Вы находитесь на странице: 1из 14

Hisahiro Junji Kido


Account/Review for
Materials Innovation
Document type: Review/Account

Account/Review for Materials Innovation

Review of Molecular Engineering for Horizontal Molecular Orientation

in Organic Light-Emitting Devices

Yuichiro Watanabe,1 Hisahiro Sasabe,*1,2 and Junji Kido*1,2

Department of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
Research Center for Organic Electronics (ROEL), Frontier Center for Organic Materials (FROM), Yamagata University,
4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
E-mail: h-sasabe@yz.yamagata-u.ac.jp (H. Sasabe), kid@yz.yamagata-u.ac.jp (J. Kido)

Received: November 5, 2018; Accepted: December 20, 2018; Web Released: March 7, 2019

Yuichiro Watanabe
Yuichiro Watanabe received his diploma from Tokyo Tech High School of Science and Technology in 2009
and Ph. D. degree in Organic Materials Engineering from Yamagata University, Japan in 2018. His doctoral
thesis was on horizontally oriented organic semiconductors using hydrogen bonds for highly efficient organic
light-emitting devices. He is currently a Japan Society for the Promotion of Science postdoctoral fellow with
the Prof. Alexander Wei research group at Purdue University, USA.

Hisahiro Sasabe
Hisahiro Sasabe received his Ph.D. degree in 2005 from the Department of Applied Chemistry of Osaka
Prefecture University. He joined the OITD at Yamagata, then went for a postdoctoral stay at Yamagata
University. His academic position began at the Department of Organic Device Engineering, Yamagata
University in Yonezawa as an assistant professor, and an associate professor (2016–now). His work has
been recognized with awards from the Society for Information Display, U.S.A. (Special Recognition Award) in
2018. His current research interest includes design and synthesis of high-performance organic semi-
conductor materials for organic devices.

Junji Kido
Junji Kido received his B.S. degree in applied chemistry from Waseda University, Tokyo, Japan, in 1984 and
M.S. and Ph.D. degrees in polymer chemistry from Polytechnic University, New York, in 1987 and 1989,
respectively. In 1989, he joined the department of polymer chemistry at Yamagata University in Japan as an
assistant professor and was promoted to an associate professor in 1995, and to full professor in 2002. His
work has been recognized by awards from the Society of Polymer Science, Japan (SPSJ, Society Award),
and the Society for Information Display, U.S.A. (Special Recognition Award and Fellow Award) in 2002 and
in 2008. He also received the Herman F. Mark Technology Medal from Polytechnic University (2007), the
Medal with Purple Ribbon from the Japanese Emperor (2013), and the SPSJ Fellow Award (2018).

Abstract a crucial parameter for determining key optoelectronic functions

Organic light-emitting devices (OLEDs) are widely used in of organic devices, such as device lifetime, efficiency, ioniza-
next-generation eco-friendly solid-state display and lighting tion potential, and carrier mobility of semiconductor amorphous
technologies. Most key optoelectronic functions of organic films films. In this review, we discuss horizontal molecular orienta-
used in organic semiconductor devices are dependent on two tion from a molecular engineering perspective considering the
important factors: the electronic properties of single molecules, three essential layers of OLEDs: the hole transport layer, elec-
and the molecular orientations. The molecular orientation has tron transport layer, and emissive layer. In addition, we address
recently attracted considerable attention, and been recognized as the future challenges of next-generation OLED materials.

716 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Keywords: Organic light-emitting devices j of a hole-transport layer (HTL), EML, and electron-transport
Molecular orientation j Organic semiconductors layer (ETL), and are commonly used for current multilayer
OLEDs.27­34 This device structure achieves efficient carrier
injection into the EML from the HTL and ETL to reduce the
1. Introduction required driving voltage of the OLED. When suitable HTL and
Organic optoelectronic devices based on organic semi- ETL materials are used, these layers also block electrons and
conductors, such as organic light-emitting devices (OLEDs), holes, respectively, thereby confining both carriers in the EML
organic photovoltaic cells (OPVs), and organic field-effect and ensuring good carrier balance.
transistors (OFETs), are currently revolutionizing our daily life Recently, molecular orientation in organic semiconductor
by replacing conventional inorganic electronics.1­8 A represen- amorphous films has been recognized as another key parameter
tative example is OLED displays used for smart phones, smart in determining the performance of organic optoelectronic
watches, and large-area televisions (TVs). In the case of a devices, including the device efficiency, lifetime, ionization
large-area OLED TV commercialized by LG in Korea using potential, and carrier mobility (Figure 1).35­39 In 2000, Friend
tandem white OLED technology, the so-called multiphoton et al. experimentally demonstrated the importance of the molec-
technology is critical for realizing high efficiency and long- ular orientation of the emitter molecule using conjugated-
term stability at a high brightness of several thousand polymer-based OLEDs.40 They estimated that horizontally
cd m¹2.9,10 This technology can be used for general lighting oriented emitting dipole moments of the emitter increased the
requiring 3000­5000 cd m¹2 and has shown long-term stability OLED efficiency by a factor of over 1.5 compared with a ran-
of several years.9­19 OLED displays are becoming a vital tech- domly oriented emitter. In 2008, Duhm et al. showed the effect
nology for many consumer products; however, considering the of molecular orientation on the ionization potential (Ip), which
theoretical limit of the efficiency of white OLED, there are is a fundamental parameter determining the carrier injection
significant opportunities to improve the materials and tech- properties.41 By controlling the molecular orientation of an
nologies enabling OLED displays using the ultimate green oligothiophene derivative, Ip can be significantly increased,
technology.20,21 by up to 0.6 eV. Given that the density-of-states is typically
To improve the efficiency of OLEDs, researchers generally 0.2 eV in organic amorphous films,42 such an increase in the
use two major approaches. The first is to introduce phospho- Ip value is surprisingly large. In 2011, Sasabe and Yokoyama
rescent22­24 and/or thermally activated delayed fluorescent reported a 100-fold increase in the carrier mobility in a series of
(TADF)25 emitters, so-called second- and third-generation pyrimidine-based electron-transporters by inducing horizontal
emitters instead of first-generation fluorescent emitters, into molecular orientation.43,44 In 2018, Reineke et al. demonstrated
the emissive layer (EML); this increases the internal quantum that organic amorphous layers with very high thermodynamic
efficiency (IQE) to unity by harvesting all electrically generated stability realized a five-fold enhancement of OLED lifetime.45
molecular excitons. The other approach is to use organic Hence, molecular orientation is crucial for tailoring the opto-
multilayer structures with different electrochemical properties electronic properties of organic semiconductor films used in
to produce devices with low power consumption. Three-layer practical devices; however, only few passive methodologies
devices, the so-called double heterostructure,26 typically consist for controlling the molecular orientation have currently been

Figure 1. Schematic diagram showing the importance of molecular orientation in OLED performance.

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 717
developed. Therefore, there is a great and urgent need to amine (m-MTDATA,53 S = ¹0.04) have random orientation
develop a method for actively controlling molecular orientation (Figure 2A).54 This is mainly due to their sterically hindered
in order to improve the performance of organic optoelectronics. structures and isotropic propeller-like molecular geometries
In this review, we summarize the current status, important with a large number of molecular conformations. Indeed, it is
challenges, and future perspective of molecular orientation in difficult to control their molecular orientation using straightfor-
OLEDs from the viewpoint of molecular engineering. We ward TPA groups.
present three sections, focusing on state-of-the-art HTL, ETL, One strategy for constructing horizontally oriented films is
and EML technologies. In contrast to the previous excellent the introduction of planar and disk-like molecular geometries
reviews,35­39 which mainly considered enhancement of phys- composed of TPA groups, which has been extensively studied.
ical aspects, we focus on the chemical structures of materials For example, Yokoyama et al. reported that molecules having
used in OLEDs. In addition, we highlight the current state-of- planar or long-and-winding geometries, such as TPA oligomers
the-art molecular orientation technologies using weak non- TPD1555 and TPT155,56 are horizontally oriented in the films.54
covalent interactions and evaluate their potential for creating Even when the molecular length increases and the molecules
next-generation smart materials. have various conformations, the transition dipole moment of
the molecule is along the π-conjugation system. In addition,
2. Molecular Orientation in the HTL: Kim et al. reported substantially horizontally oriented mole-
Molecular Structure and Orientational Relationship cules with star-burst or disk-like geometry, TPA-TPE (S =
As the molecular orientation of carrier transport layers in ¹0.27) and PDA-TPE (S = ¹0.28), which contain triphenyl-
OLEDs can increase carrier mobilities, it contributes to reduc- ethene (TPE) at the end of the TPA or N,N,N¤,N¤-tetraphenyl-p-
ing the operational voltage of these devices and increasing its phenylenediamine (PDA) (Figure 2A).57 These results suggest
operational lifetime. However, since the first demonstration of that the molecules with two-dimensional prolonged π-systems
OLED technology in 1987 by Tang and VanSlyke based on have a strong tendency toward parallel alignment on the
small molecules,46 and in 1990 by Burroughes et al. based on a substrate, despite their bulky propeller-shaped TPE units. This
polymer emitter,47 researchers have focused on the electronic is mainly due to a decrease in the positional and energetic
properties of single molecules and the correlation between disorders in the molecular-oriented states. The TPA and PDA
single molecular properties and device efficiency, rather than cores retain their intrinsic hole-transporting functionality even
molecular orientation. In addition, analytical techniques for after being substituted with the TPE peripheries. Using the
evaluating molecular orientation were not well established at space-charge-limited current technique, it has been shown that
that time. As conventional small molecules in OLEDs do not the hole mobility (®h) of the PDA-TPE and TPA-TPE thin
possess long-range ordered structures, common analytical films exceeds 10¹2 cm2 V¹1 s¹1 (estimated values of ®h from
methods, such as X-ray thin-film structure analysis, are not literature are on Figure 2), which is about one order of magni-
highly effective. In 2002, materials with strong blue emis- tude higher than that of amorphous α-NPD, and two orders of
sion and high bipolar carrier mobilities (®), such as ter(9,9- magnitude higher than that of m-MTDATA.55,58 In addition,
diarylfluorene) (TF) derivatives, were demonstrated.48­50 They these values are the highest among those reported for hole-
observed that the long molecular axis of TF derivatives was transporting amorphous molecular materials.59­62 One of the
oriented parallel to the substrate using variable angle spectro- most important insights provided by VASE analysis is that
scopic ellipsometry (VASE)35,51 analysis. VASE is one of the molecular orientation can be observed, even in amorphous thin
analytical methods used to detect molecular orientation in films, by systematic selection of the molecular structure.
amorphous organic films. The molecular orientation in thin Recently, Wakamiya’s group have been taking advantage of
solid films is discussed using two optical constants, the refrac- various synthesis methods in order to introduce quasiplanar
tive index (n) and extinction coefficient (k) in the horizontal structures into TPA groups by reducing the steric hindrance of
and vertical directions, respectively. They concluded that the hydrogen atoms.63­65 In 2014, they reported partially oxygen-
high mobility is critically dependent on the molecular orienta- bridged triarylamines as HTL materials (Figure 2C).63 They
tion. This was the first report of optical anisotropy and molec- presented a synthesis route of two-fold intramolecular nucleo-
ular orientation in amorphous films of small-molecular-based philic aromatic substitution to cyclize triarylamine, which yield-
OLEDs. Although the specific mechanism was not discussed in ed a disk-like quasiplanar molecular geometry. The quasiplanar
this seminal paper, the molecular orientation was probably due molecule possessed face-on π-stacking in amorphous films,
to the rigid and linear molecular geometry. as analyzed by two-dimensional grazing-incidence X-ray dif-
In the early stages of studying molecular orientation in fraction (2D GIXD) with a synchrotron radiation source.66,67
HTLs, the triphenylamine (TPA) derivatives conventionally Although they did not quantitatively analyze S, the molecular
used for OLEDs were systematically investigated using VASE design strategy can be applied to various HTL materials for
analysis. In addition to determining their molecular orientation, horizontal molecular orientation. In addition, the high intensity
the degree of orientation can be quantified using the orienta- and directionality of X-rays make such methods powerful tools
tion order parameter (S). This value is close or equal to 0 for analyzing molecular orientation in amorphous OLED
when the transition dipole moments of molecules have com- films.68 It should be noted, that for optoelectronic devices,
pletely random orientation and is ¹0.5 when they have a fully changes in the crystallinity of the molecules and electronic
horizontal orientation. For example, N,N¤-Di(1-naphthyl)-N,N¤- properties of single molecules due to the π-extension need to be
diphenyl-(1,1¤-biphenyl)-4,4¤-diamine (α-NPD,52 S = ¹0.01), considered. Both the covalent and non-covalent interactions
and 4,4¤,4¤¤-Tris [(3-methylphenyl) phenylamino] triphenyl- can be used to design horizontally oriented molecules.

718 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Figure 2. Schematic diagrams of the molecular structures and orientational relationships in the HTL.

Carbazole (Cz) groups, which have also been used for contrast, the orientation of BCS and BSB-Cz, which are
fabricating HTLs and p-type host molecules for EMLs, possess elongated by the ethenylphenyl units, is highly dependent on
a more planar molecular framework than that of TPA groups the molecular length. In particular, the linear BSB-Cz struc-
and tend to be π-stacked. Cz derivatives have been produced ture showed a high S value of ¹0.33. Hence, there is a clear
with a high degree of molecular orientation by taking advan- correlation between the molecular length and S. These results
tage of the molecular planarity. For example, Yokoyama et al. demonstrate that linear molecules with a high aspect ratio can
investigated the influence of the length of the molecular core be horizontally oriented in vacuum-deposited amorphous films
structure for Cz derivatives, such as 4,4¤-bis(N-carbazolyl)-1,1¤- depending on their molecular length.
biphenyl (CBP69,70), 4,4¤-bis(N-carbazolyl)-stilbene (BCS71),
and 4,4¤-bis[(N-carbazole)styryl]-biphenyl (BSB-Cz72).73 In the 3. Molecular Orientation in ETLs:
case of CBP with a compact molecular geometry, the S value Molecular Structure, Non-Covalent Molecular
was almost isotropic (S = ¹0.07) (Figure 2D). This indicates Interactions, and Orientation Relationship
that the orientation of the transition dipole moment attributed The discussion in the previous section showed that a key
to the high absorption was almost random in these films. In design rule for obtaining horizontally oriented films is to

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 719
Figure 3. Representative optoelectronic units A) for hole-transport layers, and B) for electron-transport layers.

produce molecules with linear and disk-like molecular struc- to its bulky tert-butyl terminal substituents, while Bpy-OXD
tures, rather than the spherical structure of tris-(8-hydroxy- showed significant anisotropy due to its planar Bpy terminal
quinoline)aluminum (Alq3),74 which is the most common elec- substituents induced by the transoid structure86 with intra-
tron transport material (Figure 3 and Figure 4A). In general, molecular hydrogen bonds. With respect to the single molecule
the electron mobility (®e) of typical ETLs is almost a factor of geometry, high-aspect-ratio linear and planar molecules are
two lower than that of ®h of the HTL.60,76,77 Thus, development advantageous for horizontal molecular orientation.
of highly oriented ETLs is of paramount importance in order to It has been demonstrated that intermolecular interactions
increase its carrier mobility. between organic semiconductor molecules can be used to
Electron-withdrawing units have been used in a molecular increase their carrier mobility by controlling the molecular
design for the development of ETL. For example, three- orientation, for example, using weak hydrogen bonds (H-
dimensional structures, such as metal complexes (Alq3), bonds).87 H-bonds are unique non-covalent bonds with a direc-
phenylbenzimidazole (PBI) derivatives (e.g., 1,3,5-tri(1-phen- tional property, which consists of the sum of the intermolecular
yl-1H-benzo[d]imidazol-2-yl)phenyl, TPBi78,79), triphenyl- forces, such as electrostatic, induction of polarization, disper-
borane (TPB) derivatives (e.g., Tris(2,4,6-trimethyl-3-(pyri- sion, exchange-repulsion, and charge-transfer forces. Because
din-3-yl)phenyl)borane, 3TPyMB80), and triphenylphosphine of this directionality, H-bonds tend to be used as a means of
oxide (TPPO) derivatives (e.g., Bis[2-(diphenylphosphino)- molecular recognition in supramolecular chemistry (e.g., self-
phenyl] ether oxide, DPEPO81), are used for constructing complementary CH£N weak H-bonds).88,89 Hohenstein and
amorphous films (Figure 3). Refinement of the molecular struc- Sherill reported the binding energy of weak H-bonds of the
ture is desirable in order to realize horizontally oriented films. pyridine dimer to be 13 kJ mol¹1 using quantum chemical cal-
Compared to electron-rich units for hole transporters, such as culations, which is about half that of typical H-bonds (20­30
TPA and Cz (Figure 3A), there are many electron-withdrawing kJ mol¹1).90 In OLED research, several bis-4,6-(3,5-dipyridyl-
units with different shapes for electron transporters. Planar, phenyl)-2-methylpyrimidine (BPyMPM) derivatives have been
rather than spherical, units could enhance surface coupling to developed by Tanaka91 and Sasabe43,92 and used to investigate
the substrate to facilitate horizontal molecular orientation. the effect of nitrogen orientation on the physical properties
Some representative planar molecules include phenylpyridine (Figure 4B).93 Each of these BPyMPM derivatives have a
(PPy), phenanthroline (Phen), 2,2¤-bipyridyl (Bpy), and tri- different nitrogen orientation on the peripheral pyridine rings,
phenyl triazine (TPTZ) (Figure 3B). resulting in large variations in ®e at 298 K. The ®e of
Here, we consider oxadiazole (OXD) derivatives to demon- B4PyMPM is one order of magnitude higher than that of
strate the effects of molecular orientation and alignment on the B3PyMPM and two orders of magnitude higher than that of
electrical properties (Figure 4A). Yokoyama et al. studied 1,3- B2PyMPM. Yokoyama et al. have investigated the molec-
bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl] benzene ular orientation of BPyMPM derivatives using VASE and
(OXD-782) and 1,3-bis [2-(2,2¤-bipyridin-6-yl)-1,3,4-oxadia- Fourier transform infrared (FT-IR) spectroscopy.44 They noted
zo-5-yl] benzene (Bpy-OXD83,84), which have similar single- that B3PyMPM (S = ¹0.33) and B4PyMPM (S = ¹0.36)
molecule characteristics, such as their conformation struc- molecules were well aligned with the substrates compared to
tures, distribution of the lowest unoccupied molecular orbitals B2PyMPM (S = ¹0.14), due to the CH£N H-bonds in the
(LUMOs), and reorganization energies.85 Interestingly, the ®e films. Hence, molecular orientation of BPyMPM molecules
of a vapor-deposited film of Bpy-OXD was 30 times higher can be controlled by intermolecular non-covalent interaction,
than that of a similar OXD-7, even though their molecular rather than controlling the molecular structure. To further
properties are very similar. VASE analysis showed that the actively control the molecular orientation, Watanabe et al.
reason for the different ®e values was due to their different reported 2,2¤:6¤,2¤¤-terpyridine (Tpy)-based n-type molecules,
molecular orientations. OXD-7 showed random orientation due referred to as n-TerPyB (n = 2,3,4).94 This was a similar

720 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Figure 4. Schematic diagrams of the molecular structures, non-covalent interactions, and orientational relationships in the ETL.
Reproduced by permission from The Royal Society of Chemistry, 2016.75

molecular design strategy to that of BPyMPMs, but they intro- formed horizontally oriented films (S = ¹0.28) with a ®e value
duced H-bond units while also reducing intramolecular steric 10 times higher than that of 2-TerPyB. It should be noted that
hindrances using Tpy units to enhance molecular planarity. The the 4-TerPyB film had a rough surface with a root-mean-square
subtle control of steric hindrance by replacing heteroaromatic roughness (Rrms) of 10.2 nm, which was not suitable for device
rings of C­H units by N atoms is a unique approach that takes application due to the rough surface result in high leakage
advantage of the planar structures. They showed that 2-TerPyB current. This high roughness was due to the highly directional
formed randomly oriented films (S = ¹0.09), while 3-TerPyB lone-pairs of pyridines that triggered strong intermolecular

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 721
interactions with H-bonds. In addition, these H-bond interac- exhibit low photoluminescence (PL) quantum yield (PLQY)
tions strongly influenced the physical properties of the TerPyB due to concentration quenching,106 and trapping of holes and
derivatives. The three TerPyB derivatives had different melting electrons at grain boundaries. To realize high-efficiency
points (Tm) of 270, 287, and 402 °C for 2-TerPyB, 3-TerPyB, OLEDs, host materials need higher triplet energy to prevent
and 4-TerPyB, respectively, even though they are simply struc- back energy transfer from the dopant. In addition, appropriate
tural isomers. It has also been reported that 4-pyridyl terminal carrier-transport properties, HOMO/LUMO energy levels, and
substituent molecules tend to form strong H-bonds.95­97 These singlet/triplet states are required. Furthermore, rough surfaces
results indicate that introducing 3-pyridyl units, rather than 4- result in high leakage currents and low device stability. There-
pyridyl units, can effectively form horizontal orientation in fore, in the case of EML, the investigation of mixed systems
amorphous films. The weaker H-bonds of the 3-pyridyl units to achieve molecular orientation has focused on both emitter
are due to conformational isomers by its rotation. Very recently, molecular structure and molecular interactions between host
Watanabe et al. developed horizontally oriented Bpy deriva- and emitter molecules.
tives end-capped with 3-dipyryidyl units, so called 4,4¤-BPy3 The following sub-sections discuss mixed systems in two
and 6,6¤-BPy3 (Figure 4B).75 They investigated the synergistic parts. First, we discuss organic dye molecular structures, then
effect of molecular anisotropy and intermolecular H-bonds in the influence of host molecules on dipole orientation. Finally,
the Bpy derivatives on the molecular orientation. Although the we discuss an unusual pure system with a Platinum (Pt)(II)
only difference between the BPy derivatives was the position of complex.
the substituents, they observed large differences in optical and 4.1 Mixed System I: Organic Dye Molecular Structures
electronic properties in both the solution and crystal states and Orientational Relationships. Here, we describe con-
using nuclear magnetic resonance (NMR) and single crystal ventional host­dopant mixed systems, focusing on the chem-
XRD analyses. A disordered structure was observed at two of ical structure of organic dyes and emission dipole moments.
the four terminal 3-pyridyl units. In addition, H-bonds link one Considering emitter orientation, common (first-generation)
stacked column to another to form the 2D sheet structure. organic dyes are well established in the field and have been
Intermolecular interactions of H-bonds were confirmed at the studied using optical simulations and experiments that distin-
outer peripheral pyridine rings. The obtained CH£N bond guish between horizontal and vertical dipole orienta-
distances (2.61­3.14 ¡) were reasonably classified as weak H- tion.104,107,108 Frischeisen et al. investigated two TPA deriva-
bonds (Figure 4C).90 Another study reported TZ-based mole- tives (PEBA and BDASBi) that have very similar molecular
cules (B3PyPTZ) that showed highly oriented films induced structures, except for their molecular dipole orientation. By
by inter- and intramolecular H-bonding interactions (S = measuring the EQE of OLEDs prepared using these materials,
¹0.38).97 These works provide essential design guidelines for horizontally oriented BDASBi-based OLEDs enhanced light
producing horizontally oriented, yet amorphous, organic semi- outcoupling by ³45%.106 Furthermore, the effect of orientation
conductor films by controlling subtle differences in the molec- in OLEDs offers many additional benefits regarding stack
ular structures of oligopyridines. Simultaneous manipulation design and has fundamental implications for material selection.
of intra- and intermolecular interactions is a critical factor and In 2012, TADF emitters based on pure organic compounds
the most fundamental methodology for organizing molec- were experimentally demonstrated as an alternate technology to
ular assemblies in supramolecular chemistry, where the key is realize electron-to-photon conversion of 100% by harvesting
lone-pair directionality. By taking advantage of the orienta- all molecular triplets and singlets.6,25 In general, TADF dyes
tion of lone-pairs in HTL and ETL, it is expected that com- are formed using donor­acceptor (D­A) molecular systems,
plete molecular orientation in pure films will be achieved. In which are structurally defined by an electron-rich moiety
addition, several analysis techniques, such as UV-visible, covalently linked to an electron-deficient moiety. Therefore,
VASE, NMR, XRD, and FT-IR spectroscopy could be further their molecular shape can be easily tuned. For example, Ting-
used to determine molecular orientations in thin films. For An et al. reported high performance sky-blue TADF dyes with
example, Quantitative Absorbance Comparison with an Iso- horizontally oriented dipoles (Figure 5A).109 They chose a
tropically Oriented Standard (QACIOS)98,99 infrared (IR) p- series of acridine (AC) units as bulky and rigid donors,
polarized multiple-angle incidence resolution spectrometry hybridized with TPTZ units as a planar acceptor. By system-
(pMAIRS)100,101 and dynamic nuclear polarization-enhanced atically changing the rigidity of donor units, they observed that
ssNMR (DNP-ssNMR) spectroscopy102,103 could quantify the rigid donor structure enhanced the orientation factor (©) from
distribution of molecular orientations in amorphous films. 72% to 83%, as analyzed by angle-dependent PL measure-
ments;110,111 a film with isotropic dipole arrangement yielded a
4. Molecular Orientation in EMLs value of © = 67%. If the emissive dipole orientation is aligned
In this section, we discuss the orientation of emitting dipoles horizontal to the substrate, © = 100%; therefore, the maximum
of organic dye molecules, which is of direct importance for possible value of © is desired. In addition, SpiroAC-TRZ, the
increasing the OLED efficiency. Perfect horizontal orientation most rigid dye studied in this work, exhibited 100% PLQY
of the emitting dipole of the molecules can boost the light- with a maximum EQE of 36.7% at 480 nm. This is currently the
outcoupling factor by 1.5. In contrast, vertically oriented emit- highest efficiency for sky-blue OLEDs reported to date. The
ting dipoles couple strongly to surface plasmons in the metal group of Kaji and Adachi demonstrated green and deep-blue
electrodes of the OLED, decreasing the external quantum TADF dyes called DACT-II112 and CCX-II,113 with a high
efficiency (EQE).104,105 EMLs based on a mixed system, rather © of 86%, and 83% respectively with 100% PLQY. They
than a pure system, have been developed as most organic dyes achieved very high EQE of 29.6% at ­em = ³520 nm, and

722 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Figure 5. Schematic diagrams of the molecular structures of organic dyes and the orientational relationships in the EML.

25.8% at ­em = 450 nm. In their case, planar TPTZ and TZ-SBA, PX-SBA, and IPN-SBA (Figure 5B).115 SBA con-
xanthone units were introduced as acceptor units in symmetric sists of two AC units connected via σ bonds, where this unique
π-extended diphenylamino-carbazole and tercarbazolyl units. donor forms a rigid molecular framework. In addition, two
Furthermore, P. Rajamalli et al. developed pure-blue TADF dye acceptor units can connect with SBA on the line-symmetric
called 3DPyM-pDTC based on a di(pyrimidinyl)methanone axis, with an A­D­σ­D­A linear structure. These SBA deriva-
core as the new electron-accepting planar and rigid units, that tives exhibited very high © values of 86­93%. The © value is
achieved a high © of 85% with 98% PLQY, and an EQE one of the highest ever reported for phosphorescent and TADF
greater than 31% at ­em = 464 nm.114 These results demon- emitters. The sky-blue device based on IPN-SBA realized a
strated that molecular rigidity and planar geometry are impor- very high EQE of 24.7% at 466 nm. It is expected that A­D­
tant factors, even in host­matrix systems. σ­D­A linear TADF dyes will become promising alternate
Recently, spirobiacridine (SBA)-based linear TADF dyes structures to conventional D­A-type TADF dyes. As the © and
were developed by the group of Sasabe, Su, and Kido, labelled PLQY values depend on the host molecule, film thickness, and

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 723
doping concentration of the dyes, a complete summary of the host matrices. Based on density functional theory (DFT) cal-
molecular orientation of the many organic dyes is beyond the culations, the dopant­CBP and dopant­B3PyMPM mix-
scope of this review. Further systematic studies are required in tures showed the highest binding energy of 30 kcal/mol (125
order to elucidate the relationship between molecular structures kJ/mol), which is almost 10 times higher than the other host­
and their dipole orientation. host, dopant­dopant, or host­dopant interactions. It should be
In addition to pure organic dyes, the molecular orientation of noted that the randomly oriented CBP host resulted in a
phosphorescent emitters containing heavy metals (especially slightly higher horizontal dipole ratio of Ir(ppy)2 tmd than
Iridium (Ir) and Pt) is also being considered to achieve high- B3PYMPM, implying that dipole orientation was not con-
efficiency OLEDs with IQE of 100%; these rare heavy metals trolled by the orientation of host molecules, but by the binding
can harvest all electrogenerated molecular singlet and triplet geometry of host­dopant molecules. Additionally, Ir(ppy)2
excitons.116,117 Although Ir(III) complexes have aspherical tmd formed random isotropic orientation when spin coated
geometry, horizontal emitting dipole moments of heteroleptic with a poly(methyl methacrylate) (PMMA) matrix. One plau-
Ir(III) complexes (HICs) originate from the preferred direction sible reason for this is the weak intermolecular interaction
of the triplet transition dipole moment along the Ir­N direction between the dye and aliphatic chains, which randomized the
in HICs. A recent study showed that substituents at the para- orientation of the dyes by entropic energy. Another possible
position of the pyridine in the main ligands of HICs played a reason is the thermal history that the films experienced during
pivotal role in inducing the orientation (Figure 5C).117 Sub- annealing at temperature above their Tg. Recently, the impor-
stitution of aliphatic and aromatic functional moieties at the tance of the Tg of host molecules with linear molecular geom-
para-position resulted in significant horizontal emitting dipole etry was reported.120 Using linear TADF molecules of cis-
orientation, showing © values up to 86.5% with EQE values BOX2, they achieved complete horizontal orientation (© =
of 38.1% at 579 nm and 36.0% at 532 nm. They noted that 100%) at a substrate temperature of 200 K. They attributed this
elongated and planar substituents with a high aspect ratio to kinetic relaxation during film deposition and the kinetic
enhanced face-to-face or face-to-line intermolecular interac- stability of the dopant in the host matrix.121
tions between the HICs and host molecules. Hence, further 4.3 Pure System: Pt(II) Phosphors and the Strong Metal­
studies should consider molecular interactions with neighbor- Metal Interactions between Square­Planar Motifs. Emit-
ing molecules, in addition to the structure of the emitters. ters tend to be dispersed in host molecules to prevent con-
4.2 Mixed System II: Influence of Host Molecules on centration quenching and self-quenching of PLQY. However,
Molecular Orientation in EMLs. To enhance the lumines- recently, certain Pt(II) emitters have been developed that
cent properties of the emitter molecules, host molecules play show very high PLQY in a pure system or crystalline state
various key roles in e.g., the dispersion of organic dyes to (Figure 7). For example, Kim et al. reported highly efficient
obtain a high PLQY, suppression of concentration quenching red OLEDs using pure Pt(II) phosphor layers as EMLs.122
and self-quenching, and enhancement of carrier injection. In Since the Pt(II) complex has d 8 square planar geometry and a
addition, interactions between with host molecules and organic dz2 orbital placed perpendicular to the molecular plane, strong
dyes are very important for controlling the emitting dipole metal­metal intermolecular interactions between the complexes
orientation. In this section, we discuss the influence of host can be formed. Based on DFT calculations and single-crystal
molecules on the molecular orientation in EMLs. X-ray diffraction data, Pt(fppz)2 and its derivatives showed
The influence of the host molecules in vapor-deposited films strong coulomb interactions in these dimers. In addition, vapor-
has been well investigated considering the thermal properties, deposited films showed almost complete vertical molecular
such as the glass transition temperature (Tg), as well as the alignment, as measured by 2D GIXD, with a low Rrms of 0.54­
dipole moment (D) and molecular weight (Mw). Mayr and 1.17 nm. On the other hand, the emitting dipoles of these thin
Brütting correlated the orientation of fluorescent and phosphor- films were horizontally oriented with © = 93%. This is due to
escent organic dyes to physical properties of the host materials emission of the Pt(II) complex in the solid-state corresponding
(Figure 6A).118 While no significant correlation between the to the excimer originating from metal­metal-to-ligand charge
properties of the host material and the orientation of phosphor- transfer (MMLCT) caused by Pt­Pt metallophilic ligand inter-
escent Ir(III) complexes could be detected, the fluorescent dye actions. Using the oriented dyes, they achieved a maximum
Coumarin 6 showed an increasingly horizontal orientation EQE of 38.8%, which is the highest efficiency reported to
with increasing Tg of the host molecules due to a decrease in date.123 Very recently, other pyrazine-based Pt(II) complexes
the molecular surface mobility during deposition. The orienta- also achieved horizontal emitting dipole orientation (© = 87%)
tion of Coumarin 6 could be controlled between isotropic and with high EQE of 24% in the near infrared region (­em = 740
horizontal orientation by using host molecules with different nm).124 However, it is difficult to compare the © and PLQY
Tg. This was probably due to the linear molecular structure of values and further studies are required in order to elucidate
the dye and its low Mw. their relationship. It is clear that metal­metal interactions, in
Kim et al. reported the influence of host molecules on both addition to the planar molecular structure, contribute to con-
the homoleptic Ir(III) complex [Ir(ppy)3] and HIC [Ir(ppy)2 trolling the orientation.
tmd], and explored the effect of the molecular interaction
between the host and organic dyes on the emission dipole 5. Conclusion and Perspective
moments of the dyes (Figure 6B).119 In the case of Ir(ppy)2 Molecular orientation in OLEDs has developed rapidly since
tmd, the triplet transition dipole moments of Ir(ppy)2 tmd the first reports just over a decade ago. Initial studies focused
aligned with the substrate in a different manner in various on the single molecular structure in pure films. Since then, there

724 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Figure 6. Schematic diagrams showing the influence of host molecules on molecular orientation in the EML. All of the films are
fabricated by vacuum-deposition except PMMA systems.

have been several reports of methods for controlling the for tailoring molecular orientation. The studies of the molecular
molecular orientation using rational molecular interactions in structure­property relationship described here have begun to
both pure and mixed systems. In this review, we focused on elucidate the specific interactions that are the most beneficial
molecular orientation from the view point of the molecular for OLED applications, with respect to reducing the driving
structure of the key materials used in the three essential OLED voltage and enhancing light outcoupling efficiency. Most of
layers. Across a wide variety of single molecular structures, these studies have shown that carrier transport materials and
it was shown that materials with linear, or planar geometries emissive materials can be manipulated to achieve the desired
generally exhibited horizontal orientation with the substrates. molecular orientation in vacuum-deposited films. However,
In contrast, considering molecular interactions, actively con- in general, these methods are currently unsuitable for ink-
trolling lone-pairs to construct weak CH£N H-bonds is based coatings. It is surprising that ink-based coating methods
essential. In addition, metal­metal interactions and electrostatic produce randomly orientated films by using specific mole-
interactions between the host and organic dyes are important cules that can be horizontally oriented in vacuum-deposited

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 725
Figure 7. Schematic diagrams of the planar molecular structure and metal­metal interactions between Pt(II) complexes in the EML.

films.116,119,125 This is probably due to differences in the film 5 R. Das, P. Harrop, Printed, Organic & Flexible Electronics:
growth mechanisms related to kinetic stabilities and molecular Forecasts, Players & Opportunities 2013­2023, 2013; available
dynamics in solution. In the near future, we expect that via http://go.nature.com/BxrL2J.
development of all-solution ink-based films for OLEDs will be 6 C. Adachi, Jpn. J. Appl. Phys. 2014, 53, 060101.
achieved by taking advantage of the full potential of organic 7 S.-H. Bae, H. Zhao, Y.-T. Hsieh, L. Zuo, N. De Marco, Y. S.
semiconductor molecules with well-controlled molecular Rim, G. Li, Y. Yang, Chem 2016, 1, 197.
orientation. 8 A. Chortos, J. Liu, Z. Bao, Nat. Mater. 2016, 15, 937.
In order to design and discover new generations of materials 9 J. Kido, T. Nakada, J. Endo, N. Kawamura, M. K, A.
Yokoi, T. Matsumoto, Proceedings 11th International Workshop
with superior performance beyond that expected based on the
on Inorganic and Organic Electroluminescence and 2002 Interna-
molecular formula, researchers need to provide essential guide-
tional Conference on the Science and Technology of Emissive
lines, such as: (i) understanding of the origin of molecular
Displays and Lighting, Ghent, Belgium, September 23­26, 2002,
orientation; (ii) rational utilization of molecular interactions; p. 539.
(iii) biomimetic and supramolecular design of molecular 10 T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura,
assemblies; (iv) development of analytical methods to achieve A. Yokoi, J. Kido, SID Int. Symp. Dig. Tech. Pap. 2003, 34, 979.
3D molecular orientation mapping; and (v) simulation of 11 L. S. Liao, K. P. Klubek, C. W. Tang, Appl. Phys. Lett.
molecular aggregation in thin films.126­130 If the community 2004, 84, 167.
embraces these challenges, we anticipate that molecular engi- 12 T. Tsutsui, M. Terai, Appl. Phys. Lett. 2004, 84, 440.
neering for horizontal orientation in OLEDs could enter a 13 H. Kanno, R. J. Holmes, Y. Sun, S. Kena-Cohen, S. R.
golden era of vibrant research. We believe that this review will Forrest, Adv. Mater. 2006, 18, 339.
contribute to the fast and accurate discovery of game-changing 14 T.-W. Lee, T. Noh, B.-K. Choi, M.-S. Kim, D. W. Shin, J.
molecules for applications in advanced OLED materials. Kido, Appl. Phys. Lett. 2008, 92, 043301.
15 L. S. Liao, K. P. Klubek, Appl. Phys. Lett. 2008, 92,
Our work written in this review was partially supported by 223311.
the Center of Innovation (COI) Program from the Japan 16 K. S. Yook, S. O. Jeon, S.-Y. Min, J. Y. Lee, H.-J. Yang, T.
Science and Technology Agency (JST) and the Japan Society Noh, S.-K. Kang, T.-W. Lee, Adv. Funct. Mater. 2010, 20, 1797.
for the Promotion of Science (JSPS) KAKENHI Grant 17 S. Hamwi, J. Meyer, M. Kröger, T. Winkler, M. Witte, T.
(15J08167 and 17H03131). We would also like to thank all Riedl, A. Kahn, W. Kowalsky, Adv. Funct. Mater. 2010, 20, 1762.
our collaborators and laboratory members whose names are 18 T. Chiba, Y.-J. Pu, R. Miyazaki, K. Nakayama, H. Sasabe,
J. Kido, Org. Electron. 2011, 12, 710.
cited in References for their great contributions.
19 T. Chiba, Y.-J. Pu, J. Kido, Adv. Mater. 2015, 27, 4681.
20 Y. Ohno, in Book Color rendering and luminous efficacy
References of white LED spectra, SPIE, City, 2004, Vol. 5530, pp. 11.
1 S. R. Forrest, Chem. Rev. 1997, 97, 1793. doi:10.1117/12.565757.
2 J. E. Anthony, Chem. Rev. 2006, 106, 5028. 21 Y.-S. Tyan, J. Photon. Energy 2011, 1, 011009.
3 K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Rev. 22 M. A. Baldo, D. F. O’Brien, Y. You, A. Shoustikov, S.
2007, 107, 1233. Sibley, M. E. Thompson, S. R. Forrest, Nature 1998, 395, 151.
4 H. Sasabe, J. Kido, Chem. Mater. 2011, 23, 621. 23 M. A. Baldo, S. Lamansky, P. E. Burrows, M. E.

726 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan
Thompson, S. R. Forrest, Appl. Phys. Lett. 1999, 75, 4. (Amsterdam, Neth.) 1996, 217, 212.
24 C. Adachi, M. A. Baldo, M. E. Thompson, S. R. Forrest, 53 Y. Shirota, T. Kobata, N. Noma, Chem. Lett. 1989, 1145.
J. Appl. Phys. 2001, 90, 5048. 54 D. Yokoyama, A. Sakaguchi, M. Suzuki, C. Adachi, Appl.
25 H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Phys. Lett. 2008, 93, 173302.
Nature 2012, 492, 234. 55 M. Aonuma, T. Oyamada, H. Sasabe, T. Miki, C. Adachi,
26 C. Adachi, T. Tsutsui, S. Saito, Appl. Phys. Lett. 1990, 57, Appl. Phys. Lett. 2007, 90, 183503.
531. 56 S. Tokito, K. Noda, K. Shimada, S. Inoue, M. Kimura, Y.
27 G. He, M. Pfeiffer, K. Leo, M. Hofmann, J. Birnstock, R. Sawaki, Y. Taga, Thin Solid Films 2000, 363, 290.
Pudzich, J. Salbeck, Appl. Phys. Lett. 2004, 85, 3911. 57 J. Y. Kim, T. Yasuda, Y. S. Yang, C. Adachi, Adv. Mater.
28 H. Yersin, Top. Curr. Chem. 2004, 241, 1. 2013, 25, 2666.
29 S. Reineke, F. Lindner, G. Schwartz, N. Seidler, K. Walzer, 58 J. Staudigel, M. Stössel, F. Steuber, J. Simmerer, Appl.
B. Lüssem, K. Leo, Nature 2009, 459, 234. Phys. Lett. 1999, 75, 217.
30 L. Duan, D. Zhang, K. Wu, X. Huang, L. Wang, Y. Qiu, 59 H. Ohishi, M. Tanaka, H. Kageyama, Y. Shirota, Chem.
Adv. Funct. Mater. 2011, 21, 3540. Lett. 2004, 33, 1266.
31 S. Wu, S. Li, Q. Sun, C. Huang, M.-K. Fung, Sci. Rep. 60 Y. Shirota, H. Kageyama, Chem. Rev. 2007, 107, 953.
2016, 6, 25821. 61 T. Malinauskas, D. Tomkute-Luksiene, M. Daskeviciene, V.
32 N. Aizawa, Y.-J. Pu, M. Watanabe, T. Chiba, K. Ideta, N. Jankauskas, G. Juska, V. Gaidelis, K. Arlauskas, V. Getautis,
Toyota, M. Igarashi, Y. Suzuri, H. Sasabe, J. Kido, Nat. Commun. Chem. Commun. 2011, 47, 7770.
2014, 5, 5756. 62 J. Y. Kim, D. Yokoyama, C. Adachi, J. Phys. Chem. C
33 Y.-J. Pu, T. Chiba, K. Ideta, S. Takahashi, N. Aizawa, T. 2012, 116, 8699.
Hikichi, J. Kido, Adv. Mater. 2015, 27, 1327. 63 A. Wakamiya, H. Nishimura, T. Fukushima, F. Suzuki, A.
34 T. Chiba, Y.-J. Pu, J. Kido, Adv. Mater. 2015, 27, 4681. Saeki, S. Seki, I. Osaka, T. Sasamori, M. Murata, Y. Murata, H.
35 D. Yokoyama, J. Mater. Chem. 2011, 21, 19187. Kaji, Angew. Chem., Int. Ed. 2014, 53, 5800.
36 W. Brütting, J. Frischeisen, T. D. Schmidt, B. J. Scholz, C. 64 H. Nishimura, T. Fukushima, A. Wakamiya, Y. Murata, H.
Mayr, Phys. Status Solidi A 2013, 210, 44. Kaji, Bull. Chem. Soc. Jpn. 2016, 89, 726.
37 T. D. Schmidt, T. Lampe, D. M. R. Sylvinson, P. I. 65 H. Nishimura, Y. Hasegawa, A. Wakamiya, Y. Murata,
Djurovich, M. E. Thompson, W. Brutting, Phys. Rev. Appl. 2017, Chem. Lett. 2017, 46, 817.
8, 037001. 66 J. Rivnay, S. C. B. Mannsfeld, C. E. Miller, A. Salleo, M. F.
38 A. Gujral, L. Yu, M. D. Ediger, Curr. Opin. Solid State Toney, Chem. Rev. 2012, 112, 5488.
Mater. Sci. 2018, 22, 49. 67 L. J. Richter, D. M. DeLongchamp, A. Amassian, Chem.
39 K.-H. Kim, J.-J. Kim, Adv. Mater. 2018, 30, 1705600. Rev. 2017, 117, 6332.
40 J.-S. Kim, P. K. H. Ho, N. C. Greenham, R. H. Friend, 68 A. Gujral, K. A. O’Hara, M. F. Toney, M. L. Chabinyc,
J. Appl. Phys. 2000, 88, 1073. M. D. Ediger, Chem. Mater. 2015, 27, 3341.
41 S. Duhm, G. Heimel, I. Salzmann, H. Glowatzki, R. L. 69 H. Gilman, J. J. Honeycutt, Jr., J. Org. Chem. 1957, 22,
Johnson, A. Vollmer, J. P. Rabe, N. Koch, Nat. Mater. 2008, 7, 226.
326. 70 H. Kanai, S. Ichinosawa, Y. Sato, in International Confer-
42 H. Bässler, Phys. Status Solidi B 1993, 175, 15. ence on Electroluminescence of Molecular Materials and Related
43 H. Sasabe, D. Tanaka, D. Yokoyama, T. Chiba, Y.-J. Pu, K. Phenomena, Kitakyushu, Japan, 1997, 22-P-17.
Nakayama, M. Yokoyama, J. Kido, Adv. Funct. Mater. 2011, 21, 71 J. Segal, Z. Kotler, M. Sigalov, A. Ben-Asuly, V.
336. Khodorkovsky, in Book Two-photon absorption properties of
44 D. Yokoyama, H. Sasabe, Y. Furukawa, C. Adachi, J. Kido, (N-carbazolyl)-stilbenes, SPIE, City, 1999, Vol. 3796, pp. 7.
Adv. Funct. Mater. 2011, 21, 1375. doi:10.1117/12.368269.
45 J. Ràfols-Ribé, P.-A. Will, C. Hänisch, M. Gonzalez- 72 T. Aimono, Y. Kawamura, K. Goushi, H. Yamamoto, H.
Silveira, S. Lenk, J. Rodríguez-Viejo, S. Reineke, Sci. Adv. 2018, Sasabe, C. Adachi, Appl. Phys. Lett. 2005, 86, 071110.
4, eaar8332. 73 D. Yokoyama, A. Sakaguchi, M. Suzuki, C. Adachi, Org.
46 C. W. Tang, S. A. VanSlyke, Appl. Phys. Lett. 1987, 51, Electron. 2009, 10, 127.
913. 74 T.-S. Kim, D.-H. Kim, H.-J. Im, K. Shimada, R. Kawajiri,
47 J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. T. Okubo, H. Murata, T. Mitani, Sci. Technol. Adv. Mater. 2004, 5,
Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, 331.
Nature 1990, 347, 539. 75 Y. Watanabe, H. Sasabe, D. Yokoyama, T. Beppu, H.
48 K.-T. Wong, Y.-Y. Chien, R.-T. Chen, C.-F. Wang, Y.-T. Katagiri, J. Kido, J. Mater. Chem. C 2016, 4, 3699.
Lin, H.-H. Chiang, P.-Y. Hsieh, C.-C. Wu, C. H. Chou, Y. O. Su, 76 A. P. Kulkarni, C. J. Tonzola, A. Babel, S. A. Jenekhe,
G.-H. Lee, S.-M. Peng, J. Am. Chem. Soc. 2002, 124, 11576. Chem. Mater. 2004, 16, 4556.
49 C.-C. Wu, T.-L. Liu, W.-Y. Hung, Y.-T. Lin, K.-T. Wong, 77 G. Hughes, M. R. Bryce, J. Mater. Chem. 2005, 15, 94.
R.-T. Chen, Y.-M. Chen, Y.-Y. Chien, J. Am. Chem. Soc. 2003, 78 J. Shi, C. W. Tang, C. H. Chen, U.S. Patent No. 5,646,948,
125, 3710. 1997.
50 H.-W. Lin, C.-L. Lin, H.-H. Chang, Y.-T. Lin, C.-C. Wu, 79 Z. Gao, C. S. Lee, I. Bello, S. T. Lee, R.-M. Chen, T.-Y.
Y.-M. Chen, R.-T. Chen, Y.-Y. Chien, K.-T. Wong, J. Appl. Phys. Luh, J. Shi, C. W. Tang, Appl. Phys. Lett. 1999, 74, 865.
2004, 95, 881. 80 D. Tanaka, Y. Agata, T. Takeda, S. Watanabe, J. Kido, Jpn.
51 J. A. Woollam, W. A. McGaham, B. Johs, Thin Solid Films J. Appl. Phys. 2007, 46, L117.
1994, 241, 44. 81 J. Fawcett, A. W. G. Platt, S. Vickers, M. D. Ward,
52 P. M. Borsenberger, E. H. Magin, J. Shi, Physica B Polyhedron 2004, 23, 2561.

Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan | 727
82 Y. Hamada, C. Adachi, T. Tsutsui, S. Saito, Jpn. J. Appl. 108 J. Frischeisen, D. Yokoyama, C. Adachi, W. Brütting, Appl.
Phys. 1992, 31, 1812. Phys. Lett. 2010, 96, 073302.
83 M. Ichikawa, T. Kawaguchi, K. Kobayashi, T. Miki, K. 109 T.-A. Lin, T. Chatterjee, W.-L. Tsai, W.-K. Lee, M.-J. Wu,
Furukawa, T. Koyama, Y. Taniguchi, J. Mater. Chem. 2006, 16, M. Jiao, K.-C. Pan, C.-L. Yi, C.-L. Chung, K.-T. Wong, C.-C. Wu,
221. Adv. Mater. 2016, 28, 6976.
84 M. Ichikawa, N. Hiramatsu, N. Yokoyama, T. Miki, S. 110 M. Flämmich, M. C. Gather, N. Danz, D. Michaelis, A. H.
Narita, T. Koyama, Y. Taniguchi, Phys. Status Solidi RRL 2007, 1, Bräuer, K. Meerholz, A. Tünnermann, Org. Electron. 2010, 11,
R37. 1039.
85 D. Yokoyama, A. Sakaguchi, M. Suzuki, C. Adachi, Appl. 111 M. Flämmich, J. Frischeisen, D. S. Setz, D. Michaelis,
Phys. Lett. 2009, 95, 243303. B. C. Krummacher, T. D. Schmidt, W. Brütting, N. Danz, Org.
86 L. L. Merritt, E. Schroeder, Acta Crystallogr. 1956, 9, 801. Electron. 2011, 12, 1663.
87 G. R. Desiraju, T. Steiner, The Weak Hydrogen Bond: In 112 H. Kaji, H. Suzuki, T. Fukushima, K. Shizu, K. Suzuki, S.
Structural Chemistry and Biology, IUCr, Oxford University Press, Kubo, T. Komino, H. Oiwa, F. Suzuki, A. Wakamiya, Y. Murata,
New York, 1999. doi:10.1093/acprof:oso/9780198509707.001. C. Adachi, Nat. Commun. 2015, 6, 8476.
0001. 113 T. Miwa, S. Kubo, K. Shizu, T. Komino, C. Adachi, H.
88 A. Marsh, M. Silvestri, J.-M. Lehn, Chem. Commun. 1996, Kaji, Sci. Rep. 2017, 7, 284.
1527. 114 P. Rajamalli, N. Senthilkumar, P.-Y. Huang, C.-C. Ren-Wu,
89 M. Ikeda, T. Nobori, M. Schmutz, J.-M. Lehn, Chem.®Eur. H.-W. Lin, C.-H. Cheng, J. Am. Chem. Soc. 2017, 139, 10948.
J. 2005, 11, 662. 115 M. Liu, R. Komatsu, X. Cai, K. Hotta, S. Sato, K. Liu, D.
90 E. G. Hohenstein, C. D. Sherrill, J. Phys. Chem. A 2009, Chen, Y. Kato, H. Sasabe, S. Ohisa, Y. Suzuri, D. Yokoyama, S.-J.
113, 878. Su, J. Kido, Chem. Mater. 2017, 29, 8630.
91 D. Tanaka, H. Sasabe, Y.-J. Li, S.-J. Su, T. Takeda, J. Kido, 116 M. J. Jurow, C. Mayr, T. D. Schmidt, T. Lampe, P. I.
Jpn. J. Appl. Phys. 2007, 46, L10. Djurovich, W. Brütting, M. E. Thompson, Nat. Mater. 2016, 15,
92 H. Sasabe, T. Chiba, S.-J. Su, Y.-J. Pu, K. Nakayama, J. 85.
Kido, Chem. Commun. 2008, 5821. 117 K.-H. Kim, E. S. Ahn, J.-S. Huh, Y.-H. Kim, J.-J. Kim,
93 R. Komatsu, H. Sasabe, J. Kido, J. Photonics Energy, 2018, Chem. Mater. 2016, 28, 7505.
8, 032108. 118 C. Mayr, W. Brütting, Chem. Mater. 2015, 27, 2759.
94 Y. Watanabe, R. Yoshioka, H. Sasabe, T. Kamata, H. 119 C.-K. Moon, K.-H. Kim, J. W. Lee, J.-J. Kim, Chem. Mater.
Katagiri, D. Yokoyama, J. Kido, J. Mater. Chem. C 2016, 4, 8980. 2015, 27, 2767.
95 H. Sasabe, E. Gonmori, T. Chiba, Y.-J. Li, D. Tanaka, S.-J. 120 T. Komino, Y. Sagara, H. Tanaka, Y. Oki, N. Nakamura, H.
Su, T. Takeda, Y.-J. Pu, K. Nakayama, J. Kido, Chem. Mater. 2008, Fujimoto, C. Adachi, Appl. Phys. Lett. 2016, 108, 241106.
20, 5951. 121 S. F. Swallen, K. L. Kearns, M. K. Mapes, Y. S. Kim, R. J.
96 T. Kamata, H. Sasabe, Y. Watanabe, D. Yokoyama, H. McMahon, M. D. Ediger, T. Wu, L. Yu, S. Satija, Science 2007,
Katagiri, J. Kido, J. Mater. Chem. C 2016, 4, 1104. 315, 353.
97 Y. Watanabe, H. Sasabe, D. Yokoyama, T. Beppu, H. 122 K.-H. Kim, J.-L. Liao, S. W. Lee, B. Sim, C.-K. Moon,
Katagiri, Y.-J. Pu, J. Kido, Adv. Opt. Mater. 2015, 3, 769. G.-H. Lee, H. J. Kim, Y. Chi, J.-J. Kim, Adv. Mater. 2016, 28,
98 Y. Sakai, M. Shibata, D. Yokoyama, Appl. Phys. Express 2526.
2015, 8, 096601. 123 Q. Wang, I. W. H. Oswald, X. Yang, G. Zhou, H. Jia, Q.
99 M. Shibata, Y. Sakai, D. Yokoyama, J. Mater. Chem. C Qiao, Y. Chen, J. Hoshikawa-Halbert, B. E. Gnade, Adv. Mater.
2015, 3, 11178. 2014, 26, 8107.
100 T. Hasegawa, Anal. Chem. 2007, 79, 4385. 124 K. Tuong Ly, R.-W. Chen-Cheng, H.-W. Lin, Y.-J. Shiau,
101 M. Hada, N. Shioya, T. Shimoaka, K. Eda, M. Hada, T. S.-H. Liu, P.-T. Chou, C.-S. Tsao, Y.-C. Huang, Y. Chi, Nat.
Hasegawa, Chem.®Eur. J. 2016, 22, 16539. Photonics 2017, 11, 63.
102 D. A. Hall, D. C. Maus, G. J. Gerfen, S. J. Inati, L. R. 125 T. Lampe, T. D. Schmidt, M. J. Jurow, P. I. Djurovich,
Becerra, F. W. Dahlquist, R. G. Griffin, Science 1997, 276, 930. M. E. Thompson, W. Brütting, Chem. Mater. 2016, 28, 712.
103 K. Suzuki, S. Kubo, F. Aussenac, F. Engelke, T. 126 T. F. Harrelson, A. J. Moulé, R. Faller, Mol. Simul. 2017,
Fukushima, H. Kaji, Angew. Chem., Int. Ed. 2017, 56, 14842. 43, 730.
104 J. Frischeisen, D. Yokoyama, A. Endo, C. Adachi, W. 127 T. Lee, B. Caron, M. Stroet, D. M. Huang, P. L. Burn, A. E.
Brütting, Org. Electron. 2011, 12, 809. Mark, Nano Lett. 2017, 17, 6464.
105 W. H. Weber, C. F. Eagen, Opt. Lett. 1979, 4, 236. 128 C.-K. Moon, K.-H. Kim, J.-J. Kim, Nat. Commun. 2017, 8,
106 Y. Kawamura, J. Brooks, J. J. Brown, H. Sasabe, C. Adachi, 791.
Phys. Rev. Lett. 2006, 96, 017404. 129 Y. Youn, D. Yoo, H. Song, Y. Kang, K. Y. Kim, S. H. Jeon,
107 S. Nowy, J. Frischeisen, W. Brütting, in Book Simulation Y. Cho, K. Chae, S. Han, J. Mater. Chem. C 2018, 6, 1015.
based optimization of light-outcoupling in organic light-emitting 130 F. Suzuki, S. Kubo, T. Fukushima, H. Kaji, Sci. Rep. 2018,
diodes, SPIE, City, 2009, Vol. 7415, pp. 9. doi:10.1117/12. 8, 5203.

728 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336 © 2019 The Chemical Society of Japan