ................................................. 87
Figure 7.1. Equivalent circuit of an organic single-layer diode....................................... 90
Figure 7.2. Chemical structures of -NPD, P1, C
60
and pentacene. ................................ 92
Figure 7.3. Current density versus applied voltage at room temperature for -NPD diodes
with thicknesses of 80 nm and 150 nm. Plots of five devices are shown for each thickness.
........................................................................................................................................... 94
Figure 7.4. Current density as a function of the applied voltage at room temperature for
-NPD diodes with thicknesses ranging from 60 nm to 150 nm. Experimental data is
shown as empty symbols; solid lines represent the simulated curves. ............................. 95
organic diodes with organic layers of -NPD (100 nm, squares) and P1 (90 nm, circles).
Experimental data is shown as empty symbols; solid lines represent the simulated curves.
........................................................................................................................................... 96
Figure 7.6. Current density as a function of the applied voltage for an -NPD diode with
a thickness of 100 nm measured at temperatures ranging from 1 C to 72 C.
........................................................................................................................................... 97
Figure 7.7. Plot of zero-field mobility versus (1000/T)
2
for organic diodes consisting of
-NPD (100 nm, squares) and P1 (90 nm, circles). Experimental data is shown as empty
symbols; solid lines are linear fits to this data. ................................................................. 98
organic diodes with organic layers of pentacene (80 nm, triangles) and C
60
(100 nm)/
xiii
BCP (8 nm, diamonds). Experimental data is shown as empty symbols; solid lines
represent the simulated curves. ....................................................................................... 101
Figure 7.9. Current density as a function of the applied voltage for a pentacene diode
with a thickness of 80 nm measured at temperatures ranging from 1 C to 72 C.
......................................................................................................................................... 102
Figure 7.10. Plot of (J
0
/T
2
) versus (1/kT) for organic diodes consisting of three different
materials to extrapolate the injection barrier
B
and the effective Richardson constant A*.
Experimental data is shown as empty symbols; solid lines are linear fits to the data. ... 103
Figure A-1. Diagram of the substrate cleaning process. ................................................ 110
Figure A-2. Diagram of the OLED device fabrication process. .................................... 111
Figure A-3. Diagram of the fabrication process for patterned solution-processed
multilayer OLEDs. .......................................................................................................... 112
xiv
SUMMARY

Organic light-emitting diodes (OLEDs) have drawn much attention in the last two
decades because of several advantages, such as high brightness and a wide viewing angle.
In recent years, the power efficiency of OLEDs has been increased to exceed the
efficiency of fluorescent light bulbs. However, such high-efficiency devices are typically
based on small molecules that have to be evaporated in vacuum. A much higher
fabrication throughput and therefore lowered costs are expected if high-efficiency
OLEDs were processed from solution.
The present work shows how solution-processed electrophosphorescent
multilayer OLEDs can be achieved by starting with an evaporated three-layer device
structure and replacing layer by layer with a solution-processed layer. First, the hole-
transport layer will be replaced by a polymer and high efficiencies are observed when
using a hole-transport polymer with a high ionization potential and a low hole mobility.
Then, the emissive layer is replaced by a copolymer consisting of hole-transport groups
and emissive complexes in its side-chains. OLEDs with four different colors are shown
where the orange devices show the highest efficiency. The orange copolymer is further
optimized by making changes to the chemical nature of the polymer, such as different
molecular weight, different concentrations of the emissive complex and different linkers
between the side-chains and the polymer backbone.
Finally, a three-layer solution-processed OLED is fabricated by crosslinking the
hole-transport and the emissive layer, and by spin-coating an electron-transport polymer
on top. Moreover, using the photocrosslinking properties of the emissive layer, solution-
xv
processed multilayer OLEDs of two different colors (orange and blue) are patterned using
photolithography to fabricate a white-light source with a tunable emission spectrum.
Furthermore, with more and more organic semiconductors being integrated into
the circuitry of commercial products, good electrical models are needed for a circuit
design with predictive capabilities. Therefore, a model for the example of an organic
single-layer diode is introduced in the last chapter of this thesis. The model has been
implemented into SPICE and consists of an equivalent circuit that is mostly based on
intrinsic material properties, which can be measured in independent experiments. The
model has been tested on four different organic materials. Material parameters that were
extracted from a fit of the model to the experimental electrical characteristics of the
diodes agree well with values from the literature.

1
CHAPTER 1
INTRODUCTION
1.1 Organic Light-Emitting Diodes
Organic light-emitting diodes (OLEDs) have received a large interest in the
research community for the last twenty years. OLEDs consist of a thin film of an organic
compound placed between two electrodes. By applying a voltage to the electrodes,
charges get injected into the organic material where they form excited states that
recombine and generate light.
In the past nine years, OLED displays have become commercially available in
portable small electronics applications, such as mobile phones, MP3 players, car radios,
digital cameras, and TVs. OLED displays are especially suited for such applications
because of their reduced power consumption compared to LCDs. In OLED displays, only
active pixels are turned on while inactive pixels do not use any power, whereas LCD
displays require the same power for their backlight independent of whether a black or a
white picture is shown. Furthermore, since the color of an OLED can be tuned, no filters
are necessary in the fabrication of an OLED display and very thin displays can be
fabricated, which is another important factor for portable devices that have to be packed
as efficiently as possible.
Whereas small OLED displays can be produced cost-efficiently nowadays and
while Samsung has already shown prototypes of OLED displays with diagonals up to 40
inches, the fabrication of larger displays is still very cost-intensive and will have to be
improved significantly if OLEDs should ever become competitive with other
2
technologies in the computer or TV display market. Nevertheless, the first commercial
OLED TV has just been introduced to the market by Sony Corp. (see Figure 1.1) [1].
However, the price tag of $2,500 for this 11-inch TV at the time of its introduction into
the market in the year 2008 is nowhere near competitive to other display technologies.

Figure 1.1. Sony XEL-1 OLED TV.

1.2 Advantages of OLEDs
OLEDs have many advantages over other display technologies. For example,
OLEDs are very thin devices with the thickness of the organic layers in the range of
about 100 nm. As mentioned, no backlight or color filters are needed for OLED displays
either, which leads to unusually thin displays like the Sony TV with a display thickness
of 3 mm and Sonys newest prototypes with a display thickness of only 0.3 mm [1].
3
Because of the small thickness of these devices, displays can also be made much lighter,
and the main weight comes from the device substrate.
Furthermore, the close relationship of organic materials to plastics and the
thinness of the devices allow for flexibility and make OLEDs compatible with plastic
substrates. Much work has therefore been done on flexible substrates and first prototypes
of flexible color displays have already been shown [1].
Because of the vertical device structure of an OLED, with electrodes on top and
on the bottom of the device, OLEDs also have the advantage that they are theoretically
not limited in the lateral dimensions. However, with current fabrication processes OLED
devices with an area of only up to 100 cm
2
seem feasible [2].
Last but not least, OLED devices show high brightness that is suitable for display
applications as well as for lighting. The direct emission of every single pixel also leads to
wide viewing angle with every angle receiving the same amount of light (Lambertian
emitter), which makes OLEDs stand out compared to LCD displays with an increasing
but still limited viewing angle.
The biggest disadvantage of OLEDs is their degradation in air. Hence, proper
encapsulation with very low leakage of oxygen and moisture is needed. For a long time,
even the lifetime of OLEDs in inert atmosphere was considered a serious issue. However,
by optimizing the materials and the device structures, OLED lifetimes have now reached
a point where their lifetime is comparable or exceeds the expected lifetime of commercial
products [2, 3].

4
1.3 History of OLED Technology
The early history of OLEDs goes back to the 1950s and 1960s [4, 5]. In
experiments on m to mm-thick organic crystals, electroluminescence was observed
when voltages of a few hundreds of volts were applied [5]. Since such voltages are
impractical for most applications, these early results went almost forgotten until the
technical progress in semiconductor processing allowed the fabrication of thin organic
films where electroluminescence could be observed at applied voltages of only 30V [6].
Nevertheless, it took another 5 years until the first OLEDs with a reasonable power
efficiency of more than 1 lm/W were demonstrated [7]. Whereas these first devices were
all based on organic small molecules, electroluminescence was shown in polymers only a
few years later [8].
The reports by Tang et al. [7] and Burroughes et al. [8] sparked research in
OLEDs, and increasing efficiencies were reported at a steady pace by using more
efficient device architectures and, especially, by synthesizing materials with higher
photoluminescence quantum yields. However, the biggest increase in efficiency resulted
from the introduction of phosphorescent dyes into OLED devices, which multiplied the
efficiencies by a factor of four as will be shown in the next chapter [9].
Further optimization of these devices recently led to power efficiencies in the
range of 100 lm/W (see Figure 1.2). Such high-efficiency OLEDs are typically based on
small molecules that are evaporated in vacuum and that emit in the green color spectrum
since the eye is most sensitive at these wavelengths. The power efficiencies of OLEDs in
other colors are still inferior to green devices, but they have also been increased and even
white OLEDs now reach efficiencies that are close to those of fluorescent lamps and
5
therefore make OLEDs also a potential candidate for lighting applications. On the other
hand, OLEDs with a solution-processed emissive layer generally show lower efficiencies
and require some evaporated organic layers to maximize the efficiency (hybrid OLEDs).

1985 1990 1995 2000 2005
0
20
40
60
80
100
120

P
o
w
e
r

E
f
f
i
c
i
e
n
c
y

(
l
m
/
W
)
Year
vacuum-deposited
OLEDs
solution-processed
or hybrid OLEDs
white OLEDs
incandescent
light bulb
fluorescent lamp

Figure 1.2. Increase of the power efficiency of OLEDs over time.

1.4 Organic Compounds: Small Molecules and Polymers
Organic compounds are molecules that consist of several atoms (mostly carbon
atoms) held together by covalent bonds, which means that some of their atoms share
electrons, as will be explained in chapter 2. For fabrication reasons, two different classes
of organic compounds have to be distinguished: small molecules and polymers. Whereas
organic small molecules contain only a few carbon atoms, a polymer consists of a long
chain of repeated units connected to each other via covalent bonds. While the fabrication
6
of OLEDs based on small molecules are typically fabricated using thermal evaporation
with expensive equipment in high-vacuum, polymers can be dissolved in and processed
from solution using well known techniques, such as inkjet printing [10] or screen printing
[11]. Furthermore, polymers tend to entangle with each other in the solid state, which
makes them thermally more stable than small molecules that tend to crystallize at
temperatures below 100 C [12, 13].
Compared to vacuum-processing, solution-processing of semiconductor materials
can help reduce production costs since it can be done at atmospheric pressure, which
saves pumping time, and thus increases the throughput. Furthermore, extensive research
has already been put into solution-processing by the printing industry, and fabrication
processes could be optimized quickly. Organic semiconductors can even be printed in
roll-to-roll processes, as has been shown for RF ID tags with organic semiconductors by
PolyIC GmbH & Co. KG [14] and for OLEDs by General Electric Co. [15]

1.5 Figures of Merit
Different parameters have been defined to quantify the quality of an OLED, and
the most important figures of merit are the following:
Internal quantum efficiency (IQE): The internal quantum efficiency describes the
ratio between the number of photons that are emitted in the organic layers of the OLED
and the number of electrons that were injected into the device. The IQE is measured as a
percentage.
External quantum efficiency (EQE): The external quantum efficiency is probably
the most reported figure of merit. The EQE is based on the IQE; however, it also includes
7
the extraction loss of photons from the organic layers into the air. Therefore, it describes
the number of photons that are emitted by an OLED towards the viewer per injected
electron. Like the IQE, the EQE is given as a percentage.
Current efficiency: The current efficiency has a unit of cd/A and is proportional to
the EQE. However, in the current efficiency, the number of photons is weighed by the
spectral response of the eye.
Power efficiency: Similar to the current efficiency, the power efficiency also takes
into account the applied voltage that is necessary to achieve a particular brightness. The
power efficiency is given in lm/W.
Maximum luminance: The maximum luminance describes the highest brightness
that can be observed from a device before it disintegrates. This parameter determines
what application a device is suitable for since different applications have different
brightness requirements.
Lifetime: For commercial applications, the lifetime of a device is essential. Due to
material and interface degradation in an OLED under operation, a decrease in brightness
can be observed over time. The lifetime of a device is therefore defined as the time it
takes for an OLED to show half of the initial brightness with the OLED being driven
either at a constant current or at a constant voltage.
Color purity: For display applications, it is important that a wide color gamut can
be achieved. For that purpose, the three primary colors red, green, and blue should be as
pure as possible, meaning that their emission spectrum should be as narrow as possible to
approximate an almost monochromatic emission. For an optimized gamut,
8
monochromatic light with a wavelength of 700 nm, 546.1 nm, and 435.8 nm for red,
green, and blue is required [16].
Since the efficiencies and the lifetime of OLEDs are dependent on the brightness
of the device, they are usually measured at 100 cd/m
2
or 1,000 cd/m
2
. 100 cd/m
2
is the
typical brightness of small, portable display applications, such as laptop displays. For
lighting applications, 5,000 cd/m
2
or more are needed.
Even though all these parameters have to be optimized for most commercial
applications, this task is very time-consuming and cannot be done efficiently in the time
of a Ph.D. program. The present work therefore focuses on optimizing the external
quantum efficiency.

1.6 Goal and Structure of the Dissertation
As has been discussed above, solution-processed electrophosphorescent OLEDs
show many advantages in the fabrication of devices. However, their efficiencies are still
significantly lower than the efficiencies that have been measured for vacuum-deposited
small-molecule OLEDs. The present work shows how efficient solution-processed
OLEDs can be achieved. Starting from a multilayer device structure for vacuum-
deposited small-molecule OLEDs that has been reported in the literature, layers will be
replaced one by one with a solution-processed material until all organic layers are
processed from solution. Furthermore, the last chapter introduces a device model for
simple organic diodes that can be used for electrical design of circuits that incorporate
organic materials and is therefore essential for the successful integration of organic
semiconductors into commercial products.
9
This thesis is structured as follows. Chapter 2 reviews the basic background on
organic semiconductors, the OLED device architecture, and chapter 3 explains the used
test setup for OLED measurements. Chapter 4 then describes the state of the art for
vacuum-deposited electrophosphorescent OLEDs and shows how high efficiencies can be
achieved in a simplified hybrid OLED device structure where the hole-transport material
is deposited from solution.
In chapter 5, methods to achieve multilayer devices from solution are explained.
Then, the current state of the art for OLEDs with solution-processed emissive layers is
discussed, and our approach of electrophosphorescent copolymers as the emissive layer is
introduced. Copolymers with different colors are incorporated in OLEDs and the
chemical structure of one of these copolymers is optimized to achieve high efficiencies in
an OLED.
Chapter 6 concludes the fabrication of a solution-processed three-layer OLED by
introducing an insoluble emissive layer and two newly synthesized electron-transport
polymers. By patterning the emissive layers, a light source consisting of two different
colors is used to generate light with a tunable emission spectrum.
Finally, chapter 7 introduces a model for the electrical characteristics of an
organic diode that can be used to design circuits with organic semiconductors. By fitting
the model to experimental data of organic diodes with several materials, intrinsic
parameters of these organic semiconductors are extracted and compared to values from
the literature.

10
CHAPTER 2
BACKGROUND ON ORGANIC SEMICONDUCTORS AND
ORGANIC LIGHT-EMITTING DIODES
2.1 Organic Semiconductors
Whereas inorganic semiconductors are based on a large network of covalent
bonds between atoms, organic semiconductors consist of organic (carbon-based)
molecules that interact through dipole-dipole forces, the van der Waals force. For a long
time, organic semiconductors were only seen as insulators with wide bandgaps and a
rather low conductivity [17-20]. However, in recent years, mobilities in organic thin-film
devices exceeding 1 cm
2
/Vs have been reported [21-23], which is comparable to
mobilities measured in amorphous silicon. Moreover, although organic semiconductors
typically also exhibit an amorphous structure, fewer intrinsic defects are found in a
system of nonradical molecules compared to inorganic amorphous semiconductors where
a large number of dangling bonds exists.
Furthermore, not only do many organic semiconductors have bandgaps in the
range of 1.5 to 3.5 eV, and can therefore emit light in the visible region, but the organic
molecules can also be tailored to show any desired property, such as a specific ionization
potential or a particular emission spectrum, and an almost unlimited number of
semiconductor materials are feasible. The origin of the semiconductor properties of
organic materials will be reviewed in the following subsections.

11
2.1.1 Atomic Orbitals
To understand the origin of charge transport in organic semiconductors, atomic
orbitals and their tendency to form chemical bonds have to be considered first. By
solving the Schrdinger equation for a hydrogen atom, wavefunctions can be defined that
describe the region where one or two electrons can be found for the atom, the orbitals.
Even though the Schrdinger equation includes additional terms for heavier atoms, it can
be assumed that these terms just cause slight distortions to the orbitals of the hydrogen
atom. Therefore, orbitals are often used in organic compounds to describe chemical
bonds between atoms, where the bond results from the overlap of orbitals from separate
atoms. In carbon, each atom has four valence orbitals (2s, 2p
x
, 2p
y
, and 2p
z
) that are
responsible for the formation of covalent bonds (see Figure 2.1) [24]. However, for
covalent bonds, it turns out that the s- and p-orbitals are linearly superposed to new
orbitals, the hybrid orbitals. Three different kinds of hybrid orbitals are possible: sp
1
, sp
2
,
and sp
3
where the subscript denotes the number of p-orbitals that are part of the
superposition (see Figure 2.1).
12

Figure 2.1. Illustration of the 2s- (a), the 2p- (b), and the hybrid (c) orbitals for a carbon
atom [24].

2.1.2 Chemical bonds
With the introduction of hybrid orbitals, the formation of covalent bonds is
straightforward. First, by overlapping the hybrid orbitals sp
1
, sp
2
, or sp
3
of two atoms, the
covalent single bonds, or -bonds, are formed. However, more important in organic
semiconductors are the double and triple bonds, which consist of one -bond and one or
two -bonds, respectively, and which occur in systems with sp
2
or sp
1
hybridization. In
such systems, the -bond results from the overlap of atomic orbitals with pure p-character
as shown in Figure 2.2.
13
Whereas the spatial overlap between the hybrid orbitals in -bonds is large, the
overlap of p-orbitals in -bonds is rather small, and therefore, the bonding energy is
smaller in -bonds than in -bonds. However, because of the weaker coupling between
the p-orbitals, the electrons in these orbitals tend to be more delocalized in space, and
more polarization of the electrons can be expected. In molecular systems in which single
and double bonds or double and triple bonds alternate, the conjugated systems, the
delocalization of the electrons can be achieved over an even longer range of distance than
just two atoms, since p-orbitals keep overlapping each other along the chain (Figure 2.2).

Figure 2.2. Illustration of an ethylene molecule (C
2
H
4
) with a - and a -bond between
the carbon atoms (top), and part of a conjugated polymer with overlapping p-orbitals
(bottom) [24].

14
2.1.3 Molecular Energy Levels and Energy Bands
Because of the above mentioned delocalization of the electrons, wavefunctions
have to be defined that describe the location of an electron on the whole molecule rather
than just on an atom, the molecular orbitals. Since the Schrdinger equation becomes
very complicated in a system with several atoms and electrons, eigenfunctions and
eigenvalues of the Hamiltonian are usually approximated by neglecting certain terms in
the Hamiltonian. The following section will describe one of these approximations for
molecular orbitals, the linear combination of atomic orbitals-molecular orbitals (LCAO-
MO). It has been mentioned before that the bonding energy is larger in -bonds than in -
bonds. Hence, electrons in -bonds are harder to remove than electrons in -bonds, and
their contribution to the electrical current can be neglected [25]. Therefore, the following
part of this section will only focus on the -molecular orbitals.
The wavefunction
of a -molecular orbital can be defined in first

approximation as linear combinations of the atomic p-orbitals with wavefunction
l
:
=
=
N
l
l l
a
1
(2.1)
where N is the number of carbon atoms in the molecule, a
l
are linear coefficients, and the
sum goes over all carbon atoms [25]. For N carbon atoms, we can define N molecular
orbitals that are orthogonal given the hermiticity of the Hamiltonian. In the ground state
of a molecule, the molecular orbitals of the lowest energies are filled with two electrons
of opposite spin (Pauli-Principle). The filled molecular orbital with the highest energy is
then called the highest occupied molecular orbital (HOMO), whereas the molecular
orbital with the next higher energy contains no electron and is called the lowest
unoccupied molecular orbital (LUMO) (see Figure 2.3).
15

E
HOMO
LUMO
N=1 N=2 N=3 N=

Figure 2.3. Illustration of the interaction between the p-orbitals of N ethylene (C
2
H
4
)
molecules with band formation in the case of an infinite number of molecules stacked on
top of each other. The two p-orbitals on the carbon atoms are shown with the different
phases of the wavefunction. Arrows indicate the presence of electrons in a certain energy
level with the direction of the arrow denoting the direction of the spin (modified from
[26]).

In molecular solids where organic molecules are within a close distance to each
other, molecular orbitals of different molecules overlap. Even a system of two molecules
can therefore not be considered like two separate molecules, but the energy of the
molecular orbitals splits because of interactions between the molecules. Hence, if many
molecules start interacting, the splitting of the energies causes a bandlike structure
comparable to valence and conduction bands in inorganic semiconductors (see Figure
2.3) [26].
16

2.2 Principle of Operation of OLEDs
OLEDs operate in a similar fashion to inorganic light-emitting diodes. By
applying a voltage to the anode and the cathode, charges are injected from the electrodes
into the organic semiconductor. Holes and electrons then travel in the semiconductor
toward the opposite electrodes. When the charges meet, they create an electron-hole pair
that can further diffuse in the organic semiconductor until it recombines to form a
molecular excited state, which relaxes and emits light (see Figure 2.4). Each of these
steps is explained in more details in the following subsections.

Anode Cathode
E
F
E
F
Organic
Semiconductor
HOMO
LUMO
-
+
+
+
-
-
1
1
2
2
5
+
-
3
4
-
+

Figure 2.4. Principle of operation of an organic light-emitting diode with charge injection
(1), charge transport (2), electron-hole pair creation (3) and its migration (4), followed by
recombination resulting in an excited state of a molecule, which relaxes radiatively (5).
E
F
denotes the Fermi energy level of the metal electrode.

17

2.2.1 Charge Injection
As for inorganic semiconductor devices, the contact of the metal electrode to the
organic semiconductor plays an important role in the operation of the device. Although
the physics at the metal-organic interface is not quite clear on a microscopic basic, it is
generally understood that the injection current from a metal electrode into an organic
semiconductor can be adapted from equations for Schottky contacts in inorganic
semiconductors [27]. To get injected, charges have to get across the energy barrier that is
formed between the work function W of the injecting electrode and the HOMO or LUMO
energy level of the organic semiconductor depending on whether hole- or electron-
injection, respectively, is considered (Figure 2.5). The current density J across this energy
barrier is then given by the general diode equation:
J = J
0
exp
qV
nkT

1

(2.2)
where J
0
is the saturation current density, q is the elementary charge, V is the applied
voltage, n is the ideality factor, k is the Boltzmann constant, and T is the temperature. The
saturation current density is dependent on the chosen model for injection and can be
attributed to either thermionic emission or charge tunneling [28-30]. Many studies have
found good agreement of experimental data to the thermionic emission model [29, 31,
32], where the saturation current density J
0
is given by the equation:

=
kT
T A J
B
exp *
2
0
(2.3)
with A* the effective Richardson constant and
B
the injection barrier for charges as
shown in Figure 2.5 [33].
18

Anode Cathode
E
F
Organic
Semiconductor
HOMO
LUMO
HOMO
LUMO
E
F
Vacuumlevel
W
B
I
p
B
W

Figure 2.5. Metal-to-organic semiconductor interface in the Schottky-Mott limit where
the vacuum level is assumed to be constant for hole injection (left) and electron injection
(right) with the Fermi energy E
F
and the work function W of the metals, the HOMO and
LUMO levels of the organic semiconductor, the ionization potential I
p
, the electron
affinity , and the injection barrier
B
.

2.2.2 Charge Mobility
In a microscopic
view, charge transport in a molecular material can be seen as a hopping process
that is based on an electron-transfer reaction, in which an electron is moving between two
neighboring molecules as schematized in the following equation for a hole hopping
process:
A+ B
+
A
+
+ B (2.4)
where A and B are two neighboring molecules. This reaction results in a motion of
19
positive charge, which can be directed by an applied electric field. The rate constant k
ET
of the electron-transfer reaction can be described by Marcus theory as

=
T k
A k
B
ET
4
exp

0
(2.5)
where A
0
is a prefactor related to the electron coupling matrix element between donor A
and acceptor B, and is the reorganization energy [34, 35]. The reorganization energy
represents the energy that is necessary to transfer an electron from molecule A to
molecule B
A A
+
and B
+
B. (2.6)
while the geometries of both molecules remains fixed since the electron-transfer process
occurs in a much faster time frame than the molecules can relax into a geometry that is
energetically most stable (see Figure 2.6).

Figure 2.6. Representation of the reorganization energy for a hopping process
according to Marcus theory. The two parabolas represent the potential energies of
reactants and products.
20
From the assumption that all charge transport results from charges hopping
through a manifold of localized states with superimposed positional disorder, the so-
called disorder formalism has been derived [36, 37]. In this formalism, hopping site
energies and distances have Gaussian distributions, i.e. for the hopping sites energies the
distribution is
g() = (2
2
)
1/ 2
exp

2
2
2

(2.7)
where the energy is measured relative to the center of the distribution and is the width
of the energetical disorder distribution.
Furthermore, assuming significant disorder effects such that electron-phonon
coupling is weak enough to neglect polaronic effects [38], and assuming that each
hopping event is statistically independent and that hopping between sites i and j with
energies
i
and
j
, respectively, can be described by jump rates
ij
of the Miller-Abrahams
form
( )

=
kT
R
j i
ij ij

exp 2 exp
0
;
i
>
j
(2.8)
( )
ij ij
R = 2 exp
0
;
i
<
j
(2.9)
where
0
is a pre-factor, is the inverse wave function decay constant, and R
ij
is the
intersite distance between sites i and j [39, 40]. Monte Carlo simulations of a system
based on the equations above, led to an empirical equation of the mobility as a function
of the temperature and the applied electric field E
21

=
2 / 1 2
2 2
0 , 0
exp
3
2
exp ) , ( E
kT
C
kT
E

(2.10)
where
0,0
is the disorder-free mobility, C is an empirical constant with a value of 2.9
10
-4
(cm/V)
1/2
, and is the width of the positional disorder distribution [37]. Equation
(2.10) is only valid for high electric fields larger than 10
5
V/cm and for temperatures
below the glass transition temperature T
g
[41], and for a width of the position disorder
distribution 1.5 [37].

2.2.3 Space-Charge-Limited Current
For low applied electric fields, the charge transport in organic semiconductors is
given by the ohmic drift current:
J = n
0
e
V
L
(2.11)
where e is the elementary charge, n
0
the charge carrier density, the charge mobility, V
the applied voltage and L the device thickness. However, assuming an ohmic contact that
can supply an infinite number of charges and due to the low free-carrier density in
organic semiconductors, it is possible at higher applied electric fields that more charges
are injected than can be transported and excess charges start building up in the
semiconductor [42].
Because of these excess charges, the electric field inside the semiconductor is no
longer constant, and the current behavior cannot be explained with the ohmic drift current
anymore. Instead, Mott and Gurney have shown that this space-charge-limited current
(SCLC) follows the equation:
22
J =
9
8
0
V
2
L
3
(2.12)
where is the dielectric constant, and
0
is the permittivity of free space [25, 43].
Alternatively, in the presence of trap states with an exponential distribution, a trap-charge
limited current density can be written as
1 2
1
1
0
1
1 2
1
+
+
+
+
+
+
=
l
l
l l
l
eff
L
V
l
l
l
l
e H
e N
J

(2.13)
where N
eff
is the effective density of states in the transport band, H is the total
concentration of traps, and l is a characteristic distribution parameter [44].
As has been discussed above (section 2.2.2), the mobility in organic
semiconductors is typically field-dependent while the general equation (2.12) for SCLC
was derived for field-independent mobilities. By introducing the Frenkel effect into the
derivation for SCLC, where only one set of traps with an effective trap depth that is
reduced by the effective field is considered, P.N. Murgatroyd has shown that the equation
for SCLC can be written as
J =
9
8
0
exp 0.891
V
L

V
2
L
3
(2.14)
with
0
the zero-field mobility and the field-dependence factor of the mobility [45].

2.2.4 Langevin Recombination
After both holes and electrons have been injected into an organic semiconductor,
the two charges start interacting and recombination can occur. The recombination of
statistically independent oppositely charged carriers has been studied by Paul Langevin in
1903 [46]. Assuming that just one particle is moving with a thermal energy of kT while
23
the other particle is stationary, the moving charge gets trapped in the Coulomb potential
of the stationary charge once they are within a distance of less than the coulombic capture
radius r
c
, where the coulomb attractive potential energy is equal to the thermal energy:
kT
r
e
c
=
0
2
4
(2.15)
or
kT
e
r
c
0
2
4
= . (2.16)
It can be assumed that the same effect occurs even when both carriers are moving
as long as their mean free path is smaller than the coulombic capture radius, which is
given for organic materials with mobilities below 1 cm
2
/Vs and a coulombic capture
radius of roughly 20 nm at room temperature and with = 3 [25]. Thus, the
recombination in organic semiconductors can be viewed as a drift of the opposite charges
towards each other because of the coulombic field. The electron-hole pair can then
diffuse through the organic semiconductor [47, 48] until it recombines, which results in a
charge-neutral excited state of a molecule where one electron is found in one of the
usually unoccupied molecular orbitals, while one hole is present in one of the normally
occupied molecular orbitals. The recombination rate for the Langevin recombination is
given by
0
/ ) (
h e
e n n n n + = =
+ +
& & . (2.17)
where n
+
is the density of holes, n
-
is the density of electrons,
0
is the permittivity of free
space, is the dielectric constant, and
e
and
h
are the electron and the hole mobility,
respectively [49].

24
2.2.5 Singlet and Triplet Excited States
The electronic excited states of a molecule, where one electron is excited from an
occupied state into an unoccupied state and thus leaves a hole, can be described in
quantum mechanics. Since a hole represents just a missing electron, both the hole and the
electron can be represented by similar wavefunctions. In a system with two particles of
spin 1/2, eigenstates of the Hamiltonian have to be antisymmetric in respect to the
exchange of the particles (Pauli Principle) [50]. Since the wavefunctions can be written as
the product of the spatial and the spin wavefunctions, the spin wavefunction can therefore
be either symmetric or antisymmetric as long as the spatial wavefunction has the opposite
parity. For the electron and the hole, the spin part of the wavefunction can be represented
by
spin
= | or | where the arrow describes the direction of the spin. The four possible
combinations of the spin wavefunctions can therefore be differentiated between one
antisymmetric (singlet) state S
n
:
( ) =
2
1
spin
(2.18)
and three symmetric (triplet) states T
n
:
( ) + =
2
1
spin
(2.19)
=
spin
(2.20)
=
spin
. (2.21)
It has to be noted that the Langevin recombination does not necessarily generate
excited singlet and triplet states with the lowest energy (S
1
or T
1
) at their formation, but
higher excited states (S
n
or T
n
) can be generated initially. However, while higher excited
25
states are important for the formation ratio between singlet and triplet states [51], they
have a very short lifetime and decay quickly into the lowest excited states through a
nonradiative process, known as internal conversion. In the following parts, we therefore
concentrate on the lowest excited states and their recombination.

2.2.6 Light Emission
After its generation, the excited electronic state of a molecule has a given lifetime
until it relaxes back to the ground state in a radiative or nonradiative process. The
probability P of radiative relaxation from state
i
to state
j
is proportional to the square
of the transition dipole moment
2
2
= d M M P
j i j i
(2.22)
where M is the dipole moment operator and the integration over d covers the whole
space of all 3N coordinates with N the number of electrons. Since
=
i
i
er M (2.23)
where e is the electron charge and r
i
is the distance of the ith electron from the origin of a
coordinate system that is fixed to the molecule, the dipole moment operator does not
affect the spin part of the wavefunction of a state. Therefore, only transitions with similar
spin symmetry result in a transition dipole moment that is unequal to zero. Hence, with
the ground state S
0
being a singlet state, radiative transitions are only possible between
the lowest singlet excited state S
1
and the ground state S
0
, whereas transitions from the
lowest triplet excited state T
1
to the ground state are forbidden. The resulting radiation
from such transitions is called fluorescence.
26
However, this assumption holds only in first approximation where the total
Hamiltonian is assumed to include just the ordinary Hamiltonian and electron repulsion.
Some relativistic effects can be included by adding the first term of the relativistic
expansion of the Dirac equation, the so-called spin-orbit coupling term. The x-component
of the spin-orbit coupling Hamiltonian can be written as
( )( ) ( )( )

+ + + =
n
i
n
k
xk xi xk k xi i
n
i
n
k
xk xi xk k xi i
x
SO
s s l A l A
n
s s l A l A
n
H
2
1
2
1
(2.24)
where
ij
ij
m
j ij
i
dr
r dV
r
A
) (
1
(2.25)
with j a particular nucleus, r
ij
the distance from electron i to the nucleus j, l the atomic
orbital operator, s the spin operator, V the nuclear potential, n the number of electrons,
and m the number of nuclei [52].
Whereas the spin part of the first term in equation (2.24) is symmetric with
respect to the exchange of electrons, the spin part of the second term is asymmetric for
electron wavefunctions with the same angular quantum number l. Therefore,
wavefunctions with different spin symmetry are no longer orthogonal to each other, but
the triplet states gain some singlet character and vice versa. It turns out that when spin-
orbit coupling is considered, radiative recombination from a triplet state to the ground
state, the so-called phosphorescence, is allowed and its probability is proportional to the
transition probability from the singlet state S
1
to the ground state S
0
without spin-orbit
coupling. For a central field potential, the strength of the spin-orbit coupling is
proportional to Z
8
where Z is the atomic number of the atom [53]. Because of this strong
dependence of the phosphorescence on the atomic number of the atom, organometallic
27
complexes with a heavy metal such as iridium, platinum or osmium typically exhibit
good phosphorescence and are used in OLEDs [54].
In addition to phosphorescence, the mixing of singlet and triplet character of the
excited states in spin-orbit coupling is also responsible for transitions between the lowest
excited singlet state S
1
and the lowest excited triplet state T
1
, the so-called intersystem
crossing. Since the energy of T
1
is generally lower than the energy of S
1
(Hunds rule), it
can be beneficiary for an excited singlet state to relax to the ground state through
intersystem crossing to the triplet state followed by phosphorescent emission instead of a
fluorescent relaxation. A diagram of the discussed radiative and nonradiative transitions
is shown in Figure 2.7.

E
S
0
S
1
S
2
S
n
T
1
T
2
T
n
F
l
u
o
r
e
s
c
e
n
c
e
Phosphorescence
ISC
I
C
I
C

Figure 2.7. Jablonski diagram of electronic singlet and triplet states and possible
transitions between these states. Solid arrows represent radiative transitions, curvy lines
show nonradiative transitions from higher excited states to the lowest excited state
(internal conversions, IC) and the nonradiative transition from the lowest singlet to the
lowest triplet state (intersystem crossing, ISC).
28
2.2.7 Energy Transfer from Host to Guest
In phosphorescent devices, some of the lowest excited triplet states T
1
can be lost
through the so-called triplet exciton fusion or triplet-triplet annihilation. When two
triplets with the energy of T
1
collide, the energy of one excited state is transferred to the
other excited state, which results in the loss of an excited state [25, 55]:
n 0 1 1
T S T T + + or (2.26)
n 0 1 1
S S T T + + (2.27)
where S
n
or T
n
denote a higher excited singlet or triplet state.
Because of this quenching mechanism, it is not efficient to make OLEDs with
emitting layers that consist solely of phosphorescent complexes. Hence, a small amount
of phosphorescent complexes is typically doped into a host material that acts as a buffer
layer between the phosphorescent complexes [56]. However, for a high probability of
radiative transitions on the phosphorescent complex, good energy transfer from the host
to the guest molecule is necessary. The energy transfer in such host-guest systems can be
explained by either the Frster or the Dexter mechanism.
The Frster mechanism, also called the Coulomb mechanism, represents the
classical interaction between charge distributions or, in first approximation, the
interaction between two electrical dipoles. The probability of Frster energy transfer
decays with R
-6
where R is the distance between the molecules, and dipole interactions up
to a distance of 10 nm can be expected [57]. Since the dipole operator does not interact
with the spin, spin conservation of the molecules is required, which leads to a singlet
transfer
29
* 1 1 1 * 1
B A B A + + (2.28)
where the superscript 1 denotes a singlet state and the star marks an excited state.
Dexter transfer is also called exchange interaction and is a purely quantum
mechanical phenomenon that requires the overlap of the orbitals in which the energy
transfer occurs. For the exchange interaction, the total spin of both molecules before and
after the process has to prevail, which leads to processes with spin conservation of the
molecules
* 1 1 1 * 1
B A B A + + (2.29)
and to processes with spin transfer between the molecules:
* 3 1 1 * 3
B A B A + + . (2.30)
However, since the probability of the exchange interaction decreases exponentially with
increasing molecular distance and is occurring over distances of 1 nm [57], singlet-singlet
transfers as shown in equation (2.28) and (2.29) are dominated by Frster transfers. Both
energy transfer mechanisms are shown in Figure 2.8.
It should be noted that the Dexter energy transfer is dominant in host-guest
systems such as CBP:Ir(ppy)
3
[58]. Also, note that for efficient devices, it is important
that the host has good charge-transport properties to move charges from the electrodes to
the emissive complexes, but it is even more important that the singlet and triplet energy
level in the host are higher than the triplet level in the emissive complex to support good
charge transfer from the host to the emissive complex.

30
host guest
1
A
* 1
B +
1
A
1
B
*
+
3
A
* 1
B +
1
A
3
B
*
+
Frster
Dexter

Figure 2.8. Frster (top) and Dexter (bottom) energy transfer in a host-guest system. The
arrows denote electrons with the direction of their spin.

2.3 OLED Efficiency
The most often reported figure of merit for an OLED is its external quantum
efficiency (EQE). The EQE is defined as the ratio between the number of photons
emitted from the surface of an OLED divided by the number of injected electrons. The
external quantum efficiency
ext
can also be written as the product of the internal quantum
efficiency
int
(number of photons emitted in the organic material divided by number of
electrons injected) times the out-coupling efficiency
ph
[59]:
31
ph int ext
= (2.31)
where the internal quantum efficiency is dependent on the device architecture and the
material properties of the OLED:
p ex int
= (2.32)
with the electron-hole charge-balance or Langevin recombination factor,
ex
the
efficiency of the formation of excited electronic states that lead to radiative transitions,
and
p
the photoluminescence quantum yield.
The photoluminescence quantum yield
p
is a material constant that describes the
ratio between the number of radiative transitions and the number of total transitions from
the excited states to the ground state in a material. Similarly, the efficiency
ex
is
dependent on the material and is given by the nature of the emission. As has been shown
above, radiative transitions in fluorescent devices only occur from the singlet excited
state, and it is therefore expected from spin statistics that
ex
has an upper limit of 25%
since only one out of four excited states is a singlet state, which has been confirmed in
experiments on small molecules [60]. It has to be noted, however, that
ex
can exceed this
limit in polymers where experiments suggested that up to 60% of excited states were
singlet excited states [61], which has been attributed to a faster decay of higher excited
singlet states to the lowest excited singlet state compared to triplet excited states in
compounds with a longer chain length [51, 62]. In phosphorescent devices on the other
hand, all three triplet states participate in the light emission. Additionally, since the
singlet excited state has higher energy than the triplet excited state, singlets can relax into
the triplet state through intersystem crossing, and therefore,
ex
= 100% can be achieved
[59].
32
Unlike these first two parameters, and
ph
can be partially controlled in the
design of the device architecture. The optimization of these two parameters and their
limits are explained in the following two subsections.

2.3.1 OLED Device Architecture
The simplest device structure for an OLED is the so-called single-layer device
where only one organic material is placed between the two electrodes (see Figure 2.9). It
seems obvious that the efficiency for such a device architecture is the highest if the
number of holes and electrons in the device are equal, such that potentially every charge
has a countercharge with which it can recombine [63, 64]. If either charge occurs more
often in the organic layer, it is likely that these charges will not recombine before they get
extracted at the opposite electrode, and therefore and the efficiency of the device are
decreased. Charge balance can be achieved by adjusting the injection energy barrier for
the minority or majority carriers [65, 66], or by blending the organic layer with materials
that support the charge transport of the minority carriers [63, 67].
However, even with optimized charge balance in a single-layer OLED, it is not
very likely that all charges will recombine. Instead, some charges are able to travel to the
opposite electrode, and efficiencies in single-layer devices are therefore typically low
[68]. However, great improvement of the efficiency can be achieved by adding a hole-
blocking layer (HBL) between the emissive layer and the cathode. Because of its high
ionization potential, the hole-blocking layer inhibits holes from traveling all the way to
the cathode, which leads to a higher recombination probability of the accumulated
charges at the interface between the emissive layer and the hole-blocking layer [69].
33
Similarly, a hole-transport material with low electron affinity can be placed between the
emissive layer and the anode as an electron-blocking layer (EBL, Figure 2.9) [68]. For
very high efficiencies, even more complex multilayer structures with up to six different
layers have been used [70].

Anode Cathode EL
++ ++
++ ++ ++

Anode Cathode EBL /
HTL
++
++
++ ++
++
EL HBL /
ETL

Figure 2.9. Single-layer (left) and multilayer (right) OLED device architecture with
electron-blocking layer (EBL), hole-transport layer (HTL), emissive layer (EL), hole-
blocking layer (HBL), and electron-transport layer (ETL).

2.3.2 Light Outcoupling
Typically, OLEDs are fabricated on glass substrates that are coated with an
indium tin oxide (ITO) layer, which acts as a transparent and conductive electrode.
Organic layers are then deposited on the substrates, and the devices are capped with a
metal cathode. Since the light is extracted through the glass substrate, such devices are
usually referred to as bottom-emitting OLEDs (see Figure 2.10). However, it turns out
34
that this device geometry is not very efficient in coupling out the generated light through
the substrate and into the viewers eyes.
Assuming that the cathode acts as a perfect mirror, an estimation of the maximum
light output of the bottom-emission geometry can be calculated from simple ray theory.
The amount of light energy transmitted from a medium 1 with refractive index n
1
into a
medium 2 with refractive index n
2
normalized by the light energy incident on the
interface between medium 1 and 2 is given by [71, 72]
2
1
2
2
1
2
5 . 0 1 1

=
n
n
n
n
ph
(2.33)
This equation holds even for multilayer structures as long as there is no local minimum of
the refractive index within the multilayer structure [73]. With a refractive index of the
organic material n
organic
= 1.8 [74] and with n
air
= 1, an outcoupling efficiency
ph
of
approximately 15% can be calculated. This value is only a crude approximation of the
outcoupling efficiency, but even more involving calculations resulted in only slightly
higher outcoupling efficiencies between 20 and 25% for thin-film devices on top of ITO
coated glass substrates [71, 75].
There have been some research studies on improving the outcoupling efficiency
of bottom-emitting OLEDs [76-81]. In most reports, the emitting surface of the glass
substrate is manipulated to avoid internal total reflection between glass and air [77, 79,
80]. Alternatively, the ITO to glass interface is modified to avoid waveguiding effects in
the ITO [73, 78, 81]. Outcoupling improvements of up to 300% have been measured [78].
However, it has to be noted that such improvements occur mostly in the direction
perpendicular to the glass substrate. Whereas basic bottom-emitting OLEDs have the
35
same intensity independent of the observers angle (Lambertian emitter), geometries with
improved outcoupling are typically not Lambertian [78].

Organic layers
ITO
Glass
Metal
Organic layers
Metal electrode
Glass
Transparent
electrode

Figure 2.10. Bottom-emitting (left) and top-emitting (right) OLEDs. Small arrows in the
bottom-emitting OLED represent light that is waveguided in the ITO or in the glass.

In a completely different approach, top-emitting OLEDs have been proposed to
avoid waveguiding effects in the ITO layer and the glass substrates [82, 83]. Top-
emitting OLEDs are fabricated on metal coated substrates that fully reflect the light,
while the top electrode, the cathode, is transparent. However, the EQE of top-emitting
OLEDs seems to be limited to about 20 to 25% as well [84], which has been attributed to
surface plasmon-polariton modes that occur at the metal surfaces [85].

36
CHAPTER 3
EXPERIMENTAL METHODS
3.1 OLED Test Setup
Current-voltage (I-V) measurements were made using a Keithley 2400
sourcemeter where the current was measured as a function of the applied voltage.
Simultaneously, by placing the OLED substrate behind a quartz window, the light output
of the device was measured using a calibrated photodiode (FDS 100 from Thorlabs, Inc.).
The generated photocurrent was converted into a voltage by a current-to-voltage
converter with an Analog Devices 549LH operational amplifier and a resistor R of 5 M
(Figure 3.1). In such a converter, the output voltage V
det
is related to the photocurrent I
det

according to Ohms Law:
det det
RI V = (3.1)
The output voltage from the light power measurement was read by a computer
using a digital acquisition board (DAQPad 6020E from National Instruments). The light
and current measurements were implemented in a LabView program for simultaneous
testing. The whole current-voltage test setup is shown in Figure 3.1. The testing was done
immediately after the deposition of the metal cathode onto the organic layers of the
OLED in a nitrogen atmosphere without exposing the devices to air.
37

5 M
Keithley 2400
sourcemeter
LabVIEW
software
-
+
DAQPad
6020E
h
OLED
FDS
100
AD 549LH

Figure 3.1. Illustration of the current-voltage test setup.

3.2 Electroluminescence Spectra Measurements
Similar to the current-voltage measurements, the OLED substrate was placed
behind a quartz window and a voltage was applied using the Keithley sourcemeter. The
electroluminescence spectra in the visible region were then measured by an Oceanoptics
spectrometer USB 4000. By implementing the spectrometer measurements and the
voltage control in a LabView program, spectra could be measured as a function of the
applied voltage to ensure that no changes of the spectra occurred with increasing voltage.

3.3 CIE Spectral Coordinates
To categorize colors, the International Commission in Illumination (CIE) in 1931
created a color space that addresses an (x,y) coordinate to any color spectrum [16]. This
color space is based on the color perception of the eye where three different kinds of
receptors are used to register the light in the long, middle, and short wavelength ranges
38
[86]. Each test color can therefore be described by how much its spectrum overlaps with
the response spectra of each of the receptors, which results in the tristimulus values.
Likewise, the CIE color space is based on three color-matching functions, one in the red
( x ), one in the green ( y ), and one in the blue ( z ) as shown in Figure 3.2.

400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8

S
p
e
c
t
r
a
l

W
e
i
g
h
t

(

)
Wavelength (nm)
x
z
y

Figure 3.2. Color-matching functions x , y , and z as a function of the wavelength.

The tristimulus value X that represents the spectral overlap between the color-
matching function x and the test color is then calculated from
X = S
TEST
()x ()d
(3.2)
where S
TEST
is the test spectrum. The tristimulus values Y and Z are calculated in the
same manner. Normalizing the tristimulus values of any test color to
39
x =
X
X +Y + Z
(3.3)
and likewise for the y coordinate results in the chromaticity diagram shown in Figure 3.3.

Figure 3.3. CIE 1931 chromaticity diagram. The outer curved boundary is delimited by
monochrome light with the according wavelengths in nanometers. The corners of the
triangle represent the RGB primary colors, and E marks the equal energy point
corresponding to a constant energy distribution in the visible wavelength range.

In display applications, colors are generally achieved by additive mixing of the
light that is emitted from red, green and blue (RGB) pixels. The CIE color coordinates for
the RGB primary colors in CIE are (0.73, 0.27), (0.27, 0.72), and (0.17, 0.01),
respectively, which corresponds to monochromatic light with a wavelength of 700 nm,
546.1 nm, and 435.8 nm, respectively.
40

3.4 Luminance Calculation
Since OLED displays are ultimately designed for the human eye, the light output
of such devices is not measured in radiometric units (i.e. watt), but in photometric units
(i.e. candela). Photometric units are always weighed in response to the photopic
sensitivity function, which is the response of the human eye (see Figure 3.4). The
radiated power of light-emitting diodes is therefore reported as the luminance in cd/m
2
,
which describes the amount of light that is emitted from an area of 1 m
2
and falls into a
given solid angle.
With
the luminous flux per watt:
= d S S
watt
lumen
OLED ph v
) ( ) ( 683 (3.4)
where S
ph
is the photopic response and S
OLED
is the normalized spectrum of the OLED,
and with R
det
the weighed detector response:
= d S S R
OLED det det
) ( ) ( (3.5)
where S
det
is the response of the detector as shown in Figure 3.4, we can calculate the
luminance L as
det
v
det
det
A
d
A
R R
V
L
2
= (3.6)
where R is the resistor in the current-to-voltage converter at the calibrated photodiode (as
shown in section 3.1), V
det
is the measured output of the detector circuit, A is the area of
the device, d is the distance between the device and the detector, and A
det
is the area of
the detector. The first term in the equation for the luminance describes the power that is
41
measured by the photodiode, while the last term is the inverse of the solid angle assuming
that the OLED can be approximated as a point source from the view of the detector.

400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
P
h
o
t
o
p
i
c

R
e
s
p
o
n
s
e

(
l
m
/
W
)
Wavelength (nm)
D
e
t
e
c
t
o
r

R
e
s
p
o
n
s
e

(
A
/
W
)

Figure 3.4. Photopic (S
ph
) and detector (S
det
) response as a function of the wavelength in
the visible range.

3.5 OLED Efficiency Calculation
As mentioned above (section 2.3, page 30), the external quantum efficiency
(EQE) describes the number of photons that are emitted in the forward viewing direction
divided by the number of electrons that are injected into the diode. Therefore, to calculate
the EQE, the measured spectral light output first has to be converted into the number of
photons n
ph
per unit of energy:
42
n
ph
=
1
hc
S
OLED
()d
(3.7)
where h is the Planck constant and c is the speed of light. Assuming a Lambertian emitter,
we can then calculate the EQE as
det
ph
det
det
A
d
I
q
n
R R
V
EQE
2
= (3.8)
where I is the measured current and q is the elementary charge. The last term in this
equation yields the total emitted light for a Lambertian emitter.
The current efficiency L
eff
, which is given in cd/A and is similar to the external
quantum efficiency but also includes the photopic response, can be calculated directly
from the luminance L and the current density J as
L
eff
=
L
J
(3.9)

43
CHAPTER 4
HYBRID ELECTROPHOSPHORESCENT OLEDS WITH A
SOLUTION-PROCESSED HOLE-TRANSPORT LAYER
4.1 State-of-the-Art High-Efficiency OLEDs
As has been mentioned before, there has been a strong interest in
electrophosphorescent OLEDs recently because singlet and triplet excited states can
contribute to light emission, which can lead to an internal quantum efficiency of 100%. In
one of the first reports of an electrophosphorescent OLED, Baldo et al. used the green
phosphorescent emitter fac tris(2-phenylpyridinato-N,C
2
) iridium (Ir(ppy)
3
, Figure 4.1)
as the emissive complex and obtained an external quantum efficiency (EQE) of 7.5% (26
cd/A) at 100 cd/m
2
[56]. Their device structure consisted of 4,4-bis[N-(1-naphthyl)-N-
phenyl-amino]biphenyl (-NPD) as a hole-transport layer (HTL), 4,4-di(carbazol-9-yl)-
biphenyl (CBP) as a host for Ir(ppy)
3
, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
(BCP) as a hole-blocking layer, and tris-(8-hydroxyquinolinato-N,O) aluminum (Alq
3
) as
an electron-transport layer (Figure 4.1). The device was capped with a Mg:Ag cathode.
Generally, OLEDs show higher efficiencies when alkali metal compounds,
especially lithium compounds, are used as a buffer layer between the organic layers and
the cathode [65, 87]. Such buffer layers enhance electron injection, which leads to lower
turn-on voltages and higher efficiencies because of a better charge balance in the device.
For example, Tsutsui et al. have been able to improve the performance of the previously
mentioned devices by using a Li
2
O/aluminum cathode instead of the Mg:Ag cathode [88].
External quantum efficiencies of 13.7% at 105 cd/m
2
were measured.
44

N N
O
Al
N
O
N
O
N
N N
N N
BCP
N
N
N
Ir
Ir(ppy)
3
CBP
-NPD
Alq
3

glass substrate
ITO
-NPD (40 nm)
CBP:Ir(ppy)
3
(20 nm)
BCP (6 nm)
Mg:Ag
Alq
3
(20 nm)

Figure 4.1. Chemical structures of -NPD, CBP, BCP, Ir(ppy)
3
, and Alq
3
(top), and the
device structure of the first efficient devices reported by Baldo et al. [56] (bottom).

Since then, several teams have modified the device architecture and the nature of
the materials in those devices to improve efficiency, light output, and turn-on voltage [59,
68, 70, 89-91]. Most commonly, different host-guest materials have been used to improve
the energy transfer from the host to the guest [59]. J. Kido et al., on the other hand,
demonstrated higher efficiencies by introducing a doped hole transport layer for better
hole injection [90] and by using hole- and electron-blocking materials with larger energy
45
barriers for better confinement of the excitons in the emissive layer [89]. Combinations of
these methods have also been reported [68, 70, 91]. Most of the cited references report
efficiencies of up to 19% for optimized devices while Kido et al. reach efficiencies of up
to 29% [89]. However, the most efficient devices (higher than 20% EQE) are based on
complex device structures with at least four organic layers, three of which are deposited
from the vapor phase. As mentioned earlier (chapter 1.4, page 5), the rather slow
deposition rate of organic layers (~1 /s) can be a limiting factor in the manufacturing
cost of such devices. Therefore, device geometries in which fewer organic materials and
fewer layers are deposited from the vapor phase and in which high efficiency is
maintained are desirable.

4.2 Ionization Potential Study
In this chapter, it will be shown that the efficiency of phosphorescent OLEDs
based on the well-known host-guest matrix CBP:Ir(ppy)
3
can be significantly improved
by tuning the ionization potential (I
p
) and the hole-mobility (
h
) of the hole-
injection/transport layer. In addition, the device structure is simplified by using a wet-
processable material and by reducing the number of subsequent evaporated layers
without compromising the performance. For this study, a series of crosslinkable side-
chain copolymers based on N,N-bis(m-tolyl)-N,N-diphenyl-1,1-biphenyl-4,4-diamine
(TPD) was used as the hole-transport layer [92]. The ionization potential of these
copolymers can easily be tuned by using differently substituted TPD side-chain moieties
(Figure 4.2. Structure of crosslinkable TPD-based copolymers.). The estimated ionization
potential of these TPD copolymers (P1 to P4) ranges from 5.2 eV to 5.5 eV while the
46
hole mobilities, characterized by the time-of-flight technique at an applied electric field
of 4 10
5
V/cm at room temperature, decrease from 1.8 10
-5
to 5.9 10
-7
cm
2
/Vs [93].
To complete the study, poly(N-vinyl-carbazole) (PVK) which has a higher ionization
potential of 5.8 eV [94] and a lower mobility in the range of 10
-8
to 10
-7
cm
2
/Vs [95] was
also tested. The TPD-based copolymers were synthesized by the group of Prof. Seth
Marder of the School of Chemistry and Biochemistry at the Georgia Institute of
Technology.

Figure 4.2. Structure of crosslinkable TPD-based copolymers.

For the fabrication of the devices, TPD-copolymer films of 35 nm thickness (25
nm for PVK) were spin-coated from toluene onto air-plasma treated ITO coated
substrates in an inert nitrogen atmosphere. Air-plasma treatment of ITO increases the
workfunction of the anode and therefore reduces the energy barrier for hole-injection into
the organic semiconductor [96, 97]. The TPD-copolymer films were crosslinked for one
minute under a broadband UV-light with 0.7 mW/cm
2
power density. The substrates were
47
then loaded into a Kurt J. Lesker Spectros vacuum system without being exposed to
atmosphere. For all subsequent organic layers, materials were first purified using gradient
zone sublimation and were then thermally evaporated at a rate of 1 /s at a pressure
below 1 10
-7
Torr on top of the hole-transport layers. For the emitting layer, a
concentration of 6% Ir(ppy)
3
was co-evaporated into a 20 nm-thick film of CBP. A 6 nm-
thick layer of BCP was used as a hole-blocking layer, followed by a 20 nm-thick layer of
Alq
3
as an electron-transport layer. Finally, a 1 nm-thick layer of lithium fluoride (LiF)
was deposited as an electron-injection layer, followed by a 200 nm-thick aluminum
cathode. Schematics of the substrate cleaning and OLED fabrication processes are shown
in the Appendix.

Table 4.1. Ionization potentials I
p
, mobility, and triplet energy values of different hole-
transport materials (HTM) and device performance at 100 cd/m
2
of OLEDs with device
3
(6%, 20 nm)/BCP (6 nm)/Alq
3
(20 nm)/LiF
(1 nm)/Al.
HTM I
p
(eV)
Hole
mobility
c

(cm
2
/Vs)
Triplet
energy
(eV)
EQE (%)
Luminous
efficiency
(cd/A)
Power
efficiency
(lm/W)
P1 5.25
a

1.8 10
-5

2.48
d
4.0 14 7
P2 5.34
a

6.4 10
-6

2.49
d
10.2 35 18
P3 5.45
a

7.2 10
-7

2.51
d
12.0 41 17
P4 5.47
a

5.9 10
-7

2.56
d
14.3 49 25
PVK 5.8
b

4.5 10
-7

3.0
e
18.1 62 29
a
calculated from electrochemistry (see Ref. [93])
b
estimated from photoemission spectroscopy (see Ref. [94])
c
measured at 4 10
5
V/cm and T = 297 K. The mobilities of P1-P4
were reported by Domercq et al. (see Ref. [93]). The hole
mobility of PVK was measured by a time-of-flight experiment.
d
calculated in a similar framework as Ref. [98].
e
see Ref. [99]
48

0.1 1 10 100
1
10
PVK
P4
P3
P2
P1

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)

Current Density (mA/cm
2
)

Figure 4.3. External quantum efficiencies as a function of the current density for OLEDs
with device structure ITO/HTM (25-35 nm)/CBP:Ir(ppy)3 (6%, 20 nm)/BCP (6
nm)/Alq3 (20 nm)/LiF (1 nm)/Al.

The external quantum efficiencies (EQEs) are shown as a function of the current
densities in Figure 4.3 for the devices with the five different hole-transport materials
(HTM). EQE, luminous efficiency, and power efficiency at 100 cd/m
2
are listed in Table
4.1. While devices with P1 (I
p
= 5.2 eV,
h
= 1.8 10
-5
cm
2
/Vs) show the lowest external
quantum efficiency of 4.0% at 100 cd/m
2
, devices with PVK (I
p
= 5.8 eV,
h
= 4.5 10
-7

cm
2
/Vs) exhibit an EQE of up to 18.1% at 100 cd/m
2
. These results indicate that the
efficiency increases with an increasing ionization potential and a decreasing hole
mobility of the hole-transport material. These two effects both lead to a reduction of the
49
injected hole current relative to the electron current, resulting in an improved charge
balance. This hypothesis is in agreement with previous studies [100-104]. However, it
should also be noted that other studies do not show any relation between the ionization
potential of the hole-transport material and the efficiency of the OLED [12, 105, 106].
To further investigate the observed effect, we prepared and characterized hole
carrier devices with the structure ITO/HTM (25-35 nm)/CBP:Ir(ppy)
3
(6%, 20
nm)/aluminum. A significant decrease in current density was observed in devices using
hole-transport materials with increasing ionization potential and decreasing hole mobility,
therefore further supporting the charge balance optimization explanation (Figure 4.4).

0 2 4 6 8
0
5
10
15
PVK
P3
P1

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

Figure 4.4. Current density as a function of the applied voltage for devices with the
3
(6%, 20 nm)/Al.

50
Nevertheless, another possible origin of the increase in device efficiency can be
attributed to an increase of the triplet energy of the hole-transport material. While hole-
transport materials with a low triplet energy allow nonradiative recombination through
energy transfer from the emissive excited state of Ir(ppy)
3
to the triplet state of the hole-
transport material, this loss mechanism can be reduced if the triplet energy of the hole-
transport material is higher than that of the emissive complex [106]. As shown in Table
4.1, the calculated triplet level energies of polymers P1 to P4 vary only by 0.08 eV.
However, their average value is close to that of Ir(ppy)
3
(2.40.1 eV) [107]. Hence, small
variations could lead to rather big changes in efficiency. On the other hand, when using
PVK with a triplet energy of 3.0 eV [99], the nonradiative loss mechanism should be
significantly reduced. The triplet level energy values were estimated from theoretical
calculations performed by the group of Prof. Jean-Luc Brdas of the School of Chemistry
and Biochemistry at the Georgia Institute of Technology.

4.3 Simplification of the Device Architecture
For the efficient OLEDs that have been presented above with PVK as the hole-
transport material, the fabrication can now be further improved by reducing the number
of layers in the device architecture. It has been shown previously that BCP exhibits a
higher electron mobility than Alq
3
. BCP can therefore also be used as an electron-
transport layer with integrated hole-blocking properties [108, 109]. Hence, we fabricated
devices where the Alq
3
layer was removed and the thickness of the BCP layer was
increased (see Figure 4.5, bottom). The luminance and the efficiencies as a function of
the applied voltage are shown in Figure 4.5 for the devices with 3 and 4 organic layers. A
51
lower turn-on voltage can be observed for the devices with 3 organic layers while the
efficiency at high luminance is similar to the devices with 4 organic layers. However, due
to some leakage in the current at low luminance, the efficiency for the 3-layer devices is
low at 100 cd/m
2
.

0
5
10
15
20
0 2 4 6 8 10 12
10
0
10
1
10
2
10
3
10
4
Device A
Device B
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)

glass substrate
ITO
PVK (25 nm)
CBP:Ir(ppy)
3
(20 nm)
BCP (6 nm)
LiF/Al
Alq
3
(20 nm)
glass substrate
BCP (40 nm)
A B

a function of the applied voltage for a device with 4 organic layers (device A, squares):
3
(6%, 20 nm)/BCP (6 nm)/Alq
3
(20 nm)/LiF (1 nm)/Al,
and for a device with 3 organic layers (device B, circles): ITO/PVK (25
nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al. The bottom part of the
figure illustrates the different device architectures.
52

To reduce the leakage at low luminance, the thickness of PVK was increased to
35 nm. The slight increase in thickness resulted in a higher turn-on voltage for the new
devices while the efficiency remained similar (Figure 4.6). Moreover, the electron-
injection was optimized by varying the thickness of LiF. An optimized LiF thickness of
2.5 nm led to devices with external quantum efficiencies of up to 21.2% and luminous
efficiencies of 72 cd/A at 100 cd/m
2
. This is the highest efficiency achieved in a device
comprised of less than four organic layers. It should also be noted that all of the materials
used for this high-efficiency device are commercially available while other reports with
high efficiencies typically include some specialty compounds. Furthermore, the hole-
transport layer is processed from solution, which reduces the overall deposition time of
the remaining two organic layers that are deposited from the vapor phase at low
deposition rates (1 /s).
As mentioned above, only 20 to 25% of the light emission can theoretically be
collected in the forward direction of a bottom-emitting OLED due to total internal
reflection effects in the device [73, 75]. The high efficiencies measured in this study
therefore suggest that we obtain an internal quantum efficiency close to 100%.

53
0
5
10
15
20
0 2 4 6 8 10
10
0
10
1
10
2
10
3
10
4
Device B
Device C
Device D
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)

a function of the applied voltage for device B (circles): ITO/PVK (25 nm)/CBP:Ir(ppy)
3

(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al, for device C (diamonds): ITO/PVK (35
nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (40 nm)/LiF (1 nm)/Al, and for device D
(triangles):. ITO/PVK (35 nm)/CBP:Ir(ppy)
3
(6%, 20 nm)/BCP (40 nm)/LiF (2.5 nm)/Al.

54
CHAPTER 5
HYBRID ELECTROPHOSPHORESCENT OLEDS WITH
SOLUTION-PROCESSED HOLE-TRANSPORT AND EMISSIVE
LAYERS
5.1 Introduction
While high efficiencies were first achieved in vacuum-deposited OLEDs [56, 59,
88], only recently have comparable efficiencies been measured in devices with solution-
processed emissive layers [68, 110]. The performance of solution-processed devices has
been increased using various approaches, such as synthesizing dendrimers of
phosphorescent complexes to provide site isolation of the emissive material and therefore
reduce triplet-triplet annihilation [110, 111], molecularly doping a hole-transport polymer
with phosphorescent complexes and an electron-transport material [68, 112, 113], or
synthesizing copolymers that combine all these properties [114-116].
Independently of the emissive layer, it has been shown that OLED efficiencies
increase if a hole-transport/electron-blocking layer is used between the anode and the
emissive layer, as explained in section 2.3.1, page 32 [68, 117-120]. However, the
fabrication of solution-processed multilayer stacks is not straightforward since previously
processed layers have to be insoluble in the solvent of the subsequent layer.
In this chapter, the fabrication of solution-processed multilayer structures will be
explained first. Then, the two most successful fabrication methods for solution-processed
emissive layers to date, molecularly doped layers and emissive layers based on
55
dendrimers, will be discussed and the state of the art in such devices will be shown. Next,
the problems of such mixed layers will be mentioned and our approach of a copolymer-
based emissive layer will be presented. Finally, devices based on copolymers with
different colors will be shown where the copolymer with an orange electroluminescence
spectrum will be optimized for highest efficiencies in an OLED structure.

5.1.1 Solution-Processed Multilayer Stacks and Crosslinking
Multilayer structures can easily be achieved with small molecules in vacuum
deposition. However, the device fabrication for solution-processed multilayer OLEDs is
more complicated since it is necessary that the previously deposited layer does not
dissolve when the next layer is deposited. In general, there are four different methods to
achieve multilayer stacks from solution [121]. First, layers can be processed from a
precursor that turns insoluble upon heating [122]. Alternatively, orthogonal solvents can
be used for neighboring layers where the solvent of the second layer does not dissolve the
previously deposited material [69, 112, 123]. Furthermore, films can also be made
insoluble by crosslinking [100, 124-129]. Finally, an intermediate liquid buffer layer can
be used that does not dissolve the previous layer, but protects it from the solvent of the
subsequent layer [130]. In the present work, crosslinking has been used for the
fabrication of solution-processed multilayer devices since it does not impose any
restriction on the choice of solvent for the following layer.
In the crosslinking process, enough energy has to be supplied to the material such
that chemical bonds on the specific crosslinking groups can rearrange to make a link
between separate molecules or polymers, which creates a network of connected
56
molecules or polymers that can no longer be dissolved. Crosslinking of polymers can be
achieved thermally or optically. In this work, optical crosslinking will be used for
solution-processed multilayer depositions because of its additional advantage that devices
can be patterned during crosslinking using photolithography [100]. In fact, fully solution-
processed multicolor displays based on fluorescent organic materials have already been
demonstrated using photocrosslinkable materials [131, 132].

5.1.2 Molecularly Doped OLEDs
Most of the research in electrophosphorescent OLEDs with solution-processed
emissive layers has been done on molecularly doped OLEDs. In this approach, a solution
of a charge transport polymer (hole- or electron-transport) is doped with a
phosphorescent dye and possibly other materials. Layers that are processed from these
mixed solutions typically show properties of all the materials combined. With the
growing commercial availability of small molecules for organic electronic applications,
materials for molecularly doped OLEDs can be acquired easily whereas materials for the
dendrimer and the copolymer approach have to be synthesized first.
As has been shown in chapter 3, Ir(ppy)
3
doped into CBP can lead to high
efficiencies. Therefore, poly(N-vinyl-carbazole) (PVK) as a close relative of CBP is an
obvious candidate as a host for the same emissive complex. Hence, the combination of
PVK and Ir(ppy)
3
was used in the first molecularly doped OLEDs [133]. To increase and
optimize the efficiency, a thermally evaporated hole-blocking/electron-transport layer
had to be deposited between the molecularly doped layer and the cathode, and external
quantum efficiencies of up to 7.5% at 100 cd/m
2
were observed.
57
However, later studies have shown that the efficiency improves significantly if an
electron-transport material, such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-
oxadiazole (PBD, Figure 5.1), is blended into the emissive layer [63, 134]. The electron-
transport material increases the number of electrons in the emissive layer to balance the
number of holes, which leads to a higher recombination rate. Efficiencies of up to 8.5% at
100 cd/m
2
were reported for devices with an emissive layer consisting of PVK, Ir(ppy)
3

and PBD [69].

N Ir
N
N
PBD
N N
O
Ir
N
O
O
3
Ir(mppy)
3
Iridium
Dendrimer

Figure 5.1. Chemical structure of Ir(mppy)
3
, PBD, and the dendrimer reported by Lo et
al. [110].

Nevertheless, external quantum efficiencies of optimized molecularly doped
OLEDs based on the phosphorescent emitter Ir(ppy)
3
typically do not exceed 10% with
the exception of one report by Kim et al. where 15.5% EQE was measured at 100 cd/m
2

in an OLED that consisted of just one molecularly doped layer in a single-layer device
58
architecture [112]. It has been shown that this upper limit is caused by aggregation and
phase separation of the Ir(ppy)
3
molecules in the emissive layer that lead to triplet-triplet
annihilation and therefore to lower efficiencies [135]. Adding alkyl substituents to the
ligands of the complex, however, has been shown to improve the interaction between the
emissive complex and the polymer matrix, leading to a better solubility and to a more
homogeneous distribution of the phosphorescent dye [136, 137]. Hence, record-high
efficiencies for OLEDs with a solution-processed emissive layer have been reported
using Ir(mppy)
3
(Figure 5.1) [68].

5.1.3 Dendrimers
In an attempt to combine charge-transport and emission on the same molecule,
fluorescent and phosphorescent dendrimers have been reported [111]. Dendrimers are
large molecules that consist of a core and of branches, called dendrons (see Figure 5.1).
Phosphorescent dendrimers typically have a core that consists of a heavy metal atom that
is surrounded by some charge transport units with good solubility. By adjusting the
length of the dendrons, the probability of interactions between the molecules can be
decreased and the triplet-triplet annihilation is lowered. Nevertheless, the external
quantum efficiencies of OLEDs with solution-processed dendrimer emissive layers and
thermally evaporated hole-blocking layers just barely exceeded 10%, which was
attributed to low charge balance in the dendrimer layer [111, 138]. Therefore, to date,
dendrimers have to be blended with an additional charge-transport material, a hole-
transport material for the cited references, to achieve good charge balance, similar to
59
molecularly doped OLEDs [110, 139]. Using a dendrimer blend and an evaporated hole-
blocking layer, EQEs of up to 16% at 100 cd/m
2
have been measured [110].

5.1.4 Emissive Layers from Copolymers
In a different approach, clustering of the organometallic complexes can
potentially be circumvented by incorporation of the host material and the organometallic
phosphorescent complex in a copolymer. By choosing the right synthetic methodology, it
is possible to fabricate copolymers that are derived from monomers with specified
functionalities, such as phosphorescent emission, hole and electron transport, or
crosslinking properties. Furthermore, in contrast to many guest-host approaches,
copolymers may be less subject to morphological changes, such as phase separation and
crystallization, over time. Therefore, copolymers have the potential for higher stability,
especially in applications that require large light output and consequently generate heat
under operational conditions. This stability at higher temperatures can also further ease
packaging and processing requirements.

60
N
O
O
N
N
O
N
Ir
N
N
N
N
Ir
O
O
C
8
H
17
C
8
H
17
C
8
H
17
C
8
H
17
(a)
x y z
m n
(b)

Figure 5.2. Electrophosphorescent copolymers with an iridium complex in the polymer
backbone as described in [116] with m:n = 1:99 (a), and with an iridium complex in a
side-chain of the polymer as reported in [114] with x:y:z = 18:79:3 (b)

OLEDs based on copolymers in which an iridium complex is directly attached to
or even inserted into the polymer backbone generally exhibit low efficiencies, apart from
a report by Zhen et al. on a red-emitting chelating copolymer that was incorporated in
devices with up to 6.5% external quantum efficiency (see Figure 5.2) [116, 140, 141]. In
a different approach, Evans et al. have demonstrated that polymers with an iridium
complex attached to the polymer as a side-chain are preferable to achieve high
efficiencies in OLED devices [142]. This approach has often been used in the literature,
and in many cases, iridium complex units (for phosphorescent emission) and carbazole
units (for hole transport) have been attached as side groups to vinyl polymer backbones
61
[115, 143-146]. However, the external quantum efficiencies of single-layer devices based
on these copolymers rarely exceed 1%. As before, more efficient OLEDs result from
devices with a thermally evaporated hole-blocking and/or electron-transport [143, 144],
or as Tokito et al. demonstrated, from devices where a small molecule with electron-
transport properties is dispersed in the copolymer [115]. However, because of the
versatility that can be achieved in copolymers, electron-transport properties can also be
incorporated in the copolymer directly. In fact, the highest efficiency reported for a
device with an emissive layer based on copolymers resulted when all three components
the hole-transport material, the electron-transport material, and the emissive material -
were copolymerized from side-chain monomers. Using a copolymer with a polyvinylic
backbone and with side groups consisting of iridium complexes for emission, N,N-
diphenyl-N,N-bis(3-methylphenyl)-[1,1-biphenyl]-4,4-diamine (TPD) for hole
transport, and 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) for electron-
transport, external quantum efficiencies of up to 11.8% were achieved (see Figure 5.2)
[114].

5.2 Experimental Results
In the present study, copolymers based on the very efficient host-guest system of
CBP:Ir(ppy)
3
were synthesized by the group of Prof. Markus Weck of the School of
Chemistry and Biochemistry at the Georgia Institute of Technology and their structure
was optimized to achieve high efficiencies in an OLED. For that purpose, iridium
complexes and a 2,7-di(carbazol-9-yl)fluorene group, a very close relative of CBP, were
covalently attached to the polymer backbone by randomly copolymerizing the two
62
functional monomers using a ring-opening metathesis polymerization (ROMP), which is
a living polymerization that allows high control over the molecular weight and the
monomer distribution within the copolymer from random to block copolymers [147]. By
synthesizing the copolymer in this manner, the structure of each monomer can be
optimized independently without drastically modifying the polymerization reactivity.

N
O
O
O
N
N
N
N
Ir
R
N
O
O
N
N
Ir
R
N
N
N Ir
F
F
F
F
F
F
O
O
R
N
O
O
Ir
S
N
S
N
n m
R
R
P6
P8
P5
P7

Figure 5.3. Chemical structures of carbazolyl-fluorene based copolymers with different
iridium complexes where the ratio m:n is 9:1.

It is well known that the color of iridium complexes can be tuned by the
attachment of substituents to the ligands that are surrounding the heavy metal atom [148-
152]. Therefore, by incorporating different iridium complexes in the copolymer,
63
materials with four different emission spectra were synthesized and used in OLED
devices (see Figure 5.3) [147]. With the goal of optimizing the efficiency of OLEDs
based on these copolymers, structural changes were then made to the copolymer with the
orange-emitting iridium complex, which showed the highest efficiency in the initial
screening of the four copolymers with different electroluminescence spectra.

5.2.1 Iridium Complex Variation
Figure 1.1 shows the electroluminescence spectra of devices in which the
copolymers P5-P8 have been used as the emitting layer between the crosslinked TPD-
based copolymer P1 (see Figure 4.2, page 46) as the hole-transport material (35 nm) and
vacuum-deposited layers of BCP (6 nm), AlQ
3
(20 nm), LiF (1 nm), and aluminum (150
nm) as hole-blocking, electron-transport, electron-injection, and cathode layer,
respectively (Figure 5.7, page 68). Devices fabricated using copolymers P6-P8 show
electroluminescence spectra with emission maxima that are similar to those measured in
photoluminescence experiments performed on the copolymers in solid state [147].
However, it should be noted that the electroluminescence (EL) spectra of devices
fabricated using copolymer P5 show a shift toward longer wavelengths with a maximum
at 511 nm compared to a maximum of 465 nm in photoluminescence spectra (Figure 5.4).

64
400 450 500 550 600 650 700 750 800
1
P5
P6
P7
P8

E
l
e
c
t
r
o
l
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Wavelength (nm)

P7
P8
P6
P5

Figure 5.4. Electroluminescence spectra for devices with the structure ITO/P1 (35
nm)/P(5-8) (25 nm)/BCP (6 nm)/AlQ
3
(20 nm)/LiF (1 nm)/Al and the corresponding CIE
1931 coordinates.

65

0
1
2
3
4
5
0 2 4 6 8 10 12
0.1
1
10
100
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
100
P7
P8

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)

voltage for devices with the structure ITO/P1 (35 nm)/(P7 or P8) (25 nm)/BCP (6
nm)/AlQ3 (20 nm)/LiF (1 nm)/Al.

Figure 5.5 shows the electrical characteristics of devices fabricated with
copolymer P7 and P8 as emitting layers. External quantum efficiencies at 100 cd/m
2
were
0.9% and 1.9% for devices with copolymer P7 and P8, respectively. These results are
encouraging given the low photoluminescence quantum efficiency of these two
copolymers (7% and 10% for copolymers P7 and P8, respectively, in solution) compared
to that of Ir(ppy)
3
(40% in solution and 97% in doped thin films) [153, 154]. Devices
fabricated from copolymers P5 and P6, on the other hand, yielded low light output and
66
very low efficiencies. The origin of the lower performance in our copolymer materials,
especially in P5 and in P6, compared to their small-molecule counterparts is not well
understood at this stage and has to be further investigated.

5.2.2 Optimization Rationale
Since the orange copolymer P8 showed the highest efficiency of copolymers P5-
P8 in this first screening of copolymers with different colors, this copolymer was further
used in a study with the goal of optimizing the performance of such copolymers in
OLEDs. In this study, several properties of the copolymer P8, including its iridium
concentration, its molecular weight, and the nature and length of the linker group
between the side groups and the polymer backbone were varied. The molecular weight
M
n
was varied because it may influence processing and the morphology of the films,
which in turn will impact device performance. Likewise, the concentration of the iridium
emitter was varied and optimized to mitigate the adverse effects of concentration
quenching and to avoid any insufficient energy transfer from host to guest material in the
emissive layer, as has been reported previously for evaporated and molecularly doped
OLEDs [55, 155].
Finally, the nature and length of the linker group between the side-chains and the
polymer backbone was varied (Figure 5.6). While a short spacer between the emissive
center and the polymer backbone might be desirable to minimize the number of inactive
groups, a long spacer for the emitter may be desirable to achieve better mixing with the
host material units. Furthermore, the variation of the length of the linker group between
the emitter and the backbone was also motivated by the work of Evans et al. [142] that
67
suggested that a longer linker could minimize the wavefunction overlap between the
organometallic complex and the hole-transport moiety, reducing Dexter triplet energy
back-transfer from the emitter to the host material.
In another study, we changed the nature of the linker between the hole-transport
material and the polymer backbone to address the effect of its polarity on device
performance while keeping its length short. Hence, an ether linker was replaced by a
more polar ester linker. Such a substitution can lead to a decrease of the hole mobility of
the polymer due to the higher polarity of the ester group [128, 156], leading to better
balance between holes and electrons, as suggested previously [138].

O
O
N
N
N
Ir
O
N N
R
2
R
1
R
1
:
R
2
R
1
O
R
2
:
R
1
O
O
(CH
2
)
9
O
R
2
P8
P9 P10
m
n m
n
m
n

Figure 5.6. Chemical structure of orange copolymers with different linker groups.

In the following discussion, the different copolymers that have been synthesized
and studied will be referred to as P(8-10)(a-c)(n). The first numeric index (8-10) is used
68
to identify the polymers as shown in Figure 5.6. The second index (a-c) refers to the
molecular weight range of the copolymer where (a) is the lowest and (c) is the highest
molecular weight, and finally the third index (n) refers to the percentage of iridium
containing monomers relative to the total number of monomers that were used in the
polymerization.

5.2.3 Molecular Weight and Iridium Content Variation
For the device fabrication, a 35 nm-thick film of the TPD-based copolymer P3
(see Figure 4.2, page 46) was employed as hole-transport material. The TPD-derivative
with two fluoro groups was chosen since this derivative has a larger ionization potential
compared to P1 which leads to higher efficiencies in OLEDs, as shown in chapter 3. The
hole-transport material was spin-coated onto air plasma-treated ITO coated glass
substrates and crosslinked under a broadband UV light. A 25 nm-thick film of the
copolymers was then spin-coated on top of the hole-transport material, followed by
vacuum deposition of 40 nm of BCP as the hole-blocking layer, 1 nm LiF as the electron-
injection layer, and aluminum as the cathode layer (Figure 5.7).

glass substrate
ITO
P1 (35 nm)
P5-P8 (25 nm)
BCP (6 nm)
LiF/Al
Alq
3
(20 nm)
glass substrate
ITO
P3 (35 nm)
P(8-10)(a-c)(n) (25 nm)
BCP (40 nm)
LiF/Al
(a) (b)

Figure 5.7. Device structure of OLEDs based on copolymers with different colors (a) and
device structure for optimization of the orange-emitting copolymer P8 (b).
69

External quantum efficiencies and luminous efficiencies at 100 cd/m
2
for the
devices fabricated with different copolymers are listed in Table 5.1. The efficiency of
devices with copolymers of different molecular weight (P8a-c(10)) was found to
decrease for the copolymers with the highest molecular weight (238 kDa). However, no
significant difference in efficiencies could be found when the molecular weight was
varied between 19 kDa and 70 kDa.

Table 5.1. Characterization of copolymers with peak maxima of solid-state
photoluminescence
max,PL
and electroluminescence spectra
max,EL
, plus external quantum
efficiencies and luminous efficiencies at 100 cd/m
2
for devices based on phosphorescent
copolymers with various molecular weights, various iridium concentrations, and different
linkers between the side groups and the polymer backbone. The device structure was
ITO/P3 (35 nm)/P(8-10)(a-c)(2-40) (20-25 nm)/BCP (40 nm)/LiF (1 nm)/Al.
Polymer
m:n
[mol%]
M
n

[kDa]
max,PL

[nm]
max,EL

[nm]
EQE
[%]
Luminous
efficiency
[cd/A]
P8a(10) 89:11 19.0 594 600 2.90.3 3.90.4
P8b(10) 92:8 70.0 590 602 3.20.3 4.90.4
P8c(10) 90:10 238.0 591 607 1.50.1 2.00.1
P8a(2) 98:2 16.0 595 596 1.90.3 2.60.4
P8a(5) 95:5 23.0 605 598 3.40.4 4.60.5
P8a(7) 93:7 16.0 597 602 3.00.4 4.10.5
P8a(15) 81:19 21.0 605 607 2.40.2 3.20.3
P8a(20) 79:21 19.5 604 607 2.00.1 2.70.2
P8a(30) 75:25 19.5 612 611 1.90.1 2.60.1
P8a(40) 71:29 27.0 613 612 1.70.1 2.30.1
P9a(10) 90:10 16.0 592 605 3.90.3 5.30.4
P10a(10) 90:10 20.0 594 603 4.50.5 8.00.9
P10a(5) 95:5 16.5 595 597 4.90.4 8.80.7

70

0 5 10 15 20 25 30
0
1
2
3
4
5

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)
Iridium Loading Level (%)

Figure 5.8. External quantum efficiencies as a function of the loading level of the iridium
complex in the copolymer for OLEDs with device configuration ITO/P3 (35 nm)/P8a(2-
40) (20-25 nm)/BCP (40 nm)/LiF (1 nm)/Al.

The study of the dependence of the concentration of the iridium complex in the
copolymer (P8a(2-40)) showed that the highest efficiency could be achieved for loading
levels around 5 mol% (Figure 5.8). This is in agreement with several literature reports of
similar studies on evaporated and molecularly doped OLEDs where the best efficiencies
are generally reported for iridium complex concentrations below 8 wt%, or 5-6 mol% [55,
56, 59, 113, 116, 123, 155, 157]. For higher loading levels, concentration quenching as
mentioned in section 2.2.6 is expected [58]. For concentrations below 1 wt%, light
emission from the host and the guest can be observed simultaneously [123], indicating
that the efficiency of the energy transfer from the host to the guest is reduced. In our case,
71
a red shift in the electroluminescence spectrum was also observed for increasing iridium
concentration (Figure 5.9), comparable to the red-shift measured in the
photoluminescence spectra of these polymers. While the maximum of the spectrum is at
596 nm for the copolymer with an iridium complex concentration of 5 mol%, it shifts to
612 nm for copolymers with 29 mol% iridium concentration. For the low concentration
of 2 mol%, a slight shoulder in the spectrum at 500 nm was visible. With a 5 mol%
iridium concentration, the CIE 1931 coordinates of the emission were (0.58, 0.42).

500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
P8a(2)
P8a(10)
P8a(20)
P8a(40)

E
l
e
c
t
r
o
l
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Wavelength (nm)

Figure 5.9. Electroluminescence spectra for OLED devices using copolymers P8a(2, 10,
20, 40) with increasing iridium complex content as emitting layer.

72
5.2.4 Spacer Variation
In a next step, the influence of the linkage between the functional groups and the
polymer backbone on the efficiency of the OLEDs was studied. First, the ether group that
connects the bis(carbazolyl)fluorene group to the polymer backbone was replaced by an
ester group (P9). The efficiency of an OLED with P9a(10) as the emissive layer was 1%
higher at 100 cd/m
2
than for the copolymer with an ether linkage. Finally, inserting an
elongated linkage between the iridium complex and the polymer backbone (P10a(10))
increased the EQE by another 0.6%.
Combining the results discussed above, a copolymer with an elongated ester
linker and an iridium complex concentration of 5 mol% was synthesized (P10a(5)). The
external quantum efficiency measured in an OLED based on this copolymer as emissive
layer was the highest of the present study: 4.90.4% and 8.80.7 cd/A at 100 cd/m
2

(Figure 5.10). This result validates the trends that were established through our studies in
which we varied different properties independently. Given the low value (10% in
toluene) of the photoluminescence quantum yield of the orange iridium emitter that was
incorporated in these copolymers [147], the measured EQE of 4.9% in devices with
polymer P10a(5) indicates that the electroluminescent properties of this copolymer are
nearly optimized.

73
0
2
4
6
8
10
0 2 4 6 8 10 12 14 16
10
1
10
2
10
3
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)
1E-5
1E-4
1E-3
0.01
0.1
1
10
100

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)

Figure 5.10. Current density (solid symbols, top), luminance (solid symbols, bottom),
and external quantum efficiency (empty symbols, bottom) as a function of the applied
voltage for a device with structure ITO/P3 (35 nm)/P10a(5) (25 nm)/BCP (40 nm)/LiF (1
nm)/Al.

74
CHAPTER 6
SOLUTION-PROCESSED ELECTROPHOSPHORESCENT
MULTILAYER OLEDS
6.1 Introduction
In the previous chapter, the fabrication of OLEDs with a solution-processed hole-
transport and emissive layer was described. However, the reported devices still required
an evaporated electron-transport/hole-blocking layer to achieve maximum efficiency. The
following chapter will now focus on devices in which all organic layers are processed
from solution. First, solution-processed multilayer structures with electron-transport/hole-
blocking layers from the literature are discussed. Then, our approach for
photocrosslinking of the emissive layer is described, and devices with three solution-
processed layers will be shown. Finally, photocrosslinking of the emissive layer will be
used to fabricate patterned devices with two different colors to create a white light source
with a tunable emission spectrum.

6.1.1 State of the Art
As has been discussed in the previous chapter, many reports of OLEDs with a
solution-processed emissive layer have been published. However, with some exceptions
[68, 112], most solution-processed OLEDs show only low efficiencies if no electron-
transport/hole-blocking layer is integrated in the device structure [69, 158, 159]. To date,
almost all reports of OLEDs with a solution-processed emissive layer that show high
75
efficiencies therefore include a thermally evaporated electron-transport/hole-blocking
layer between the emissive layer and the cathode.
Nevertheless, some fully solution-processed multilayer OLEDs including a
solution-processed electron-transport layer have been reported in the literature [130, 159-
166]. Only about half of these reports are electrophosporescent OLEDs [159, 160, 164,
166]. However, for all the reported devices the efficiencies were increased because of the
additional solution-processed electron-transport layer.
Different methods for solution-processed multilayer stacks have been mentioned
before (chapter 5.1.1, page 55). The most popular approach to achieve multilayer OLEDs
from solution is the use of orthogonal solvents for adjacent layers. Typically, water- or
alcohol-soluble hole- and electron-transport materials are used whereas the emissive layer
is processed from an organic solvent [160, 162-166]. Alternatively, multilayer devices
with good efficiencies have also been fabricated by crosslinking of the emissive layer
[159, 161]. While most of the reported efficiencies in solution-processed multilayer
OLEDs are low, there is one report by Wang et al. of exceptionally high efficiencies up
to 18.0% at 100 cd/m
2
with four spin-coated organic layers [164]. The device structure
for such a highly efficient OLED consisted of a hole-injection layer of poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) processed from water on
top of an ITO substrate, followed by a hole-transport layer of PVK processed from
chlorobenzene [167]. The emissive layer was a blend of polyfluorene, PBD and a red-
emitting iridium complex in a p-xylene solution. Finally, an electron-transport layer of
poly[(9,9-bis(3-((N,N-dimethyl)-N-ethylammonium)propyl)-2,7-fluorene)-2,7-(9,9-
dioctylfluorene)-4,7-(2,1,3-benzoselenadiazole)]dibromide (PFN) was processed from a
76
methanol solution. A barium electron-injection layer and an aluminum cathode were
evaporated on top of the organic layers.

6.1.2 Crosslinking of the Emissive Layer
Although the use of orthogonal solvents is the most popular method for solution-
processed multilayer OLEDs, crosslinking places fewer restrictions on the solubility of
the materials and is therefore preferable. Furthermore, if crosslinking can be achieved by
exposure to light, fewer steps are necessary in the fabrication of patterned OLEDs [131,
132]. Therefore, a crosslinkable emissive layer will be introduced here (Figure 6.1). This
crosslinkable copolymer is based on the optimized orange copolymer, as described in
chapter 4, with the addition of a cinnamate based group that has already been used for the
crosslinkable hole-transport materials in chapter 3. The copolymer was synthesized by
the group of Prof. Markus Weck of the School of Chemistry and Biochemistry at the
Georgia Institute of Technology.

77
N
N
N
Ir
N N
O
O
O
P11
m n
O
O
O
O
O
O
o

Figure 6.1. Crosslinkable electrophosphorescent copolymer based on polymer P10a(5)
with a charge-transport moiety (left), a phosphorescent orange-emitting complex (center),
and a crosslinkable cinnamate based group (right) with m:n:o = 70:5:25.

6.1.3 Electron-Transport/Hole-Blocking Polymer
Not many electron-transport polymers for organic light-emitting diodes have been
reported in the literature, and none are commercially available. Hence, for most of the
above mentioned literature with solution-processed multilayer OLEDs, new polymers had
to be synthesized for the electron-transport layer. All of these newly synthesized electron-
transport polymers were based on polyfluorene where electron-transport groups were
added to either the backbone of the polymer (see Figure 6.2) [161, 165] or to its side-
chains [162, 164, 166]. Where electron-transport polymers were not available, electron-
78
transport small-molecules were either processed directly from solution [130, 160, 163] or
they were processed in a polymer matrix [159]. For the present work, new polymers
based on small molecules with known electron-transport properties have been
synthesized by the group of Prof. Seth Marder of the School of Chemistry and
Biochemistry at the Georgia Institute of Technology as potential candidates for a
solution-processable electron-transport/hole-blocking layer. Two of these polymers are
presented in the following paragraphs.

TPBI
C
8
H
17
C
8
H
17
C
8
H
17
C
8
H
17
N
+
N
+
N N
Se
Br
-
Br
-
PFN
N
N
N N
N
N
O
N N
SO
3
Na
m
n
t-Bu-PBD-SO
3
Na

Figure 6.2. Chemical structures of solution-processable electron-transport materials used
in the literature [130, 160, 164]. Whereas PFN and TPBI are examples of a polymer and a
small molecule, respectively, that are soluble in organic solvents, t-Bu-PBD-SO
3
Na is
soluble in ethanol.

Silacyclopentadienes (siloles) have been used primarily in fluorescent OLEDs
since their photoluminescence can be tuned and high electron mobilities can be achieved.
79
First mentioned in 1996 as an electron-transport material [168], siloles were shown to
have comparable electron affinities [169], but significantly higher electron mobilities
than Alq
3
[170]. Consequently, high external quantum efficiencies have been shown in
fluorescent OLEDs where both the emissive layer and the electron-transport layer were
comprised of different silole derivatives [171]. The small molecule equivalent of the
silole polymer that is used in this work (P12, Figure 6.3) is expected to have a high
ionization potential [169] and has been used in OLEDs before [172].

P12
Si
O
n
O
N
N
O
N N
O
O
n
P13

Figure 6.3. Chemical structures of electron-transport polymers based on a silole small-
molecule (P12) and based on a bisoxadiazole small-molecule (P13).

The second electron-transport polymer was based on a bisoxadiazole small
molecule (P13, Figure 6.3). As mentioned in the context of molecularly doped OLEDs
(section 5.1.2, page 56), oxadiazoles have been used successfully as dopants in the
emissive layer for more efficient electron-transport and better charge balance in the
device [63, 68, 173]. Electron mobilities of 10
-5
cm
2
/Vs were measured for the oxadiazole
80
derivative PBD [174]. Furthermore, some oxadiazoles have a high ionization potential,
which makes the material attractive as a hole-blocking and electron-transport material
simultaneously [175]. The bisoxadiazole polymer that is used here is derived from a
small molecule with a high ionization potential that has led to high efficiencies in
molecularly doped OLEDs [68, 133, 176].

6.2 Experimental Results
6.2.1 OLEDs with a Crosslinkable Emissive Layer
To test the effect of a crosslinked emissive layer on the device performance,
devices similar to those in chapter 4 were fabricated. A 35 nm-thick film of the hole-
transport polymer P3 was spin-coated onto air-plasma treated ITO coated glass and
crosslinked under a broadband UV light with an exposure of 40 mJ/cm
2
. An
approximately 17 nm-thick film of the crosslinkable copolymer P11 was then spin-coated
on top of the hole-transport layer. After the deposition of the crosslinkable copolymer,
some substrates were directly transferred into the vacuum chamber while others were
exposed to UV with a dose of 1250 mJ/cm
2
first. Unfortunately, such a high energy dose
is necessary to crosslink even such a thin layer of the copolymer P11 since the hole-
transport moiety of the copolymer absorbs in the same wavelength range as the
cinnamate group that is used for the photocrosslinking (Figure 6.4) [100]. To finish the
device fabrication, a 40 nm-thick film of BCP was vacuum deposited on top of the
solution-processed layers, followed by a 2.5 nm-thick film of LiF and a 200 nm-thick
film of aluminum.
81

300 350 400 450 500
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (nm)

A
b
s
o
r
p
t
i
o
n

(
a
.
u
.
)
O
N N
O

Figure 6.4. Absorption spectrum of the monomer of the hole-transport moiety in
copolymer P11.

For the resulting devices, the current density, the luminance and the external
quantum efficiency as a function of the applied voltage are shown in Figure 6.5. First of
all, it should be noted that the efficiencies for devices with the crosslinkable copolymer
as the emissive layer are generally lower than the efficiencies reported for the copolymer
without the crosslinking group (chapter 4). This decrease can be attributed to a poor
charge balance since more than a quarter of all hole-transport moieties in the copolymer
have to be replaced by cinnamate groups to achieve crosslinking of the material.
Furthermore, Figure 6.5 shows that all the measured characteristics decrease after
the long UV exposure of the emissive layer, resulting in an external quantum efficiency
of only 0.5 0.1% at 100 cd/m
2
. A similar decrease at high UV exposure has been
reported earlier for PVK-based OLEDs [177]. These results indicate that photo-
82
crosslinking is not suited for carbazole-based materials, but other crosslinking processes
will have to be pursued. Nevertheless, since OLEDs with non-negligible efficiencies can
be fabricated using the crosslinkable copolymer P11, solution-processed multilayer
OLEDs will be demonstrated using this emissive layer.

0
1
2
3
4
5
0 2 4 6 8 10 12 14 16
1
10
100
1E3
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
)
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
no UV exposure
high UV exposure

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)

voltage for devices with the structure ITO/P3 (35 nm)/P11 (17 nm)/BCP (40 nm)/LiF
(2.5 nm)/Al with (circles) and without (square) 1250 mJ/cm
2
UV exposure of P11.

6.2.2 Solution-Processed Multilayer OLEDs
For devices with a solution-processed electron-transport layer, the hole-transport
and the emissive layer were deposited and crosslinked as described in section 6.2.1.
83
Additionally, instead of the evaporation of BCP, one of the two electron-transport
polymers P12 and P13 was spin-coated from toluene (P12) or from chlorobenzene (P13)
on top of the crosslinked emissive layer to form a layer with a thickness of 40 or 35 nm,
respectively. Finally, 2.5 nm of LiF and 200 nm of aluminum were thermally evaporated
as an electron-injection layer and the cathode.

0
1
2
3
4
5
0 2 4 6 8 10 12 14 16 18 20
1
10
100
L
u
m
i
n
a
n
c
e

(
c
d
/
m
2
)

Applied Voltage (V)

E
x
t
.

Q
u
a
n
t
u
m

E
f
f
i
c
i
e
n
c
y

(
%
) 1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
100
BCP
P12
P13

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)

voltage for devices with the structure ITO/P3 (35 nm)/P11 (17 nm)/ETL (35-40 nm)/LiF
(2.5 nm)/Al where the electron-transport layer (ETL) consisted of BCP (squares), P12
(circles), or P13 (triangles).

84

300 350 400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
P12
P13
Wavelength (nm)

A
b
s
o
r
p
t
i
o
n

(
a
.
u
.
)

Figure 6.7. Absorption spectra of P12 (solid line) and P13 (dashed line).

The current density, the luminance and the external quantum efficiency as a
function of the applied voltage of these solution-processed multilayer OLEDs are shown
in Figure 6.6. A decrease of the current densities was observed for devices with a
solution-processed electron-transport layer compared to the evaporated BCP layer. This
decrease can be attributed to an electron mobility in the polymers that is expected to be
lower compared to BCP [109]. However, a decrease in the number of electrons can
increase the charge balance in the device by matching the hole current that has been
decreased because of the use of the crosslinkable emissive layer (see above). Therefore,
higher efficiencies can be measured in devices with a solution-processed electron-
transport layer. The higher efficiency of 2.0 0.2% at 100 cd/m
2
for devices with P13
compared to an efficiency of 1.3 0.1% at 100 cd/m
2
for devices with P12 can be
85
explained by the larger energy gap of P13 (see the absorption spectrum of the two
electron-transport polymers in Figure 6.7). Assuming that the two polymers P12 and P13
have similar electron affinities, we expect that P13 has a higher ionization potential than
P12, which makes it more suitable as a hole-blocking material whereas holes can be
transported more easily across a layer of P12.

6.2.3 Photopatterned OLEDs
After the successful demonstration of solution-processed multilayer OLEDs, the
photocrosslinkable emissive copolymer can be used to pattern a substrate with different
colors. Patterning is required mainly for display applications where red, green, and blue
(RGB) pixels have to be placed in close proximity to each other. For example, in mobile
display applications like cell phones, an RGB pixel containing pixels of each color
usually covers only an area in the range of 300 300 m
2
. However, patterning of areas
with different colors is also necessary for certain lighting applications, i.e. for mood-
lighting panels that are color tunable to simulate the sun light at different hours of the day.
Patterning of displays by using photocrosslinkable emissive materials has already been
reported with fluorescent and phosphorescent materials [132, 159]. Unlike those reports,
the present work focuses on color tuning in lighting applications.
To achieve a tunable white light, OLEDs of at least two different colors have to
be driven separately. Consequently, a separation of the two colors is needed in the
emissive layer and in either the cathode or the anode. Here, the ITO anode was etched
into an interdigitated pattern as shown in Figure 6.8. Linewidths of 110 m with 40 m
gap in between were chosen, which corresponds to a period of 300 m as used in RGB
86
pixels. White light was then achieved as a combination of orange and blue color [178].
For orange emission, the crosslinkable copolymer P11 was used. Blue light, on the other
hand, was generated in a layer of the crosslinkable TPD-based copolymer P3 by relying
on the fluorescence of TPD [179, 180]. Part of a substrate with patterned ITO and one
crosslinked polymer layer after development is shown in Figure 6.8.

C
o
l
o
r

2
C
o
l
o
r

1
ITO
ITO
glass
c
r
o
s
s
l
i
n
k
e
d
P
3
o
n

I
T
O
ITO
40
m
110
m
ITO

Figure 6.8. Schematic of interdigitated electrodes with photopatterned emissive layers
(left), and a micrograph of the electrodes with a photopatterned layer of P3 (right).

The following procedure was used to fabricate the photopatterned OLEDs. First,
the ITO on a glass substrate was patterned using standard etching procedures. A hole-
transport layer consisting of the crosslinkable TPD-based copolymer P3 with a thickness
of 35 nm was then spin-coated on top of the patterned ITO and crosslinked under a
broadband UV light with an exposure of 40 mJ/cm
2
. Next, a 17 nm-thick layer of the
orange crosslinkable copolymer P11 was deposited from solution on top of the hole-
transport layer and crosslinked in a mask aligner at a wavelength of 365 nm with an
exposure of 1250 mJ/cm
2
through a mask. The pattern was developed by spin-coating
chlorobenzene on top of the exposed film. For the blue lines, a 35 nm-thick layer of P3
87
was deposited as the emissive layer to achieve similar current densities and drive voltages
for the orange and the blue lines. The blue emissive layer was patterned like the orange
emissive layer except that the exposure was only 40 mJ/cm
2
. Finally, a 35 nm-thick layer
of the bisoxadiazole polymer P13 was spin-coated on top of the patterned emissive layers,
and a 200 nm-thick aluminum cathode was thermally evaporated. The final device under
operation is shown in Figure 6.9. A diagram of the fabrication process of the patterned
multilayer device is shown in the Appendix.

Figure 6.9. Photograph of photopatterned OLEDs with orange electrophosphorescent and
blue electrofluorescent lines with linewidths of 110 m.

By changing the applied voltage for the lines with different color, the spectrum of
the mixed devices could be tuned throughout the white. However, because of the low
intensity of the devices and their short lifetime, CIE coordinates could not be measured.

88
CHAPTER 7
MODELING THE CHARGE INJECTION INTO OLEDS
7.1 Introduction
As mentioned earlier, organic semiconductors have recently advanced enough to
be incorporated into a variety of solid-state devices such as organic light-emitting diodes,
organic solar cells, organic diodes, and organic field-effect transistors [23, 48, 56, 181].
When integrating these devices into circuits with increasing complexity, it becomes
critical to have accurate and relatively simple models to describe their electrical
characteristics. For instance, OLEDs are usually assumed to behave according to the
diode equation, even though the predictive capabilities of this oversimplified model in
describing the electrical properties over the full range of voltages are rather limited.
To make up for this deficiency, different approaches to model organic diodes
have been reported in the literature. Simple models are achieved with partial fits of the
electrical characteristics in the low voltage or high voltage range. For example, the steep
increase in current at low voltages has mostly been attributed to thermionic or Schottky
emission of charges across the energy barrier between the Fermi level of the electrode
and the HOMO or the LUMO of the organic layer [31, 182].
The current at higher voltages is usually assumed to be limited by space-charge
limited current (SCLC) effects [183-185]. However, besides for materials that make
nearly ohmic contact (i.e. ITO / MEH-PPV), the electrical characteristics mostly follow a
power law with an exponent that is substantially larger than two [186, 187]. Therefore,
just one circuit element typically cannot fit the full electrical characteristics, and its
89
predictions are limited to partial fits in selected regions of the current-voltage
characteristics.
Alternatively, better fits of the electrical characteristics have been achieved using
more complex models based on basic semiconductor and electromagnetic equations [188-
190]. These systems of equations are usually solved in a finite elements approach where
the carrier and field distributions inside an organic layer are calculated and optimized to
fit given boundary conditions. Although such calculations can lead to quite accurate fits
of experimental data, they are heavily dependent on parameters such as the intrinsic
charge carrier density or the intrinsic electric field that cannot be measured in an
independent experiment, and a wide range of values have been published for these
parameters [47, 188, 191, 192]. Moreover, such complicated systems of equations cannot
be easily integrated in circuit design software for accurate modeling of organic devices.
In this chapter, an equivalent-circuit approach to model the electrical
characteristics of a basic organic single-layer diode is presented and the model is
implemented in SPICE, a widely used circuit-simulation program. The equivalent-circuit
model is based on physical principles of an organic diode and will be explained in the
following section. Furthermore, temperature-dependent experimental electrical
characteristics of different single-layer diodes will be fitted with the proposed model to
extract material parameters. Finally, the resulting parameters will be compared to the
values that are reported in the literature.

90
7.2 Theory and Model
Based on the operational principles of organic diodes, such as charge injection
and charge transport (see section 2.2.1, page 17 and section 2.2.3, page 21), an equivalent
circuit model for an organic single-layer diode is proposed that consists of a thermionic
Schottky diode for injection into the organic semiconductor in series with a voltage-
dependent resistor representing the space-charge limited current (SCLC) for the bulk
conductivity in the device (Figure 7.1). A shunt resistor R
p
is placed in parallel to these
two circuit elements to account for any leakage current through the device.

Figure 7.1. Equivalent circuit of an organic single-layer diode.

In this model, the diode is described by the general diode equation
= 1 exp
0
nkT
qV
J J , (2.2)
where J
0
is the saturation current and n is the ideality factor. Using the prefactor for
thermionic emission:
91
=
kT
T A J
B
exp *
2
0
, (2.3)
the value for the saturation current can further be split into the effective Richardson
constant A* and the injection barrier
B
if the temperature dependence of the diode is
known.
Likewise, with the equation for SCLC
J =
9
8
0
V
2
L
3
, (2.12)
the voltage-dependent resistor in the equivalent circuit is dependent on the mobility and
the thickness L of the organic layer. However, as shown in section 2.2.2, page 18 in the
framework of the disorder formalism, the mobility is a function of the electric field and
the temperature:
=
2 / 1 2
2 2
0 , 0
exp
3
2
exp ) , ( E
kT
C
kT
E

. (2.10)
Assuming that the internal field of the single-layer diode is constant, and in order to
minimize the number of parameters that are used in the model, the equation for the
mobility is simplified to
=
L
V
exp
0
(7.1)
with
0
the zero-field mobility and the field-dependence factor of the mobility.

7.3 Experiment
Four different materials were used as the organic layer in a single-layer device
geometry (see Figure 7.2). As shown in the above chapters, 4,4-bis[N-(1-naphthyl)-N-
92
phenyl-amino]biphenyl (-NPD) and N,N-bis(m-tolyl)-N,N-diphenyl-1,1-biphenyl-
4,4-diamine (TPD) are well-known hole-transport materials with wide bandgaps [120,
193]. Whereas -NPD was used in its small-molecule form, a TPD-based polymer (P1)
[100] was used for another set of devices to make sure that the proposed model does not
only apply to small molecules but also to polymers. Other devices incorporated a layer of
the electron-transport organic semiconductor C
60
or a layer of the hole-transport material
pentacene. These latter two materials were selected because they have significantly
higher mobilities [22, 23] and smaller bandgaps [48] compared to -NPD and P1.

N
O
O O
O
O
O
CO
2
CH
3
N
OMe MeO
N N
m n
P1
Pentacene
-NPD
C
60

Figure 7.2. Chemical structures of -NPD, P1, C
60
and pentacene.

Diodes were fabricated on air-plasma treated ITO coated glass substrates. For the
organic layer, the small molecules of -NPD, C
60
, and pentacene were thermally
evaporated. For C
60
diodes, an additional layer of 8 nm BCP was deposited on top of the
fullerenes to avoid aluminum diffusion into the C
60
[194]. For the polymer diodes, a 90
nm thick film was spin-coated from toluene on top of the air-plasma treated ITO
93
substrates. The polymer film was crosslinked using a standard broad-band UV light with
a 0.7 mW/cm
2
power density for 1 minute. For all diodes, a 200 nm-thick aluminum
cathode was vacuum deposited on top of the organic layer. Finally, model parameter
values were determined by fitting the experimental data with the equivalent-circuit model
using the HSPICE optimization tool.

7.4 Results and Discussion
First, when testing a new model it is important to verify that the experimental
electrical characteristics to which the model is applied are highly reproducible. Figure 7.3
shows the data of 5 different devices with geometry ITO/-NPD (80 nm)/Al and 5
different devices with geometry ITO/-NPD (150 nm)/Al. The high reproducibility of
these electrical characteristics leads to a standard deviation of less than 10% of the fitted
values for the ideality factor n and the zero-field mobility
0
. For the saturation current
density J
0
and the field-dependence of the mobility , the standard deviation is higher and
can reach 100% of the fitted value.

94
0 2 4
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)
80 nm
150 nm

Figure 7.3. Current density versus applied voltage at room temperature for -NPD diodes
with thicknesses of 80 nm and 150 nm. Plots of five devices are shown for each
thickness.

In the next step, to test the validity of the space-charge limited current model, -
NPD diodes with different thicknesses were fabricated and tested. Model parameters
were extracted from fits to the experimental data (see Figure 7.4) and are summarized in
Table 7.1. The mobility parameters are found to be nearly independent of the thickness,
which supports the introduction of the SCLC voltage-dependent series resistor in our
model.
95
0 1 2 3 4
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
60 nm
80 nm
100 nm
120 nm
150 nm

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

-NPD diodes with thicknesses ranging from 60 nm to 150 nm. Experimental data is
shown as empty symbols; solid lines represent the simulated curves.

0
p
, zero-field
mobility
0
electrical characteristics at room temperature for -NPD diodes with different thicknesses
L.
L
(nm)
J
0

(mA/cm
2
)
n
R
p

(*cm
2
)
0

(cm
2
/Vs)

((cm/V)
1/2
)
60
1.1 10
-11

2.0
8.0 10
5
1.8 10
-4
1.1 10
-6

80
6.2 10
-14

1.7
4.1 10
8
1.5 10
-4
4.9 10
-6

100
1.8 10
-14

1.9
8.7 10
8
1.2 10
-4
1.5 10
-3

120
6.5 10
-12

2.5
3.8 10
8
1.8 10
-4
1.0 10
-7

150
3.5 10
-9

4.3
9.8 10
8
2.4 10
-4
1.2 10
-4

96
Likewise, the model was applied to the experimental data of diodes with
geometry ITO/P1 (90 nm)/Al, and good fits were obtained except for the low voltage
range (Figure 7.5). In our model, the current in that region is dominated by the parallel
resistor R
p
, even though the experimental data does not show a linear increase. However,
since diodes, especially organic light-emitting diodes, are operated at higher voltage
where current injection is more efficient, a certain discrepancy of the equivalent circuit at
low voltages does not seem to be very problematic.

-1 0 1 2 3 4
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
-NPD
P1

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

organic diodes with organic layers of -NPD (100 nm, squares) and P1 (90 nm, circles).

From the electrical characteristics of the -NPD diodes and the diodes of P1 at
room temperature, the mobility values were determined to be 1.2 10
-4
cm
2
/Vs and 4.5
97
10
-6
cm
2
/Vs respectively (see Table 7.2, page 99). These values are in good agreement
with mobility values measured in time-of-flight experiments and SCLC measurements
[93, 195, 196]. Furthermore, the temperature-dependence of the mobility can be
determined from measurements of the organic single-layer diode at different temperatures,
as shown in Figure 7.6 for a device with geometry ITO/-NPD (100 nm)/Al.

0.5 1.0 1.5 2.0 2.5 3.0
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
1C
12C
24C
41C
54C
72C

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

Figure 7.6. Current density as a function of the applied voltage for an -NPD diode with
a thickness of 100 nm measured at temperatures ranging from 1 C to 72 C.

Combining equations (2.1) and (7.1), the mobility at zero-field and zero-
temperature
0,0
as well as the width of the energetical disorder distribution can be
calculated from the intercept and the slope, respectively, of a linear fit when plotting the
logarithm of the zero-field mobility
0
versus T
-2
. In fact, such plots of our extracted
98
parameters resulted in reasonable fits for the -NPD diodes and the diodes incorporating
P1 (Figure 7.7). The width of the energetical disorder distribution was calculated to be
0.096 eV and 0.128 eV for diodes incorporating -NPD and P1, respectively. The
corresponding zero-field and zero-temperature mobility values were
0,0
= 7.0 10
-2

cm
2
/Vs for -NPD and
0,0
= 3.8 10
-1
cm
2
/Vs for P1.

0 2 4 6 8 10 12
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
-NPD
P1

0

(
c
m
2
/
V
s
)
(1000/T)
2
(1/K
2
)

Figure 7.7. Plot of zero-field mobility versus (1000/T)
2
for organic diodes consisting of
-NPD (100 nm, squares) and P1 (90 nm, circles). Experimental data is shown as empty
symbols; solid lines are linear fits to this data.

99

0
p
, zero-field
mobility
0
electrical characteristics at room temperature for organic diodes with thickness L. For
pentacene and C
60
diodes, the series resistance R
s
is noted instead of any mobility. The
effective Richardson constant A* and the injection barrier
B
were extrapolated from
current measurements at different temperatures.

L
(nm)
J
0

(mA/cm
2
)
n
( )
R
p
(*cm
2
)
0

(cm
2
/Vs)

((cm/V)
1/2
)
R
s

(*cm
2
)
A*
(A/(cm
2
*K
2
))
B
(eV)
-NPD 100 1.8 10
-14
1.9 8.7 10
8
1.2 10
-4
1.5 10
-3
N/A 1.9 10
-5
0.99
P1 90 1.5 10
-14
2.2 1.3 10
6
4.5 10
-6
2.8 10
-3
N/A - -
Pentacene 80 7.7 10
-4
1.6 1.7 10
6
N/A N/A 1.4 1.2 10
-4
0.42
C
60
100 3.6 10
-9
1.7 2.7 10
4
N/A N/A 1.1 1.8 10
-5
0.72

Despite the good agreement of the proposed model for the previous diodes, some
adjustments to the equivalent circuit were necessary to fit the electrical characteristics of
diodes based on pentacene and C
60
. Typically, organic semiconductors show ohmic
behavior before space-charge limited current occurs. Combining Equation (2.12) with the
equation for ohmic drift current
J = n
0
e
V
L
(2.11)
where e is the elementary charge and n
0
the charge carrier density, a crossover voltage V
C

from ohmic to space-charge limited current can be calculated yielding
0
2
9
8
n L
e
V
C
= (7.2)
with
100

kT
E
n
g
2
exp
0
(7.3)
where E
g
is the bandgap of the material. From equation (7.2), it can be seen that the
crossover voltage between the ohmic and SCLC regimes increases for materials with
smaller bandgaps such as pentacene and C
60
. Hence, ohmic (linear) drift current can still
be observed at higher voltages in diodes based on pentacene or C
60
(E
g
: 1.9 eV and 1.7
eV, for pentacene and C
60
[48], respectively) compared to diodes based on -NPD or
TPD (E
g
: 3.1 eV and 3.2 eV, for -NPD [197] and TPD [182], respectively). In fact, by
replacing the SCLC resistor in our model with a constant resistor R
s
, good fits to the
experimental data of pentacene and C
60
diodes can be achieved (see Figure 7.8), which
has already been shown in equivalent circuits of pentacene/C
60
organic photovoltaic cells
[198]. However, no mobility values can be determined from R
s
since both the charge
carrier concentration n
0
and the mobility are unknown in the equation for R
s
:
R
s
=
L
n
0
e
. (7.4)

101
-1.0 -0.5 0.0 0.5 1.0
1E-5
1E-4
1E-3
0.01
0.1
1
10
100
Pentacene
C
60

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

organic diodes with organic layers of pentacene (80 nm, triangles) and C
60
(100 nm)/
BCP (8 nm, diamonds). Experimental data is shown as empty symbols; solid lines
represent the simulated curves.

Finally, to calculate the injection barrier and the effective Richardson constant,
current density measurements in single-layer diodes were performed as a function of
temperature (see Figure 7.6 for -NPD and Figure 7.9 for pentacene diodes). By plotting
the logarithm of (J
0
/T
2
) versus (1/kT), the injection barrier and the effective Richardson
constant can be determined from the slope and the intercept, respectively, of a linear fit to
the experimental data as a function of temperature, as shown in Figure 7.10. Calculated
values of the fitted parameters are summarized in Table 7.2. Note that data from diodes
incorporating P1 did not yield a linear fit. Hence, the values of the effective Richardson
constant and the injection barrier energy could not be extracted.
102

0.0 0.2 0.4 0.6 0.8 1.0
1E-4
1E-3
0.01
0.1
1
10
100
1C
12C
24C
41C
54C
72C

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Applied Voltage (V)

Figure 7.9. Current density as a function of the applied voltage for a pentacene diode
with a thickness of 80 nm measured at temperatures ranging from 1 C to 72 C.

All calculated effective Richardson constants were in the range of 10
-5
to 10
-4

A/(cm
2
K
2
), which is in the upper range of experimentally determined effective
Richardson constants in organic materials [182, 199, 200] but below the theoretical value
of ~10
-2
A/(cm
2
K
2
) [29]. The fitted injection barrier for the C
60
diodes (
B
= 0.72 eV)
seems to suggest that electrons are in fact not injected from the aluminum (work function
W = 4.2 eV) into the C
60
film (LUMO: 4.5 eV [48]) through defect states in the BCP, as
was mentioned in earlier reports [201]. More likely, electrons get injected into the LUMO
of BCP first, since the measured injection barrier corresponds well with the barrier
between aluminum and BCP (LUMO of BCP: 3.5 eV [48]).
103

0 10 20 30 40
1E-28
1E-24
1E-20
1E-16
1E-12
1E-8
1E-4
-NPD
Pentacene
C
60

J
0
/
T
2

(
A
/
(
c
m
2
T
2
)
)
1/kT (eV
-1
)

Figure 7.10. Plot of (J
0
/T
2
) versus (1/kT) for organic diodes consisting of three different
materials to extrapolate the injection barrier
B
and the effective Richardson constant A*.
Experimental data is shown as empty symbols; solid lines are linear fits to the data.

In the case of the -NPD and the pentacene diodes, both values for the injection
barriers that were calculated from the fits in Figure 7.10 are higher than the energy
barriers that are expected between the work function of plasma treated ITO (W = 4.7 eV)
[202] and the HOMO energies of -NPD [197] (5.5 eV) and pentacene [48] (4.9 eV).
However, similar values for the energy barrier have resulted from x-ray and ultraviolet
photoemission spectroscopy (XPS and UPS) measurements [203, 204], and the increased
barrier energies have been attributed to dipoles that form at the interface with ITO, which
causes a vacuum level misalignment and therefore an increase in the injection barrier.
104
CHAPTER 8
CONCLUSIONS AND OUTLOOK
8.1 Conclusions
In summary, this work reports on the fabrication of OLEDs with solution-
processed organic layers. Whereas chapter 4 and 5 still require the thermal evaporation of
one or two organic layers, all organic layers of the devices shown in chapter 6 were
deposited from solution.
In chapter 4, it has been shown that the efficiency in devices based on an
evaporated emissive layer of CBP:Ir(ppy)
3
can be improved by using solution-processed
hole-transport materials with higher ionization potentials and lower hole mobilities.
Furthermore, even higher efficiencies were achieved in a simplified 3-layer device
architecture where BCP was used as the hole-blocking and electron-transport material
simultaneously. A device structure with ITO/PVK/CBP:Ir(ppy)
3
/BCP/LiF/Al showed an
improved EQE of 21.2% (72 cd/A) at 100 cd/m
2
, which is the highest efficiency that has
been for a device with less than four organic layers. Furthermore, this device structure
requires the deposition of only two organic layers from the vapor phase.
In chapter 5, OLED devices with a solution-processed hole-transport layer and a
copolymer based emissive layer have been shown where the copolymers had
bis(carbazolyl)fluorene charge-transport groups and phosphorescent iridium complexes
in the side-chains. By incorporating phosphorescent complexes with different ligands, the
photoluminescence spectrum of the copolymer was tuned, and devices with four different
105
electroluminescence spectra were presented where the OLEDs based on copolymers with
orange/red emission showed higher efficiency than the devices with blue/green emission.
Furthermore, the orange copolymer that showed the highest efficiency in this
initial screening was further optimized by introducing systematic changes to the chemical
nature of the polymer, and the effects of the changes on the efficiencies of OLEDs were
measured. The molecular weight of the copolymer only displayed significant influence on
the efficiency of the device at high molecular weights (>70 kDa). More significant
changes in the efficiency could be observed when the loading level of the iridium group
was varied. The highest efficiencies were measured in OLEDs based on copolymers with
an iridium loading level around 5 mol%. Improvements were found when different
linkers were used between the side-chains and the polymer backbone. Introducing an
ester group into the linker between the hole-transport group and the polymer backbone
helped to increase the efficiency. Furthermore, the replacement of the short linkage
between the iridium complex and the polymer backbone with a longer carbon chain led to
an even larger improvement. Efficiencies of 4.90.4% at 100 cd/m
2
were measured in
optimized devices. This is the first study of all these effects on one copolymer system.
Moreover, there is only a handful of reports about OLEDs incorporating copolymers as
the emissive layers where higher efficiencies have been reported.
In chapter 6, using a photocrosslinkable hole-transport polymer and a
photocrosslinkable polymeric orange-emitting layer, solution-processed multilayer
OLEDs were fabricated. For these devices, newly synthesized electron-transport
polymers based on small molecules with good electron charge-transport properties were
used. Efficiencies of up to 2.0 0.2% were achieved. Unlike most other reports of
106
solution-processed multilayer OLEDs, this work presents a multilayer fabrication based
on a crosslinkable emissive layer. It represents the first implementation of electron-
transport polymers that are soluble in organic solvents whereas other electron-transport
polymers are water-soluble, which is unfavorable for the lifetime of the devices since
OLEDs are heavily sensitive to oxygen and water.
By photopatterning of the emissive layer, a white light source with tunable color
was fabricated. The color of the light source could be tuned from blue through the white
to orange. This is the first successful report of such a light source with solution-processed
emissive layers where the different colors were patterned directly without the
introduction of additional sacrificial layers.
Finally, in chapter 7, an equivalent-circuit model for organic diodes was proposed.
The model assumes that the injection of charges from an electrode into the organic
semiconductor is governed by thermionic emission. The drift current across the
semiconductor is then described by a voltage-dependent resistor representing space-
charge limited current (SCLC) in series with the injecting diode.
Applying this model to the experimental data of two single-layer diodes
consisting of either -NPD or a TPD-based polymer returned mobilities that are similar
to published results. Furthermore, the extracted values are consistent with the disorder
formalism of the mobility, which was confirmed by temperature dependent
measurements of the electrical characteristics.
For pentacene and C
60
diodes, the equivalent circuit had to be modified by
replacing the voltage-dependent resistor with a constant resistor to represent the ohmic
drift current that can be observed in such diodes due to the small bandgap of the two
107
materials. No information about the mobility values could be gained from this model
since the current within the considered voltage range did not reach an SCLC regime in
these devices with lower-bandgap materials.
Finally, effective Richardson constants and injection barrier energies could also
be extracted from temperature dependence measurements of the electrical characteristics
of the diodes. Both parameters were in good agreement with measured parameters in the
literature.
Combining these results, it has been shown that the proposed equivalent circuit is
a simple but reliable model to simulate organic single-layer diodes. The model is mainly
based on parameters that can be extracted from independent experiments, such as
mobility or UPS measurements. With the implementation of the equivalent circuit in
SPICE, the model can also be readily used in circuit optimizations. However, it has to be
noted that the proposed model at this stage does not fit well for high-efficiency OLEDs
comprised of multiple layers and that further refinements to the current model will be
required.

8.2 Outlook
Since devices with PVK as a hole-transport material resulted in the highest
efficiency for the devices that were shown in chapter 4, OLEDs with a solution-processed
emissive layer as shown in chapter 5 and 6 are potentially more efficient if a
crosslinkable hole-transport material with an ionization potential and a mobility
comparable to PVK were to be used. However, because of the wide bandgap of carbazole
compounds, they absorb in the same range as the cinnamate crosslinking group that was
108
used in this work for photocrosslinkable materials. Therefore, photocrosslinking is not
suitable for carbazole compounds since high UV exposure doses are necessary for
crosslinking (see chapter 6). Thus, different crosslinking methods, such as thermal
crosslinking, will have to be pursued.
While good efficiencies have been shown for copolymers that incorporated an
orange phosphorescent emitter, copolymers with a green and blue emitter yielded only
low efficiencies. It can be assumed that an optimization of the green and blue copolymers
similar to the optimization of the orange copolymer will lead to higher efficiencies for
those two colors, too. However, it is possible that the low efficiencies in the green and the
blue copolymers result from bad energy transfer from the host materials to the
phosphorescent emitter and different host monomers might have to be incorporated into
the copolymers to achieve higher efficiencies.
For high efficiency in OLEDs with solution-processed organic layers only,
photocrosslinking of the emissive copolymers is not suitable either because of the high
UV exposure doses that are necessary to crosslink the copolymer, similarly to the
carbazole compounds as hole-transport materials. Likewise, it is therefore necessary to
pursue other crosslinking methods although the advantage of easy patternability is lost.
Finally, the equivalent circuit that has been introduced for single-layer diodes will
have to be expanded for organic light-emitting diodes to include a circuit element that
represents the recombination in the diode. This additional element has a very significant
influence on the current flow in highly efficient devices where almost all electrons
recombine and the space-charge limited current across the device becomes negligible.

109
8.3 List of Publications
A. Haldi, B. Domercq, B. Kippelen, R. D. Hreha, J. Y. Cho, and S. R. Marder,
"Highly efficient green phosphorescent organic light-emitting diodes with simplified
device geometry," Applied Physics Letters, vol. 92, p. 253502, 2008.

A. Haldi, A. Kimyonok, B. Domercq, L. E. Hayden, S. C. Jones, S. R. Marder, M.
Weck, and B. Kippelen, "Optimization of orange-emitting electrophosphorescent
copolymers for organic light-emitting diodes," Advanced Functional Materials, 2008,
accepted.

A. Haldi, A. Sharma, W. J. Potscavage Jr., and B. Kippelen, "Equivalent circuit
model for organic single-layer diodes," Journal of Applied Physics, 2008, accepted.

A. Haldi, J. B. Kim, B. Domercq, A. P. Kulkarni, S. Barlow, A. P. Gifford, S. A.
Jenekhe, S. R. Marder, and B. Kippelen, "Fabrication of a blue M N pixel organic light-
emitting diode video display incorporating a thermally stable emitter," Journal of Display
Technology, 2008, submitted.

110
APPENDIX - DEVICE FABRICATION

ITO
Glass
1. Cut sheet of ITO on glass into squares of 1 1
2. Clean ITO i n ultrasonic bath:
deionized water with soap/deionized water/acetone/reagent alcohol
20 minutes each
3. Bake in vacuum oven at 70 degrees Celsius overnight
4. Deposit 200 nm of Sil icon Oxide (SiO
x
)
SiO
x
5. Clean in ultrasonic bath:
reagent alcohol/isopropanol
15 minutes each
6. Air plasma treatment of the ITO surface
using a Plasma-Preen II 862 by Plasmatic Systems, Inc.:
2 minutes, 50% power
7. Load i nto vacuum chamber or deposit fi rst layer from solution immediately

Figure A-1. Diagram of the substrate cleaning process.

111

1. Deposit organic semiconductor (OSC)
thermal evaporat ion in vacuum solut ion-processing
1. Spin-coat solution
2. Crosslink processed layer
3. Spin-coat subsequent layer 2. Deposit subsequent layer
4. Wipe off organic material for anode contact
5. Thermal evaporation of the metal cathode
Metal
OSC
OSC
SiO
Anode
contact
Cathode
contact

Figure A-2. Diagram of the OLED device fabrication process.

112

ITO
Glass
P3 (35 nm)
1. Pattern ITO 2. Spin-coat P3 and crosslink
Shadow mask
UV light
3. Spin-coat P11 and crosslink 4. Develop P11
Shadow mask
UV light
5. Spin-coat P3 and crosslink 6. Develop P3
P13 (35 nm)
7. Spin-coat P13
LiF/Al
8. Deposit LiF/Al
P11 (~17 nm)
P3 (35 nm)

Figure A-3. Diagram of the fabrication process for patterned solution-processed
multilayer OLEDs.

113
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PATTERNABLE ELECTROPHOSPHORESCENT ORGANIC

LIGHT-EMITTING DIODES WITH SOLUTION-PROCESSED

of a -molecular orbital can be defined in first

the luminous flux per watt:

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