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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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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

Horizontal dipole proportion (%)

76

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0.5 0.6 0.7 0.8 0.9 1.00.5

0.6

0.7

0.8

0.9

1.0EQE (%)

PL

Qu

an

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Yie

lds

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

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1.2

FIrpic

No

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d in

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sity (

a.u

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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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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35

40

25

6054

30

50

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35

40

25

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30

50

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35

40

25

6054

30

50

45

35

40

25

6054

30

50

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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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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30

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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)

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Ir-1

PLQY = 94%

=74%

Th

ickn

ess o

f H

TL

(n

m)

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32Maximum achievable EQE (%)

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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

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16

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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: hyun1005@snu.ac.kr

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