Hisahiro Junji Kido

Sasabe

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

1
Department of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
2
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
next-generation eco-friendly solid-state display and lighting
technologies. Most key optoelectronic functions of organic films
used in organic semiconductor devices are dependent on two
important factors: the electronic properties of single molecules,
and the molecular orientations. The molecular orientation has
recently attracted considerable attention, and been recognized as
of organic devices, such as device lifetime, efficiency, ioniza-
tion potential, and carrier mobility of semiconductor amorphous
films. In this review, we discuss horizontal molecular orienta-
tion from a molecular engineering perspective considering the
three essential layers of OLEDs: the hole transport layer, elec-
tron transport layer, and emissive layer. In addition, we address
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
Molecular orientation j Organic semiconductors
1. Introduction
Organic optoelectronic devices based on organic semi-
conductors, such as organic light-emitting devices (OLEDs),
organic photovoltaic cells (OPVs), and organic field-effect
transistors (OFETs), are currently revolutionizing our daily life
by replacing conventional inorganic electronics.1­8 A represen-
tative example is OLED displays used for smart phones, smart
watches, and large-area televisions (TVs). In the case of a
large-area OLED TV commercialized by LG in Korea using
tandem white OLED technology, the so-called multiphoton
technology is critical for realizing high efficiency and long-
term stability at a high brightness of several thousand
cd m¹2.9,10 This technology can be used for general lighting
requiring 3000­5000 cd m¹2 and has shown long-term stability
of several years.9­19 OLED displays are becoming a vital tech-
nology for many consumer products; however, considering the
theoretical limit of the efficiency of white OLED, there are
significant opportunities to improve the materials and tech-
nologies enabling OLED displays using the ultimate green
technology.20,21
To improve the efficiency of OLEDs, researchers generally
use two major approaches. The first is to introduce phospho-
rescent22­24 and/or thermally activated delayed fluorescent
(TADF)25 emitters, so-called second- and third-generation
emitters instead of first-generation fluorescent emitters, into
the emissive layer (EML); this increases the internal quantum
efficiency (IQE) to unity by harvesting all electrically generated
molecular excitons. The other approach is to use organic
multilayer structures with different electrochemical properties
to produce devices with low power consumption. Three-layer
devices, the so-called double heterostructure,26 typically consist
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
of a hole-transport layer (HTL), EML, and electron-transport
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
required driving voltage of the OLED. When suitable HTL and
ETL materials are used, these layers also block electrons and
holes, respectively, thereby confining both carriers in the EML
and ensuring good carrier balance.
Recently, molecular orientation in organic semiconductor
amorphous films has been recognized as another key parameter
in determining the performance of organic optoelectronic
devices, including the device efficiency, lifetime, ionization
potential, and carrier mobility (Figure 1).35­39 In 2000, Friend
et al. experimentally demonstrated the importance of the molec-
ular orientation of the emitter molecule using conjugated-
polymer-based OLEDs.40 They estimated that horizontally
oriented emitting dipole moments of the emitter increased the
OLED efficiency by a factor of over 1.5 compared with a ran-
domly oriented emitter. In 2008, Duhm et al. showed the effect
of molecular orientation on the ionization potential (Ip), which
is a fundamental parameter determining the carrier injection
properties.41 By controlling the molecular orientation of an
oligothiophene derivative, Ip can be significantly increased,
by up to 0.6 eV. Given that the density-of-states is typically
0.2 eV in organic amorphous films,42 such an increase in the
Ip value is surprisingly large. In 2011, Sasabe and Yokoyama
reported a 100-fold increase in the carrier mobility in a series of
pyrimidine-based electron-transporters by inducing horizontal
molecular orientation.43,44 In 2018, Reineke et al. demonstrated
that organic amorphous layers with very high thermodynamic
stability realized a five-fold enhancement of OLED lifetime.45
Hence, molecular orientation is crucial for tailoring the opto-
electronic properties of organic semiconductor films used in
practical devices; however, only few passive methodologies
for controlling the molecular orientation have currently been
© 2019 The Chemical Society of Japan | 717
developed. Therefore, there is a great and urgent need to
develop a method for actively controlling molecular orientation
in order to improve the performance of organic optoelectronics.
In this review, we summarize the current status, important
challenges, and future perspective of molecular orientation in
OLEDs from the viewpoint of molecular engineering. We
present three sections, focusing on state-of-the-art HTL, ETL,
and EML technologies. In contrast to the previous excellent
reviews,35­39 which mainly considered enhancement of phys-
ical aspects, we focus on the chemical structures of materials
used in OLEDs. In addition, we highlight the current state-of-
the-art molecular orientation technologies using weak non-
covalent interactions and evaluate their potential for creating
next-generation smart materials.
2. Molecular Orientation in the HTL:
Molecular Structure and Orientational Relationship
As the molecular orientation of carrier transport layers in
OLEDs can increase carrier mobilities, it contributes to reduc-
ing the operational voltage of these devices and increasing its
operational lifetime. However, since the first demonstration of
OLED technology in 1987 by Tang and VanSlyke based on
small molecules,46 and in 1990 by Burroughes et al. based on a
polymer emitter,47 researchers have focused on the electronic
properties of single molecules and the correlation between
single molecular properties and device efficiency, rather than
molecular orientation. In addition, analytical techniques for
evaluating molecular orientation were not well established at
that time. As conventional small molecules in OLEDs do not
possess long-range ordered structures, common analytical
methods, such as X-ray thin-film structure analysis, are not
highly effective. In 2002, materials with strong blue emis-
sion and high bipolar carrier mobilities (®), such as ter(9,9-
diarylfluorene) (TF) derivatives, were demonstrated.48­50 They
observed that the long molecular axis of TF derivatives was
oriented parallel to the substrate using variable angle spectro-
scopic ellipsometry (VASE)35,51 analysis. VASE is one of the
analytical methods used to detect molecular orientation in
amorphous organic films. The molecular orientation in thin
solid films is discussed using two optical constants, the refrac-
tive index (n) and extinction coefficient (k) in the horizontal
and vertical directions, respectively. They concluded that the
high mobility is critically dependent on the molecular orienta-
tion. This was the first report of optical anisotropy and molec-
ular orientation in amorphous films of small-molecular-based
OLEDs. Although the specific mechanism was not discussed in
this seminal paper, the molecular orientation was probably due
to the rigid and linear molecular geometry.
In the early stages of studying molecular orientation in
HTLs, the triphenylamine (TPA) derivatives conventionally
used for OLEDs were systematically investigated using VASE
analysis. In addition to determining their molecular orientation,
the degree of orientation can be quantified using the orienta-
tion order parameter (S). This value is close or equal to 0
when the transition dipole moments of molecules have com-
pletely random orientation and is ¹0.5 when they have a fully
horizontal orientation. For example, N,N¤-Di(1-naphthyl)-N,N¤-
diphenyl-(1,1¤-biphenyl)-4,4¤-diamine (α-NPD,52 S = ¹0.01),
and 4,4¤,4¤¤-Tris [(3-methylphenyl) phenylamino] triphenyl-
718 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
amine (m-MTDATA,53 S = ¹0.04) have random orientation
(Figure 2A).54 This is mainly due to their sterically hindered
structures and isotropic propeller-like molecular geometries
with a large number of molecular conformations. Indeed, it is
difficult to control their molecular orientation using straightfor-
ward TPA groups.
One strategy for constructing horizontally oriented films is
the introduction of planar and disk-like molecular geometries
composed of TPA groups, which has been extensively studied.
For example, Yokoyama et al. reported that molecules having
planar or long-and-winding geometries, such as TPA oligomers
TPD1555 and TPT155,56 are horizontally oriented in the films.54
Even when the molecular length increases and the molecules
have various conformations, the transition dipole moment of
the molecule is along the π-conjugation system. In addition,
Kim et al. reported substantially horizontally oriented mole-
cules with star-burst or disk-like geometry, TPA-TPE (S =
¹0.27) and PDA-TPE (S = ¹0.28), which contain triphenyl-
ethene (TPE) at the end of the TPA or N,N,N¤,N¤-tetraphenyl-p-
phenylenediamine (PDA) (Figure 2A).57 These results suggest
that the molecules with two-dimensional prolonged π-systems
have a strong tendency toward parallel alignment on the
substrate, despite their bulky propeller-shaped TPE units. This
is mainly due to a decrease in the positional and energetic
disorders in the molecular-oriented states. The TPA and PDA
cores retain their intrinsic hole-transporting functionality even
after being substituted with the TPE peripheries. Using the
space-charge-limited current technique, it has been shown that
the hole mobility (®h) of the PDA-TPE and TPA-TPE thin
films exceeds 10¹2 cm2 V¹1 s¹1 (estimated values of ®h from
literature are on Figure 2), which is about one order of magni-
tude higher than that of amorphous α-NPD, and two orders of
magnitude higher than that of m-MTDATA.55,58 In addition,
these values are the highest among those reported for hole-
transporting amorphous molecular materials.59­62 One of the
most important insights provided by VASE analysis is that
molecular orientation can be observed, even in amorphous thin
films, by systematic selection of the molecular structure.
Recently, Wakamiya’s group have been taking advantage of
various synthesis methods in order to introduce quasiplanar
structures into TPA groups by reducing the steric hindrance of
hydrogen atoms.63­65 In 2014, they reported partially oxygen-
bridged triarylamines as HTL materials (Figure 2C).63 They
presented a synthesis route of two-fold intramolecular nucleo-
philic aromatic substitution to cyclize triarylamine, which yield-
ed a disk-like quasiplanar molecular geometry. The quasiplanar
molecule possessed face-on π-stacking in amorphous films,
as analyzed by two-dimensional grazing-incidence X-ray dif-
fraction (2D GIXD) with a synchrotron radiation source.66,67
Although they did not quantitatively analyze S, the molecular
design strategy can be applied to various HTL materials for
horizontal molecular orientation. In addition, the high intensity
and directionality of X-rays make such methods powerful tools
for analyzing molecular orientation in amorphous OLED
films.68 It should be noted, that for optoelectronic devices,
changes in the crystallinity of the molecules and electronic
properties of single molecules due to the π-extension need to be
considered. Both the covalent and non-covalent interactions
can be used to design horizontally oriented molecules.
© 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
fabricating HTLs and p-type host molecules for EMLs, possess
a more planar molecular framework than that of TPA groups
and tend to be π-stacked. Cz derivatives have been produced
with a high degree of molecular orientation by taking advan-
tage of the molecular planarity. For example, Yokoyama et al.
investigated the influence of the length of the molecular core
structure for Cz derivatives, such as 4,4¤-bis(N-carbazolyl)-1,1¤-
biphenyl (CBP69,70), 4,4¤-bis(N-carbazolyl)-stilbene (BCS71),
and 4,4¤-bis[(N-carbazole)styryl]-biphenyl (BSB-Cz72).73 In the
case of CBP with a compact molecular geometry, the S value
was almost isotropic (S = ¹0.07) (Figure 2D). This indicates
that the orientation of the transition dipole moment attributed
to the high absorption was almost random in these films. In
Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
contrast, the orientation of BCS and BSB-Cz, which are
elongated by the ethenylphenyl units, is highly dependent on
the molecular length. In particular, the linear BSB-Cz struc-
ture showed a high S value of ¹0.33. Hence, there is a clear
correlation between the molecular length and S. These results
demonstrate that linear molecules with a high aspect ratio can
be horizontally oriented in vacuum-deposited amorphous films
depending on their molecular length.
3. Molecular Orientation in ETLs:
Molecular Structure, Non-Covalent Molecular
Interactions, and Orientation Relationship
The discussion in the previous section showed that a key
design rule for obtaining horizontally oriented films is to
© 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-
tures, rather than the spherical structure of tris-(8-hydroxy-
quinoline)aluminum (Alq3),74 which is the most common elec-
tron transport material (Figure 3 and Figure 4A). In general,
the electron mobility (®e) of typical ETLs is almost a factor of
two lower than that of ®h of the HTL.60,76,77 Thus, development
of highly oriented ETLs is of paramount importance in order to
increase its carrier mobility.
Electron-withdrawing units have been used in a molecular
design for the development of ETL. For example, three-
dimensional structures, such as metal complexes (Alq3),
phenylbenzimidazole (PBI) derivatives (e.g., 1,3,5-tri(1-phen-
yl-1H-benzo[d]imidazol-2-yl)phenyl, TPBi78,79), triphenyl-
borane (TPB) derivatives (e.g., Tris(2,4,6-trimethyl-3-(pyri-
din-3-yl)phenyl)borane, 3TPyMB80), and triphenylphosphine
oxide (TPPO) derivatives (e.g., Bis[2-(diphenylphosphino)-
phenyl] ether oxide, DPEPO81), are used for constructing
amorphous films (Figure 3). Refinement of the molecular struc-
ture is desirable in order to realize horizontally oriented films.
Compared to electron-rich units for hole transporters, such as
TPA and Cz (Figure 3A), there are many electron-withdrawing
units with different shapes for electron transporters. Planar,
rather than spherical, units could enhance surface coupling to
the substrate to facilitate horizontal molecular orientation.
Some representative planar molecules include phenylpyridine
(PPy), phenanthroline (Phen), 2,2¤-bipyridyl (Bpy), and tri-
phenyl triazine (TPTZ) (Figure 3B).
Here, we consider oxadiazole (OXD) derivatives to demon-
strate the effects of molecular orientation and alignment on the
electrical properties (Figure 4A). Yokoyama et al. studied 1,3-
bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl] benzene
(OXD-782) and 1,3-bis [2-(2,2¤-bipyridin-6-yl)-1,3,4-oxadia-
zo-5-yl] benzene (Bpy-OXD83,84), which have similar single-
molecule characteristics, such as their conformation struc-
tures, distribution of the lowest unoccupied molecular orbitals
(LUMOs), and reorganization energies.85 Interestingly, the ®e
of a vapor-deposited film of Bpy-OXD was 30 times higher
than that of a similar OXD-7, even though their molecular
properties are very similar. VASE analysis showed that the
reason for the different ®e values was due to their different
molecular orientations. OXD-7 showed random orientation due
720 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
to its bulky tert-butyl terminal substituents, while Bpy-OXD
showed significant anisotropy due to its planar Bpy terminal
substituents induced by the transoid structure86 with intra-
molecular hydrogen bonds. With respect to the single molecule
geometry, high-aspect-ratio linear and planar molecules are
advantageous for horizontal molecular orientation.
It has been demonstrated that intermolecular interactions
between organic semiconductor molecules can be used to
increase their carrier mobility by controlling the molecular
orientation, for example, using weak hydrogen bonds (H-
bonds).87 H-bonds are unique non-covalent bonds with a direc-
tional property, which consists of the sum of the intermolecular
forces, such as electrostatic, induction of polarization, disper-
sion, exchange-repulsion, and charge-transfer forces. Because
of this directionality, H-bonds tend to be used as a means of
molecular recognition in supramolecular chemistry (e.g., self-
complementary CH£N weak H-bonds).88,89 Hohenstein and
Sherill reported the binding energy of weak H-bonds of the
pyridine dimer to be 13 kJ mol¹1 using quantum chemical cal-
culations, which is about half that of typical H-bonds (20­30
kJ mol¹1).90 In OLED research, several bis-4,6-(3,5-dipyridyl-
phenyl)-2-methylpyrimidine (BPyMPM) derivatives have been
developed by Tanaka91 and Sasabe43,92 and used to investigate
the effect of nitrogen orientation on the physical properties
(Figure 4B).93 Each of these BPyMPM derivatives have a
different nitrogen orientation on the peripheral pyridine rings,
resulting in large variations in ®e at 298 K. The ®e of
B4PyMPM is one order of magnitude higher than that of
B3PyMPM and two orders of magnitude higher than that of
B2PyMPM. Yokoyama et al. have investigated the molec-
ular orientation of BPyMPM derivatives using VASE and
Fourier transform infrared (FT-IR) spectroscopy.44 They noted
that B3PyMPM (S = ¹0.33) and B4PyMPM (S = ¹0.36)
molecules were well aligned with the substrates compared to
B2PyMPM (S = ¹0.14), due to the CH£N H-bonds in the
films. Hence, molecular orientation of BPyMPM molecules
can be controlled by intermolecular non-covalent interaction,
rather than controlling the molecular structure. To further
actively control the molecular orientation, Watanabe et al.
reported 2,2¤:6¤,2¤¤-terpyridine (Tpy)-based n-type molecules,
referred to as n-TerPyB (n = 2,3,4).94 This was a similar
© 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-
duced H-bond units while also reducing intramolecular steric
hindrances using Tpy units to enhance molecular planarity. The
subtle control of steric hindrance by replacing heteroaromatic
rings of C­H units by N atoms is a unique approach that takes
advantage of the planar structures. They showed that 2-TerPyB
formed randomly oriented films (S = ¹0.09), while 3-TerPyB
formed horizontally oriented films (S = ¹0.28) with a ®e value
10 times higher than that of 2-TerPyB. It should be noted that
the 4-TerPyB film had a rough surface with a root-mean-square
roughness (Rrms) of 10.2 nm, which was not suitable for device
application due to the rough surface result in high leakage
current. This high roughness was due to the highly directional
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-
tions strongly influenced the physical properties of the TerPyB
derivatives. The three TerPyB derivatives had different melting
points (Tm) of 270, 287, and 402 °C for 2-TerPyB, 3-TerPyB,
and 4-TerPyB, respectively, even though they are simply struc-
tural isomers. It has also been reported that 4-pyridyl terminal
substituent molecules tend to form strong H-bonds.95­97 These
results indicate that introducing 3-pyridyl units, rather than 4-
pyridyl units, can effectively form horizontal orientation in
amorphous films. The weaker H-bonds of the 3-pyridyl units
are due to conformational isomers by its rotation. Very recently,
Watanabe et al. developed horizontally oriented Bpy deriva-
tives end-capped with 3-dipyryidyl units, so called 4,4¤-BPy3
and 6,6¤-BPy3 (Figure 4B).75 They investigated the synergistic
effect of molecular anisotropy and intermolecular H-bonds in
the Bpy derivatives on the molecular orientation. Although the
only difference between the BPy derivatives was the position of
the substituents, they observed large differences in optical and
electronic properties in both the solution and crystal states
using nuclear magnetic resonance (NMR) and single crystal
XRD analyses. A disordered structure was observed at two of
the four terminal 3-pyridyl units. In addition, H-bonds link one
stacked column to another to form the 2D sheet structure.
Intermolecular interactions of H-bonds were confirmed at the
outer peripheral pyridine rings. The obtained CH£N bond
distances (2.61­3.14 ¡) were reasonably classified as weak H-
bonds (Figure 4C).90 Another study reported TZ-based mole-
cules (B3PyPTZ) that showed highly oriented films induced
by inter- and intramolecular H-bonding interactions (S =
¹0.38).97 These works provide essential design guidelines for
producing horizontally oriented, yet amorphous, organic semi-
conductor films by controlling subtle differences in the molec-
ular structures of oligopyridines. Simultaneous manipulation
of intra- and intermolecular interactions is a critical factor and
the most fundamental methodology for organizing molec-
ular assemblies in supramolecular chemistry, where the key is
lone-pair directionality. By taking advantage of the orienta-
tion of lone-pairs in HTL and ETL, it is expected that com-
plete molecular orientation in pure films will be achieved. In
addition, several analysis techniques, such as UV-visible,
VASE, NMR, XRD, and FT-IR spectroscopy could be further
used to determine molecular orientations in thin films. For
example, Quantitative Absorbance Comparison with an Iso-
tropically Oriented Standard (QACIOS)98,99 infrared (IR) p-
polarized multiple-angle incidence resolution spectrometry
(pMAIRS)100,101 and dynamic nuclear polarization-enhanced
ssNMR (DNP-ssNMR) spectroscopy102,103 could quantify the
distribution of molecular orientations in amorphous films.
4. Molecular Orientation in EMLs
In this section, we discuss the orientation of emitting dipoles
of organic dye molecules, which is of direct importance for
increasing the OLED efficiency. Perfect horizontal orientation
of the emitting dipole of the molecules can boost the light-
outcoupling factor by 1.5. In contrast, vertically oriented emit-
ting dipoles couple strongly to surface plasmons in the metal
electrodes of the OLED, decreasing the external quantum
efficiency (EQE).104,105 EMLs based on a mixed system, rather
than a pure system, have been developed as most organic dyes
722 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
exhibit low photoluminescence (PL) quantum yield (PLQY)
due to concentration quenching,106 and trapping of holes and
electrons at grain boundaries. To realize high-efficiency
OLEDs, host materials need higher triplet energy to prevent
back energy transfer from the dopant. In addition, appropriate
carrier-transport properties, HOMO/LUMO energy levels, and
singlet/triplet states are required. Furthermore, rough surfaces
result in high leakage currents and low device stability. There-
fore, in the case of EML, the investigation of mixed systems
to achieve molecular orientation has focused on both emitter
molecular structure and molecular interactions between host
and emitter molecules.
The following sub-sections discuss mixed systems in two
parts. First, we discuss organic dye molecular structures, then
the influence of host molecules on dipole orientation. Finally,
we discuss an unusual pure system with a Platinum (Pt)(II)
complex.
4.1 Mixed System I: Organic Dye Molecular Structures
and Orientational Relationships. Here, we describe con-
ventional host­dopant mixed systems, focusing on the chem-
ical structure of organic dyes and emission dipole moments.
Considering emitter orientation, common (first-generation)
organic dyes are well established in the field and have been
studied using optical simulations and experiments that distin-
guish between horizontal and vertical dipole orienta-
tion.104,107,108 Frischeisen et al. investigated two TPA deriva-
tives (PEBA and BDASBi) that have very similar molecular
structures, except for their molecular dipole orientation. By
measuring the EQE of OLEDs prepared using these materials,
horizontally oriented BDASBi-based OLEDs enhanced light
outcoupling by ³45%.106 Furthermore, the effect of orientation
in OLEDs offers many additional benefits regarding stack
design and has fundamental implications for material selection.
In 2012, TADF emitters based on pure organic compounds
were experimentally demonstrated as an alternate technology to
realize electron-to-photon conversion of 100% by harvesting
all molecular triplets and singlets.6,25 In general, TADF dyes
are formed using donor­acceptor (D­A) molecular systems,
which are structurally defined by an electron-rich moiety
covalently linked to an electron-deficient moiety. Therefore,
their molecular shape can be easily tuned. For example, Ting-
An et al. reported high performance sky-blue TADF dyes with
horizontally oriented dipoles (Figure 5A).109 They chose a
series of acridine (AC) units as bulky and rigid donors,
hybridized with TPTZ units as a planar acceptor. By system-
atically changing the rigidity of donor units, they observed that
rigid donor structure enhanced the orientation factor (©) from
72% to 83%, as analyzed by angle-dependent PL measure-
ments;110,111 a film with isotropic dipole arrangement yielded a
value of © = 67%. If the emissive dipole orientation is aligned
horizontal to the substrate, © = 100%; therefore, the maximum
possible value of © is desired. In addition, SpiroAC-TRZ, the
most rigid dye studied in this work, exhibited 100% PLQY
with a maximum EQE of 36.7% at 480 nm. This is currently the
highest efficiency for sky-blue OLEDs reported to date. The
group of Kaji and Adachi demonstrated green and deep-blue
TADF dyes called DACT-II112 and CCX-II,113 with a high
© of 86%, and 83% respectively with 100% PLQY. They
achieved very high EQE of 29.6% at ­em = ³520 nm, and
© 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
xanthone units were introduced as acceptor units in symmetric
π-extended diphenylamino-carbazole and tercarbazolyl units.
Furthermore, P. Rajamalli et al. developed pure-blue TADF dye
called 3DPyM-pDTC based on a di(pyrimidinyl)methanone
core as the new electron-accepting planar and rigid units, that
achieved a high © of 85% with 98% PLQY, and an EQE
greater than 31% at ­em = 464 nm.114 These results demon-
strated that molecular rigidity and planar geometry are impor-
tant factors, even in host­matrix systems.
Recently, spirobiacridine (SBA)-based linear TADF dyes
were developed by the group of Sasabe, Su, and Kido, labelled
Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
TZ-SBA, PX-SBA, and IPN-SBA (Figure 5B).115 SBA con-
sists of two AC units connected via σ bonds, where this unique
donor forms a rigid molecular framework. In addition, two
acceptor units can connect with SBA on the line-symmetric
axis, with an A­D­σ­D­A linear structure. These SBA deriva-
tives exhibited very high © values of 86­93%. The © value is
one of the highest ever reported for phosphorescent and TADF
emitters. The sky-blue device based on IPN-SBA realized a
very high EQE of 24.7% at 466 nm. It is expected that A­D­
σ­D­A linear TADF dyes will become promising alternate
structures to conventional D­A-type TADF dyes. As the © and
PLQY values depend on the host molecule, film thickness, and
© 2019 The Chemical Society of Japan | 723
doping concentration of the dyes, a complete summary of the
molecular orientation of the many organic dyes is beyond the
scope of this review. Further systematic studies are required in
order to elucidate the relationship between molecular structures
and their dipole orientation.
In addition to pure organic dyes, the molecular orientation of
phosphorescent emitters containing heavy metals (especially
Iridium (Ir) and Pt) is also being considered to achieve high-
efficiency OLEDs with IQE of 100%; these rare heavy metals
can harvest all electrogenerated molecular singlet and triplet
excitons.116,117 Although Ir(III) complexes have aspherical
geometry, horizontal emitting dipole moments of heteroleptic
Ir(III) complexes (HICs) originate from the preferred direction
of the triplet transition dipole moment along the Ir­N direction
in HICs. A recent study showed that substituents at the para-
position of the pyridine in the main ligands of HICs played a
pivotal role in inducing the orientation (Figure 5C).117 Sub-
stitution of aliphatic and aromatic functional moieties at the
para-position resulted in significant horizontal emitting dipole
orientation, showing © values up to 86.5% with EQE values
of 38.1% at 579 nm and 36.0% at 532 nm. They noted that
elongated and planar substituents with a high aspect ratio
enhanced face-to-face or face-to-line intermolecular interac-
tions between the HICs and host molecules. Hence, further
studies should consider molecular interactions with neighbor-
ing molecules, in addition to the structure of the emitters.
4.2 Mixed System II: Influence of Host Molecules on
Molecular Orientation in EMLs. To enhance the lumines-
cent properties of the emitter molecules, host molecules play
various key roles in e.g., the dispersion of organic dyes to
obtain a high PLQY, suppression of concentration quenching
and self-quenching, and enhancement of carrier injection. In
addition, interactions between with host molecules and organic
dyes are very important for controlling the emitting dipole
orientation. In this section, we discuss the influence of host
molecules on the molecular orientation in EMLs.
The influence of the host molecules in vapor-deposited films
has been well investigated considering the thermal properties,
such as the glass transition temperature (Tg), as well as the
dipole moment (D) and molecular weight (Mw). Mayr and
Brütting correlated the orientation of fluorescent and phosphor-
escent organic dyes to physical properties of the host materials
(Figure 6A).118 While no significant correlation between the
properties of the host material and the orientation of phosphor-
escent Ir(III) complexes could be detected, the fluorescent dye
Coumarin 6 showed an increasingly horizontal orientation
with increasing Tg of the host molecules due to a decrease in
the molecular surface mobility during deposition. The orienta-
tion of Coumarin 6 could be controlled between isotropic and
horizontal orientation by using host molecules with different
Tg. This was probably due to the linear molecular structure of
the dye and its low Mw.
Kim et al. reported the influence of host molecules on both
the homoleptic Ir(III) complex [Ir(ppy)3] and HIC [Ir(ppy)2
tmd], and explored the effect of the molecular interaction
between the host and organic dyes on the emission dipole
moments of the dyes (Figure 6B).119 In the case of Ir(ppy)2
tmd, the triplet transition dipole moments of Ir(ppy)2 tmd
aligned with the substrate in a different manner in various
724 | Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
host matrices. Based on density functional theory (DFT) cal-
culations, the dopant­CBP and dopant­B3PyMPM mix-
tures showed the highest binding energy of 30 kcal/mol (125
kJ/mol), which is almost 10 times higher than the other host­
host, dopant­dopant, or host­dopant interactions. It should be
noted that the randomly oriented CBP host resulted in a
slightly higher horizontal dipole ratio of Ir(ppy)2 tmd than
B3PYMPM, implying that dipole orientation was not con-
trolled by the orientation of host molecules, but by the binding
geometry of host­dopant molecules. Additionally, Ir(ppy)2
tmd formed random isotropic orientation when spin coated
with a poly(methyl methacrylate) (PMMA) matrix. One plau-
sible reason for this is the weak intermolecular interaction
between the dye and aliphatic chains, which randomized the
orientation of the dyes by entropic energy. Another possible
reason is the thermal history that the films experienced during
annealing at temperature above their Tg. Recently, the impor-
tance of the Tg of host molecules with linear molecular geom-
etry was reported.120 Using linear TADF molecules of cis-
BOX2, they achieved complete horizontal orientation (© =
100%) at a substrate temperature of 200 K. They attributed this
to kinetic relaxation during film deposition and the kinetic
stability of the dopant in the host matrix.121
4.3 Pure System: Pt(II) Phosphors and the Strong Metal­
Metal Interactions between Square­Planar Motifs. Emit-
ters tend to be dispersed in host molecules to prevent con-
centration quenching and self-quenching of PLQY. However,
recently, certain Pt(II) emitters have been developed that
show very high PLQY in a pure system or crystalline state
(Figure 7). For example, Kim et al. reported highly efficient
red OLEDs using pure Pt(II) phosphor layers as EMLs.122
Since the Pt(II) complex has d 8 square planar geometry and a
dz2 orbital placed perpendicular to the molecular plane, strong
metal­metal intermolecular interactions between the complexes
can be formed. Based on DFT calculations and single-crystal
X-ray diffraction data, Pt(fppz)2 and its derivatives showed
strong coulomb interactions in these dimers. In addition, vapor-
deposited films showed almost complete vertical molecular
alignment, as measured by 2D GIXD, with a low Rrms of 0.54­
1.17 nm. On the other hand, the emitting dipoles of these thin
films were horizontally oriented with © = 93%. This is due to
emission of the Pt(II) complex in the solid-state corresponding
to the excimer originating from metal­metal-to-ligand charge
transfer (MMLCT) caused by Pt­Pt metallophilic ligand inter-
actions. Using the oriented dyes, they achieved a maximum
EQE of 38.8%, which is the highest efficiency reported to
date.123 Very recently, other pyrazine-based Pt(II) complexes
also achieved horizontal emitting dipole orientation (© = 87%)
with high EQE of 24% in the near infrared region (­em = 740
nm).124 However, it is difficult to compare the © and PLQY
values and further studies are required in order to elucidate
their relationship. It is clear that metal­metal interactions, in
addition to the planar molecular structure, contribute to con-
trolling the orientation.
5. Conclusion and Perspective
Molecular orientation in OLEDs has developed rapidly since
the first reports just over a decade ago. Initial studies focused
on the single molecular structure in pure films. Since then, there
© 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
molecular orientation using rational molecular interactions in
both pure and mixed systems. In this review, we focused on
molecular orientation from the view point of the molecular
structure of the key materials used in the three essential OLED
layers. Across a wide variety of single molecular structures,
it was shown that materials with linear, or planar geometries
generally exhibited horizontal orientation with the substrates.
In contrast, considering molecular interactions, actively con-
trolling lone-pairs to construct weak CH£N H-bonds is
essential. In addition, metal­metal interactions and electrostatic
interactions between the host and organic dyes are important
Bull. Chem. Soc. Jpn. 2019, 92, 716–728 | doi:10.1246/bcsj.20180336
for tailoring molecular orientation. The studies of the molecular
structure­property relationship described here have begun to
elucidate the specific interactions that are the most beneficial
for OLED applications, with respect to reducing the driving
voltage and enhancing light outcoupling efficiency. Most of
these studies have shown that carrier transport materials and
emissive materials can be manipulated to achieve the desired
molecular orientation in vacuum-deposited films. However,
in general, these methods are currently unsuitable for ink-
based coatings. It is surprising that ink-based coating methods
produce randomly orientated films by using specific mole-
cules that can be horizontally oriented in vacuum-deposited
© 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
growth mechanisms related to kinetic stabilities and molecular
dynamics in solution. In the near future, we expect that
development of all-solution ink-based films for OLEDs will be
achieved by taking advantage of the full potential of organic
semiconductor molecules with well-controlled molecular
orientation.
In order to design and discover new generations of materials
with superior performance beyond that expected based on the
molecular formula, researchers need to provide essential guide-
lines, such as: (i) understanding of the origin of molecular
orientation; (ii) rational utilization of molecular interactions;
(iii) biomimetic and supramolecular design of molecular
assemblies; (iv) development of analytical methods to achieve
3D molecular orientation mapping; and (v) simulation of
molecular aggregation in thin films.126­130 If the community
embraces these challenges, we anticipate that molecular engi-
neering for horizontal orientation in OLEDs could enter a
golden era of vibrant research. We believe that this review will
contribute to the fast and accurate discovery of game-changing
molecules for applications in advanced OLED materials.
Our work written in this review was partially supported by
the Center of Innovation (COI) Program from the Japan
Science and Technology Agency (JST) and the Japan Society
for the Promotion of Science (JSPS) KAKENHI Grant
(15J08167 and 17H03131). We would also like to thank all
our collaborators and laboratory members whose names are
cited in References for their great contributions.
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