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공학박사 학위논문
Exciplex based Organic Light-
Emitting Diodes with Theoretical
Efficiency and Long Operational
Lifetime
이론효율과 장수명을 갖는 엑시플렉스 기반의
유기발광다이오드
2018년 8월
서울대학교 대학원
재료공학 전공
신 현
i
Abstract
Exciplex based Organic Light-
Emitting Diodes with Theoretical
Efficiency and Long Operational
Lifetime
Hyun Shin
Department of Materials Science and Engineering
The Graduate School
Seoul National University
Display industry has been vastly expanding in the last few decades
because of demands for large area display, high quality of panel and
development of electronic devices adopting display. Currently most panels
adopt two types of display, one is the conventional liquid crystal display with
white light-emitting diode (LED) back-light, the other is organic light-emitting
diodes (OLEDs). Different from conventional display, OLEDs have potential
applying to next generation technology of display with flexible, transparent and
biocompatible characteristics because OLEDs have modest substrate
ii
dependency. Despite these promising application of OLEDs, still several
problems awaiting solution remain.
Major challenges in organic light-emitting diodes (OLEDs) are
classified into three categories: ⅰ) color quality, ⅱ) high efficiency and ⅲ)
long-term stability. These challenges should be improved for practical
usabilities in OLED industries.
Generally, color quality of OLEDs is appraised by electroluminesecent
(EL) spectrum. Shape of EL spectrum determines Commission Internationale
de L’Eclairage (CIE) coordinates affecting color gamut, temperature and
rendering of OLEDs. Basically, CIE coordinates are determined by intrinsic
emission color of emitter whose spectrum is determined by their own excited
state. Therefore, proper selection of the emitter is crucial for intrinsic color of
OLEDs. Efficiencys is also main index of evalution of OLEDs because it
corresponds with energy consumption of device straightly. Therefore, many
researchers working on organic semiconductor field, have been developing
efficient emitter, host and device structure with light extracting structures.
Despite of their effort, efficiency of blue OLEDs is still difficult compared to
other primary colors, red and green due to limitation of material selection and
design of structure result from its high energy over 2.6 eV. Therefore,
developing high energy materials for blue OLEDs is always present progressive
issue. Even though OLEDs have proper spectrum and high efficiency, device
cannot be utilized for practical use because operational lifetime of OLEDs
iii
should be long enough to use in daily life or industry. Over the last decades,
improving long-term stability of OLEDs has been studying. Nowadays, green,
red phosphorescent OLEDs (PhOLEDs) and blue fluorescent OLEDs
(FlOLEDs) are used in display panel due to their operational stability. However,
most stable OLEDs show low efficiency especially external quantum efficiency
(EQE) compared to theoretical limit of efficiency. In other words, achiving both
theoretical efficiency and long operational lifetime is the solution for the
ultimate conundrum of OLEDs.
This thesis considers aspects of two topics: (1) blue PhOLEDs with
efficiency of theoretical limit, and (2) OLED with long operational lifetime by
using stable materials with high bond dissociation energy.
In Chapter 2, the first report of exciplex-based blue PhOLEDs with
efficiency of theoretical limit is introduced. Due to large bandgap and high
triplet energy (T1) of blue phosphorescent emitter, exciplex forming co-host for
blue emission had been regarded as unattainable thing. However, using the
combination of carbazole containing high T1 hole transporting material (HTM)
and pridine/pyrimidine containing electron transporting material (ETM), novel
exciplex forming co-host was designed with the energy of 2.99 eV. Utilizing
new new exciplex system, blue PhOLED achieved 29.5% of EQE, which is
theoretical limit of EQE confirmed by optical simulation. Using both
experimental result and optical calculation, we showed that achievement of
exciplex for blue emission and theoretical limt of efficiency is possible.
iv
Expanding on the application of blue exciplex, we introduced that
fundamental limit of EQE can be increased utilizing low refractive index
materials. In Chapter 3, innate theoretical limit of EQE can be expanded using
low refractive index material containing exciplex forming co-host system. We
simulated maximum achievable EQE with different various refractive indices
of HTMs and ETMs for several emitting dipole orientations (Θ). For the case
of 1.8 of refractive index, general refractive index of organic thin film, the
theoretical maximum achievable EQE of blue OLEDs is around 30% under
condition of 100% of PLQY and isotropic Θ. However, citing our simulation,
low refractive index materials containing OLEDs can achieve over 60% of EQE
with horizontal Θ and 100% of PLQY of emitter. To verify the prediction, we
fabricated blue PhOLEDs using exciplex forming co-host possessing low
refractive index ETM, whose refractive index is ~0.1 lower than conventional
ETM in blue wavelength region. Fabricated device showed the maximum EQE
of 34.1% and power efficiency (PE) of 79.6 lm W-1, which are the highest value
among sky blue PhOLEDs.
Unlike the case of sky blue, the maximum efficiency of deep blue
OLEDs (CIE y < 0.2) is not high enough because of their low PLQY, Θ and
device structure hard to optimize. To solve this problem, we adopted novel deep
blue Ir-complex with high PLQY and Θ. In Chapter 4, highly efficient deep
blue PhOLEDs are introduced. We analyzed the effect of ancillary ligand on the
Θ. Even small difference of chemical structure of ancillary ligand, local
electron density can significantly be changed that the direction of transition
v
dipole moment (TDM) aligned horizontally to the plane of emitting surface. We
obtained theoretical EQE of 31.9% with deep blue emission due to 86% of Θ,
19% higher than isotropic orientation.
The last remaining pulling teeth of OLEDs, operational stability is
concerned in the next part. In Chapter 5, exciplex based red PhOLEDs
possessing both high efficiency and long-term stability is introduced. Exciplex
forming co-host is generally known for boosting the efficiency but exciplex
based OLEDs have suffered form the short operational lifetime. We showed
that the certain exciplex system constituting of materials stable in ionic states
has both high efficiency and long-term stability. Using new exciplex system,
red PhOLEDs achieved EQE of 34.1% and a long operational lifetime 2249 h
from 1000 cd m-2 to 900 cd m-2 (LT90).
In Chapter 6, we studied fundamental origin of long-term stability of
OLEDs. From a macro perspective, degradation occurs via two pathways. One
is external factor and the other is internal origin like chemical reaction including
dissociation and reunion. Essentially, if chemicals constituting OLEDs were not
dissociated in the operation, emitting characteristics of OLEDs could not be
changed. Base on this idea, we designed stable materials possessing high bond
dissociation energy (BDE) and T1 level. Most HTMs possessing high T1 contain
single C-N bond like phenyl-carbazole bond, which can be a bond cleavage site
in the molecules because most single C-N bonds have low BDE lower than 2.0
eV. To prohibit the bond cleavage and sustain high T1, we got rid of single C-N
vi
bond and adopted fused carbazole moiety. Using this methodology, homolysis
cannot be occurred by single bond cleavage in newly designed HTM. We
compared its properties with conventional material and finally obtained
elongated operational lifetime and enhanced luminance by change of HTM in
the OLEDs.
Keywords: Blue organic light-emitting diodes, exciplex, theoretical limit of
efficiency, low refractive index material, stable material, high bond dissociation
enenrgy
Student Number: 2013-20606
vii
Contents
Abstract .................................................................................. i
Contents ............................................................................... vii
List of Tables ........................................................................ xi
List of Figures ..................................................................... xii
Introduction ................................................... 1
1.1 Brief introduction to organic light-emitting diodes ...................... 1
1.2 Generation of OLEDs ................................................................... 4
1.3 Efficiency of OLEDs and its determining factors......................... 8
1.4 Degradation and stability issues of OLEDs ................................ 11
1.5 Outline of the thesis .................................................................... 15
Blue Phosphorescent Organic Light
Emitting Diodes using an Exciplex Forming Co-host with
the External Quantum Efficiency of Theoretical Limit . 18
2.1 Introduction ................................................................................. 18
2.2 Experimental ............................................................................... 20
2.3 Result and discussion .................................................................. 22
2.4 Conclusion .................................................................................. 33
viii
Blue Phosphorescent OLEDs with 34.1%
External Quantum Efficiency using a Low Refractive
Index Electron Transporting Material ............................ 34
3.1 Introduction ................................................................................. 34
3.2 Experimental ............................................................................... 37
3.2.1 Materials Characterization ................................................... 37
3.2.2 Device fabrication and characterization ............................... 38
3.2.3 Lambertian correction factor and calibration of EQE .......... 38
3.3 Result and discussion .................................................................. 40
3.4 Conclusion .................................................................................. 64
Controlling Horizontal Dipole Orientation
and Emission Spectrum of Ir complex by Chemical
Design of the Ligands for Efficient Deep-Blue Organic
Light-Emitting Diodes........................................................ 65
4.1 Introduction ................................................................................. 65
4.2 Experimental ............................................................................... 68
4.2.1 Device and sample fabrication ............................................. 68
4.2.2 Measurements of the devices and samples ........................... 68
4.2.3 The DFT calculation conditions ........................................... 69
ix
4.3 Design and density functional theory (DFT) calculation of deep-
blue emitting Ir-complexes ............................................................... 70
4.3 Result and discussion .................................................................. 75
4.3.1 Characterization of the Ir complexes ................................... 75
4.3.2 Photophysical properties of the Ir complexes in films ......... 78
4.3.3 Verification of photophysical properties of Ir complexes
through the fabrication of the OLEDs ........................................... 82
4.4 Conclusion .................................................................................. 88
Exciplex-forming Co-host-based Red
Phosphorescent Organic Light-emitting Diodes with Long
Operational Stability and High Efficiency ....................... 89
5.1 Introduction ................................................................................. 89
5.2 Experimental ............................................................................... 91
5.2.1 Device and sample fabrication ............................................. 91
5.2.2 Device characterization ........................................................ 91
5.3 Result and discussion .................................................................. 93
5.4 Conclusion ................................................................................ 106
Enhanced Long-Term Stability and
Maximum Luminance of Blue Orgainc Light-Emitting
x
Diode using Novel Hole Transporting Material without
Weak C-N Bond ................................................................ 107
6.1 Introduction ............................................................................... 107
6.2 Experimental ............................................................................. 109
6.2.1 Device and sample fabrication ........................................... 109
6.2.2 Device characterization ...................................................... 109
6.2.3 Density functional theory (DFT) calculation ..................... 110
6.3 Result and discussion ................................................................ 111
6.4 Conclusion ................................................................................ 128
Summary and outlook ............................... 129
Bibliography ..................................................................... 132
초 록 .................................................................................. 144
CURRICULUM VITAE .................................................. 150
Awards ............................................................................... 152
List of Publications ........................................................... 153
List of Presentations ......................................................... 155
List of Patents ................................................................... 162
xi
List of Tables
Table 3.1 Summary of the performances of the OLEDs ................................ 60
Table 3.2 Power dissipation into different modes at the maximum air mode
conditions ....................................................................................................... 63
Table 4.1 Optical and electric properties of the Ir-complexes. ....................... 77
Table 5.1 Summary of the performance of the red PhOLEDs. .................... 101
Table 6.1 Calculated bond dissociation energies of HTMs ........................... 112
Table 6.2 PLQY of the EML at various doping concentration of emitter. .... 118
xii
List of Figures
Figure 1.1 (a) Samsung Galaxy S9 employing curved OLED panel (Samsung
Electronics 2018). (b) OLED wave roof (LG Display 2018). (c) Flexible OLED
lighting (LG Display 2016). (d) Transparent display (Samsung Display 2016).
.......................................................................................................................... 3
Figure 1.2 Schematic illustration of the excited state processes (1st generation:
upper left, 2nd generation: upper middle, 3rd generation: upper right, 4rd
generation: bottom). ......................................................................................... 7
Figure 2.1 (a) Normalized PL spectra of mCP, B3PYMPM and
mCP:B3PYMPM co-deposited films. (b) Time resolved PL spectra of
mCP:B3PYMPM co-deposited film at various times after the excitation at 35
K. .................................................................................................................... 23
Figure 2.2 (a) Transient PL decay curve of the mCP:B3PYMPM co-doposited
film at the wavelength of 418 nm (b) Experimentally obtained angle-dependent
PL intensity of the p-polarized light emitted from a 30 nm-thick
mCP:B3PYMPM:FIrpic (10 wt%) film at 470 nm on the fused silica substrate
(circle) compared to simulated spectra (solid line). ....................................... 24
Figure 2.3 Schematic diagram of the device structure and energy levels of the
consisting layers. ............................................................................................ 26
Figure 2.4 (a) Current density-voltage-luminance characteristics of the OLEDs
according to the thickness of ETL. Inset: scatters = emission patterns of the EL
xiii
intensity, solid line = Lambertian emission pattern. (b) EQE and power
efficiency of the OLEDs. Inset is the normalized PL intensity of the
mCP:B3PYMPM:FIrpic (10 wt%) and EL intensity of ETL 55 nm device at
1,000 nit.......................................................................................................... 28
Figure 2.5 (a) Calculated EQEs as a function of the thickness of an ETL with
experimentally measured maximum EQEs (circles). Solid line for Θ = 0.76. A
singlet-triplet factor of 1 and perfect charge balance were used for the
simulation. (b) Contour plot of the predicted maximum EQEs as function of
ΦPL and Θ for blue phosphorescent OLEDs with a representative blue emission
spectrum, FIrpic, where perfect charge balance was assumed. The device
structure is shown in Figure 1d. The dashed line is the horizontal transition
dipole ratio of the emitter. .............................................................................. 30
Figure 3.1 Normalized PL intensity of mCBP:PO-T2T:10 wt% FIrpic thin film
(30 nm). .......................................................................................................... 41
Figure 3.2 (a)-(c) Contour plots of the simulated maximum achievable
outcoupling efficiencies of OLEDs with different refractive indices of HTMs
and ETMs for different emitting dipole orientations; (a) random orientation, (b)
fully horizontal orientation, and (c) 78% horizontal and 22% vertical
orientation corresponding to FIrpic in the mixed host as described in the text.
OLEDs with the structure ITO (70 nm)/HTL/EML (30 nm)/ETL/Al were used
for the simulation and the thicknesses of the HTL and EML were optimized to
maximize the EQE for the given refractive indices of HTL and ETL. Refractive
xiv
indices averaged in the sky-blue region for commonly used HTMs and ETMs
are displayed as dotted lines. .......................................................................... 42
Figure 3.3 Simulated outcoupling efficiency against the position of the
recombination zone in the emitting layer measured from the HTL - EML
interface. ......................................................................................................... 43
Figure 3.4 Ordinary refractive indices of (a) HTMs and (b) ETMs. .............. 45
Figure 3.5 Maximum achievable outcoupling efficiencies are plotted as a
function of emitting dipole orientation with the refractive indices of the organic
layers as a parameter. ..................................................................................... 46
Figure 3.6 (a) Molecular structures of EML constituting materials, a schematic
diagram of the device structure with HOMO and LUMO energy levels, and T1
diagram of the emitters and exciplex. (b) Normalized PL spectra of mCBP
(black line with squares), PO-T2T (red line with circles) and mCBP:PO-T2T
co-deposited film (blue line with triangles). .................................................. 49
Figure 3.7 Time resolved PL spectra of mCBP:PO-T2T films at low
temperatures (35 K) with various gate delay times from 10 ns to 10 µs. ....... 50
Figure 3.8 A plot of the angle-dependent PL intensity against the wavelength of
the p-polarized light emitted from mCBP:PO-T2T:FIrpic (10 wt%) film (30 nm)
at whole emitting wavelength of FIrpic. Experimental data (contour) are
compared to simulated data (dashed line). ..................................................... 51
xv
Figure 3.9 A schematic diagram of the setup for the measurement of angle-
dependent PL spectra. p- and s-polarizations are indicated by the blue and red
arrows, respectively. Horizontal and vertical transition dipole moments of the
emitters in the film align parallel and perpendicular to substrate (x-y plane),
respectively. Ratio of px and pz was calculated by fitting the p-polarized
emission pattern using an optical simulation and amount of py was assumed to
be the same as px. ........................................................................................... 52
Figure 3.10 A plot of the angle-dependent PL intensity of the p-polarized light
emitted from mCBP:PO-T2T:FIrpic (10 wt%) film (30 nm) at the maximum
peak wavelength of FIrpic (471 nm). Experimental data (scatter) are compared
to simulated data (black dashed line: Θ = 0.74, red short dashed line: Θ = 0.76,
black solid line: Θ = 0.78 and green dotted line: Θ = 0.80). Inset: enlarged
angle-dependent PL intensity around 55 degree. ........................................... 53
Figure 3.11 Comparison of the refractive indices of doped and undoped EML
(30 nm-thick film on a Si substrate). .............................................................. 56
Figure 3.12 (a) Current density-voltage-luminance (J-V-L) characteristics of the
devices with various thicknesses of the ETL. Inset shows the emission patterns
of the devices. b) EQEs and PEs of OLEDs as a function of luminance. ...... 57
Figure 3.13 Mode analysis of sky-blue OLEDs with PO-T2T (solid line) and
B3PYMPM (dashed line) as the ETL and experimental data are included for
comparison (PO-T2T: orange open circle, B3PYMPM: violet open circle). The
xvi
device structures described in the text (PO-T2T) and in Figure 3.14 are used for
the simulation and experiments. ..................................................................... 61
Figure 3.14 Schematic diagram of the device structure and energy levels of the
consisting layers of mCP:B3PYMPM co-host based OLED. ........................ 62
Figure 4.1 Chemical structures of Ir-1, 2 and 3. ............................................. 71
Figure 4.2 (a) Simulated ESP (left) with the range of energy and TDM with the
directions and angle to the long axis (right) of the Ir complexes. (b) Simulated
ESP of host molecules, TSPO1 (left) and mCBP (right). ............................... 72
Figure 4.3 Photoluminescence spectra of the Ir complexes in methylene
chloride (10−5 M). ........................................................................................... 76
Figure 4.4 Molar extinction coefficients of the Ir complexes in methylene
chloride (10−5 M) and the photoluminescence spectra of the host materials (30-
nm-thick thin films). ....................................................................................... 79
Figure 4.5 Normalized transient PL decay curves of EMLs (30-nm-thick
mCBP:TSPO1:1 wt% Ir complex deposited on a fused silica substrate). ...... 80
Figure 4.6 Angle-dependent PL intensity of the Ir complexes plotted against
their peak wavelength of p-polarized emission of mCBP:TSPO1:dopant (1 wt%)
film (30 nm). Measured intensities (scatters) are compared with simulated
values (line). ................................................................................................... 81
xvii
Figure 4.7 (a-c) Contour plot of the simulated maximum achievable EQE of
OLEDs with thickness of ETL and HTL; (a) Ir-1 doped OLED (b) Ir-2 doped
OLED (c) Ir-3 doped OLED. ......................................................................... 83
Figure 4.8 (a) Optimized device structure of blue PhOLEDs. (b) J-V-L curves
for each Ir complex-doped PhOLED. (c) EQE of the PhOLEDs as a function of
current density. [Line with squares: Ir-1 doped OLED, line with circles: Ir-2
doped OLED, line with triangles: Ir-3 doped OLED, Inserted photo: EL
emission of the devices at the luminance of 1 cd m-2.] .................................. 84
Figure 4.9 EL spectra of the blue PhOLEDs throughout the region of the driving
voltages. EL spectra of (a) Ir-1, (b) Ir-2, and (c) Ir-3 doped devices.............. 86
Figure 5.1 (a) Red-emitting PhOLED structure, energy levels of the organic
layers, molecular structures of the component materials, and triplet energy level
of the host and dopant molecules. (b) Molar absorption coefficient of the dopant
molecules, Ir(mphmq)2(tmd) (solid line), Ir(MDQ)2(acac) (dashed line),
normalized photoluminescence (PL) spectra of NPB (line with squares), PO-
T2T solution (line with circles), PO-T2T film (line with triangle), NPB:PO-T2T
co-deposited thin films (line with inverted triangles), NPB:PO-T2T:5 wt%
Ir(mphmq)2(tmd) (line with left-pointing triangles), and NPB:PO-T2T:5 wt%
Ir(MDQ)2(acac) (line with right-pointing triangles)....................................... 94
Figure 5.2 Magnified feature of molar extinction coefficients of the dopants.
Molar absorption coefficient of the dopant molecules, Ir(mphmq)2(tmd) (black
dashed line), Ir(MDQ)2(acac) (red dashed line), normalized photoluminescence
xviii
(PL) spectra of NPB (line with squares), PO-T2T solution (line with circles),
NPB:PO-T2T co-deposited thin films (line with triangles), NPB:PO-T2T:5
wt%. ............................................................................................................... 95
Figure 5.3 Transient PL spectra of the NPB:PO-T2T co-deposited film at room
temperature. The prompt (red, inset) and delayed (blue) lifetimes are fitted to
be 14.1 ns and 8.84 μs, respectively. .............................................................. 95
Figure 5.4 Angle-dependent PL intensities at peak wavelength of
Ir(mphmq)2(tmd) and Ir(MDQ)2(acac) in a 30 nm-thick NPB:PO-T2T matrix.
........................................................................................................................ 96
Figure 5.5 (a) Current densityvoltageluminance (JVL) characteristics of
the PhOLEDs. (b) EQEs of PhOLEDs as a function of luminance................ 98
Figure 5.6 PEs of the devices as a function of luminance. ............................. 99
Figure 5.7 Normalized electroluminescence (EL) decay curves of the PhOLEDs
as a function of operational time at an initial luminance (L0) of 1000 cd m-2. For
comparison, the EL decay curves of reported highly efficient red PhOLEDs are
shown. (Inset: magnified time region from 0–80 hours) .............................. 102
Figure 5.8 Cyclic voltammetry (CV) curves of PO-T2T in acetonitrile solution.
The concentration of the solution was 1 mM. .............................................. 103
Figure 6.1 (a) Chemical structure of EML constituting materials (b) Exctinction
coefficient of emitter and PL spectra of host materials. ................................ 113
xix
Figure 6.2 Triplet emission of the HTMs (in MC solvent, 10-5 M and 77 K).
....................................................................................................................... 115
Figure 6.3 Exciplex PL emission of meta-IBI:DBTTrz, para-IBI:DBTTrz and
mCP:DBTTrz. (30 nm-thick thin film) ......................................................... 115
Figure 6.4 Triplet energy diagram of host materials with their exciplexes. .. 116
Figure 6.5 PL spectra of EML at various doping concentration of emitter. .. 118
Figure 6.6 Emitting dipole orientation of each EML. ................................... 119
Figure 6.7 (a) Current density-Electric field characteristics of hole only devices
of HTMs (b) The hole mobilities of HTMs as a function of electricfield. ... 120
Figure 6.8 Chemical structures of host and charge transporting materials used
in Device 1 and 2. ......................................................................................... 123
Figure 6.9 Device structures of Device 1 and 2. Device 1 used meta-IBI for
HTM and p–type host. Device 2 used mCP for HTM and p–type host. ...... 124
Figure 6.10 (a) J-V-L characteristics of OLEDs (b) EQE of OLEDs as a function
of current density. ......................................................................................... 125
Figure 6.11 Operational lifetime of OLEDs. (Dashed line means LT95.) ..... 126
1
Introduction
1.1 Brief introduction to organic light-emitting diodes
This chaper is an overview on the historical and technological progress
of organic light-emitting diodes (OLEDs). Whole history of OLEDs is not
provided but rather recent achievements and important issues in organic
electroluminescent devices are reviewed.
Since organic electroluminescence (EL) was observed from single
crystal of anthracene by W. Helflich and W. G. Schneider, various organic
materials and device structures have been studied.1 For example, perylene
based materials and several polymers like poly vinylcarbazole and poly3-
methylthiophene were used of organic EL devices.2,3 One of the representative
EL device reported by C. W. Tang and S. A. VanSlyke.4 They used a double-
layer structure of organic thin film. The basic structure of OLEDs constituting
diode was also represented: anode/electron transporting material (ETM)/hole
transporting material (HTM)/cathode. At that time, this type of device structure
was a revolution. Because it was the first report of more than 1000 cd m-2 and
EQE of 1% in organic-based diodes. Nowadays, OLEDs show over 30% of
EQE or the large color gamut satisfying BT.2020, the latest parameter value for
ultra-high definition television system for production and international
programme exchange5–13
Apart from the beginning of the development of OLEDs, major display
2
and solid state lighting in the market are consisted of a liquid crystal display
(LCD), light-emitting diodes (LEDs), incandescent lamps and fluorescent tubes.
These conventional display and lighting still take possession of the largest
proportion of the market. However, conventional light sources have
fundamental limitation of their innate efficiency and color gamut. For example,
incandescent lamps, one of the traditional light source has about 15 lm W-2 and
about 73 lm W-2 for compact fluorescent light bulbs.14 Those power efficiencies
(PE) are applicable for daily use. But as social interest in energy reduction
increases, need of more efficient light source has been increased. For display,
since the demand for large area display with high color reproduction range was
increased, researches on OLEDs have been conducted naturally in various ways.
Fundamentally, different from conventional display like a LCD, white LED
backlight is needless in OLEDs containing display because the light of OLEDs
comes from self radiation. Due to absence of backlight, OLEDs can realize pure
black corresponding to high color reproduction range and be packaged in thin
exterior. Moreover, low susbstrate dependency gives OLEDs flexibility and
tranparancy, which is important property for future application.15,16 Figure 1.1
shows the commercial products and applications using OLEDs such as a smart
phone adopting curved OLEDs, wave roof with extremely thin outfit, warm
white OLED lighting and transparent display applied in large area television.
As with these examples, the number of products using OLEDs will increase
more and more.
3
Figure 1.1 (a) Samsung Galaxy S9 employing curved OLED panel (Samsung
Electronics 2018). (b) OLED wave roof (LG Display 2018). (c) Flexible OLED
lighting (LG Display 2016). (d) Transparent display (Samsung Display 2016).
4
1.2 Generation of OLEDs
Due to the innate advantages of OLEDs compared to the conventional
light sources, there have been many efforts to improve the performance of
OLEDs like color quality, efficiency and long-term stability. Especially,
external quantum efficiency (EQE) has been increased immmersly over the last
few years owing to development of efficient system.5,9,17–30
At the initial stage, light-emitting layer (EML) of OLEDs was consisted
of a single sort of molecule. Since EL was observed from single crystal of
anthracene, various organic materials have been researched for its EL. One of
the representative EL device reported by C. W. Tang and S. A. VanSlyke
adopted a double layer composed by HTM and ETM.4 However, their EQE was
very low ~1% to use, many researchers have studied to enhance the efficiency
of OLEDs and doped EML system appeared.31,32 Unlike traditional EML
consisting single small molecule, two materials are used for EML. One is the
matrix, so called host and the other is emitter, fluorescent dopant. Doped EML
gives EML low concentration of emitter resulting in low concentration
quenching. At present, we refer to OLEDs based on such fluorescent OLEDs
as the first generation.32
Since advent of the first generation of OLEDs, researchers have begun
to study how to increase the internal quantum efficiency (IQE). In other words,
the trend of research has shifted to studying how to use the wasted triplet, whose
portion is 75%. The great breakthough enhancing order of efficiency was
5
development of triplet emitter. In the past decade, organo-metallic compounds
like iridium complex have become highly attractive because of its ability of
triplet harvestment.33–35 For conventional OLEDs, fluorescent emitter cannot
utilize triplet excitons, which are wasted to non-radiative processes. However,
triplet emitter can utilize both singlet and triplet state of excitons, which
enhance the efficiency of OLEDs immensely. Compared to the singlet emitter,
triplet emitter can obtain four times higher maximum efficiency because
organo-metallic compound contains heavy metal like iridirum or platinum,
which enables phosphorescent emission through the transition from the lowest
excited electronic state to the singlet ground state by spin-orbit coupling
(SOC).33 This kind of phosphorescent emitters are so called second generation
of OLEDs.
Meanwhile, other triplet harvesting methods also studied. Several
pioneers wanted to make triplet emitter without heavy metal because most
heavy metals are classified as rare earth metal. Since the cost of rare earth
materials is very high, a plan to overcome the problem has been studied.
Nowadays, excited-state intramolecular proton transfer (ESIPT) or thermally
activated delayed fluorescence (TADF), so called third generation, is the most
popular concept utilizing both singlet and triplet excitons without heavy
metal.29,36 Although TADF has the same characteristics as conventional
fluorescent OLEDs in that it exhibits fluorescence, it is based on the small
energy difference between triplet and singlet levels (∆EST) to convert the triplet
into singlet thorugh obtaining external thermal energy. To achieve small ∆EST,
6
is separating highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) of TADF emitter. However, there is a
trade-off between separation of orbital and HOMO-LUMO transition. In other
words, proper design of TADF emitter is difficult because a small ∆EST reduces
oscillator strength harmful to photoluminsescence quantum yield
(PLQY).29,37,38
Very recently, exciplex based hybrid EMLs using both conventional
fluorescent emitter and triplet harvesting emitter have been introduced.394041
The hybrid EMLs are classified into two types according to triplet sensitizer.
There are two types of sensitizers, one is organo-metallic compound and the
other is TADF sensitizer. For organo-metalic compound, heavy metal induces
large spin-orbit interaction causing spin-mixing.39 For TADF sensitizer, triplet
state can be upconverted to singlet, which can be transferred to singlet excited
state of conventional fluorescent dopant.41 Consequently, adavatages of the
exciplex, high ratio of radiative excitons and fluorescent emission are combined
into a single EML and OLEDs can achieve high EQE using conventional
fluorescent emitter with improved stability. These sort of hybrid OLEDs are so-
called the fourth generation OLEDs.
Schematic diagram of excited state processes is described in Figure 1.2.
In case of the fourth generation, an example in which a phosphorescent emitter
is used as a sensitizer in an exciplex host.
7
S1
S0
T1
1st Generation(25% upper limit)
S1
S0
T1
2nd Generation
(organo-metallic compound)
R
NR
ISC
R
S1
S0
T1
3rd Generation (TADF)
R
NR
Fluorescence
Phosphorescence
RISC
Delayed
fluorescence
S1
S0
T1
Exciplex
R
NR
ISC
RISC
S1
S0
T1
Sensitizer
ISC
NR
NR
ISC
NR
R NR
S1
S0
T1
Fluorescent emitter
Fӧrster energy transfer
Dexter energy transfer
Radiative Decay
Non-radiative Decay4rd Generation (Hybrid)
Figure 1.2 Schematic illustration of the excited state processes (1st generation: upper left,
2nd generation: upper middle, 3rd generation: upper right, 4rd generation: bottom).
8
1.3 Efficiency of OLEDs and its determining factors
Basically, due to the development of organo-metallic compound and
TADF emitter, the room of the maximum achievable efficiency of OLEDs has
been increased. However, for actual device, high efficiencies have rarely been
reported because reduction of optical and electrical loss of OLEDs is hard to be
fulfilled. To prevent these losses, it is necessary to understand that the factors
determine EQE.
The number of photons per injected electrons in OLEDs is the definition
of the EQE. The specific expression of EQE is decribed by followed equation.5
int / ( , ) ( , )EQE out S T eff PL outq (1.1)
Fundamentally, radiative processes can be divided into two parts, one is internal
process of organic materials and the other is light outcoupling process.
Therefore, EQE is expressed as the product of
int , internal quantum
efficiency and out , outcoupling efficiency. In detail,
int is consisted of
three parts. is the charge balance factor, which is unity when the number of
recombinating electrons and holes are matched by the ratio of 1:1. /S T is the
fraction of radiative excitons; i.e., singlet-triplet factor. /S T is equal to 0.25
for pure fluorescence and 1 for phosphorescent emitter because phosphorescent
emitter can utilize both singlet and triplet excitons through spin-orbit coupling
process by heavy metal. ( , )eff PLq is the effective quantum yield, which is
a function of PLQY and geometrical factor, , representing recombination
9
zone. ( , )out is the outcoupling efficiency, which is a function of Θ and
geometrical factor. In other words, when the emitter has preferred orientation
horizontally, outcoupled light is enhanced. Because, vertical dipoles are hard to
be extracted to the direction of emitting plane.42 Fortunately, these points to
consider are manipulated by structural design of OLEDs and synthesis of new
materials.
Host is one of the important part to determine efficiency of OLEDs
because it has multi-roles in the EML. The type and configuration of the host
affect transporting property of each charge carrier, energy transfer to dopant
and regulation of the concentration quenching of the emitter. In this view points,
several new concepts for well charge balanced system have been introduced.
One of the key system is excited charge transfer complex (exciplex), which
contributes well charge balanced structure of OLEDs.25 Previously, exciplex
was regarded as a harmful factor in OLEDs because exciplex formed at the
organic interface acts as an exciton quencher, which seriously reduces
efficiency.43–45 However, the sterotype was changed. Since several efforts
utilizing exciplex as a host for triplet harvesting emitters like iridium complex
were reported, many highly efficient phosphorescent OLEDs (PhOLEDs) have
been developed.6,8,21,23,25,46–48 Exciplex utilizing OLEDs have almost no
injection barrier from charge transporting layer to light-emitting layer (EML)
because neighbor layers of EML are consisted of each p–type and n–type host.
Therefore, hole and electron can be injected easily into the EML. Moreover,
exciplex forming co-host has bipolar character, which makes balanced amount
10
of hole and electron. These advantages grant exciplex based OLEDs low
electrical loss and high efficiency.
Another main factors determining EQE are optical properties of emitter
including photoluminescent quantum yield (PLQY) and horizontal ratio of
emitting dipole (Θ).5 In the recent studies, many researches have reported the
design of emitter possessing horizontally oriented emitting dipoles.20–22,49–56
Using chemical modification of ligands and attachment of small alkyl group in
the ligand, emitters obtain preferred orientation horizontally. Due to high Θ,
out-coupling efficiency of OLEDs increased dramatically and theoretical limit
of EQE was also renewed.
Several reports focused on not the emitter but the host and transporting
materials. Even though same emitter is adopted, EQE of OLEDs can be
changed by refractive index of the constituting materials.6,57 Understandably,
low refractive index of the organic layer reduces confined lays by total
reflection. However, refractive indices of general organic thin films formed by
thermal vacuum evaporation are not too different each other. Of course, several
conducting polymer showed low refractive index around 1.5 (like PEDOT:PSS)
but it is very rare in small molecules. Additionally, low refractive index
accompanies with low electrical conductivity because of its hallow structure
hinders electrical hopping of charge carrier in the bulk organic solid. Therefore,
study on achiving both high electrical conductivity and low refractive index of
materials is still on going.
11
1.4 Degradation and stability issues of OLEDs
Stability is one of the main issue in OLEDs. There are lots of works
reporting high efficiency and color quality but still publication referring long-
term stability, especially long operational lifetime is very rare. OLED panel is
already shown in the market, but the present operational lifetime is very short
compared to the conventional display like LED. Certainly, recent commercial
devices show long operational lifetime but the color is limited to red and green.
Because of high energy level of the blue emission, blue OLEDs is still suffering
design of the proper device structure and selection of stable materials.
Meanwhile, discussion of origin of long-term stability is not active. So far, there
is no concrete description of the origin of degradation. There are so many
papers reporting degradation mechanism but very few discussion goes through
center of the conundrum.58–68
From a macroscopic perspective, degradation of OLEDs can be
classified into two parts. One is the intrinsic factor and the other is extrinsic
factor. Both intrinsic and extrinsic factors affect significantly on the stability of
the devices. However, control of extrinsic factors is very difficult in the
academia compared to the industry. In other words, subtle change of the
extrinsic factors like a particle, temperature, moisture, oxygen, out gassing,
condition of encapsulation and quality of the vacuum state causes dark spot,
impurities in organic layers and oxidation or chemical reaction in the device
originating low operational stability of OLEDs.58 In addition, regulating
12
extrinsic factors is a very expensive way but necessary for practical use. For
this reason, the vast majority of academic researches on operational stability
focus on intrinsic factors.
Different from external mechanism of degradation, most intrinsic factors
are not affected by environmental parameters. Most intrinsic mechanisms have
reported the effect of charge balance, accumulation at the heterojuction or
interfaces including recombination zone in the EML.
In the early stage of the study, drift, diffusion and acculmulation of
mobile ion and charge were investigated to understand degradation process.
Using depth profiling by mass spectroscopy analysis, materials constituting the
electrode can be diffused into the organic layers.69,70 For example,
electromigration of the mobile ions from Ca and ITO electrode was reported in
OLEDs by H. Vestwever et al in 1997.71 Mobile ions change internal energy
structure of OLEDs accompanying decay of the luminance and I-V
characteristics of OLEDs. These kind of researches about electromigration had
been developed to accumulation of charge or quencher. Basically, the difference
of mobility between charge transporting materials and EML is very large in
OLEDs. Understandably, general bulk hetero structure has both electron
donating and accepting materials therefore, hoping rate of each carrier
decreases. This phenomenon makes charge accumulation at the interface at the
EML.72,73 Charge density of charge accumulated interface is very high, that give
the polaron interaction with other polaron or excitons. These interactions cause
13
annihilation, which makes high energy deteriorating chemical stability. High
energy can be a driving force of chemical dissociation or reaction. In addition,
excitons containing annihilation reduces the efficiency by itself.74,75 Another
method to understand charge induced degradation is confirmation of ionic
statbility.76 In other words, comparison of PL between pristine and aged single
carrier device have been perfomed. Charges in the OLEDs exist in polaron
form.77 If the neutral state material is converted to an unstable ionic state, their
chemical dissociation will be accelerated, which will accelerate the
deterioration of the devices.
The electrochemical or photochemical reaction inside the device may
also cause degradation. In the early research, H. Aziz and G. Xu reported a
novel degradation mechanism describing the electrochemical reaction on
interfaces of both electron and hole injecting electrodes.78–80 They found out the
reduced indium (In) concentration of transparent anode when the device is aged.
Similary, irregular structures were found at the Al cathode suggesting certain
chemical or electrochemical reactions at the organic/electrode interfaces. Other
electrochemical reactions that occur at electrodes by moisture and oxygen have
also been reported. Most of the reactions change the morphologies, electrical
and optical properties of electrodes that downgrades the performance of OLEDs.
Several groups have reported the role of bond dissociation energy (BDE)
in degradation of OLEDs.81–84 Using density functional theory (DFT)
calculation, BDE can be calculated, that can indirectly predict the stability of
14
organic materials. Achilles Heels of organic materials are weak bonds like C-P
and C-N bonds. Some reports assigning the dissociation of C-P and C-N bond
had introduced. Using the laser desorption ionization (LDI) mass spectra (MS)
dissociated chemical species can be observed by assignment of the mass. The
common thing of the dissociated species is containing weak bonds but concrete
mechanism and process of dissociation is not fully discovered. Only a few
plausible models or reaction paths have reported.73,85–87
To date, various cuases for OLEDs degradation have been identified and
many hypotheses and verifications have been made. However, the approach to
sovling fundamental problem of operational stability is still very rare, and
research on this topic is still active in the academica and industry.
15
1.5 Outline of the thesis
In this thesis, we describe the OLEDs achieving theoretical limit of
efficiency using an exciplex forming co-host. Especially, we focused on the
efficiency of blue PhOLEDs because the low efficiency of blue PhOLEDs is an
obstacle to the industrialization of OLEDs, which is necessary to be solved.
The first exciplex forming co-host for blue phosphorescent emitter is
developed. Using that exciplex system, we desgined simple device structure
with theoretical limit of EQE with negligible electrical loss. The effectiveness
of the efficiency was also confirmed by optical simulation. The prediction
shows the maximum EQE of blue PhOLEDs can be enhanced over 40% when
the EDO and PLQY are unity (Chapter 2).
Although we achieved the theoretical limit of efficiency of the blue
PhOLEDs, the prediction and efficiency were not universal because it is for the
certain system. Therefore, we have attempted to estimate the general efficiency
and to improve the fundamental efficiency of blue PhOLEDs. We proceeded to
calculate the general efficiency prediction of the blue PhOLEDs with the
refractive index as the main parameter. According to the results, blue PhOLEDs
can achieve higher than EQE of 60% when the perfect-horizontal EDO and
PLQY=1. To demonstrate the validity of the calculation, we developed a novel
exciplex using low refractive index material was introduced. Through an
exciplex based on a material with a low refractive index, we have developed a
blue PhOLEDs with an EQE of over 34% (Chapter 3).
16
As mentioned previously, studies on high efficiency blue PhOLEDs have
been carried out, but it has been difficult to achieve high efficiency in the deep
blue emitting OLEDs due to the high energy level and large bandgap of
constituting materials. To solve this problem, we have developed a simple
device structure with a high triplet energy and a large badgap of HTM and ETM
pair. In addition, a new phosphorescent emitter with 86% EDO was used to
develp a deep blue OLEDs with a CIE y of less than 0.2 with a high EQE of
more than 31%. We explained through the DFT calculation that deep blue
emitters can achieve a large horizontal orientation rate with minor modification
of chemical structure of ancillary ligand (Chapter 4).
Among the major problems of OLEDs, low efficiency of blue OLEDs
has reached adequate level of resolution, so we have been studying the
remaining operational stability, the core problem. Until recently, exciplex has
been evaluated as a structure suitable for obtaining high efficiency, but it has
not exhibited good performance in terms of operational lifetime. However,
since the reported exciplexes are often composed of specific substance groups,
it is not yet confirmed that all exciplexes have a detrimental effect on the
operational lifetime. Therefore, it is possible that exciplexes composed of stable
pair of material can simultaneously achieve high efficiency and long
operational lifetime. In this regard, we developed a new exciplex using a stable
electron donor and acceptor pair, and developed a red PhOLEDs with a high
EQE of 34.1% and an operational lifetime, LT90 of 2243 hours (Chapter 5).
17
In addition to the red color, it is necessary to study the operational
lifetime of the blue OLEDs. However, unlike red, the pool of materials is so
narrow that it crucial to design new materials and stable device structure or
concept. We note that the nature of degradation is a chemical change in the
material that makes up the deivce. We have studied the chemical structure
which can prevent the bond dissociation at the same time while maintaining the
charge transfer characteristics of the materials. Especially, new HTMs are
designed without using carbazole moiety commonly used as the HTM. Newly
designed HTM has both hole transporting property and chemical stability over
the existing carbazole based HTMs. Using this material, we proposed a novel
device structure that does not have weak bond, and obtained a luminance over
50000 cd m-2 and an operational lifetime of more than 10 times compared with
the carbazole based HTM used device (Chapter 6).
In the last chapter, the contents of thesis will be summarized and a brief
discussion about the prospect of OLEDs research will be followed.
18
Blue Phosphorescent Organic Light
Emitting Diodes using an Exciplex Forming Co-
host with the External Quantum Efficiency of
Theoretical Limit
2.1 Introduction
Blue phosphorescent organic light-emitting diodes (OLEDs) are the
most difficult to achieve high efficiency among three primary colors due to it’s
limitation on the selection of materials satisfying the requirements of host
materials and neighboring charge transporting materials with higher triplet
energy than that of the blue emitter for efficient triplet confinement within
emitter. In addition, the out-coupling efficiency of blue emission is smaller than
those of other primary colors because the shorter wavelength of the blue
emission increases the waveguide mode in transparent conducting oxide and
organic layers.88
Bipolar materials possessing high triplet energy have been used as the
host materials for blue phosphorescent OLEDs to achieve electron and hole
balance in the light-emiiting layer (EML). There are two approaches to realize
bipolar hosts. One approach is to synthesize a new material consisting of a hole
transporting unit and an electron transporting unit.26,89–102 The other approach is
to use a co-host composed of a hole transporting material (HTM) and an
19
electron transporting material (ETM).103–105 The latter approach has does not
require a new synthesis. Furthermore, hole and electron mobilities in the EML
can be tuned by adjusting the ratio of HTM to ETM in the co-host. From this
point of view, exciplex forming co-hosts are particularly interesting because
they exhibited high efficiencies, low driving voltages and low efficiency roll-
offs by using a simple device structure.5,8,24,25,51,106,107 Unfortunately, highly
efficient blue emitting phosphorescent OLEDs employing exciplex forming
hosts have not been reported yet even though green, orange and red OLEDs
have been reported with external quantum efficiency (EQEs) over 30% using
exciplex forming co-hosts.
20
2.2 Experimental
OLEDs were fabricated by thermal deposition onto cleaned glass
substrates pre-coated with 70 nm-thick indium tin oxide (ITO). Before thermal
deposition of organic layer, the ITO substrates were exposed to a UV-ozone
flux for 10 min, following degreasing in acetone and isopropyl alcohol. PL
samples were fabricated by thermal deposition onto fused silica substrates.
Layers were deposited at a base pressure of <5 ×10-7 Torr. PL spectra of
organic films were obtained by using an spectrofluorometor (Photon
Technology International, Inc.). A monochromator-attached pulsed xenon flash
(300 nm and 325 nm) was used as an excitation light source and a
monochromator (Acton Research Co.) was used as an optical detection system.
For time resolved PL and transient PL measurements, a pulsed Nd:YAG laser
(355 nm, Continuum) was used as the excitation light source and an intensified
charge-coupled device (ICCD) was used as an optical detection system. Low-
temperature PL spectra were measured in a cryostat (SHI Cryogenics, Inc.).
Experimental setup of angle-dependent PL measurement was composed of a
motorized rotation stage, a fused silica-based half cylindrical lens with a sample
holder, a dichroic mirror to filter the excitation beam, a polarizer to classify the
polarity of the emitted light, a fiber-guided detector combined with a
monochromator and a PMT. A continuous-wave He/Cd laser (325 nm,
Mellisgriots Co.) was used as the excitation source and incident angle was 45°.
p-polarized emitted light at 473 nm corresponding to the peak wavelength of
21
the PL spectrum of FIrpic was detected.
Current density, luminance and EL spectra were measured using a
Keithley 2400 programmable source meter and SpectraScan PR650 (Photo
Research) radiometer. The EQE and power efficiency of the OLEDs were
calculated from the current density, the luminance which is measured by CS100
(Minolta). The EQE and power efficiency of the OLEDs were calculated from
current density, luminance, EL spectra, and emission pattern of angle-
dependent EL intensity. The emission patterns of angle-dependent EL were
measured using the Keithley 2400 programmable source meter, a rotating stage,
and an Ocean Optics S2000 fiber optic spectrometer.
22
2.3 Result and discussion
In this work, we report a high efficiency blue phosphorescent OLED
approaching the theoretical limit using an exciplex forming co-host doped with
Iridium(III)bis[(4,6-difluorophenyl)-pyridinato-N,C2′]picolinate (FIrpic). The
OLED showed a maximum EQE of 29.5%, which agrees very well with the
theoretical prediction based on the measured photoluminescent quantum yield
(ΦPL) and orientation of the transition dipole moments of FIrpic under the
assumption of negligible electrical loss. The OLED also displayed a low driving
voltage of 3 V and low efficiency roll-off.
N,N’-dicarbazolyl-3,5-benzene (mCP), bis-4,6-(3,5-di-3-
pyridylphenyl)-2-methylpyrimi-dine (B3PYMPM) were selected as the
exciplex forming co-host and FIrpic as the blue dopant. Figure 2.1a shows the
normalized PL spectra of the mCP, B3PYMPM and mCP:B3PYMPM co-
deposited films. The molar ratio of mCP to B3PYMPM in the co-deposited film
was 1:1. The energy of the mCP:B3PYMPM emission peak was calculated to
be 2.97 eV which energy is close to the gap between the highest occupied
molecular orbital (HOMO) level of mCP and the lowest unoccupied molecular
orbital (LUMO) level of B3PYMPM and red shifted spectrum of the
mCP:B3PYMPM co-deposited film from those of mCP and B3PYMPM
indicates that mCP and B3PYMPM molecules effectively form an exciplex in
23
Figure 2.1 (a) Normalized PL spectra of mCP, B3PYMPM and
mCP:B3PYMPM co-deposited films. (b) Time resolved PL spectra of
mCP:B3PYMPM co-deposited film at various times after the excitation at 35
K.
350 400 450 500 5500.0
0.2
0.4
0.6
0.8
1.0
1.2
373 nm350 nm 400 nm
Norm
aliz
ed P
L (
a.u
.)
Wavelength (nm)
mCP:B3PYMPM
mCP
B3PYMPM
418 nm
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
1.2
10 ns
5 μs
1 ms
10 ms
Nom
aliz
ed P
L (
a.u
.)
Wavelength (nm)
462.5 nm
2.68 eV
(a)
(b)
24
Figure 2.2 (a) Transient PL decay curve of the mCP:B3PYMPM co-doposited
film at the wavelength of 418 nm (b) Experimentally obtained angle-dependent
PL intensity of the p-polarized light emitted from a 30 nm-thick
mCP:B3PYMPM:FIrpic (10 wt%) film at 470 nm on the fused silica substrate
(circle) compared to simulated spectra (solid line).
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
Norm
aliz
ed inte
nsity (
a.u
.)
Angle (degree)
Measurement
FIrpic in mCP:B3PYMPM
Simulation
Fitted P(H):P(V) = 76:24
0.0 0.3 0.6 0.9 1.2 1.510
-4
10-3
10-2
10-1
100
Norm
aliz
ed I
nte
nsity (
a.u
.)
Time (s)
mCP:B3PYMPM (50 nm)
(a)
(b)
25
the excited state. Figure 2.1b shows the normalized time resolved PL spectra of
mCP:B3PYMPM film at different delay times at 35 K. The exciplex PL
emission around 415 nm was observed at the entire delay time up to 10 ms,
indicating that the delayed fluorescence was facilitated by exciplex
formation.108,109 The emission peaks around 462 and 500 nm were developed at
the delay time of 10 ms. These peaks are the same as the triplet emission from
B3PYMPM film at 4.2 K.110 Phosphorescence from B3PYMPM in the co-
deposited film was also detected because of its lower triplet energy level than
that of the exciplex and mCP. The transient PL decay curve of the
mCP:B3PYMPM film at the wavelngth of 418 nm (Figure 2.2a) showed a long
delayed component with the lifetime of ~0.5 s following the prompt decay
with the lifetime of ~20 ns. The long delayed component from the transient PL
indicates that the reverse intersystem crossing is efficient in this system.
The orientation of the transition dipole moments of FIrpic in the co-host
matrix was determined from the analysis of the angle-dependent PL spectrum
of the film5,50 because the dipole orientation influences the EQE of OLEDs and
the charateristics of organic semiconductors.111–113 Figure 2.2b shows the
experimental data and the simulation results of the angle-dependent PL
intensity of the p-polarized light emitted from a 30 nm-thick FIrpic (10 wt%)
doped mCP:B3PYMPM film at 470 nm corresponding to the PL maximum of
FIrpic. The experimental data are well fitted by a horizontal-to-vertical dipole
ratio of 0.76:0.24, indicating that the transition dipole moments of FIrpic
molecules have a preferred orientation in horizontal direction. Uncertainty of
26
Figure 2.3 Schematic diagram of the device structure and energy levels of the
consisting layers.
mC
P:
4 w
t% R
eO
3
B3
PY
MP
M:
4 w
t% R
b2C
O3
B3
PY
MP
M
mC
Pm
CP
:B3P
YM
PM
:
10 w
t% F
Irp
ic
ITO
LiF/Al
-2.4
-6.1
-3.1
-6.0
-3.2
-6.8
70 45 15 15 20 X 0.7/100
Unit: nm
27
this orientation measurement is less than 0.02.
A schematic diagram of the device structure and the energy levels of the
consisting layers are shown in Figure 2.3. The device has a simple structure
consisting of one HTM and one ETM. mCP and B3PYMPM were selected as
for the HTM and the ETM, respectively and also used as an exciplex forming
co-host in EML because they have higher triplet energy than FIrpic. ReO3
doped mCP and Rb2CO3 doped B3PYMPM were used as the hole and electron
injection layers, respectively.114–120 The doping concentrations were
experimentally optimized to 4 wt% in charge injection layers. The device
structure is as followed: ITO (70 nm) / mCP : ReO3 (45 nm, 4 wt%) / mCP (15
nm) / mCP : B3PYMPM : FIrpic (15 nm, 10 wt%) / B3PYMPM (15 nm) /
B3PYMPM : Rb2CO3 (x nm, 4 wt%) / LiF (0.7 nm) / Al (100 nm). The molar
ratio of mCP to B3PYMPM in the EML was 1:1. The thickness of n-doped
electron transporting layer (ETL) was changed from 30 nm to 60 nm at an
interval of 10 nm. The device was designed to confine electrons and holes in
the EML with very high injection barriers from the EML to the hole transporting
layer (HTL) (0.8 eV) for electrons and the EML to the ETL (0.67 eV) for holes.
Andthere are no injection barriers from the charge transporting layers to the
EML. It was also designed to confine the excitons on the dopant molecules
because the triplet energies of the HTM (mCP, T1=2.9 eV), ETM (B3PYMPM,
T1=2.68 eV) and the exciplex (T1=2.97 eV) are higher than that of the FIrpic
(T1=2.62 eV). Figure 2.4a shows the current density-voltage-luminance (J-V-
L) characteristics with different thicknesses of the n-doped ETL. The J-V
28
Figure 2.4 (a) Current density-voltage-luminance characteristics of the OLEDs
according to the thickness of ETL. Inset: scatters = emission patterns of the EL
intensity, solid line = Lambertian emission pattern. (b) EQE and power
efficiency of the OLEDs. Inset is the normalized PL intensity of the
mCP:B3PYMPM:FIrpic (10 wt%) and EL intensity of ETL 55 nm device at
1,000 nit.
0 1 2 3 4 5 6 710
-6
10-5
10-4
10-3
10-2
10-1
100
101
102
90
75
60
45
3015 0
No
rmali
zed
In
ten
sit
y (
a.u
)
1
0Emissioin angle (deg)C
urr
en
t d
en
sity (
mA
/cm
2)
Voltage (V)
ETL 75 nm
ETL 65 nm
ETL 55 nm
ETL 45 nm
10-1
100
101
102
103
104
105
Lu
min
an
ce (
cd
/m2)
1 10 100 1000 100000
5
10
15
20
25
30
35
40
450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0
No
rmali
zed
inte
nsit
y (
a.u
.)
Wavelength (nm)
PL
EL (ETL 55nm)
EQ
E (
%)
Luminance (cd/m2)
ETL 75 nm ETL 65 nm
ETL 55 nm ETL 45 nm
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iency (
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)
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(b)
29
characteristics of all the devices are almost the same and the turn-on voltages
of the OLEDs were 3.0 V for all the devices. The turn-on voltage is a little
higher than the photon energy of the emitted light devided by the unit charge,
indicating that some over potential is required for hole injection due to the low
HOMO level of mCP. The driving voltages of the OLEDs were about 4.8~5.0
V and 5.4~5.75 V at 1,000 cd m-2 and 5,000 cd m-2, respectively. The highest
luminance was obtained when the thickness of the ETL was 55 nm. The inset
of Figure 2.4a shows viewing angle dependent emission intensity of the OLEDs.
Increasing the ETL thickness increased the portion of non-normal emission.
The emission patterns of the OLEDs with the ETL thicker than 65 nm showed
super Lambertian distribution and others were narrower than Lambertian
distribution.
Figure 2.4b shows the calibrated EQEs and power efficiencies of the
OLEDs using the emission patterns in Figure 2.2b. The inset of Figure 2.4b
shows the normalized PL intensity of the EML and the electroluminescence
(EL) intensity of the OLED with the 55 nm thick ETL at 1,000 cd m-2. The EL
spectrum showed higher red emission than the PL spectrum due to the cavity
effect of the OLED. The maximum EQE of 29.5% and the maximum current
efficiency of 62.2 cd A−1 were obtained with 55 nm thick ETL. Because of the
high EQE and low driving voltage, OLED also gives high power efficiency of
55.4 lm W−1. To the authors’ best knowledge, this EQE value is the highest one
for blue phosphorescent OLEDs. There is a paper reporting an EQE of 30.2%
and current efficiency of 53.6 cd A−1 using FIrpic, where the authors assumed
30
Figure 2.5 (a) Calculated EQEs as a function of the thickness of an ETL with
experimentally measured maximum EQEs (circles). Solid line for Θ = 0.76. A
singlet-triplet factor of 1 and perfect charge balance were used for the
simulation. (b) Contour plot of the predicted maximum EQEs as function of
ΦPL and Θ for blue phosphorescent OLEDs with a representative blue emission
spectrum, FIrpic, where perfect charge balance was assumed. The device
structure is shown in Figure 1d. The dashed line is the horizontal transition
dipole ratio of the emitter.
0 20 40 60 80 1000
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Measurement
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E (
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0.5 0.6 0.7 0.8 0.9 1.00.5
0.6
0.7
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1.0EQE (%)
PL
Qu
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Proprotion of horizontal dipole
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29.9 % 40.1 %
(a)
(b)
31
Lambertian distribution of emission pattern.93 This work showed ~10% higher
current efficiency than previously reported the best result. The high
performance of the OLEDs must be related to the charge transport and
recombination processes in the devices which will be reported separately.
Optical simulation of the EQE of the devices was performed as a function of
thickness of the ETL using the classical dipole model under the assumption that
all the injected electrons and holes recombine in the EML.5,42,88,121,122 The
measured horizontal dipole ratio (Θ) of 76% and the ΦPL of 100% were used
and the emission zone was assumed to be located at the center of the EML in
the simulaton.123 The experimental results agree very well with the simulated
results as shown in Figure 2d, indicating that the electrical loss is indeed
negligible.in the devices. The excellent match between the experimental and
theoretical results also indicate that the theoretical limit of EQE was achieved
in the FIrpic based blue phosphorescent OLEDs.We extended our analysis to
calculate the maximum achievable EQE with different values of ΦPL and Θ for
blue OLEDs with a representative blue emission spectrum, FIrpic. Again
negligible electrical loss was assumed. The contour plot of the simulated
maximum EQEs as functions of ΦPL and Θ for blue phosphorescent OLEDs is
shown in Figure 3. A maximum EQE of 40.1% is achievable in normal ITO-
based bottom-emitting blue OLEDs without any out-coupling enhancement
structures if ΦPL = 1 and Θ = 1. It is interesting to note that the maximum
achievable EQE of blue OLEDs is less than those of green and red OLEDs,
because the waveguide mode in transparent conducting oxide and organic
32
layers is higher in blue OLEDs.58
33
2.4 Conclusion
In conclusion, we report a high efficiency blue emitting OLED
approaching the theoretical efficiency using an exciplex forming co-host
composed of mCP and B3PYMPM. FIrpic was used as the emitter which was
turned out to have a preferred horizontal dipole orientation in the EML. The
OLED showed a maximum EQE of 29.5% (a maximum current efficiency of
62.2 cd A-1), which agrees very well with the theoretical prediction under the
assumption of negligible electrical loss. The excellent match between the
experimental and theoretical results indicate that almost all the injected
electrons and holes recombined in the OLEDs with negligible electrical loss.
The OLED also exhibited a low driving voltage of 3 V and low efficiency roll-
off. Our analysis indicated that a maximum EQE of 40% is achievable in
normal ITO-based bottom-emitting blue OLEDs without any out-coupling
enhancement structures if ΦPL = 1 and Θ = 1.
34
Blue Phosphorescent OLEDs with
34.1% External Quantum Efficiency using a Low
Refractive Index Electron Transporting Material
3.1 Introduction
Over the last few decades, predicting the theoretical limit for the external
quantum efficiency (EQE) in organic light-emitting diodes (OLEDs) has been
a hot research topic due to the importance of OLEDs from the points of view
of fundamental research and industrial applications.5,8,23,88,124–136 Recently, the
maximum achievable EQEs have been calculated to be around 45% for green
and red OLEDs and 40% in blue OLEDs using the classical dipole model, while
assuming that the triplet harvesting emitters have horizontally oriented emitting
dipoles with a photoluminescent quantum yield (PLQY) of 100%.5,8,23 In
addition, the model could predict the maximum achievable EQEs from
optimized OLEDs if the exact values for PLQY and the horizontal dipole ratios
(Θ) of the emitting dipoles are known. The experimental results from the
OLEDs with no electrical loss accorded very well with the theoretical
predictions. By adopting phosphorescent dyes with high PLQY and Θ, highly
efficient red, green, and blue phosphorescent and fluorescent OLEDs with
EQEs over 30% have been successfully realized in recent years and the results
are in good agreement with theoretical predictions.5,8,11,51,93,137–139
35
However, the theoretical calculations for estimating the achievable
EQEs (using the PLQY and Θ as the material parameters for emitters) were
performed only for certain combinations of hole transporting and electron
transporting materials (HTM and ETM, respectively), namely, the materials
wherein it was assumed that the refractive indices of the constituting layers did
not change significantly. This assumption is sometimes not valid, especially in
the blue region, where the refractive index changes rapidly with wavelength
given that this region is close to the resonance wavelength for most conjugated
materials. Some non-conjugated materials show much lower refractive indices
than conjugated materials, especially in the blue region. Certainly, the
refractive indices including the birefringence of the hole and electron
transporting layers (HTL and ETL, respectively) influence the outcoupling
characteristics, and hence change the EQEs of OLEDs as reported in recent
papers.140–143
In this paper, we report a highly efficient sky-blue PhOLED with an
EQE of 34.1% and an exceptionally high power efficiency (79.6 lm W-1) using
a low refractive index ETL (1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-
diyl))tris(diphenylphosphine oxide) (PO-T2T); the average refractive index is
below 1.8 at the emission wavelength. In addition, we calculated the maximum
achievable EQEs as a function of both the emitting dipole orientation as well
as the refractive indices of the emitting and charge transporting layers. We show
that the maximum achievable EQEs are over 61.5% for fully horizontal
emitting dipoles and around 40.1% for randomly oriented emitting dipoles
36
without any extra outcoupling structures if the refractive indices of the organic
layers constituting the OLEDs are equal to 1.5.
37
3.2 Experimental
3.2.1 Materials Characterization
Ellipsometry (ESM-300, J.A. Woollam Co.) was used to determine the
refractive index of the organic layers deposited on Si wafers. Measurements
were made from 200~1,650 nm at 45~75°. The thickness of the oxide layer on
the Si wafer was 1.4 nm, which was used in the curve-fitting model. Cauchy
and B-spline models were used to fit the measured ellipsometric data in order
to obtain the thickness and refractive index.
The PL spectra of thin films of the organic materials deposited on fused
silica were measured using a spectrofluorometer (Photon Technology
International, Inc.). The excitation source was a continuous Xenon lamp (290
nm, 325 nm) combined with a monochromator (Acton Research Co.). Time
resolved PL spectra were measured using a pulsed Nd:YAG laser (355 nm,
Continuum) as the excitation light source and an intensified charge-coupled
device (iCCD) as the optical detection system. Low temperature experiments
were performed using a cryostat (SHI Cryogenics, Inc.).
Angle-dependent PL experiments were performed on a motorized
rotational stage with a half cylinder lens made of fused silica (Figure 3.9).
Substrate of the film made of fused silica was attached to the half-cylinder lens
with refractive index matching liquid. A continuous-wave He/Cd laser (325 nm,
Melles Griot Co.) was used as the excitation source and the incident angle of
the laser was 45° to the detection plane. A dichroic mirror was used to filter the
38
excitation beam and a linear polarizer was used to control the polarity of the
emitted light. Angle-dependent p-polarized PL spectra of the film were detected
by a fiber guided spectrometer (Maya2000 Pro, Ocean Optics Inc.) with
automated rotation of the stage.
3.2.2 Device fabrication and characterization
70 nm-thick ITO coated glass substrates were cleaned by dipping in
acetone and boiling in isopropyl alcohol followed by UV-ozone cleaning for 10
min prior to the fabrication of the sky-blue PhOLEDs. All the organic and metal
layers were deposited by thermal evaporation at a base pressure of < 5 ×10-7
Torr. Current densities were measured by a Keithley 2400 programmable source
meter and EL spectra and intensities in the normal direction were measured by
a PR650 (Photo Research) spectrometer in power / unit wavelength / unit
steradian / unit area (W nm-1 sr-1 m-2), respectively. The luminance of the OLED
was calculated using the spectral intensity in the normal direction and the CIE
luminosity function. The angle-dependent EL spectra and intensities were
measured by a Keithley 2400 programmable source meter with a rotating stage
and a fiber optic spectrometer (Ocean Optics S2000).
3.2.3 Lambertian correction factor and calibration of EQE
The EQEs were calculated using the angle-dependent EL spectral
intensities. Firstly, the Lambertian correction factor was calculated from the
angle-dependent spectral intensities by following equations:
39
0
Lambertian correction factor in the visible wavelength
number of emitted photons of a device/ unit area
number of emitted photons of a Lambertian surface with in the normal direction/unit areaP
760 22
0 380 0
760 22
0
0 380 0
760
380
760
0
380
( , )sin
/
( )cos sin
/
( , )2 sin
/
( )2 cos sin
/
( 0, , , ( ), )36 2 36 2
ii i
i
i i i
i
i
Pd d d
hc
Pd d d
hc
Pd
hc
Pd
hc
(3.1)
where ( , )P is the spectral intensity in W nm-1 sr-1 m-2, 0 ( )P is spectral
intensity in the normal direction, is the wavelength in nm, h is the Planck
constant, c is the speed of light, is the emitting angle and is the
azimuthal angle.
Finally, the EQE was calculated using the following equation:
760
0
380
( )
/Lambertian correction factor
/ (current density/unit charge)
Pd
hcEQE
J q
(3.2)
40
3.3 Result and discussion
The outcoupling efficiencies of the OLEDs were calculated using an
OLED structure consisting of glass/ITO (70 nm)/HTL/EML (30 nm)/ETL/Al,
where EML represents the emitting layer. The refractive indices of the HTL
and ETL were selected as the main parameters and the birefringence effect was
not considered in the calculation. A classical dipole model was used for the
calculation.125,134,136,144 The refractive index of the EML was taken to be the
average of the corresponding values for the HTL and ETL in view of the
composition of the mixed host consisting of a 1:1 mixture of HTM and ETM.
The PLQY of the emitter was measured to be 1. The photoluminescent (PL)
spectrum of Iridium(III)bis[(4,6-difluorophenyl)-pyridinato-N,C2′]picolinate
(FIrpic) shown in Figure 3.1 was used for the calculation. This spectrum was
chosen because, among the three prime colors, the variation of the refractive
indices of organic materials is the largest in the blue region. For convenience,
we used constant wavelength-independent refractive indices in our calculation.
Even though the values for the refractive indices of organic semiconductors are
dispersive, the use of the average value within the emission wavelength range
turned out to be good enough for practical use because the differences in the
outcoupling efficiencies between the simulated values using the dispersed
refractive index and the averaged refractive index are less than 1%. Figure
3.2a-c show the contour plots of the maximum achievable outcoupling
efficiencies of the device as a function of the refractive indices of HTL and
ETL with optically optimized thicknesses for the isotropic emitting dipole
41
Figure 3.1 Normalized PL intensity of mCBP:PO-T2T:10 wt% FIrpic thin film
(30 nm).
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0
1.2
FIrpic
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
42
Figure 3.2 (a)-(c) Contour plots of the simulated maximum achievable
outcoupling efficiencies of OLEDs with different refractive indices of HTMs
and ETMs for different emitting dipole orientations; (a) random orientation, (b)
fully horizontal orientation, and (c) 78% horizontal and 22% vertical
orientation corresponding to FIrpic in the mixed host as described in the text.
OLEDs with the structure ITO (70 nm)/HTL/EML (30 nm)/ETL/Al were used
for the simulation and the thicknesses of the HTL and EML were optimized to
maximize the EQE for the given refractive indices of HTL and ETL. Refractive
indices averaged in the sky-blue region for commonly used HTMs and ETMs
are displayed as dotted lines.
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40
25
6054
30
50
45
35
40
25
6054
30
50
45
35
40
25
6054
30
50
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25
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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30
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35
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30
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40
25
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30
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25
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30
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35
40
25
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30
50
45
35
40
25
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30
50
45
35
40
25
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30
50
45
35
40
25
6054
30
50
45
35
40
25
6054
30
50
45
35
40
25
6054
30
50
45
35
40
25
6054
30
50
45
35
40
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35
401.5 1.6 1.7 1.8 1.9 2.0
1.5
1.6
1.7
1.8
1.9
2.0
B3PYMPM
(extraordinary)
NP
B
20
Re
fra
cti
ve
in
de
x o
f E
TL
Refractive index of HTL
15
25
35
45
55
65
= 0.67
Outcoupling
efficiency (%)
40 TcT
a
mC
BP
, m
CP
TA
PC
PO-T2T
TPBi
Alq3
B3PYMPM (ordinary)
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
45
30
60
35
54
52
40
45
30
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35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
45
30
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35
54
52
40
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30
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35
54
52
40
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30
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35
54
52
40
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30
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35
54
52
40
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30
60
35
54
52
40
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30
60
35
54
52
40
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30
60
35
54
52
40
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30
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35
54
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40
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30
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35
54
52
40
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30
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35
54
52
40
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30
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35
54
52
40
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30
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35
54
52
40
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30
60
35
54
52
40
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30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
45
30
60
35
54
52
40
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30
60
35
54
52
40
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30
60
35
54
52
40
45
30
60
35
54
52
40
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30
60
35
54
52
40
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30
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35
54
52
40
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30
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35
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52
40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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52
40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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52
40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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52
40
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30
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35
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52
40
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30
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35
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52
40
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30
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35
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52
40
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30
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35
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40
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30
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35
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40
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30
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35
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52
40
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30
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35
54
52
40
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30
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35
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40
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30
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35
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52
40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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40
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40
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40
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40
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40
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35
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40
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30
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35
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40
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30
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35
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40
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30
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35
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40
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40
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40
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40
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40
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35
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30
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40
45
30
60
35
54
52
40
45
1.5 1.6 1.7 1.8 1.9 2.01.5
1.6
1.7
1.8
1.9
2.0
Alq3
TPBi
TA
PC
Re
fra
cti
ve
in
de
x o
f E
TL
Refractive index of HTL
15
25
35
45
55
65
B3PYMPM
PO-T2T
TcT
a
mC
BP
, m
CP
Outcoupling
efficiency (%)
NP
B
= 0.78
Experimental data
= 0.76
in mCP:B3PYMPM host
B3PYMPM
(extraordinary)
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1.5 1.6 1.7 1.8 1.9 2.01.5
1.6
1.7
1.8
1.9
2.0
Alq3
TPBi
TA
PC
Re
fra
cti
ve
in
de
x o
f E
TL
Refractive index of HTL
15
25
35
45
55
65
B3PYMPM
PO-T2TT
cT
a
mC
BP
, m
CP
Outcoupling
efficiency (%)
NP
BB3PYMPM
(extraordinary) = 1
(a)
(b)
(c)
43
Figure 3.3 Simulated outcoupling efficiency against the position of the
recombination zone in the emitting layer measured from the HTL - EML
interface.
0 5 10 15 20 25 300
5
10
15
20
25
30
35
40
Maxim
um
achie
vable
EQ
E (
%)
Position of Rec. zone from
interface between HTL and EML (nm)
44
orientation (Figure 3.2a), horizontal orientation (Figure 3.2b) and 78%
horizontal orientation (Figure 3.2c), respectively. The location of the
recombination zone was assumed to be in the middle of the EML because there
is no significant difference in the outcoupling efficiency with the position of
the recombination zone in the EML (Figure 3.3). The refractive indices in the
figures vary between 1.5 (the refractive index of PEDOT:PSS) and 2.0. Several
widely used HTMs and ETMs are included in the figures for comparison. Using
a HTM and an ETM with the refractive index of 1.5 is the extreme case, which
can result in outcoupling efficiencies of 40.1% for an isotropic orientation of
the emitter and 61.5% for a fully horizontal orientation. This is much higher
than the values of 26.2% and 41.5% for a refractive index of 1.8, respectively,
demonstrating the importance of the refractive index of the constituting layers
in the performance of OLEDs. The refractive indices of mCBP and PO-T2T are
compared with the refractive indices of commonly used HTLs and ETLs in
Figure 3.4a and 3.4b respectively. mCBP and PO-T2T have average refractive
indices of 1.76 and 1.72, respectively, in the emission range of FIrpic. These
values are lower than those for commonly used HTLs (TCTA and NPB) and
ETLs (TPBI, Alq3, and B3PYMPM). The low refractive index of PO-T2T may
result from the low mass density originating from the twisted diphenyl
phosphine oxide moieties from the plane of the 1,3,5-triphenyltriazine core with
random molecular orientations in the film and from the short conjugation length
leading to low polarization at the optical frequency.
45
Figure 3.4 Ordinary refractive indices of (a) HTMs and (b) ETMs.
350 400 450 500 550 600 650 700 750 8000.0
0.5
1.0
1.5
2.0
2.5
mCBP
mCP
TAPC
TcTa
Re
fra
ctive
in
de
x
Wavelength (nm)
n
k
350 400 450 500 550 600 650 700 750 8000.0
0.5
1.0
1.5
2.0
2.5
PO-T2T
B3PYMPM
Alq3
TPBi
Re
fra
ctive
in
de
x
Wavelength (nm)
k
n
(a)
(b)
46
Figure 3.5 Maximum achievable outcoupling efficiencies are plotted as a
function of emitting dipole orientation with the refractive indices of the organic
layers as a parameter.
0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Maxim
um
achie
va
ble
outc
ouplin
g e
ffic
ien
cy
Horizontal dipole ratio of emitter ()
With increase of refractive
index from 1.5 to 2.0
1.5
1.6
1.7
1.8
1.9
2.0
47
Figure 3.5 shows the variation of the maximum achievable outcoupling
efficiencies as a function of Θ and the refractive index of the organic layers as
a parameter under the assumption that all the consisting layers have the equal
refractive index in each condition. The outcoupling efficiency increases almost
linearly with increasing Θ and decreases with increasing refractive index.
In order to demonstrate the effect of the refractive index on EQE, we
selected 3,3-di(9H-carbazol-9-yl)biphenyl (mCBP) as the HTM and PO-T2T
as the ETM to fabricate efficient sky-blue-emitting PhOLEDs with FIrpic as
the emitter. The chemical structures of the selected materials are displayed in
Figure 3.6a along with the energy levels. The HTM and ETM were used as the
co-host for the EML. The mCBP and PO-T2T have high triplet energy levels
(T1) of 2.9 eV and 2.99 eV, respectively.145–147 The combination of TAPC and
PO-T2T can result in a higher efficiency when only the refractive index is
considered. However, the film with TAPC and PO-T2T mixture forms an
exciplex whose energy (~2.1 eV) is lower than the triplet energy of FIrpic (2.62
eV). As a result, efficient FIrpic emission cannot be obtained if the mixed film
is used as the host.
Figure 3.6b shows the PL spectra of the host materials, mCBP, PO-T2T,
and the mCBP:PO-T2T co-deposited film at room temperature. The mCBP:PO-
T2T mixed film shows a featureless emission spectrum that is red-shifted with
respect to the constituting materials with the peak wavelength of 471 nm
corresponding to 2.63 eV. This value is close to the energy difference between
48
the highest occupied molecular orbital (HOMO) level of mCBP and the lowest
unoccupied molecular orbital (LUMO) level of PO-T2T, and which is also
close to the T1 of FIrpic (2.62 eV). The time resolved PL spectra of the
mCBP:PO-T2T mixed film at low temperatures (35 K) showed a delayed
emission with no additional peak (Figure 3.7).
49
Figure 3.6 (a) Molecular structures of EML constituting materials, a schematic
diagram of the device structure with HOMO and LUMO energy levels, and T1
diagram of the emitters and exciplex. (b) Normalized PL spectra of mCBP
(black line with squares), PO-T2T (red line with circles) and mCBP:PO-T2T
co-deposited film (blue line with triangles).
FIrpic
mCBP
PO-T2T
PO
-T2T
mC
BP
Excip
lex
ga
p
(2.6
3 e
V)
2.4
6.1
3.47
7.5
S0
T1
mCBP
2.9 eV
PO-T2T
2.99 eVExciplex
2.63 eV
Firpic
2.62 eV
350 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
2nd harmonic
of excitation
light source
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
mCBP
PO-T2T
mCBP:PO-T2T(exciplex)
excimer
471 nm
(a)
(b)
50
Figure 3.7 Time resolved PL spectra of mCBP:PO-T2T films at low
temperatures (35 K) with various gate delay times from 10 ns to 10 µs.
350 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
1.2 0~10 ns
100~150 ns
500~750 ns
10~15 μs
Norm
aliz
ed in
tensity (
a.u
.)
Wavelength (nm)
51
Figure 3.8 A plot of the angle-dependent PL intensity against the wavelength
of the p-polarized light emitted from mCBP:PO-T2T:FIrpic (10 wt%) film (30
nm) at whole emitting wavelength of FIrpic. Experimental data (contour) are
compared to simulated data (dashed line).
0 20 40 60 80450
500
550
600
dashed line (simulation,=0.78)
Wavele
ngth
(nm
)
Angle (degree)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Normalized intensity (a.u.)
contour plot (experimental)
52
Figure 3.9 A schematic diagram of the setup for the measurement of angle-
dependent PL spectra. p- and s-polarizations are indicated by the blue and red
arrows, respectively. Horizontal and vertical transition dipole moments of the
emitters in the film align parallel and perpendicular to substrate (x-y plane),
respectively. Ratio of px and pz was calculated by fitting the p-polarized
emission pattern using an optical simulation and amount of py was assumed to
be the same as px.
Laser incidence
spectrometer
sample
Fused silica half-cylinder lens
Rotation stage
p-polarization
s-polarization
Horizontal dipoles
(px, py)
Vertical dipole
(pz)
x
y
zrotation
-90º
0º
90º
x
yz
53
Figure 3.10 A plot of the angle-dependent PL intensity of the p-polarized light
emitted from mCBP:PO-T2T:FIrpic (10 wt%) film (30 nm) at the maximum
peak wavelength of FIrpic (471 nm). Experimental data (scatter) are compared
to simulated data (black dashed line: Θ = 0.74, red short dashed line: Θ = 0.76,
black solid line: Θ = 0.78 and green dotted line: Θ = 0.80). Inset: enlarged
angle-dependent PL intensity around 55 degree.
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Simulation
FIrpic in mCBP:PO-T2T
=0.74 =0.76
=0.78 =0.80
Measurement
FIrpic in
mCBP:PO-T2T
mixed host
Norm
aliz
ed in
tensity (
a.u
.)
Angle (degree)
50 55 600.6
0.7
0.8
0.9
No
malized
inte
nsit
y (
a.u
.)
Angle (degree)
54
These observations indicate that the mCBP:PO-T2T mixed host forms
an exciplex with a lower T1 value than the charge transporting layers. Similar
observations have been found in an earlier report.147 In addition, the energy of
the exciplex T1 is higher than that of the phosphorescent dopant FIrpic, so that
efficient energy transfer from the exciplex to the dopant and the confinement
of the triplet energy in the blue phosphorescent dopant are expected, resulting
in OLEDs with high EQE and low driving voltages.11
Figure 3.8 shows a contour plot of the angle-dependent PL intensity of
the p-polarized light emitted from the 30 nm thick mCBP:PO-T2T:FIrpic
(0.45:0.45:0.1 in weight ratio) film. The corresponding experimental setup is
shown in Figure 3.9.50 The observed profile fits well with a 78% of horizontal
dipole ratio in the mCBP:PO-T2T host, which is also clearly manifested by the
fitting at the peak wavelength of FIrpic emission (Figure 3.10). The value is
a little higher than those obtained for the N, N’-dicarbazolyl-3,5-benzene
(mCP):bis-4,6-(3,5-di-3-pyridylphenyl)-2-methylpyrimi-dine (B3PYMPM)
(76%), mCP:PO-T2T (76%), mCP (76%) and 4,4’-Bis(carbazol-9-yl)biphenyl
(CBP) (74%) hosts.23,148
Using the values of 78% for Θ and inputting the values for the refractive
indices of the host, the contour plot of the EQE was calculated as a function of
the refractive indices of HTL and ETL (Figure 3.2c). The results indicate that
the maximum achievable EQE for the sky-blue PhOLED fabricated using the
mCBP:PO-T2T host doped with FIrpic is 34.3% (blue dots) when the average
55
refractive indices in the sky-blue region are used. If wavelength-dependent
refractive indices are used, the calculated maximum achievable EQE decreases
to 34.0%. We have reported the maximum achievable EQE of 29.9% using
FIrpic in mCP:B3PYMPM host, which is a little lower than the maximum
achievable outcoupling efficiency (30.8%, red dot in Figure 3.2c).23 This
difference is due to the higher refractive index of B3PYMPM when compared
to PO-T2T and the lower horizontal dipole orientation of FIrpic in the
mCP:B3PYMPM host as compared to that in the mCP:PO-T2T host.
In order to verify the simulation, we fabricated PhOLEDs with the
following optimized structure obtained after optical simulation: ITO (70
nm)/pdoped mCBP (40 nm)/mCBP (15 nm)/mCBP:PO-T2T: FIrpic
(0.45:0.45:0.1 in weight ratio, 30 nm)/PO-T2T (20 nm)/ndoped PO-T2T (20,
30, 40 and 50 nm)/Al (100 nm), and compared with the previously reported
mCP:B3PYMPM host based OLEDs.149 pdoped (6 wt%) mCBP and ndoped
(12 wt%) PO-T2T were used as the hole injection layer (HIL) and the electron
injection layer (EIL) with ReO3 and Rb2CO3 as the pand ntype dopants,
respectively.11,23,24,115–117,150–152 We have optimized the doping concentrations of
the charge injection layers for charge balance and low electrical losses. In the
simulation, the refractive indices of the pHTL, nETL and emitter doped EML
are assumed to be the same as for pristine layers since the volume ratios of the
dopants are very small due to their much higher mass densities. The volume
concentrations of the dopants are 1.0, 3.4, and 6.0% in the p, n and emitting
56
Figure 3.11 Comparison of the refractive indices of doped and undoped EML
(30 nm-thick film on a Si substrate).
200 300 400 500 600 7000.0
0.4
0.8
1.2
1.6
2.0
2.4
Re
fra
ctive
in
dex
Wavelength (nm)
n of mCBP:PO-T2T
k of mCBP:PO-T2T
n of mCBP:PO-T2T:10wt% FIrpic
k of mCBP:PO-T2T:10wt% FIrpic
57
Figure 3.12 (a) Current density-voltage-luminance (J-V-L) characteristics of
the devices with various thicknesses of the ETL. Inset shows the emission
patterns of the devices. b) EQEs and PEs of OLEDs as a function of luminance.
0 1 2 3 4 5 6 7 8 9 1010
-6
10-5
10-4
10-3
10-2
10-1
100
101
102
103
0 10 2030
40
50
60
70
80
90
Lambertian
ETL 40nm
ETL 50nm
ETL 60nm
ETL 70nm
No
rmali
zed
In
ten
sit
y (
a.u
)
1
0Emissioin angle (deg)
ETL 40 nm
ETL 50 nm
ETL 60 nm
ETL 70 nm
Curr
ent density (
mA
/cm
2)
Voltage (V)
100
101
102
103
104
105
106
Lum
inance (
cd
/m2)
0 5000 10000 15000 200000
5
10
15
20
25
30
35
40 ETL 40 nm
ETL 50 nm
ETL 60 nm
ETL 70 nm
EQ
E (
%)
Luminance (cd m-2)
0
20
40
60
80
100
120
Pow
er
effic
iency (
lm W
-1)
(a)
(b)
58
layers, respectively. For instance, the difference in the refractive indices
between the doped (10 wt% FIrpic) and undoped emitting layers is less than
0.7% in the wavelength of FIrpic emission (Figure 3.11).
Figure 3.12a shows the J-V-L characteristics of the PhOLEDs. The
mCBP:PO-T2T exciplex based devices have a low turn-on voltage of 2.6 V at
1 cd m-2 and the maximum value of luminance reaches to > 20,000 cd m-2. In
addition, the current density begins to rise abruptly at low voltages (around 2.0
V), due to the diffusion current at low external bias values.24 Such a low driving
voltage is due to the simple device structure based on an exciplex forming co-
host that enables a barrier free charge injection from the transporting layers to
the emitting layer. The variation of EQEs and power efficiencies (PEs) as a
function of the luminance is shown in Figure 3.12b. The EQEs and PEs are
calibrated through the angle-dependent electroluminescent (EL) patterns of the
devices shown in the inset of Figure 3.12a, which have different emission
patterns according to thicknesses of the ETL. Lambertian correction factors
vary from 0.92 to 1.08. The calibration scheme is described in Section 3.2.3.
The mCBP:PO-T2T exciplex-based device shows the maximum EQE of 34.1%
with a value of 33.9% at 100 cd m-2. To the best of our knowledge, this is the
highest value obtained in sky-blue PhOLEDs with a single EL unit using the
FIrpic emitter. The device also shows an exceptionally high maximum PE of
79.6 lm W-1 (65.5 lm W-1 at 100 cd m-2) due to the low driving voltage and a
low efficiency roll-off at high current densities. The obtained efficiencies at
different luminances are summarized in Table 1. The efficiencies are a little
59
higher than the mCP:PO-T2T mixed host based device due to the difference in
the horizontal orientation of the emitting dipoles of FIrpic in the two hosts (78%
in mCBP: PO-T2T against 76% in mCP:PO-T2T) and also due to the optimized
device structure used in this work.141,153
The reason why the low refractive index of the ETL increases the
outcoupling efficiency can be understood from the mode analysis of the OLEDs
as a function of the thickness of the ETL (Figure 3.13), where the simulation
results are compared with the experimental data. For this purpose, the same
structure described in the previous paragraph is used and compared with the
previously reported mCP:B3PYMPM based structure (Figure 3.14).23 The
wavelength dependent refractive indices of the consisting layers were used in
the simulation. The dissipation of power into the different modes at the
maximum of the air mode is summarized in Table 2. Replacing B3PYMPM by
PO-T2T in the devices lowers the average refractive index of the ETL from
1.86 to 1.72 and increases Θ from 0.76 to 0.78. Resultantly, it increases the air
mode (from 29.9% to 34.0%) and the substrate confined mode (from 23.5% to
24.5%) at the expense of the waveguide mode (from 18.1% to 15.4%) and the
surface plasmon polariton mode (from 26.0% to 23.5%) at the ETL thickness
corresponding to the maximum of the air mode. According to the simulation,
major contribution in the increase of the air mode (4.1%) between the devices
comes from the refractive index difference (3.2%) rather than from the emitting
dipole orientation (0.9%).
60
Table 3.1 Summary of the performances of the OLEDs
Thickness
of the ETL
Voltage (V) EQE (%) Power efficiency (lm W-1)
Turn-
on
10,000
cd m-2 Max
100
cd m-2
1,000
cd m-2
10,000
cd m-2 Max
100
cd m-2
1,000
cd m-2
10,000
cd m-2
40 nm 2.6 6.4 32.0 31.9 29.1 19.3 67.5 56.6 40.3 17.9
50 nm 2.6 6.3 34.1 33.9 32.2 25.0 79.6 65.6 48.6 25.5
60 nm 2.6 6.8 31.6 31.6 29.6 19.2 73.2 62.1 44.5 18.1
70 nm 2.6 7.1 29.9 29.9 27.7 16.6 73.5 64.4 45.3 16.5
61
Figure 3.13 Mode analysis of sky-blue OLEDs with PO-T2T (solid line) and
B3PYMPM (dashed line) as the ETL and experimental data are included for
comparison (PO-T2T: orange open circle, B3PYMPM: violet open circle). The
device structures described in the text (PO-T2T) and in Figure 3.14 are used for
the simulation and experiments.
0 20 40 60 80 1000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Experimental data
PO-T2T, B3PYMPM
Simulation
PO-T2T, B3PYMPM
Mode f
raction
Thickness of ETL (nm)
Absorption
SPP Wave-guided
Substrate-guided
Air
62
Figure 3.14 Schematic diagram of the device structure and energy levels of the
consisting layers of mCP:B3PYMPM co-host based OLED.
mC
P:B
3P
YM
PM
:
10
wt%
FIr
pic
B3P
YM
PM
mC
P2.4
6.0
3.2
6.1
3.1
6.77
70 45 15 30 20 35 100
Unit: nm
4 w
t% R
b2C
O3
:B3P
YM
PM
4 w
t%
ReO
3:m
CP
ITO
Al
63
Table 3.2 Power dissipation into different modes at the maximum air mode
conditions
Mode fraction
ETL Θ Air Substrate
confined
Wave
guided
Surface
plasmon
polariton
(SPP)
Absorption
Non-
radiative
loss
PO-T2T 0.78 0.340 0.245 0.154 0.235 0.019 0.008
B3PYMPM 0.76 0.299 0.235 0.181 0.260 0.018 0.008
64
3.4 Conclusion
In summary, highly efficient sky-blue-emitting PhOLEDs with FIrpic
are demonstrated using an exciplex-forming host composed of low refractive
index (below 1.8) hole and electron transporting layers, i.e., mCBP and PO-
T2T. The devices show a maximum EQE of 34.1%, and a low turn-on voltage
of 2.6 V resulting in a high maximum PE of 79.6 lm W-1 and 65.5 lm W-1 at
100 cd m-2. The experimental data are well matched with the simulation results.
The simulation results also indicate that an EQE of 61.5% is achievable in the
sky-blue PhOLEDs if the refractive indices of the constituting organic layers
are close to 1.5 and the emitters have a PLQY of unity with fully horizontal
emitting dipoles.
65
Controlling Horizontal Dipole
Orientation and Emission Spectrum of Ir complex
by Chemical Design of the Ligands for Efficient
Deep-Blue Organic Light-Emitting Diodes
4.1 Introduction
In the last decade, using horizontally oriented emitting dipoles, high
photoluminescence quantum yield (PLQY), well-matched electron-hole charge
balance, and effective energy transfer systems such as an exciplex forming co-
host, red, green, and sky-blue organic light-emitting diodes (OLEDs) with high
external quantum efficiencies (EQEs) have been
developed.5,6,8,11,21,23,46,51,52,55,93,106,137,154–160 In the case of deep-blue OLEDs,
however, the high EQEs using the aforementioned factors have rarely reported.
While there are several reports of sky-blue OLEDs, including phosphorescent
and thermally activated delayed fluorescence OLEDs, with EQE >
30%,6,9,11,20,23,138,161,162 no highly efficient deep-blue OLEDs (The 1931
Commission Internationale de L’Eclairage y coordinate, CIE y < 0.2) achieving
EQE > 30% have been reported. This is because there are few host materials
with high triplet energy (T1) or deep-blue Ir complexes with high PLQY and
the ratio of horizontally orientated emitting dipole (Θ).163,164 Therefore, it is
necessary to develop new materials for highly efficient deep-blue OLEDs.
66
Recently, emitting dipole orientation of Ir complexes has been studied
in the viewpoints of chemical engineering.21,51,165–167 Two mechanism are
widely used to increase Θ of Ir complex. One is an addition of long and bulky
structure to the main ligand and the other is chemical modification of ancillary
ligand. Firstly, the addition of the long and bulky structure to the main ligand
leads to increase the interaction between emitter and host molecules.21 Secondly,
for the heteroleptic Ir complex, bulkiness of ancillary ligand affects the Θ,
because bulky ancillary ligand attributes high vertical orientation of triplet
emitting dipole against the C2 axis.51,52 On the other hand, there is a report
describing that the aromatic ligand enhances the chance to interact with host
molecule due to π-π interaction.166 The aliphatic ancillary ligands are oriented
to the vacuum, while the main ligands are oriented to the host molecules on the
surface of the organic layer. Therefore, the aliphatic ancillary ligand increases
Θ due to the increase of preferred orientation of the emitters. However, most
reports relate to green and red emitting Ir complexes and study on blue emitting
Ir complexes is barely reported.165,167
There are only few studies reporting emitting dipole orientation of the
blue Ir complex. Similar to the previous report in green OLEDs, there is a report
that heteroleptic blue Ir complex has a higher Θ than that of the homoleptic blue
Ir complex.168 However, enhanced Θ of the heteroleptic compound was not
analyzed. Meanwhile, bis-tridentate structure used blue Ir complexes were also
reported. The rigidity of tridentate gives blue Ir complex high PLQY but their
Θ was not higher than isotropic orientation.169
67
Several design strategies have been studied to achieve the blue emission
of Ir complex with CIE y < 0.2. Some group developed the structures of the Ir
complex using difluorophenylpyridine backbone with the strong electron
withdrawing structures.170–173 Other groups have suggested the nonconjugated
ancillary chelates such as a pyrazole, an N-heterocyclic carbene and etc.164,174
The other approaches to achieve deeper blue are development of the main
ligand. Ir complexes using a carbene, an imidazole, a triazolyl group, and a
fluorine substituted bipyridine moieties were reported for deep-blue emission,
CIE y < 0.2. However, the EQEs of the majorities are lower than 15%.175–178
In order to simultaneously obtain the deep-blue color (CIE y < 0.2) and
the high EQE, we focus on the two perspectives. One is a design of new main
ligand for deep-blue, and the other is controlling Θ and spectra through
chemical engineering of ancillary ligand. We designed novel main ligand, 2′,6′-
difluoro-4-(trimethylsilyl)-2,3′-bipyridine (dfpysipy). Adoption of a
trimethylsilyl group at the pyridine and a nitrogen at the difluoropyrido group
increases bandgap of emitter attributing deep-blue emission. Furthermore, we
controlled Θ and spectrum of Ir complex using ancillary ligand. Due to the
addition of methyl group in pic, electron density at mpic ligand is increased,
that makes ancillary ligand prefer to interact with the host molecules. We also
modified the acetate in pic ligand substituting by trifluoromethyl-triazole
possessing strong electron withdrawing property. To confirm the effect of
chemical design, time-dependent density functional theory (TD-DFT)
calculations and device fabrication were performed.
68
4.2 Experimental
4.2.1 Device and sample fabrication
To fabricate the PhOLEDs, organic layers and a metal cathode were
deposited on a 70-nm-thick indium tin oxide (ITO) pre-coated glass substrate.
The layers were stacked using thermal vacuum evaporation with a base pressure
of < 5 × 10−7 Torr. Before the thermal vacuum deposition, the substrate was
pre-cleaned using acetone and isopropyl alcohol immersion. Next, the ITO-
coated substrates were exposed to a UV-ozone flux for 10 minutes. After the
deposition process, the OLEDs were encapsulated in a glovebox filled with N2
gas using UV-curable resin with glass capsule lids. Samples for PLQY and Θ
were also fabricated under the same thermal vacuum deposition conditions used
for OLED fabrication. To eliminate the absorption by glass, fused silica
substrates were used for the PLQY and Θ measurements.
4.2.2 Measurements of the devices and samples
The extinction coefficients of the Ir-complexes were measured using a
Cary 5000 UV-vis-NIR spectrophotometer (Agilent Technologies). The
concentration of the solution used for the absorption (extinction coefficients)
and PL spectra measurements was 1 × 10−5 M using MC solvent. The PL spectra
of the materials were obtained using a spectrofluorometer (Photon Technology
International). A pulsed xenon flash was used for the excitation source. The
excitation wavelengths were selected using a monochromator (290 nm for
TSPO1 and mCBP, 325 nm for the Ir-complexes). The EL spectra and J-V-L
69
characteristics were measured using a SpectraScan PR650 (Photo Research),
radiometer, and CS100 (Minolta) with a Keithley 2400 source meter. All of the
EQEs were estimated under the assumption of a Lambertian emission pattern.
For the PLQY and angle-dependent PL (ADPL) measurements, a continuous
wave He/Cd laser (325 nm, Melles Griot) was used as the excitation source.
The ADPL measurements were performed on a fused silica half cylinder, which
was attached to the automated rotating stage. The incident angle of the He/Cd
laser was 45° to the film and a linear polarizer was used to control the polarity
of the PL. A fiber-guided spectrometer (Maya 2000 Pro, Ocean Optics) was
used to detect the ADPL spectra.
4.2.3 The DFT calculation conditions
Geometry optimization, energy levels, and TDMs of Ir-complexes were
calculated with a time-dependent DFT calculation using Maestro Materials
Science (Schrödinger). For optimization, B3LYP and the 6-31G** and
LACVP** basis sets were used. To calculate the TDMs, the DYALL-
2ZCVP_ZORA-J-PT-GEN basis set was also used.
70
4.3 Design and density functional theory (DFT) calculation of deep-
blue emitting Ir-complexes
Ir complexes containing 2′,6′-difluoro-4-(trimethylsilyl)-2,3′-bipyridine
(dfpysipy) main ligands, are newly synthesized for deep-blue spectrum. Based
on the chemical structure of bis(4,6-difluorophenylpyridinato-
N,C2)picolinatoiridium (FIrpic), chelating (C^N) ligand is modified.
Introduction of an electron donating trimethylsilyl group to the pyridine and
withdrawing nitrogen at difluoropyrido group results in a decrease of the
highest occupied molecular orbital (HOMO) and an increase of lowest
unoccupied molecular orbital (LUMO) level leading to deep-blue emission. As
shown in Figure 4.1, three types of Ir complexes were prepared according to
the design of the ancillary ligands, namely, pic, mpic, and fptz (for
Ir(dfpysipy)2(pic), Ir(dfpysipy)2(mpic), and Ir(dfpysipy)2(fptz), respectively).
In case of mpic, a methyl group was added to pyridine of the pic ligand to
increase the electron density leading to enhance the interaction with the host,
thereby obtaining a high Θ. fptz was obtained by replacing the acetate structure
of pic with a perfluoromethyl-triazole structure and intending to gain a deeper
blue emission using strong electron withdrawing characteristics.
To predict the effect of ancillary ligand, we compared the electrostatic
potential (ESP) and direction of the transition dipole moments (TDMs) of the
dopants. Figure 4.2a shows the ESPs of the dopants. As shown in the figure,
71
Figure 4.1 Chemical structures of Ir-1, 2 and 3.
72
Figure 4.2 (a) Simulated ESP (left) with the range of energy and TDM with th
e directions and angle to the long axis (right) of the Ir complexes. (b) Simulate
d ESP of host molecules, TSPO1 (left) and mCBP (right).
31.8°
TDM
Long axis plane
6.5°
TDM
Long axis plane
Ir-1
Ir-2
Ir-3
-3 eV 3 eV
29.8°
TDM
Long axis plane
Min -2.45 eV, Max 1.39 eV
TSPO1 (front and opposite projection)
Min -0.84 eV, Max 1.25 eV
mCBP
-3 eV 3 eV
(a)
(b)
73
the pic, mpic, and fptz ancillary ligands contain the lowest ESPs in each
complex (−2.22, −2.60, and −2.27 eV for Ir-1, Ir-2, and Ir-3, respectively). mpic
ancillary ligand has lower ESP than that of pic because attached methyl group
increases local electron density at the ancillary ligand, reducing ESP on the
ancillary ligand in Ir-2. Taken as a whole, the ancillary ligands can serve as
preferred interaction sites with the host materials because the host molecules,
mCBP and TSPO1 mostly have positive ESPs throughout the region, except for
the phosphine oxide moiety in TSPO1 (−2.45 eV).8 Isosurfaces of ESP for the
host molecules are shown in Figure 4.2b.
In order to predict if changes in the ancillary ligand will affect the
orientation of emitting dipole, directions of TDM were analyzed. We calculated
the energy of emission and direction of TDM using TD-DFT. The calculated
energies of emissions were 2.70 eV for Ir-1 and Ir-2, 2.81 eV for Ir-3. Figure
4.2a shows the directions of the TDMs in the emitters. The Ir complexes are
depicted in the direction of the plane containing the long. Interestingly, the
angles between the TDM vectors and the plane included in the main ligand (i.e.,
the direction of the long axis) clearly differ. Ir-1 and Ir-3 have similar angles
with values of 31.8° and 29.8°, respectively, while the TDM of Ir-2 almost
parallels (6.5°) the main ligand plane. The tendency of the angle has order of
mpic < fptz < pic. If the molecular orientation of the Ir complexes is aligned
along the vertical direction of the ancillary ligand due to the local negative ESP
of the dopants, TDMs would have horizontally preferred orientation. This
phenomenon can also be explained in a roundabout way. If the concentration
74
of the Ir complexes in the EML is low enough (~1 wt%), namely, there would
be far more host molecules than dopant molecules. In other words, the
deposition conditions are like emitter-only deposition onto the pre-deposited
host film. Even if the Ir complexes move freely in a vacuum, their interaction
site is limited. Therefore, when dopants adsorb onto the host, the angle of the
TDM to the emitting plane can be determined, as in Figure 4.2a. This implies
that Ir complexes can be deposited in the vertical direction of the ancillary
ligand.
75
4.3 Result and discussion
4.3.1 Characterization of the Ir complexes
Although all the dopants have the same main ligands, in the case of Ir-
3, due to the strong electron withdrawing group, it was expected that the
bandgap would increase, resulting in a deeper blue emission. Different from Ir-
3, Ir-2 was expected similar spectrum to Ir-1 because methyl group does not
attribute radiative processes. To confirm the design concept of ligands,
photoluminescence (PL) spectra are measured as shown in the Figure 4.3. The
maximum peak positions in the PL spectra of Ir-1, Ir-2, and Ir-3 were located
at 449, 450, and 445 nm, respectively. Unlike Ir-1 and Ir-2, Ir-3 has deeper blue
emission that come from the strong electron-withdrawing nature of the ancillary
ligand containing trifluoromethyl-triazole.179, 173 The complexes had vibronic
emissions around 471–475 nm and their contribution was smaller than at the
maximum peak position. Nevertheless, the Commission Internationale de
L’Eclairage (CIE) color coordinates of the PL spectra are limited at (0.14, 0.15).
Optical and thermal properties of Ir complexes are summarized in Table 4.1.
76
Figure 4.3 Photoluminescence spectra of the Ir complexes in methylene chlor
ide (10−5 M).
400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
10-5 M in Methylene Chloride
Ir-1
Ir-2
Ir-3
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
77
Table 4.1 Optical and electric properties of the Ir-complexes.
a) PLQY and Θ were measured using a 30-nm-thick mCBP:TSPO1:1 wt% Ir-complex-doped film (molar ratio 0.495:0.495:0.01) deposited on a
fused silica substrate.
Ir-complex Absorption Emission
Eg [eV] HOMO [eV] LUMO
[eV] Td [℃] Θa)
PLQY
[%]a) kr [s-1] knr [s-1]
λmax (nm) λmax (nm)
Ir-1 256, 299, 361 449, 474 3.18 -6.13 -2.95 379 74 94 1.1x104 7.1x102
Ir-2 255, 363 450, 475 2.95 -6.35 -3.40 369 86 80 1.2 x104 3.1 x103
Ir-3 256, 299, 361 445, 471 2.97 -6.16 -3.19 352 77 48 3.1 x103 3.3 x103
78
4.3.2 Photophysical properties of the Ir complexes in films
To confirm the calculated the characteristics of the Ir complexes in the
emitting layer (EML), 3,3-di(9H-carbazol-9-yl)biphenyl (mCBP) and
diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1) were chosen as a
mixed host because they have T1 levels (2.90 eV for mCBP and 3.36 eV for
TSPO1) that confine the triplet energy of the dopants (~2.75 eV). Figure 4.4
shows the molar extinction coefficients of the dopants and PL spectra of the
hosts. The characteristics of the Ir complexes, including the extinction
coefficients and PL spectra, were measured at a concentration of 10−5 M in
methylene chloride. Different absorption comes from their different 3MLCT or
3LC transition (or both). Ir-1 and Ir-2 have similar absorption spectrum because
a single methyl group does not change transition state dramatically. However,
Ir-3 shows discriminated spectrum due to different transition state of fptz
possessing strong electron withdrawing chemical structure compared to Ir-1
and Ir-2. Despite all the Ir complexes are featured different absorption spectra,
the overlaps between the absorption of the dopants and PL of the hosts is
sufficiently large to transfer the energy from host to the dopants.
To analyze optical properties of emitters, EML films were fabricated
using an mCBP:TSPO1 (1:1 molar ratio) mixed host. Doping concentration of
emitter was optimized to 1 wt% and the thickness of each EML are 30 nm. The
PLQYs of the mCBP:TSPO1:1 wt% Ir-1, 2, and 3 are 94%, 80%, and 48%,
respectively. We have performed transient PL analysis to investigate the origin
79
Figure 4.4 Molar extinction coefficients of the Ir complexes in methylene
chloride (10−5 M) and the photoluminescence spectra of the host materials (30-
nm-thick thin films).
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2Molar extinction coefficient
Ir-1 Ir-2 Ir-3
Mola
r extinction
coeff
icie
nt
(10
-5 m
ol-1
cm
-1)
Wavelength (nm)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Photoluminescence
mCBP
TSPO1
Norm
aliz
ed inte
nsity (
a.u
.)
80
Figure 4.5 Normalized transient PL decay curves of EMLs (30-nm-
thick mCBP:TSPO1:1 wt% Ir complex deposited on a fused silica substrate).
0 10 20 30 40 50 60 70 8010
-4
10-3
10-2
10-1
100
101
Ir-1
Ir-2
Ir-3
Norm
aliz
ed inte
nsity (
a.u
.)
Time (s)
81
Figure 4.6 Angle-dependent PL intensity of the Ir complexes plotted against
their peak wavelength of p-polarized emission of mCBP:TSPO1:dopant (1 wt%)
film (30 nm). Measured intensities (scatters) are compared with simulated
values (line).
0 10 20 30 40 50 60 70 80 90 1000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Measurements
Ir-1
Ir-2
Ir-3
Simulation
Fitted P(H):P(V)=74:26
Fitted P(H):P(V)=86:14
Fitted P(H):P(V)=77:23
Norm
aliz
ed inte
nsity (
a.u
.)
Degree (˚)
82
of different PLQYs. As shown in Figure 4.5, the extracted PL lifetimes of the
Ir-1, 2 and 3 are 8.49 μs, 6.44 μs and 15.6 μs respectively. The extracted
radiative decay rate (kr) and non-radiative decay rate (knr) are listed in Table 4.1
demonstrating low PLQY of Ir-3 resulted from relatively low kr and high knr.
To confirm the result of DFT calculation, orientation of emitting dipoles
was also measured. As shown in the angle-dependent PL (ADPL) data in Figure
4.6, the Θ values of Ir-1 and Ir-3 are 74% and 77%, respectively, while Ir-2 has
a clearly distinct value of 86%. The only difference between Ir-1 and Ir-2 is a
methyl group attached at the ancillary ligand. A methyl group located at the
ancillary ligand does not contribute considerably to the emission mechanism of
Ir complexes. Similarly, the PL spectra of Ir-1 and Ir-2 are not very distinct.
However, from the perspective of the orientation of the emitting dipole, this
methyl group significantly affects Θ. Of course, these results well matched with
the prediction obtained from DFT and TD-DFT calculation shown in Figure
4.2a and b.
4.3.3 Verification of photophysical properties of Ir complexes through the
fabrication of the OLEDs
To realize the characteristics of the dopants, OLEDs were designed
using optical simulation.5,6 Figure 4.7a-c show the maximum achievable EQE
of the devices as a function of the thickness of ETL and HTL. As shown in the
figure, calculated maximum achievable EQEs for the devices doped with Ir-1,
Ir-2, and Ir-3 are 30.1%, 31.3% and 18.0%, respectively. Using these results,
83
Figure 4.7 (a-c) Contour plot of the simulated maximum achievable EQE of
OLEDs with thickness of ETL and HTL; (a) Ir-1 doped OLED (b) Ir-2 doped
OLED (c) Ir-3 doped OLED.
(a)
(b)
(c)
30
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0 20 40 60 80 1000
20
40
60
80
100
Ir-1
PLQY = 94%
=74%
Th
ickn
ess o
f H
TL
(n
m)
Thickness of ETL (nm)
0.0
8.0
16
24
32Maximum achievable EQE (%)
30.1%
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24
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30
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30
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8.0
30
16
16
24
0 20 40 60 80 1000
20
40
60
80
100Maximum achievable EQE (%)
Th
ickn
ess o
f H
TL
(n
m)
Thickness of ETL (nm)
0.0
8.0
16
24
32
Ir-2
PLQY = 80%
=86%31.3%
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
8.0
8.0
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8.0
8.0
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8.0
8.0
16
8.0
8.0
16
8.0
8.0
16
0 20 40 60 80 1000
20
40
60
80
100Maximum achievable EQE (%)
Th
ickn
ess o
f H
TL
(n
m)
Thickness of ETL (nm)
0.0
8.0
16
24
32
Ir-3
PLQY = 48%
=77%18.0%
84
Figure 4.8 (a) Optimized device structure of blue PhOLEDs. (b) J-V-L curves
for each Ir complex-doped PhOLED. (c) EQE of the PhOLEDs as a function of
current density. [Line with squares: Ir-1 doped OLED, line with circles: Ir-2
doped OLED, line with triangles: Ir-3 doped OLED, Inserted photo: EL
emission of the devices at the luminance of 1 cd m-2.]
(a)
(b)
mC
BP
:6w
t%
ReO
3
TS
PO
1
mC
BP
mC
BP
:TS
PO
1:
1w
t% d
op
ant
ITO
Rb2CO3/Al
-2.4
-6.1
-2.5
-6.8
70 40 10 30 10 45 1/100
Unit of thickness: nm
Unit of energy: eV
(c)
0 2 4 6 8 1010
-5
10-4
10-3
10-2
10-1
100
101
102
Doping concentration: 1 wt%
Ir-1
Ir-2
Ir-3
Curr
ent
density (
mA
/cm
2)
Voltage (V)
100
101
102
103
104
105
106
Lum
inance (
cd/m
2)
10-3
10-2
10-1
100
101
102
0
5
10
15
20
25
30
35
Ir-1
Ir-2
Ir-3
EQ
E (
%)
Current density (mA/cm2)
85
structure of the OLEDs is determined. The optimized structure of the OLEDs
is as follows: ITO (70 nm)/mCBP:6 wt% ReO3 (40 nm)/mCBP (10
nm)/mCBP:TSPO1:1 wt% Ir complex (30 nm)/ TSPO1 (55 nm)/Rb2CO3 (1
nm)/Al (100 nm). Figure 4.8a depicts the device structure with its energy levels.
Figure 4.8b shows the current density–voltage–luminance (J-V-L)
characteristics of the devices. The devices have a turn-on voltage (voltage at
luminance of 1 cd m−2) of 3.3 V, which is 0.5 eV higher than the photon energy
of the dopants, which have values of 2.8 eV. This can be explained by the
lowest unoccupied molecular orbital (LUMO) level of TSPO1. The LUMO
level of 2.5 eV is not sufficiently low to inject an electron from the cathode
under barrier-free conditions. Figure 4.8c shows the EQEs of the devices as a
function of the current density with the photo showing EL emission of each
device at 1 cd m-2. The maximum EQEs of the devices doped with Ir-1, Ir-2,
and Ir-3 were 29.0%, 31.9%, and 19.5%, respectively. The experimentally
obtained EQEs are in good agreement with the calculated EQEs shown in the
Figure 4.7a-c within 0.5 ~ 1.5% difference.
There are several reports of highly efficient blue phosphorescent OLEDs
(PhOLEDs)with a CIE color y-coordinate of y < 0.2; however, their EQEs were
around 20%, which is not comparable with the efficiencies of other color-
emitting highly efficient PhOLEDs.163, 164 To our knowledge, an EQE of 31.9%
is the highest value within the Ir complex based PhOLEDs with a CIE y-
coordinate of y < 0.2. The CIE color coordinates were obtained from the
86
Figure 4.9 EL spectra of the blue PhOLEDs throughout the region of the drivi
ng voltages. EL spectra of (a) Ir-1, (b) Ir-2, and (c) Ir-3 doped devices.
400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
(0.143, 0.188)
480 nm
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
Ir-2452 nm
400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
(0.144, 0.185)
Norm
aliz
ed inte
nsity (
a.u
.)
Wavelength (nm)
452 nm476 nm Ir-1
400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
(0.147, 0.179)
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
444 nm 472 nm Ir-3
(a)
(b)
(c)
87
electroluminescence (EL) spectra of the PhOLEDs. For Ir-1, Ir-2, and Ir-3, CIE
coordinates were (0.144, 0.185), (0.143, 0.188), and (0.147, 0.179),
respectively (Figure 4.9). The EL spectra of the devices indicate that they
produce a lighter blue color than that of the PL emission spectra because the
thicknesses of the organic layers are optimized for the maximum EQE utilizing
the cavity structure. Therefore, the sky-blue region of the EL emissions is
enhanced relative to the deep-blue region. Although the deep-blue emitting
region is decreased in all of the devices, the CIE y-coordinate is still y < 0.2.
88
4.4 Conclusion
In conclusion, we introduced novel deep-blue Ir complexes employing
dfpysipy main ligands. We analyzed the effect of ancillary ligand on Θ and
spectrum. Using both DFT calculation and experiment, we verified that
adoption of a methyl group in an ancillary ligand increases Θ from 74% to 86%
due to enhanced local electron density in the terminal. Moreover, CIE y < 0.18
was obtained by partial substitution of the ancillary ligand to strong electron
withdrawing moiety, trifluoromethyl-triazole.
Utilizing controlled orientation and spectrum, we have achieved the
highest EQE of 31.9% for the deep-blue PhOLED with CIE y < 0.2. Our
achievements on the ancillary ligands and their optical properties would
provide the guidelines for synthesis the Ir complexes possessing high Θ with
deep-blue emission spectra.
89
Exciplex-forming Co-host-based Red
Phosphorescent Organic Light-emitting Diodes
with Long Operational Stability and High
Efficiency
5.1 Introduction
Organic light-emitting diodes (OLEDs) are now predominant in small-
sized displays and are increasingly being used in large displays, and their
application is being expanded to lighting. Still many scientific and
technological innovations are occurring in this field. For example, the external
quantum efficiency (EQE) of both fluorescent and phosphorescent OLEDs has
been improved incredibly in the last few years and now exceeds 30% with no
external outcoupling structures, through the appropriate management of the
excitons’ singlet and triplet states as well as control of Θ.5–
9,20,23,93,110,138,139,145,161,180–189 Improving efficiency itself is important, but it
would be much better if high efficiency were realized with excellent device
stability. There have been many reports on the long operational lifetime of red
and green OLEDs. Unfortunately, most stable OLEDs are not very efficient
because the reported stable red OLEDs have had an EQE lower than 15%.12,190–
199 Few studies have focused on the lifetime of highly efficient OLEDs. In fact,
many of the recently reported highly efficient red OLEDs are not very stable,
90
as will be apparent from this paper, indicating that operational stability is still
a challenging issue in high-efficiency OLEDs.
This work presents highly efficient red phosphorescent OLEDs
(PhOLEDs) with a long operational lifetime based on a new exciplex-forming
co-host consisting of a hole-transporting material [N,N'-diphenyl-N,N'-bis(1,1'-
biphenyl)-4,4''-diamine (NPB)] and an electron-transporting material
containing phosphine oxide and triazine [(1,3,5-triazine-2,4,6-
triyl)tris(benzene-3,1-diyl))tris(diphenylphosphine oxide) or PO-T2T] doped
with two different red phosphorescent dyes: bis(4-methyl-2-(3,5-
dimethylphenyl)quinoline))Ir(III)(tetramethylheptadionate) [Ir(mphmq)2
(tmd)] and bis(2-methyldibenzo-[f,h]-quinoxaline)Ir(III) (acetylacetonate)
(Ir(MDQ)2(acac)). The red PhOLED with the NPB:PO-T2T exciplex host has
a maximum EQE of 34.1% and a power efficiency (PE) of 62.2 lm W-1 with
low operating voltages of 2.42, 3.32, and 5.19 V at 100, 1000, and 10,000 cd
m-2, respectively. More importantly, the device using the NPB:PO-T2T
exciplex host has an LT90 of 2249 hours at 1000 cd m-2. The efficiencies of the
devices are the highest for red OLEDs with an LT90 > 1000 hours.
91
5.2 Experimental
5.2.1 Device and sample fabrication
To fabricate red PhOLEDs, the organic layers and a metal cathode were
stacked on top of 100-nm-thick indium tin oxide (ITO) pre-patterned glass
substrate by thermal vacuum-evaporation under a base pressure of < 5 × 10-7
Torr. Metal masks were used to define an active area of 2 × 2 mm2 and to isolate
the cathode and anode. Before deposition, all the substrates were pre-cleaned
using isopropyl alcohol and acetone in an ultra-sonication bath. Next, the
substrates were treated under a UV-ozone flux for 10 minutes. Before
measurement, all of the devices were encapsulated in a glovebox filled with
nitrogen gas using a glass lid and UV-curable resin. The organic films for
photoluminescence (PL) measurement were thermally deposited on fused silica
substrate under same vacuum conditions used for device fabrication.
5.2.2 Device characterization
To measure the PL spectra, organic materials were deposited on quartz
substrates in 50-nm layers. To measure the solution PL, PO-T2T was diluted to
10-5 M in MC solvent. The PL spectra of the organic thin films or solution were
measured using a spectrofluorometer (Photon Technology International)
connected to a monochromator (Acton Research). A xenon flash lamp was used
to excite the organic materials, and the wavelength of the lamp was adjusted by
the monochromator to 290 nm for PO-T2T and 325 nm for NPB and the
NPB:PO-T2T mixed films. To measure the time-resolved PL signals, a pulsed
92
Nd:YAG laser (355 nm) was used as the excitation light source, and an
intensified charge-coupled device was used as the optical detector for the
measurement. The performance of each red PhOLED was characterized using
a Keithley 2400 as the source meter and SpectraScan PR650 (Photo Research)
as the radiometer. A lifetime measurement system (Polaronix M6000T) was
used to measure the operational lifetimes of the PhOLEDs. The absorption
spectra were measured using a Cary 5000 UV−vis−NIR (Agilent Technologies)
spectrophotometer. The concentrations of the solutions for absorption
measurement were made to 10-5 M using MC solvent.
93
5.3 Result and discussion
Figure 5.1a shows the chemical structures of the materials used in the
devices, along with the device structure and the highest occupied molecular
orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and triplet
energy levels.47,145,200 NPB: PO-T2T (molar ratio of 1:1) co-deposited film was
used as the host. The mixed film forms exciplex manifested by the appearance
of a broad, featureless PL spectrum redshifted from those of NPB and PO-T2T
(Figure 5.1b and Figure 5.2) and a strong delayed fluorescence up to 50 μs
(Figure 5.3). The PL spectra from the exciplex hosts doped with the red dyes
showed emissions from the red dyes without host emission (Figure 1B),
indicating that energy transfer from the exciplex to the dopant molecules is
efficient. The PLQYs of Ir(mphmq)2(tmd) and Ir(MDQ)2(acac) in NPB:PO-
T2T were 0.91 and 0.78 and Θ were 0.80 and 0.79 (Figure 5.4), respectively.
The optimized device structure of the red PhOLED was as follows: ITO
(100 nm)/4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl)aniline (TAPC)
(75 nm)/NPB (10 nm)/NPB:PO-T2T:5 wt% red phosphorescent dyes (30
nm)/PO-T2T (10 nm)/0.5% Rb2CO3:PO-T2T (40 nm)/Al (100 nm) (Device 1
for Ir(mphmq)2(tmd) doped emitting layer (EML), Device 2 for
Ir(MDQ)2(acac) doped EML).8
In comparison, the reported efficient red PhOLEDs were also fabricated
using a different exciplex-forming co-host [NPB:4,6-bis(3,5-di-3-
pyridylphenyl)-2-methylpyrimidine (B3PYMPM)] for Device 3, single
94
Figure 5.1 (a) Red-emitting PhOLED structure, energy levels of the organic
layers, molecular structures of the component materials, and triplet energy level
of the host and dopant molecules. (b) Molar absorption coefficient of the dopant
molecules, Ir(mphmq)2(tmd) (solid line), Ir(MDQ)2(acac) (dashed line),
normalized photoluminescence (PL) spectra of NPB (line with squares), PO-
T2T solution (line with circles), PO-T2T film (line with triangle), NPB:PO-T2T
co-deposited thin films (line with inverted triangles), NPB:PO-T2T:5 wt%
Ir(mphmq)2(tmd) (line with left-pointing triangles), and NPB:PO-T2T:5 wt%
Ir(MDQ)2(acac) (line with right-pointing triangles).
(a)
(b)
300 350 400 450 500 550 600 650 700 750 8000.0
2.0x103
4.0x103
6.0x103
8.0x103
1.0x104
1.2x104
Ir(mphmq)2(tmd)
Ir(MDQ)2(acac)
Mo
lar
extin
ctio
n c
oe
ffic
ien
t (L
cm
-1 m
ol-1
)
Wavelength (nm)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.410
-5 M, MC solvent
NPB
PO-T2T (sol.)
NPB:PO-T2T
Ir(mphmq)2(tmd)
Ir(MDQ)2(acac)
No
rma
lize
d P
L in
ten
sity (
a.u
.)
95
Figure 5.2 Magnified feature of molar extinction coefficients of the dopants.
Molar absorption coefficient of the dopant molecules, Ir(mphmq)2(tmd) (black
dashed line), Ir(MDQ)2(acac) (red dashed line), normalized photoluminescence
(PL) spectra of NPB (line with squares), PO-T2T solution (line with circles),
NPB:PO-T2T co-deposited thin films (line with triangles), NPB:PO-T2T:5
wt%.
Figure 5.3 Transient PL spectra of the NPB:PO-T2T co-deposited film at room
temperature. The prompt (red, inset) and delayed (blue) lifetimes are fitted to
be 14.1 ns and 8.84 μs, respectively.
350 400 450 500 550 600 650 7000.0
5.0x102
1.0x103
1.5x103
2.0x103
Molar extinction coeffi.
Ir(mphmq)2(tmd)
Ir(MDQ)2(acac)
Mola
r extinction c
oeffic
ient (L
cm
-1 m
ol-1
)
Wavelength (nm)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.410
-5 M, MC solvent
Norm. PL
NPB
PO-T2T (sol.)
NPB:PO-T2T
Norm
aliz
ed P
L inte
nsity (
a.u
.)
(S2)
0 10 20 30 40 5010
0
101
102
103
104
NPB:PO-T2T
Fitted lines
prompt
delayed
Inte
nsity (
a.u
.)
Time (s)
0 20 4010
0
101
102
103
104
Inte
nsity (
a.u
.)
Time (ns)
96
Figure 5.4 Angle-dependent PL intensities at peak wavelength of
Ir(mphmq)2(tmd) and Ir(MDQ)2(acac) in a 30 nm-thick NPB:PO-T2T matrix.
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4Simulation
Ir(mphmq)2(tmd)
Ir(MDQ)2(acac)
Measurement
Fitted P(H):P(V) = 80:20
Fitted P(H):P(V) = 79:21
No
rma
lize
d in
ten
sity (
a.u
.)
Angle (Degree)
in NPB:PO-T2T co-host
97
hostsbis(10-hydroxybenzo[h]quinolinato)beryllium (Bebq2) for device 4, and
4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) for device 5 with the same red
dopant Ir(mphmq)2(tmd) or Ir(MDQ)2(acac).8,47,200 The detailed structures of
the devices are as follows:
Device 3: ITO (100 nm)/TAPC (75 nm)/NPB (10
nm)/NPB:B3PYMPM:3.5% Ir(mphmq)2(tmd) (30 nm)/B3PYMPM (10
nm)/B3PYMPM:2 wt%Rb2CO3 (45 nm)/Al (100 nm).11
Device 4: ITO (100 nm)/ N,N′-diphenyl-N,N′-bis-[4-(phenyl-m-tolyl-
amino)-phenyl]-biphenyl-4,4 ′ -diamine (DNTPD) (60 nm)/Bebq2:5%
Ir(mphmq)2(tmd) (30 nm)/Bebq2 (75 nm)/LiF (1 nm)/Al (100 nm).37
Device 5: ITO (100 nm)/MoO3 (1 nm)/CBP (65 nm)/CBP:2% bis(2-
phenylpyridine)iridium(III)acetylacetonate(Ir(ppy)2(acac)):2% Ir(MDQ)2(acac)
(15 nm)/ 2,2′,2″-(1,3,5-benzinetriyl)-Tris(1-phenyl-1-H-benzimidazole) (TPBi)
(75 nm)/LiF (1 nm)/Al (100 nm).47
Figure 5.5a shows the current densityvoltageluminance (JVL)
characteristics of the red PhOLEDs. The exciplex-based OLEDs (Devices 1~3)
had low operating voltages of 3.1~3.4 V at 1000 cd m-2. Similar characteristics
have been described elsewhere.5,6,8,11,55,106,149,153,161,183,184,186,189 The red
PhOLEDs with single hosts had relatively higher operating voltages of ca. 5.1
V for Bebq2 and ca. 6.7 V for CBP at 1000 cd m-2. Figure 5.5b and Figure 5.6
present the calibrated EQEs and PEs of the devices considering the distribution
98
Figure 5.5 (a) Current densityvoltageluminance (JVL) characteristics of
the PhOLEDs. (b) EQEs of PhOLEDs as a function of luminance.
(a)
(b)
0 2000 4000 6000 8000 100000
5
10
15
20
25
30
35
40
EQ
E (
%)
Luminance (cd m-2)
device 1
device 2
device 3
device 4
device 5
0 2 4 610
-6
10-5
10-4
10-3
10-2
10-1
100
101
102
Cu
rre
nt
De
nsity (
mA
cm
-2)
Voltage (V)
0 2 4 6 8 10 12
LJ device 1
device 2
device 5
100
101
102
103
104
105
device 3
device 4
Lu
min
an
ce
(cd
m-2)
J LJ L
99
Figure 5.6 PEs of the devices as a function of luminance.
0 2000 4000 6000 8000 100000
10
20
30
40
50
60
70
Pow
er
eff
icie
ncy (
lm W
-1)
Luminance (cd m-2)
Device 1
Device 2
Device 3
Device 4
Device 5
100
of angle-dependent emission. Device 3 has the highest maximum EQE and PE:
35.6% and 66.2 lm W-1, followed by Device 1 with 34.1% and 62.2 lm W-1,
respectively. Table 5.1 summarizes the detailed characteristics of the devices.
The Commission Internationale d'Eclairage (CIE) 1931 coordinates were
(0.648, 0.352) at 1000 cd m-2 and (0.646, 0.353) at 10,000 cd m-2 for Device 1,
and (0.621, 0.378) at 1000 cd m-2 and (0.618, 0.380) at 10,000 cd m-2 for Device
2.
Figure 5.7 shows the normalized EL decay curves of the red-emitting
PhOLEDs as a function of operating time measured at an initial luminance (L0)
of 1000 cd m-2. The NPB:PO-T2T exciplex-based PhOLEDs exhibited
remarkably stable operation under the continuous flow of a constant current
among the devices. The operational lifetime using LT90 was 2243 hours for
Device 1 and 1102 hours for Device 2. As shown in Figure 3, device 3 had an
LT90 10,000 times shorter than that of Device 1, although the B3PYMPM-based
PhOLED was measured under a lower constant current density of 2.03 mA cm-
2 at an initial luminance of 1000 cd m-2.
The devices with exciplex hosts (devices 1~3) resulted in higher
efficiencies and lower deriving voltages than single hosts (devices 4 and 5) as
reported before due to better charge balance and low injection barriers. The
devices based on the NPB:PO-T2T exciplex host resulted in much longer
lifetimes than the other devices. The long operational stability of the NPB:PO-
T2T exciplex-based PhOLEDs may result from stable materials used for the
101
Table 5.1 Summary of the performance of the red PhOLEDs.
Device
Operating voltage Efficiency
Turn-on 1 cd m-2
1000 cd m-2
EQE (%) PE (lm W-1)
Max. 1000
cd m-2 Max.
1000 cd m-2
Device 1 1.90 3.32 34.1 32.4 62.2 42.0
Device 2 1.90 3.10 26.8 25.9 48.9 33.8
Device 3 2.10 3.16 35.6 35.1 66.2 53.6
Device 4 2.10 5.08 24.8 21.0 50.0 16.8
Device 5 3.25 6.78 21.1 19.7 45.8 22.1
102
Figure 5.7 Normalized electroluminescence (EL) decay curves of the PhOLE
Ds as a function of operational time at an initial luminance (L0) of 1000 cd m-
2. For comparison, the EL decay curves of reported highly efficient red PhOL
EDs are shown. (Inset: magnified time region from 0–80 hours)
0.01 0.1 1 10 100 1000 1000050
55
60
65
70
75
80
85
90
95
100
105
device 1
device 2
device 3
device 4
device 5
L/L
o(%
), L
0 =
1,0
00 c
d m
-2
Time (hours)
0 10 20 30 40 50 60 70 8085
90
95
100
L/L
o(%
)
Time (hours)
103
Figure 5.8 Cyclic voltammetry (CV) curves of PO-T2T in acetonitrile solution.
The concentration of the solution was 1 mM.
-1.2 -0.9 -0.6 -0.3 0.0 0.3 0.6-15
-10
-5
0
5
Cu
rre
nt
(A
)
Potential vs. Ag/Ag+ (V)
104
devices. NPB is a representative hole-transporting material with long-term
stability.80,201 In addition, the cyclic voltammogram of PO-T2T in acetonitrile
solution (Figure 5.8) exhibited a reversible reaction in the anodic scan,
indicating that the anion state of the PO-T2T is stable. Interestingly, there is a
difference of operational lifetime even same exciplex is utilized in the Device
1 and 2 as depicted in the Figure 3. The operational lifetime of Device 1 was
2.04 times longer than that of Device 2 probably due to the higher efficiency
requiring less electrical stress in Device 1 than Device 2. Peculiarly, the
luminance of Device 1 increased slightly at the initial stage. This finding can
be explained by a recombination zone shift or a slight change in the charge
balance as the OLEDs operate continuously. In comparison, the other devices
had much shorter lifetimes with LT90 = 0.2~74 hours. During operation, the
exciplex host keeps the holes in the stable hole-transporting material (stable
cations) and electrons in the stable electron-transporting material (stable
anions) separate in the emitting layer. The stable positive and negative polarons
form exciplexes if they get close to each other, instead of forming excitons in a
single molecule. This condition reduces the density of both cation and anion
radicals in the hole- or electron-transporting molecules, respectively, which
significantly reduces the operational lifetime.202,203 However, not all the
exciplex hosts guarantee a long operational lifetime. When PO-T2T is replaced
with B3PYMPM (device 3), another electron-transporting material that also
had a high EQE, power efficiency, and low roll-off,11 we did not obtain an LT90
as long as that of the device with PO-T2T. These results indicate that exciplex
105
host consisting of stable charge transporting materials will results in highly
efficient OLEDs with long operation lifetimes.
The lifetimes of red-emitting PhOLEDs based on the NPB:PO-T2T-
based exciplex hosts in this work are among the longest reported values for
devices for which all of the information about the device and molecular
structures was disclosed. However, the lifetimes are still shorter than those
reported from industry. The materials used by industry are very pure and
involve little contamination between molecules in a single chamber. Therefore,
it is difficult to directly compare industrial performance with academic
achievement.
106
5.4 Conclusion
A high-performance red PhOLED with a long operational lifetime, an
LT90 of 2249 hours at an L0 of 1000 cd m-2, was realized using an exciplex
formation of NPB and PO-T2T. The red-emitting PhOLED with the long
lifetime also had a high efficiency, with a maximum EQE of 34.1% and a PE
of 62.2 lm W-1. The device also had very low driving voltages of 2.42, 3.32,
and 5.19 V at 100, 1000, and 10,000 cd m-2, respectively. These findings
suggest that certain combinations of a stable donor and acceptor for an exciplex
host and phosphorescent dopant can increase both operational lifetime and
efficiency of OLEDs, which are both important factors from a commercial
perspective. We anticipate that these findings can be easily extended to white
OLEDs for flexible, solid-state lighting and displays.
107
Enhanced Long-Term Stability and
Maximum Luminance of Blue Orgainc Light-
Emitting Diode using Novel Hole Transporting
Material without Weak C-N Bond
6.1 Introduction
Recently, researches on the degradation phenomenon of the organic
light-emitting didoes (OLEDs) are being carried out. Various methodologies
have been introduced to analyze the external and internal factors of the device,
but the exact origin of the underlying degradation has not yet been fully
elucidated.201,204–207
We have noticed that the electrical and optical properties of the device
are essentially unchanged unless the chemical that makes up the OLED is
denatured. Therefore, it was deduced that the degradation of OLEDs could be
reduced by using a material which has high BDEs (> 2.8 eV=,photon blueE ) and
can not easily dissociate. Especially, we focused on hole transporting material
(HTM). Currently, HTM reported in the academia mostly uses carbazole and
always contains a single C-N bond.6,11,76,84,173,208–219 However, that bond has a
disadvantage that the bond dissociation energies (BDEs) are very low in all the
ionic states of molecule. In this perspective, we did not include a single C-N
bond, so we designed a structure in which the material is not cleaved into two
108
chemical species by homolysis of the C-N bond. In addition to this, a new
device structure is proposed that does not use materials with low BDEs for all
the layers constituting the device based on the newly densigned material except
for the emitter. Throgh the device structure, a blue OLED ahieving a luminance
exceeding 50000 cd m-2 was fabricated with a 10 times or more improvement
in the comparative operational lifetime.
109
6.2 Experimental
6.2.1 Device and sample fabrication
To fabricate blue OLEDs, the organic layers and a metal cathode were
stacked on top of 70-nm-thick indium tin oxide (ITO) pre-patterned glass
substrate by thermal vacuum-evaporation under a base pressure of < 5 × 10-7
Torr. Metal masks were used to define an active area of 2 × 2 mm2 and to isolate
the cathode and anode. Before deposition, all the substrates were pre-cleaned
using isopropyl alcohol and acetone in an ultra-sonication bath. Next, the
substrates were treated under a UV-ozone flux for 10 minutes. Before
measurement, all of the devices were encapsulated in a glovebox filled with
nitrogen gas using a glass lid and UV-curable resin. The organic films for PL
measurement were thermally deposited on fused silica substrate under same
vacuum conditions used for device fabrication.
6.2.2 Device characterization
To measure the PL spectra, organic materials were deposited on quartz
substrates in 30-nm layers. To measure the solution PL, materials were diluted
to 10-5 M in MC solvent. The PL spectra of the organic thin films or solution
were measured using a spectrofluorometer (Photon Technology International)
connected to a monochromator (Acton Research). A xenon flash lamp was used
to excite the organic materials, and the wavelength of the lamp was adjusted by
the monochromator to 290 nm. The performance of each blue OLED was
characterized using a Keithley 2400 as the source meter and SpectraScan
110
PR650 (Photo Research) as the radiometer. A lifetime measurement system
(Polaronix M6000T) was used to measure the operational lifetimes of the
PhOLEDs. The absorption spectra were measured using a Cary 5000
UV−vis−NIR (Agilent Technologies) spectrophotometer. The concentrations
of the solutions for absorption measurement were made to 10-5 M using
methylene chloride (MC) solvent.
Angle-dependent PL experiments were performed on a motorized
rotational stage with a half cylinder lens made of fused silica. The substrate of
the film made of fused silica was attached to a half-cylinder lens with refractive
index matching liquid. A continuous-wave He/Cd laser (325 nm, Melles Griot
Co.) was used as the excitation source and the incident angle of the laser was
45° to the detection plane. A dichroic mirror was used to filter the excitation
beam and a linear polarizer was used to control the polarity of the emitted light.
Angle-dependent p-polarized PL spectra of the film were detected by a fiber
guided spectrometer (Maya 2000 Pro, Ocean Optics Inc.) with automated
rotation of the stage.
6.2.3 Density functional theory (DFT) calculation
Geometry optimization, energy levels, and BDEs of HTMs were
calculated with a time-dependent DFT calculation using Maestro Materials
Science (Schrödinger). For optimization, B3LYP and the 6-31G basis sets were
used.
111
6.3 Result and discussion
Two kinds of HTMs with the same structure were designed by using
Indolo[3,2,1-jk]carbazole (indolocarbazole) moiety. The basic skeleton of
HTMs are composed of indolocarbazole-linker-indolocarbazole, which are
classified according to the binding site of indolocarbazole. One is the 1,3-
bis(indolo[3,2,1-jk]carbazol-2-yl)benzene (meta-IBI), in which the
indolocarbazole is bonded to the benzene likner at the meta position, and the
other is the 1,4-bis(indolo[3,2,1-jk]carbazol-2-yl)benzene (para-IBI) bound to
the para position. These materials have no single C-N bond in the structure and
moiety-linker bonds are consisted of C-C bonds. Indolocarbazole moiety is
used for hole transporting characteristics of meta-IBI and para-IBI. For the
purpose of well-balanced charge and transport in EML, electron accepting
material for n–type host is also selected. In this research, 2,8-bis(4,6-diphenyl-
1,3,5-triazin-2-yl)dibenzo[b,d]thiophene (DBTTrz) is used as an n–type host
and hole blocking material (HBL). In order to compare the device
characteristics, mCP is set as a comparative group, which is the same structure
as meta-IBI, but is a conventional HTM using carbazole instead of
indolocarbazole.
Table 6.1 shows the calculated properties of the materials. As shown in
the Table 6.1, BDEs of the meta-IBI and para-IBI are higher than those of mCP
for all the ionic state of materials. Major dissocating path of the mCP is the
break of the C-N bond in at the carbazole and phenyl linker for whole ionic
112
Table 6.1 Calculated bond dissociation energies of HTMs
Name BDE (eV)
anion neutral cation
meta-IBI 4.49 4.88 5.63
para-IBI 4.53 4.90 6.09
mCP 1.36 3.59 4.23
113
Figure 6.1 (a) Chemical structure of EML constituting materials (b)
Exctinction coefficient of emitter and PL spectra of host materials.
meta-IBI
DBTTrz
SEL-BDpara-IBI
(a)
(b)
350 400 450 500 550 600 6500.0
2.0x104
4.0x104
6.0x104
Absorption
SEL-BD
Exctinction C
oeffic
ient (L
mol-1
cm
-1)
Wavelength (nm)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Norm
aliz
ed inte
nsity (
a.u
.)
Photoluminescence
SEL-BD
meta-IBI (solution)
mCP
DBTTrz
meta-IBI:DBTTrz
mCP:DBTTrz
114
states. However, meta-IBI and para-IBI has no single C-N bond because
indolocarbazoles of meta-IBI and para-IBI are connected using C-C bonds to
benzene linker.
Figure 6.1a and b show the chemical structures of molecules and the
molar extinction coefficient of emitter and PL spectra of host materials. For
solution PL, all the materials are dissolved in methylene chloride (MC) and
concentration of the solutions is 10-5 M and for solid PL, 30 nm-thick films
were utilized. Low temperature solution PL spectra are also measured to define
triplet states of the materials used in the EMLs at the temperature of 77 K.
Figure 6.2 shows the triplet emission of the meta-IBI, para-IBI and the
comparative, mCP. As shown in that figure, meta-IBI shows 2.78 eV of the
highest triplet emission and 2.59 eV of second highest emission spectrum.
Different from meta-IBI, triplet emission spectrum of para-IBI dispersed
around 500~550 nm region mainly due to long conjugation length of para-
linked structure compared to meta-IBI. mCP possesses higher triplet levels
(3.02~2.82 eV) whereas indolocarbazole moiety containing materials have
lower triplet energy than 2.8 eV. When it comes to conjugation length of
aromatic molecule, fused carbazole must possess longer conjugation length
compared to carbazole. Therefore, lower T1 levels of meta-IBI and para-IBI
compared to mCP are natural.
All the co-deposited films show exciplex emission whose energy levels
are 2.87 eV, 2.70 eV and 2.95 eV for meta-IBI:DBTTrz, para-IBI:DBTTrz and
115
Figure 6.2 Triplet emission of the HTMs (in MC solvent, 10-5 M and 77 K).
Figure 6.3 Exciplex PL emission of meta-IBI:DBTTrz, para-
IBI:DBTTrz and mCP:DBTTrz. (30 nm-thick thin film)
350 400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
2.3
0 e
V
2.4
6 e
V
2.5
9 e
V
2.7
8 e
V
2.8
2 e
V
3.0
2 e
V
Norm
aliz
ed inte
nsity (
a.u
.)
Wavelength (nm)
meta-IBI
para-IBI
mCP
350 400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
460 nm
432 nm meta-IBI:DBTTrz
para-IBI:DBTTrz
mCP:DBTTrz
Norm
aliz
ed inte
nsity (
a.u
.)
Wavelength (nm)
420 nm
116
Figure 6.4 Triplet energy diagram of host materials with their exciplexes.
2.78 eV 2.80 eV2.85 eV
2.46 eV2.80 eV2.77 eV
meta-IBIpara-IBI
DBTTrz DBTTrz
meta-IBI:
DBTTrz
exciplex
para-IBI:
DBTTrz
exciplexT1
S0
3.02 eV2.80 eV
2.95 eV
mCPDBTTrz
mCP:
DBTTrz
exciplex
117
mCP:DBTTrz, respectively (Figure 6.3). Triplet exciplexes are not confined in
the co-host systems because T1 of the exciplex constituting materials are lower
than that of each exciplex. Nevertheless, triplet energy levels of the remaining
hosts except para-IBI have higher than that of the dopant, N1,N6-bis(3-(9-
phenyl-9H-fluoren-9-yl)phenyl)-N1,N6-di-m-tolyl-3,5-dihydropyrene-1,6-
diamine (SEL-BD), resulting in OLED with theoretical efficiency without a
serious loss. Triplet energy diagram of EML is described in Figure 6.4. Due to
the low T1 of para-IBI, para-IBI containing EML is not considered for the
device. For meta-IBI and mCP, spectral overlap between PL of host and
absorption of emitter is large enough to energy transfer as shown in Figure 6.1b.
Concentration of the emitter in the exciplex forming co-host is
determined by comparison of photoluminescent quantum yield (PLQY) for
each ratio. Optimized concentration is 5 wt%, which showed the highest PLQY
of 42% (Table 6.2). As shown in the Figure 6.5, PL spectra of the EMLs are
varied with their concentration. Different from 5 and 8wt % SEL-BD doped
ETL, host emission is observed in 1 wt% doped film implying ratio of dopant
is not enough to accept excitons formed in the host. Meanwhile, 8 wt% doped
film shows 1 nm red-shifted spectrum compared to that of 5 wt% doped film
accompanying with 1% reduction of PLQY due to aggregation of the dopant.
In contrast with the PLQY, emitting dipole orientations (Θ) are not varied with
the concentration of dopant. Θ of each EML is 84%, which is described in
Figure 6.6.
118
Table 6.2 PLQY of the EML at various doping concentration of emitter.
EML PLQY (%)
meta-IBI:DBTTrz
(exciplex host) 8.8
meta-IBI:DBTTrz:SEL-BD 1wt 37.5
meta-IBI:DBTTrz:SEL-BD 5wt 42.3
meta-IBI:DBTTrz:SEL-BD 8wt 41.5
Figure 6.5 PL spectra of EML at various doping concentration of emitter.
350 400 450 500 550 600 6500.0
0.2
0.4
0.6
0.8
1.0
1.2 meta-IBI:DBTTrz:1wtEL-BD
meta-IBI:DBTTrz:5wtEL-BD
meta-IBI:DBTTrz:8wtEL-BD
No
rma
lize
d in
ten
sity (
a.u
.)
Wavelength (nm)
119
Figure 6.6 Emitting dipole orientation of each EML.
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8Measurement
meta-IBI:DBTTrz:1wtEL-BD
Simulation
Fitted(84%)
Isotropic(66.7%)
Parallel(100.0%)
Norm
aliz
ed inte
nsity (
a.u
.)
Angle (Degree)
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8Measurement
meta-IBI:DBTTrz:5wtEL-BD
Simulation
Fitted(84%)
Isotropic(66.7%)
Parallel(100.0%)
Norm
aliz
ed inte
nsity (
a.u
.)
Angle (Degree)
0 10 20 30 40 50 60 70 80 900.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8Measurement
meta-IBI:DBTTrz:8wtEL-BD
Simulation
Fitted(84%)
Isotropic(66.7%)
Parallel(100.0%)
Norm
aliz
ed inte
nsity (
a.u
.)
Angle (Degree)
(a)
(b)
(c)
120
Figure 6.7 (a) Current density-Electric field characteristics of hole only devices
of HTMs (b) The hole mobilities of HTMs as a function of electricfield.
300 400 500 600 700 800 900
10-8
10-7
10-6
10-5
10-4
10-3
Hole only device
ITO (70 nm)/ReO3 (1 nm)/meta-IBI (100 nm)/ReO
3 (1 nm)/Al (100 nm)
Moblil
ity (
cm
2/V
s)
Electric field1/2
(V1/2
/cm1/2
)
meta-IBI
mCP
(a)
(b)
103
104
105
106
10-4
10-3
10-2
10-1
100
101
102
103
104
meta-IBI
mCPC
urr
en
t d
en
sity (
mA
/cm
2)
Electric field(kV/cm)
121
To compare the hole transporting ability of the materials, hole only
devices are fabricated. The device structures are as followed:
ITO (70 nm)/ReO3 (1 nm)/HTMs (100 nm)/ReO3 (1 nm)/Al (100 nm)
where HTMs are meta-IBI and mCP. J-V characteristics and field dependent
mobility of the devices are shown in Figure 6.7a and b. Mobilities are analyzed
space charge limited current (SCLC) regime. Using Mott-Gurney theory and
Poole-Frenkel model, current density and mobility of the devices are expressed
as following equations:
2
0 3
9
8SCLC r
VJ
L (6.1)
0 exp(0.89 )F (6.2)
where J is the current density, 0 is vacuum the permittivity,
r is the
dielectric constant, is the mobility, V is voltage, L is thickness of the film.
can be expressed by a function of the zero field mobility(0 ) and Poole-
Frenkel coefficient ( ) and the electric field (F). As shown in the Figure 6.7a,
materials showed the high field dependency after Ohmic region. The hole
mobility of the meta-IBI is 10-5 (V cm-1)1/2 range, which is higher than that of
mCP at the whole field.152,220
Using optical simulation, the device structures are optimized. The
structures of devices are as followed:
122
ITO (70 nm)/MoO3 (1 nm)/H2 (45 nm)/HTM (5
nm)/HTM:DBTTrz:SEL-BD (0.475:0.475:0.05 in weight ratio, 30
nm)/DBTTrz (5 nm)/CN-T2T (35 nm)/LiF (0.7 nm)/Al (100 nm)
where HTMs are meta-IBI or mCP for Device 1 and 2, repectively. As shown
in the Figure 6.8 and 6.9, whole materials constituting Deivce 1 has no single
C-N bond. However, Device 2 used mCP instead of meta-IBI for HTM and p–
type host. Figure 6.10a shows J-V-L characteristics of OLEDs. Devices showed
different turn- on voltage and maximum luminance. Device 1 has turn-on
voltage of 2.7 V, which is correspond to the photon energy of emitter. However,
device 2 showed turn-on voltage of 3.0 V due to deep HOMO level compared
to the meta-IBI. The only difference between device 1 and 2 is the HTM.
Therefore, the difference in maximum luminance between the two devices can
be attributed to the distinction in the stability of the positive polaron. During
operation, the HTM constantly assumes a positive polaron state, and stability
in that state plays an important role in stability of OLEDs. In particular, when
using a co-host, p–type host can be in a state capable of receiving electrons, and
the BDE in the anion state of the HTM can also greatly affect the stability of
EML. In other words, for all the ionic states, meta-IBI with higher BDEs than
mCP can have longer operational lifetime of the device and higher stability
when high voltage and current are applied.
The maximum EQE of the Device 1 and 2 were 5.1 and 5.8%,
respectively, and at high current densities, Device 1 exhibited lower efficiency
123
Figure 6.8 Chemical structures of host and charge transporting materials used
in Device 1 and 2.
H2
meta-IBIDBTTrz
mCP
CN-T2T
Device 1 Device 2
124
Figure 6.9 Device structures of Device 1 and 2. Device 1 used meta-IBI for
HTM and p–type host. Device 2 used mCP for HTM and p–type host.
ITOH
2(T
1=
2.9
eV
)
2.4
5.6
MoO
3
6.7
me
ta-I
BI (T
1=
2.8
5 e
V)
2.73
5.94
6.6
3.19
DB
TT
rz(T
1=
2.8
eV
)
me
ta-I
BI:D
BT
Trz
:5
wt%
SE
L-B
D
+ S
en
sitiz
er
CN
-T2
T(T
1=
2.8
eV
)
6.7
2.8
LiF/Al
(Thickness unit: nm)
1 570 45 3530 0.7 / 1005
(Energy unit: eV)
ITO
H2
(T1=
2.9
eV
)
2.4
5.6
MoO
3
6.7
mC
P(T
1=
3.0
5 e
V)
2.4
6.1
6.6
3.19
DB
TT
rz(T
1=
2.8
eV
)
mC
P:D
BT
Trz
:5
wt%
SE
L-B
D
+ S
en
sitiz
er
CN
-T2
T(T
1=
2.8
eV
)
6.7
2.8
LiF/Al
(Thickness unit: nm)
1 570 45 3530 0.7 / 1005
(Energy unit: eV)
125
Figure 6.10 (a) J-V-L characteristics of OLEDs (b) EQE of OLEDs as a
function of current density.
0 2 4 6 8 10 1210
-5
10-4
10-3
10-2
10-1
100
101
102
103
33,340 nit
Curr
ent density (
mA
/cm
2)
Voltage (V)
Device 1 (meta-IBI)
Device 2 (mCP)
54,000 nit
100
101
102
103
104
105
Lum
inance (
cd/m
2)
10-2
10-1
100
101
102
103
0
2
4
6
8
10
12
14HTM
Device 1 (meta-IBI)
Device 2 (mCP)
EQ
E (
%)
Current density (mA/cm2)
(a)
(b)
126
Figure 6.11 Operational lifetime of OLEDs. (Dashed line means LT95.)
0 1 2 3 4 540
50
60
70
80
90
100
Device 1
(meta-IBI)
Device 2
(mCP)
LT95
(L/L
0)*
100 (
%)
Time (hour)
127
roll-off as shown in the Figure 6.10b. In addition to this, the actual operational
lifetime of Device 1 was 12 times longer than that of Device 2. Figure 6.11
shows the operational lifetime of OLEDs. Initial luminance was 400 cd m-2.
Operational lifetime to 95% of initial luminances (LT95) of each device were
2.6 and 0.22 h.
128
6.4 Conclusion
Novel HTMs are designed for the stable blue OLEDs. We used
indolocarbazole moiety to make the HTMs without a single C-N bond and
designed the materials with BDE above 4.49 eV in all ionic states and with a T1
greater than 2.7 eV was designed. The device structure without a single C-N
bond based on the meta-IBI obtained high luminance of 54000 cd m-2 and
operational lifetime improvement of 12 times compared to the case of using
carbazole based conventional HTM, mCP.
129
Summary and outlook
Organic light-emitting diodes (OLEDs) are no longer a future display.
Throgh decades of development, the industry has grown ripe and is now being
applied to a veriety of products. However, many improvements in terms of
efficiency and long-term stability are still required and if these problems ar
solved, it will be applied to a much wider range of future technologies. In this
respect, this thesis quantitatively calculated and achieved the efficiency and
limitations of blue phosphorescent OLEDs (PhOLEDs), and further designed
new compunds and novel device structure by extracting elements that affect the
operational lifetime. As a result, improved maximum luminance and enhanced
stability were obtained.
In Chapter 2 and 3, we developed the world’s highest efficiency (34.1%)
blue PhOLEDs using exciplex forming co-host with low refractive material and
quantitatively analyzed external quantum efficiency (EQE) that can be achieved
ultimately through optical calculation. The results show that a blue OLEDs with
a horizontal emitting dipole orientation and PLQY of 1 and refractive index of
1.5 can achieve an EQE of up to 61.5%.
In Chapter 4, using the deep blue phosphorescent emitter, the world’s
highest efficiency (31.9%) of CIE y < 0.2 OLED was achieved. In particular,
the phosphorescent emitter exhibited a extraordinary ratio of horizontal
emitting dipole orientation (EDO) of 86%, which indirectly showed that small
chemical changes in ancillary ligands could significantly improve the EDO
130
through interaction with the host matrix.
In Chapter 5, using novel exciplex forming co-host, red PhOLEDs were
fabricated possessing both high EQE and long operational lifetime. We
experimentally demonstrated that introducing an exciplex using an
electrochemically stable material provides both high EQE and long-term
stability.
As we continued our studies on operational lifetime, we began to study
the fundamental causes of degradation. In Chapter 6, we considered that
degradation would not occur fundamentally if the material could be retained in
the device without chemical dissocation. Therefore, we noted the chemical
stability of the materials. We found something in common among the weak
materials. Most weak materials contain single C-N bond, which has low bond
dissociation energy (BDE) for all ionic states. By focusing on these properties,
we designed indolocarbazole based new hole transporting material (HTM) with
high triplet energy without a single C-N bond. Using that materials, novel
device structure was suggested. The device structure without a single C-N bond
based on the meta-IBI obtained high luminance of 54000 cd m-2 and operational
lifetime improvement of 12 times compared to conventional HTM, mCP used
device.
Through the studies in this paper, we could present the future direction
of OLEDs development. In particular, the design of low refractive charge
transport materials, ancillary ligand of Ir-complex and new chemical structures
131
with high bond dissociation energy have been shown to be necessary for
OLEDs for long operational lifetime. Based on this, if a material with enhaced
electro-optical properties and chemical stability is developed, the ultimate
OLEDs will be born.
132
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초 록
디스플레이 산업은 대면적 디스플레이, 고품질 패널을 채택한
전자 기기 개발에 대한 수요로 지난 수십 년 동안 크게 확장되었다.
현재 대부분의 패널은 두 가지 유형의 디스플레이를 채택하고
있는데, 하나는 백색 발광다이오드 백라이트가 포함된 액정
디스플레이이고 다른 하나는 유기발광다이오드이다. 기존
디스플레이와는 달리, 유기발광다이오드는 기판 선택에 대한 제한이
적기 때문에 유연, 투명 기판에 적용하기 쉬우며, 생체 적합성
특성을 가진 차세대 디스플레이 기술에 적용될 수 있다. 하지만,
이러한 유기발광다이오드의 확장성에도 불구하고 여전히 해결책을
기다리고있는 문제가 남아 있다.
유기발광다이오드의 주요 문제점은 ⅰ) 색 품질, ⅱ) 고효율
및 ⅲ ) 안정성으로 분류된다. 현재 이미 상용화 된 사례가
존재하지만, 유기발광다이오드의 쓰임새의 광범위화 그리고
유용성을 위해서는 이러한 문제점들이 해결되어야 한다.
일반적으로 유기발광다이오드의 색품질은 전기발광
스펙트럼으로 평가된다. 전기발광 스펙트럼의 개형은
유기발광다이오드의 색 영역, 색온도 및 연색지수에 영향을 미치는
Commission Internationale de L' Eclairage (CIE) 좌표를 결정한다.
145
기본적으로 CIE 좌표는 스펙트럼이 자신의 여기 상태에 의해
결정되는 발광체의 고유 방출 색에 의해 결정되기 때문에, 발광체의
적절한 선정은 유기발광다이오드의 본질적인 색을 결정하는 데에
매우 중요하다. 효율의 경우 유기발광다이오드의 에너지 소비에
직접적으로 연계되므로 성능 평가에 대한 주요 지표다. 효율을
개선하기 위하여, 유기반도체 분야에 종사하는 많은 연구자들은 외,
내부 광추출 구조와 효율적인 발광체, 호스트 및 소자 구조를 개발
해왔다. 이러한 노력에도 불구하고, 청색 유기발광다이오드의 경우,
청색 발광의 높은 에너지 준위로 인한 재료 및 구조의 제한성으로
인해 적색, 녹색에 비해 높은 효율을 구현하는 것이 어려운 상태다.
이 뿐만 아니라, 용도에 적합한 발광 스펙트럼과 고효율을
지니더라도 유기발광다이오드의 구동 수명이 일상 생활이나
산업에서 사용하기에 충분히 길지 못하면 실용성이 떨어질 수 밖에
없다. 이에, 유기발광다이오드의 구동 안정성을 향상시키는 연구가
다방면으로 진행되어 왔다. 현재, 녹색, 적색 인광 및 청색 형광
유기발광다이오드는 높은 구동 안정성으로 상용화 디스플레이
패널에 사용되고 있다. 그러나, 상용화된 안정한
유기발광다이오드의 경우 이론 값 보다 낮은 외부양자효율을
나타내고 있다. 즉, 이론 한계 효율과 긴 구동 수명을 동시에
146
달성하는 것이 궁극적으로 유기발광다이오드 연구가 진행되어야 할
방향이다.
본 논문은 크게 (1) 이론 한계의 효율을 갖는 청색 인광
유기발광다이오드와 (2) 높은 결합 해리 에너지를 갖는 안정한
물질을 사용하여 구동 수명이 긴 유기발광다이오드라는 두가지
주제를 다루고 있다.
제 2 장은 청색 발광에 적합한 최초의 엑시플렉스
(exciplex) 시스템에 대한 보고와 함께, 이론 한계 효율을 갖는
청색 인광 유기발광다이오드에 대한 내용을 담고있다. 청색
발광체는 큰 밴드갭과 높은 삼중항 에너지(T1)를 가지기 때문에,
청색 발광체에 적합한 엑시플렉스 시스템은 구현하기 어려운
것으로 생각되어왔다. 하지만 2.9 eV 이상의 높은 T1 을 갖는
카바졸 기반의 정공전달물질과 피리딘과 피리미딘이 포함된
전자전달물질을 이용하여 2.99 eV 의 에너지 준위를 갖는 새로운
청색 발광체 용 엑시플렉스를 설계하였다. 새롭게 개발된
엑시플렉스 시스템을 활용하여, 광학 시뮬레이션을 통해 얻을 수
있는 최대치 수준이자, 개발 당시 세계 최고 외부양자효율인
29.5%를 갖는 청색 인광 유기발광다이오드를 구현하였다. 또한
실험 결과와 광학 계산을 이용하여 엑시플렉스를 이용한 시스템이
전기적 손실이 거의 없이 이론 효율을 달성할 수 있게 한다는 것을
147
밝혔으며, 발광쌍극자의 수평배향율과 절대발광효율이 1 일 때, 최대
40% 이상의 외부양자효율을 얻을 수 있다는 것을 밝혔다.
최초의 청색 발광용 엑시플렉스를 통해 이론효율을
달성하였지만, 저굴절률 재료를 사용해, 외부로 추출되는 광량을
늘린다면 최대 외부양자효율의 근본적인 한계치를 높일 수 있다.
이러한 내용을 근간으로, 제 3 장에서는 저굴절 물질을 이용한
엑시플렉스를 통해 외부양자효율의 이론적 한계의 확장과 범용적인
효율 예측에 대한 논의를 제시한다. 발광쌍극자의 수평배향율
그리고 소자를 구성한 전하전달물질의 굴절률에 따른 이론 한계
효율을 계산하였다. 일반적인 유기 박막의 굴절률인 1.8 수준에서
청색 유기발광다이오드의 이론상 최대 달성 가능한 외부양자효율은
약 30 %이다. 하지만 본 계산에서는 소자 구성층의 굴절률을 주요
변수로 계산하여, 1.5 수준의 저굴절 물질을 사용한다면 최대
61.5% 의 외부양자효율을 달성할 수 있으며 청색 파장 영역에서
기존 전자전달물질 보다 굴절률이 약 0.1 낮은 물질을 포함하는
엑시플렉스를 사용하여 최대 외부양자효율과 전력효율이 34.1 %,
79.6 lm W-1인 청색 인광 유기발광다이오드를 보고하였다.
하늘색의 경우와 달리 진청색 인광 유기발광다이오드 (CIE y
< 0.2)의 최대 효율은 낮은 절대발광효율과 발광쌍극자의
수평배향율 때문에 이론 한계수준보다 10% 가량 낮은 상태다. 제
148
4 장에서는 이러한 문제를 해결하기 위해, 우리는 인광 도펀트의 주
리간드를 밴드갭이 커지는 방향으로 설계하고 보조 리간드의
구조적 변형을 통해 색순도의 향상과 발광 쌍극자의 수평배향율을
조정하였다. 또한 양자화학계산을 통해, 보조 리간드의 향상된 전자
밀도가 전이쌍극자모멘트의 방향을 조절하여 발광쌍극자의
수평배향율이 상승될 수 있음을 예측하였고 실험을 통해 최대
86%의 수평배향율과 이론 한계 수준의 외부양자효율인 31.9 %를
얻어 계산을 실험적으로 검증하였다.
유기발광다이오드의 핵심 난제 중 하나인 구동 안정성에 대한
논의는 제 5 장에서 다뤄진다. 해당 장에서는 고효율과 장수명을
갖는 엑시플렉스 기반의 적색 인광 유기발광다이오드에 대해
논의한다. 엑시플렉스를 구성하는 물질의 전기화학적 안정성이
소자의 구동 수명을 향상시켜, 최종적으로 이론 한계에 근접한
효율(34.1%)과 1000 cd m-2 에서 10%의 휘도 저감까지(LT90)
2249 시간이 소요되는 장수명 적색 인광 유기발광다이오드를
구현하였다.
제 6 장에서는 유기발광다이오드의 구동 수명을 화학적
측면에서 접근하여 연구 범위를 청색까지 넓혔다. 거시적인
관점에서 열화는 수분, 산소 등의 외부적 요인과 결합 해리와 같은
화학반응 등으로 발생하는 내부적 요인으로 나뉘게 된다.
149
본질적으로 유기발광다이오드를 구성하는 화학 물질이 소자의 구동
중에 해리되거나 새롭게 반응하지 않으면, 소자의 발광 특성을
변화시킬 수 없다. 이 아이디어를 바탕으로 우리는 높은 결합 해리
에너지와 T1 을 갖는 안정한 물질을 설계 했다. 높은 T1 을 갖는
대부분의 정공전달물질은 페닐-카바졸 결합과 같은 단일 C-N
결합을 포함하며, 이는 대부분의 단일 C-N 결합이 2.0 eV 보다
낮은 결합해리에너지를 가지기 때문에 분자에서 결합 해리 위치가
될 수 있다. 결합 해리를 방지하고 높은 T1 을 유지하기 위해,
우리는 단일 C-N 결합을 제거한 융합 카바졸 구조를 채택했다. 이
방법론을 사용하면 새로 설계된 정공전달물질에서 단일 결합
절단으로 호몰리시스(homolysis)를 일으킬 수 없어, 화학적
안정성이 향상될 수 있다. 우리는 그 특성을 기존의 카바졸 기반의
물질과 비교하여 청색 유기발광다이오드에서 정공전달물질을
안정한 것으로 변화시켰을 때, 50000 cd m-2 이상의 높은 휘도와
12 배 이상 향상된 구동 수명을 구현하였다.
주요어: 청색 유기발광다이오드, 엑시플렉스, 이론 한계 효율,
저굴절 물질, 안정한 물질, 높은 결합해리에너지
학번: 2013 – 20606
150
CURRICULUM VITAE
Hyun Shin
Department of Materials Science & Engineering
Seoul National University, Seoul, 151-744, Korea
+82-2-875-2412 (Office)
E-mail: [email protected]
Education
2013.09 ~ 2018.08 Ph.D. in Materials Science & Engineering
Supervisor: Professor Jang-Joo Kim
Seoul National University, Seoul, Korea
2008.03 ~ 2013.02 B.S. in Materials Science & Engineering
Seoul National University, Seoul, Korea
Research Interests
Blue organic light-emitting diodes, highly efficient organic light-emitting
diodes, blue exciplex, operational lifetime of organic light-emitting didoes,
chemical stability of organic semiconductor materials
Professional Skills
− Design and fabrication of organic electronic devices: Thermal vacuum
evaporator, Glove-box, Spin coater
− The optoelectronic analysis on organic semiconductors: UV-vis-NIR
absorption spectroscopy, OLEDs characteristic measurements, Transient
151
photoluminescence (PL) (Nd:Yag laser, N2 laser, streak camera, iCCD),
Transient electroluminescence (EL), PL efficiency measurement, Angle
dependent PL analysis
− The structural characterization of organic semiconductors: AFM, α-STEP
− Density functional theory (DFT) calculations
− Design of stable materials with high bond dissociation energy
Scholarship and Fellowship
− Brain Korea 21 Scholarship (2013.08~)
152
Awards
− Hyun Shin, “Best Paper Award (Silver)”, The Young Leaders Conference
in International Meeting on Information Display 2017 (IMID 2017),
August 30, 2017
− Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jin-Suk Huh, Bomi-Sim
and Jang-Joo Kim, “Best Poster Award”, International Conference on
Electronic Materials and Nanotechnology for Green Environment (ENGE
2017), November 9, 2016
153
List of Publications
1. Sunghun Lee, Seul-Ong Kim, Hyun Shin, Hui-Jun Yun, Kiyull Yang,
Soon-Ki Kwon, Jang-Joo Kim*, and Yun-Hi Kim*, "Deep-Blue
Phosphorescence from Perfluoro Carbonyl-Substituted Iridium
Complexes", J. Am. Chem. Soc. 135, 38 (2013)
2. Sunghun Lee, Hyun Shin and Jang-Joo Kim*, "High-efficiency Orange
and Tandem White Organic Light-emitting Diodes Using Phosphorescent
Dyes with Horizontally Oriented Emitting Dipoles", Adv. Mater. 26, 5864
(2014)
3. Hyun Shin, Sunghun Lee, Kwon-Hyeon Kim, Chang-Ki Moon, Seung-
Jun Yoo, Jeong-Hwan Lee and Jang-Joo Kim*, “Blue Phosphorescent
Organic Light-Emitting Diodes Using an Exciplex Forming Co-Host with
the External Quantum Efficiency of Theoretical Limit”, Adv. Mater. 26,
4730 (2014)
4. Jin Won Sun, Jeong-Hwan Lee, Chang-Ki Moon, Kwon-Hyeon Kim,
Hyun Shin and Jang-Joo Kim*, "A Fluorescent Organic Light Emitting
Diode with 30% External Quantum Efficiency", Adv. Mater. 26, 5684
(2014)
5. Jeong-Hwan Lee, Shuo-Hsien Cheng, Seung-Jun Yoo, Hyun Shin, Jung-
Hung Chang, Chih-I Wu, Ken-Tsung Wong*, and Jang-Joo Kim*, "An
Exciplex Forming Host for Highly Efficient Blue Organic Light Emitting
154
Diodes with Low Driving Voltage", Adv. Funct. Mater. 25, 361 (2015)
6. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jin-Suk Huh, Bomi Sim,
Jang-Joo Kim*, "Sky-Blue Phosphorescent OLEDs with 34.1% External
Quantum Efficiency Using a Low Refractive Index Electron Transporting
Layer", Adv. Mater. 28, 4920 (2016)
7. Jeong-Hwan Lee(+), Hyun Shin(+), Jae-Min Kim, Kwon-Hyeon Kim,
Jang-Joo Kim*, "Exciplex-Forming Co-Host-Based Red Phosphorescent
Organic Light-Emitting Diodes with Long Operational Stability and High
Efficiency", ACS Appl. Mater. Interfaces 9, 3277 (2017)
8. Hyoungcheol Lim, Hyun Shin, Kwon-Hyeon Kim, Seung-Jun Yoo, Jin-
Suk Huh, Jang-Joo Kim*, "An Exciplex Host for Deep-Blue
Phosphorescent Organic Light-Emitting Diodes", ACS Appl. Mater.
Interfaces 9, 37883 (2017)
9. Sohee Jeon(+), Sunghun Lee(+), Kyung-Hoon Han(+), Hyun Shin, Kwon-
Hyeon Kim, Jun-Ho Jeong*, and Jang-Joo Kim*, "High-Quality White
OLEDs with Comparable Efficiencies to LEDs", Adv. Opt. Mater.
DOI:10.1002/adom.201701349 (2018)
10. Hyun Shin, Yeon Hee Ha, Ran Kim, Soon-Ki Kwon*, Yun-Hi Kim* and
Jang-Joo Kim*, “Controlling Horizontal Dipole Orientation and Emission
Spectrum of Ir complex by Chemical Design of the Ligands for Efficient
Deep-Blue Organic Light-Emitting Diodes”, in preparation.
155
List of Presentations
International Conference
1. Jin Won Sun, Jeong-Hwan Lee, Chang-Ki Moon, Kwon-Hyeon Kim,
Hyun Shin and Jang-Joo Kim, "A Fluorescent Organic Light Emitting
Diode with 100% Internal Quantum Efficiency", The 14th International
Meeting on Information Display (iMiD 2014), August 26-29, 2014, Korea
(Poster)
2. Hyun Shin, Sunghun Lee, Kwon-Hyeon Kim, Chang-Ki Moon, Seung-
Jun Yoo, Jeong-Hwan Lee and Jang-Joo Kim, "Blue Phosphorescent
Organic Light Emitting Diodes using an Exciplex Forming Co-host with
the External Quantum Efficiency of Theoretical Limit", The 14th
International Meeting on Information Display (iMiD 2014), August 26-29,
2014, Korea (Poster)
3. Jinwon Sun, Jeong-Hwan Lee, Chang-Ki Moon, Kwon-Hyeon Kim, Hyun
Shin and Jang-Joo Kim, "A Fluorescent Organic Light Emitting Diode
with 100% Internal Quantum Efficiency", OSA Optics & Photonics
Congress: Light, Energy and Environment, December 2-5 (December 3),
2014, Australia (Poster)
4. Hyun Shin, Sunghun Lee, Kwon-Hyeon Kim, Chang-Ki Moon, Seung-
Jun Yoo, Jeong-Hwan Lee and Jang-Joo Kim, "Accomplishing the
Theoretical Limit of External Quantum Efficiency in Blue Phosphorescent
Organic Light Emitting Diodes Using an Exciplex Forming Co-Host", The
156
6th Asian Conference on Organic Electronics (A-COE 2014), November
12-14 (November 13), 2014, Taiwan (Poster)
5. Jin Won Sun, Jeong-Hwan Lee, Chang-Ki Moon, Kwon-Hyeon Kim,
Hyun Shin and Jang-Joo Kim, "Fluorescent Organic Light Emitting Diode
with 100% Internal Quantum Efficiency", The International Workshop on
Flexible & Printable Electronics 2014 (IWEFE 2014), November 5-7,
2014, Korea (Poster)
6. Hyun Shin, Sunghun Lee, Kwon-Hyeon Kim, Chang-Ki Moon, Seung-
Jun Yoo, Jeong-Hwan Lee and Jang-Joo Kim, "Achieving the Theoretical
Limit of External Quantum Efficiency in Blue Phosphorescent Organic
Light Emitting Diodes Using an Exciplex Forming Co-Host", The
International Workshop on Flexible & Printable Electronics 2014 (IWEFE
2014), November 5-7, 2014, Korea (Poster)
7. Hyun Shin, Jang-Joo Kim, "Effect of triplet exciplex confinement in
organic light-emitting diodes according to donor/acceptor forming ratio",
The 7th International Workshop on Flexible & Printable Electronics 2015
(IWFPE 2015), November 4-6 (November 5), 2015, Korea (Poster)
8. Jin Won Sun, Jeong-Hwan Lee, Chang-Ki Moon, Kwon-Hyeon Kim,
Hyun Shin, Jang Joo Kim, "A Fluorescent Organic Light Emitting Diode
with 100% Internal Quantum Efficiency", The International Symposium
on Recent Advanes and Future Issues in Organic Electroluminscence
(ISOEL2016), February 17-19 (February 18), 2016, Korea (Poster)
157
9. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jin-Suk Huh, Bomi Sim,
Jang-Joo Kim, "Highly efficient blue phosphorescent OLED with over 34%
of EQE using a Low Refractive Index Electron Transporting Material",
The International Symposium on Recent Advanes and Future Issues in
Organic Electroluminscence (ISOEL2016), February 17-19 (February 18),
2016, Korea (Poster)
10. Hyun Shin, Sunghun Lee, Kwon-Hyeon Kim, Chang-Ki Moon, Seung-
Jun Yoo, Jeong-Hwan Lee, Jang-Joo Kim, "Accomplishing the Theoretical
Limit of External Quantum Efficiency in Blue Phosphorescent Organic
Light Emitting Diodes using an Exciplex Forming Co-host", The
International Symposium on Recent Advanes and Future Issues in Organic
Electroluminscence (ISOEL2016), February 17-19 (February 18), 2016,
Korea (Poster)
11. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jinsuk Huh, Bomi Sim,
Jang-Joo Kim, "Sky-blue phosphorescent OLEDs with 34.1% external
quantum efficiency using a low refractive index electron transporting
material", SPIE Optics+Photonics 2016, August 28-September 1 (August
29), 2016, USA (Poster)
12. Jang-Joo Kim, Kwon-Hyeon Kim, Chang-Ki Moon, Hyun Shin, "Highly
efficient phosphorescent, TADF, and fluorescent OLEDs", SPIE
Optics+Photonics 2016, August 28-September 1 (August 28), 2016, USA
13. Kwon-Hyun Kim, Hyun Shin, Jinwon Sun, Jang-Joo Kim, "High
efficiency organic light emitting diodes", KJF International Conference on
158
Organic Materials for Electronics and Photonics 2016 (KJF-ICOMEP
2016), September 4-7 (September 5), 2016, Japan (Poster)
14. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Bomi Sim, Jang-Joo Kim,
"Highly Efficient Blue Phosphorescent OLED with over 34% of EQE
using a Low Refractive Index Charge Transporting Materials",
International Conference on Electronic Materials and Nanotechnology for
Green Environment (ENGE 2016), November 6-9 (November 07), 2016,
Korea (Poster)
15. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jin-Suk Huh, Bomi Sim,
Jang-Joo Kim, "Highly Efficient Sky-blue Phosphorescent OLED with
over 34% of EQE Using a Low Refractive Index Charge Transporting
Materials", The 8th International Workshop on Flexible & Printable
Electronics (2016 IWFPE), November 23-24 (November 23), 2016, Korea
(Poster)
16. Hyun Shin, Jeong-Hwan Lee, Chang-Ki Moon, Jin-Suk Huh, Bomi Sim,
Jang-Joo Kim, "Highly Efficient Sky-blue Phosphorescent OLED with
over 34% of EQE using a Low Refractive Index Electron Transporting
Material", The 8th Asian Conference on Organic Electronics (A-COE
2016), December 5-7 (December 6), 2016, Japan (Poster)
17. Sohee Jeon, Sunghun Lee, Kyung-Hoon Han, Hyun Shin, Kwon-Hyeon
Kim, Jun-Ho Jeong, Jang-Joo Kim, "High Quality White OLEDs with
Comparable Efficiencies to LEDs using randomly dispersed vacuum
nanohole array", The 28th Internaional Conference on Molecular
159
Electronics and Devices 2017 (IC ME&D 2017), May 18-19 (May 18),
2017, Korea (Poster)
18. Hyoungcheol Lim, Hyun Shin, Kwon-Hyeon Kim, Seung-Jun Yoo, Jin-
Suk Huh, Jang-Joo Kim, "Deep-blue phosphorescent organic light-
emitting diodes based on high triplet energy exciplex host", 2nd
International TADF Workshop, July 19-21 (July 19), 2017, Japan (Poster)
19. Kyung-Hoon Han, Sohee Jeon, Sunghun Lee, Kwon-Hyeon Kim, Hyun
Shin, Jun-Ho Jeong, Jang-Joo Kim, "High quality white OLEDs with LED
efficiencies", SPIE Optics+Photonics 2017, August 6-10 (August 6), 2017,
USA (Poster)
20. Hyun Shin, Yeon Hee Ha, Ran Kim, Yun-Hi Kim, Soon-Ki Kwon, Jang-
Joo Kim, "Highly Efficient Deep-blue Organic Light-Emitting Diodes
Using Novel 2'-6'-Difluoro-4-(trimethylsilyl)-2,3'-Bipyridine Ligand-
based Ir-complexes with Horizontally Oriented Transition Dipole
Moment", The 17th International Meeting on Information Display (iMiD
2017), August 28-31 (August 30), 2017, Korea (Oral)
21. Sohee Jeon, Sunghun Lee, Kyung-Hoon Han, Hyun Shin, Kwon-Hyeon
Kim, Jun-Ho Jeong, Jang-Joo Kim, "Optical Analysis of White Organic
Light Emitting Diodes with Randomly Dispersed Nano-pillar Array", The
17th International Meeting on Information Display (iMiD 2017), August
28-31 (August 31), 2017, Korea (Poster)
22. Hyun Shin, Jeong-Hwan Lee, Jae-Min Kim, Kwon-Hyeon Kim, Jang-Joo
Kim, "Stable Red Phosphorescent Organic Light-emitting Diodes using
160
exciplex forming co-host with High Efficiency", The 9th Asian Conference
on Organic Electronics (A-COE 2017), October 25-27 (October 26), 2017,
Korea (Poster)
23. Hyoungcheol Lim, Hyun Shin, Kwon-Hyeon Kim, Seung-Jun Yoo, Jin-
Suk Huh, Jang-Joo Kim, "Deep Blue Emitting Exciplex Forming System
and Its Application to Phosphorescent Organic Light-Emitting Diodes",
The 9th Asian Conference on Organic Electronics (A-COE 2017), October
25-27 (October 26), 2017, Korea (Poster)
Domestic Conference
1. 신현, 이성훈, 김권현, 문창기, 유승준, 이정환, 김장주, "Blue
Phosphorescent Organic Light Emitting Diodes using an Exciplex Forming
Co-host with the External Quantum Efficiency of Theoretical Limit", 2014
춘계고분자학회, April 9-11 (April 10), 2014 (Poster)
2. 신현, 이성훈, 김권현, 문창기, 유승준, 이정환, 김장주, "Blue
Phosphorescent Organic Light Emitting Diodes using an Exciplex Forming
Co-host with the External Quantum Efficiency of Theoretical Limit", 2014
Materials Fair, September 25, 2014, Korea (Poster)
3. 신현, 문창기, 김장주, "OLED 의 효율에 영향을 미치는 물질
특성", 2016 한국고분자학회 춘계학술대회, April 6-8 (April 7),
2016, Korea
161
4. 신현, 이정환, 문창기, 허진석, 심봄이, 김장주, "Blue
phosphorescent OLED with EQE over 34% using low refractive index
electron transporting layer", 2016 한국고분자학회 춘계학술대회, April
6-8 (April 8), 2016, Korea (Poster)
5. 신현, 이정환, 김재민, 김권현, 김장주, "Red Phosphorescent Organic
Light-emitting Diodes Using Exciplex Forming Co-host with Long
Operational Lifetime and High Efficiency", 2017 한국고분자학회
추계학술대회, October 11-13 (October 12), 2017, Korea (Poster)
6. 임형철, 김장주, 신현, 김권현, 유승준, 허진석, "An exciplex host
consisted of high triplet level materials for deep-blue phosphorescent
organic light-emitting diodes", 2017 한국고분자학회 추계학술대회,
October 11-13 (October 13), 2017, Korea (Poster)
162
List of Patents
1. 신현, 김장주, “신규 화합물 및 이를 포함한 유기 발광
소자”, 예비출원
2. 신현, 김장주, “축합환 화합물 및 이를 포함하는 유기 발광
소자”, 예비출원