Crystal Facet Engineering of TiO2 Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO4 Nanodots.

Although bismuth vanadate (BiVO4) has been promising as photoanode material for photoelectrochemical water splitting, its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes. As a hole blocking layer of BiVO4, titanium dioxide (TiO2) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity. Herein, a crystal facet engineering of TiO2 nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots. We design two types of TiO2 nanostructures, which are nanorods (NRs) and nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, and fabricate BiVO4/TiO2 heterostructure photoanodes. The BiVO4/TiO2 NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO2 NRs. Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination, which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO2 NFs. This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.

Breaking the Efficiency Limit of Deep-Blue Fluorescent OLEDs Based on Anthracene Derivatives.

Triplet harvesting is important for the realization of high-efficiency fluorescent organic light-emitting diodes (OLEDs). Triplet-triplet annihilation (TTA) is one triplet-harvesting strategy. However, for blue-emitting anthracene derivatives, the theoretical maximum radiative singlet-exciton ratio generated from the TTA process is known to be 15% in addition to the initially generated singlets of 25%, which is insufficient for high-efficiency fluorescent devices. In this study, nearly 25% of the radiative singlet-exciton ratio is realized by TTA using an anthracene derivative, breaking the theoretical limit. As a result, efficient deep-blue TTA fluorescent devices are developed, exhibiting external quantum efficiencies of 10.2% and 8.6% with Commission Internationale de l'Eclairage color coordinates of (0.134, 0.131) and (0.137, 0.076), respectively. The theoretical model provided herein explains the experimental results considering both the TTA and reverse intersystem crossing to a singlet state from higher triplet states formed by the TTA, clearly demonstrating that the radiative singlet ratio generated from TTA can reach 37.5% (total radiative singlet-exciton ratio: 62.5%), well above 15% (total 40%), despite the molecule having S1 , T2  < 2T1  < Q1 energy levels, which will lead to the development of high-efficiency fluorescent OLEDs with external quantum efficiencies exceeding 28% if the outcoupling efficiency is 45%.

TD-DFT and Experimental Methods for Unraveling the Energy Distribution of Charge-Transfer Triplet/Singlet States of a TADF Molecule in a Frozen Matrix.

Reverse intersystem crossing (RISC) rate of a thermally activated delayed fluorescence (TADF) molecule is sensitive to the energy alignment of the singlet charge-transfer state (1CT), triplet charge-transfer state (3CT), and locally excited triplet state (3LE). However, the energy distribution of the charge-transfer states originating from the conformational distribution of TADF molecules in a solid matrix inevitably generated during the preparation of a solid sample due to the rotatable donor-acceptor linkage is rarely considered. Moreover, the investigation of the energy distribution of the 3CT state is both theoretically and experimentally difficult due to the triplet instabilities of time-dependent density functional (TD-DFT) calculations and difficulties in phosphorescence measurements, respectively. As a result, the relationships between conformational distribution, configurations of excited state transition orbitals, and excited state energies/dynamics have not been clearly explained. In this work, we determined the energy distribution of CT states of the TADF emitter TPSA in frozen toluene at 77 K by the measurement of time-resolved spectra in the full time range (1 ns to 30 s) of emission including prompt fluorescence, TADF, 3CT phosphorescence, and 3LE phosphorescence. We obtained the energy band of CT states where 1CT and 3CT states are distributed in the range of 2.85-3.00 and 2.64-2.96 eV, respectively. We tested various global hybrid and long-range corrected functionals for the TD-DFT calculation of 3CT energy of TPSA and found that only the M11 functional shows consistent results without triplet instability. We performed TD-DFT with the M11* functional optimized for a robust dihedral angle scan of 3CT states without triplet instability and reproduced the energy band structure obtained from the experiment. Through TD-DFT and experimental investigations, it is estimated that the dihedral angles of donor-acceptor (θD-A) and acceptor-linker (θA) of TPSA in frozen toluene lie within the range 70° ≤ θD-A ≤ 90° and 0° ≤ θA ≤ 30° respectively. Our results show that the dihedral angle distribution must be considered for further investigation of the photophysics of TADF molecules and the development of stable and efficient TADF emitters.

Highly Efficient Deep-Blue OLEDs using a TADF Emitter with a Narrow Emission Spectrum and High Horizontal Emitting Dipole Ratio.

New blue (DBA-SAB) and deep-blue (TDBA-SAF) thermally activated delayed fluorescence (TADF) emitters are synthesized for blue-emitting organic-light emitting diodes (OLEDs) by incorporating spiro-biacridine and spiro-acridine fluorene donor units with an oxygen-bridged boron acceptor unit, respectively. The molecules show blue and deep-blue emission because of the deep highest occupied molecular energy levels of the donor units. Besides, both emitters exhibit narrow emission spectra with the full-width at half maximum (FWHM) of less than 65 nm due to the rigid donor and acceptor units. In addition, the long molecular structure along the transition dipole moment direction results in a high horizontal emitting dipole ratio over 80%. By combining the effects, the OLED utilizing DBA-SAB as the emitter exhibits a maximum external quantum efficiency (EQE) of 25.7% and 1931 Commission Internationale de l'éclairage (CIE) coordinates of (0.144, 0.212). Even a higher efficiency deep blue TADF OLED with a maximum EQE of 28.2% and CIE coordinates of (0.142, 0.090) is realized using TDBA-SAF as the emitter.

External Quantum Efficiency Exceeding 24% with CIEy Value of 0.08 using a Novel Carbene-Based Iridium Complex in Deep-Blue Phosphorescent Organic Light-Emitting Diodes.

Deep-blue triplet emitters remain far inferior to standard red and green triplet emitters in terms of exhibiting high-color-purity Commission International de l'Éclairage (CIE) y values of ≤0.1, external quantum efficiencies (EQEs), and high electroluminescent brightnesses in phosphorescent organic light-emitting diodes. In fact, no deep-blue triplet emitter with color purity and high device performance has previously been reported. In this study, a deep-blue triplet emitter, mer-tris(N-phenyl, N-benzyl-pyridoimidazol-2-yl)iridium(III) (mer-Ir1) is developed, which meets the requirements of the National Television System Committee (NTSC) CIE(x, y) coordinates of (0.149, 0.085) with an extremely high EQE of 24.8% and maximum brightness (Lmax ) of 6453 cd m-2 , by a device with a 40 vol% doping ratio. Moreover, another device demonstrates an EQEmax of 21.3%, an Lmax of 5247 cd m-2 , and CIE(x, y) coordinates of (0.151, 0.086) at a 30 vol% doping ratio. This is the first report of a high-performance, deep-blue phosphor, carbene-based Ir(III) complex device with outstanding CIE(x, y) color coordinates and a high EQE. The results of this study indicate that the novel dopant mer-Ir1 is a promising candidate for reducing power consumption in display applications.

Simple method to extract extinction coefficients of films with the resolution of 10-5 using just transmission data and application to intermolecular charge-transfer absorption in an exciplex-forming organic film.

A simple method is presented to determine the thickness, refractive index and extinction coefficient of a film with the resolutions of ±1 nm, ±2 × 10-3, and 6 × 10-5, respectively. The method requires only ultraviolet-visible-near-infrared spectroscopy measurement of the transmittance of films with thicknesses of a few micrometers. A very small extinction coefficient of intermolecular charge transfer (CT) absorption of an exciplex-forming organic film is measured in the sub-bandgap wavelength region. This is to demonstrate that the CT absorption with extinction coefficient in the range of 10-3 to 10-5 can be measured indeed using the method, which is in the same resolution as photothermal deflection spectroscopy and Fourier transform photocurrent spectroscopy. The simplicity and feasibility of the proposed approach is expected to promote active study of intermolecular CT absorption in exciplex-forming films.

A Broadband Multiplex Living Solar Cell.

Developing renewable and sustainable energy sources is a compelling goal in materials science and engineering. In particular, natural photosynthesis with its infinite energy reservoir provides profound inspiration for energy conversion and storage systems. Here, we report a multiplex living solar cell that offers a drastic power enhancement by harnessing the broadband spectra of the visible wavelength range for photosynthesis. Cyanobacteria are embedded into a nanostructural complex composed of Au nanoparticles (NPs) and ZnO nanorods (NRs). This nanocomposite system is capable of not only generating excitons but also amplifying the photosynthetic performance of the cell via a far-field scattering effect in the broadband region of the light, resulting in multiplex energy harvesting with a peak power density of 6.15 mW/m2. We envision that this study will provide a strategic way to enhance the performance of biophotovoltaics, enabling efficient and durable energy generation.

Design Strategy of Anthracene-Based Fluorophores toward High-Efficiency Deep Blue Organic Light-Emitting Diodes Utilizing Triplet-Triplet Fusion.

In contrast to the red and green regions, conventional fluorescent emitters continue to serve as blue emitters in commercialized organic light-emitting diodes. Many researchers have studied anthracene moieties as blue emitters, given their appropriate energy levels and good emission properties. We herein report two new deep blue-emitting anthracene derivatives that include p-xylene as moieties connecting the anthracene cores to side groups. We enhanced the efficiency by maximizing triplet-triplet fusion (TTF) without sacrificing emission color. The large steric hindrance imposed by the methyl groups of p-xylene creates a perpendicular geometry between p-xylene and the neighboring aromatic rings. Any extension of π-conjugation is thus disrupted, and the isolated core anthracene moiety emits a deep blue color with a high photoluminescence quantum yield. Moreover, the extensive steric hindrance suppresses vibration and rotation because the molecules are rigid. The high horizontal dipole ratio attributable to the large aspect ratio increases the outcoupling efficiency of the emitted light. Furthermore, the charge mobility and triplet harvesting ability are enhanced by decreasing the bulkiness of the side groups. Molecular dynamics simulation revealed that the bulkiness of the side group significantly impacted molecular density, which in turn affected the charge transport and TTF. We used two molecules, 2PPIAn (containing a phenyl side group) and 4PPIAn (containing a terphenyl side group), to form nondoped emission layers that exhibited maximum external quantum efficiencies of 8.9 and 7.1% with Commission Internationale de L'Eclairage coordinates of (0.150, 0.060) and (0.152, 0.085), respectively.

Growth mechanism of CH3NH3I in a vacuum processed perovskite.

In the field of halide perovskite research, the growth of high quality films has been a critical issue. Among the reported growth methods, vacuum processes have attracted much attention due to their accurate controllability and high reproducibility, as proven in the manufacture of vacuum deposited organic-light-emitting-diode industry. In a vacuum process, the major difficulty for growing a perovskite film is control of a precursor, methylammonium iodide (MAI), originating from its uncontrollable behavior i.e., a high working pressure and poor adsorption characteristics. Thus, it is crucial to understand the growth mechanism of MAI vapor for the successful application of vacuum processes in the growth of halide perovskite films. In this paper, we report the growth mechanism and deposition kinetics of MAI in a vacuum. Unlike that of conventional materials evaporated in a vacuum, the deposition rate of MAI was found to be much faster on the reactive surface, PbI2, compared to other non-reactive materials. Surprisingly, a very thin (2 nm-thick) PbI2 layer increased the initial growth rate of MAI 2.7-fold. Based on the real-time monitored data from a quartz microbalance and surface study, we suggest dipole-induced adsorption as the MAI growth mechanism on PbI2 and the perovskite in the vacuum process. We believe that this work will provide meaningful insight into film growth in vacuum processed perovskites.

Enhanced Triplet-Triplet Annihilation of Blue Fluorescent Organic Light-Emitting Diodes by Generating Excitons in Trapped Charge-Free Regions.

Three new anthracene-cored molecules, 3,3'-(5-(10-(naphthalen-1-yl)anthracen-9-yl)-1,3-phenylene)dipyridine (AP3Py-Na), 3,3'-(5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,3-phenylene)dipyridine (AP3Py-2Na), and 9,10-bis(3,5-di(pyridin-3-yl)phenyl)anthracene (ADP3Py), were synthesized to be used as an efficiency-enhancement layer (EEL) in blue fluorescent organic light-emitting diodes. Insertion of a very thin EEL (3 nm) between the deep blue emitting layer (EML) and the electron transport layer enhanced the external quantum efficiency (EQE) of the blue device by 44% compared to the device without the EEL, resulting in an EQE of 7.9% and a current efficiency of 9.0 cd A-1 at 1000 cd m-2; the CIE coordinates of the emitting color were (0.13, 0.14). The transient electroluminescence showed that the efficiency enhancement originates from the triplet-triplet annihilation (TTA) process in the EEL, followed by energy transfer to the emitting dye in the EML.

Controlling Horizontal Dipole Orientation and Emission Spectrum of Ir Complexes by Chemical Design of Ancillary Ligands for Efficient Deep-Blue Organic Light-Emitting Diodes.

Deep-blue emitting Iridium (Ir) complexes with horizontally oriented emitting dipoles are newly designed and synthesized through engineering of the ancillary ligand, where 2',6'-difluoro-4-(trimethylsilyl)-2,3'-bipyridine (dfpysipy) is used as the main ligand. Introduction of a trimethylsilyl group at the pyridine and a nitrogen at the difluoropyrido group increases the bandgap of the emitter, resulting in deep-blue emission. Addition of a methyl group (mpic) to a picolinate (pic) ancillary ligand or replacement of an acetate structure of pic with a perfluoromethyl-triazole structure (fptz) increases the horizontal component of the emitting dipoles in sequence of mpic (86%) > fptz (77%) > pic (74%). The organic light-emitting diode (OLED) using the Ir complex with the mpic ancillary ligand shows the highest external quantum efficiency (31.9%) among the reported blue OLEDs with a y-coordinate value lower than 0.2 in the 1931 Commission Internationale de L'Eclairage (CIE) chromaticity diagram.

Phenazasiline/Spiroacridine Donor Combined with Methyl-Substituted Linkers for Efficient Deep Blue Thermally Activated Delayed Fluorescence Emitters.

Phenazasiline, a sp3 hybridized silicon-bridged diphenylamine, is a promising donor moiety for deep-blue TADF emitters because of its deep highest occupied molecular orbital, high triplet level of 3.1 eV, and orthogonal connection with acceptor moieties. Herein, we report highly efficient deep-blue TADF emitters composed of phenazasiline donor and triazine acceptor combined with methyl-substituted phenylene linkers. As a series of methyl-substituted linker-based TADF emitters, we also synthesized spiroacridine donor-based sky-blue TADF emitters to study the effect of methyl-substituted linkers on the photophysical properties of TADF emitters. Deeper blue emissions of TADF emitters were obtained by substituting either one or two methyl groups at the phenylene linker of TADF molecules, and a small singlet-triplet gap below 0.2 eV was maintained for efficient reverse intersystem crossing. Organic light-emitting diodes (OLEDs) with spiroacridine-based TADF emitters, TTSA and TXSA, showed external quantum efficiencies (EQEs) of 27.9 and 20.7% with sky-blue emission of Commision Internationale de L'Eclairage (CIE) color coordinates of (0.158, 0.283) and (0.154, 0.251), respectively. With phenazasiline-based TADF emitters, TTAZ and TXAZ, highly efficient deep-blue OLEDs were realized with EQEs of 23.7 and 16% with improved CIE coordinates of (0.148, 0.158) and (0.148, 0.131), respectively.

Triplet Harvesting by a Fluorescent Emitter Using a Phosphorescent Sensitizer for Blue Organic-Light-Emitting Diodes.

The development of highly efficient blue organic light-emitting diodes (OLEDs) with good stability is currently the most important issue in OLED displays and lighting. This paper reports an efficient blue fluorescent OLED based on a deep-blue-emitting phosphorescent sensitizer [(dfpysipy)2Ir(mpic)] and a conventional fluorescent emitter (TBPe). Efficient triplet harvesting by the fluorescent emitter occurs in the OLED because of sensitization even though the difference in the emission energy between the phosphorescent and fluorescent emissions was only 0.05 eV. These results clearly demonstrate the potential for realizing highly efficient blue fluorescent OLEDs using phosphorescent sensitizers without requiring ultraviolet-emitting phosphorescent dye.

Lensfree OLEDs with over 50% external quantum efficiency via external scattering and horizontally oriented emitters.

High efficiency is important for successful deployment of any light sources. Continued efforts have recently made it possible to demonstrate organic light-emitting diodes with efficiency comparable to that of inorganic light-emitting diodes. However, such achievements were possible only with the help of a macroscopic lens or complex internal nanostructures, both of which undermine the key benefits of organic light-emitting diodes as an affordable planar light source. Here we present a systematic way to achieve organic light-emitting diodes with ultrahigh efficiency even only with an external scattering film, one of the simplest low-cost outcoupling structures. Through a global, multivariable analysis, we show that scattering with a high degree of forwardness has a potential to play a critical role in realizing ultimate efficiency. Combined with horizontally oriented emitters, organic light-emitting diodes equipped with particle-embedded films tailored for forward-intensive scattering achieve a maximum external quantum efficiency of 56%.

Control of Crystallinity in PbPc:C60 Blend Film and Application for Inverted Near-Infrared Organic Photodetector.

Inverted near-infrared (NIR) organic photodetectors (OPDs) are required to combine the OPDs with an n-channel silicon-based integrated circuit. NIR absorption in the 930-960 nm range is important because the intensity of solar irradiation is low in this wavelength regime. Here, we controlled the crystallinity of lead(II) phthalocyanine (PbPc) in a PbPc:C60 blend film to obtain NIR absorption. To form a triclinic phase responsible for NIR light absorption, a substrate was heated during fabrication and C60 was used as a templating layer, as well as an electron extraction layer, for an inverted structure. NIR absorption near 950 nm was enhanced, and the structural properties of the film changed dramatically. The OPD with enhanced NIR absorption exhibited a responsivity of 244 mA/W and an external quantum efficiency of 31.1% at a reverse bias of -3 V and 970 nm. The OPD detectivity also increased to 9.01 × 1012 and 1.36 × 1011 cm Hz1/2/W under a zero bias and a reverse bias of -3 V, respectively.

Origin and Control of Orientation of Phosphorescent and TADF Dyes for High-Efficiency OLEDs.

It has been known for decades that the emitting dipole orientation (EDO) of emitting dyes influences the outcoupling efficiency of organic light-emitting diodes (OLEDs). However, the EDO of dopants, especially phosphorescent dopants, has been studied less than that of neat films and polymer emitting layers (EMLs) due to the lack of an apparent driving force for aligning the dopants in amorphous host films. Recently, however, even globular-shaped Ir complexes have been reported to have a preferred orientation in doped films and OLEDs. External quantum efficiencies (EQEs) higher than 30% have also been demonstrated using phosphorescent and thermally activated delayed fluorescent dyes (TADF) doped in EMLs. Here, recent results on the EDO of phosphorescent and TADF dyes doped in host films, and highly efficient OLEDs using these dyes are reviewed. The origin and control of the orientation of phosphors are discussed, followed by a discussion of future strategies to achieve EQEs of over 60% without a light extraction layer, from the material point of view.

Optical Analysis of Power Distribution in Top-Emitting Organic Light Emitting Diodes Integrated with Nanolens Array Using Finite Difference Time Domain.

Recently, we have addressed that a formation mechanism of a nanolens array (NLA) fabricated by using a maskless vacuum deposition is explained as the increase in surface tension of organic molecules induced by their crystallization. Here, as another research using finite difference time domain simulations, not electric field intensities but transmitted energies of electromagnetic waves inside and outside top-emitting blue organic light-emitting diodes (TOLEDs), without and with NLAs, are obtained, to easily grasp the effect of NLA formation on the light extraction of TOLEDs. Interestingly, the calculations show that NLA acts as an efficient light extraction structure. With NLA, larger transmitted energies in the direction from emitting layer to air are observed, indicating that NLAs send more light to air otherwise trapped in the devices by reducing the losses by waveguide and absorption. This is more significant for higher refractive index of NLA. Simulation and measurement results are consistent. A successful increase in both light extraction efficiency and color stability of blue TOLEDs, rarely reported before, is accomplished by introducing the highly process-compatible NLA technology using the one-step dry process. Blue TOLEDs integrated with a N, N'-di(1-naphthyl)- N, N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine NLA with a refractive index of 1.8 show a 1.55-times-higher light extraction efficiency, compared to those without it. In addition, viewing angle characteristics are enhanced and image blurring is reduced, indicating that the manufacturer-adaptable technology satisfies the requirements of highly efficient and color-stable top-emission displays.

An Exciplex Host for Deep-Blue Phosphorescent Organic Light-Emitting Diodes.

The use of exciplex hosts is attractive for high-performance phosphorescent organic light-emitting diodes (PhOLEDs) and thermally activated delayed fluorescence OLEDs, which have high external quantum efficiency, low driving voltage, and low efficiency roll-off. However, exciplex hosts for deep-blue OLEDs have not yet been reported because of the difficulties in identifying suitable molecules. Here, we report a deep-blue-emitting exciplex system with an exciplex energy of 3.0 eV. It is composed of a carbazole-based hole-transporting material (mCP) and a phosphine-oxide-based electron-transporting material (BM-A10). The blue PhOLEDs exhibited maximum external quantum efficiency of 24% with CIE coordinates of (0.15, 0.21) and longer lifetime than the single host devices.

Unraveling the orientation of phosphors doped in organic semiconducting layers.

Emitting dipole orientation is an important issue of emitting materials in organic light-emitting diodes for an increase of outcoupling efficiency of light. The origin of preferred orientation of emitting dipole of iridium-based heteroleptic phosphorescent dyes doped in organic layers is revealed by simulation of vacuum deposition using molecular dynamics along with quantum mechanical characterization of the phosphors. Consideration of both the electronic transitions in a molecular frame and the orientation of the molecules at the vacuum/molecular film interface allows quantitative analyses of the emitting dipole orientation depending on host molecules and dopant structures. Interactions between the phosphor and nearest host molecules on the surface, minimizing the non-bonded van der Waals and electrostatic interaction energies determines the molecular alignment during the vacuum deposition. Parallel alignment of the main cyclometalating ligands in the molecular complex due to host interactions rather than the ancillary ligand orienting to vacuum leads to the horizontal emitting dipole orientation.Iridium-based phosphors show high photoluminescence quantum yield in organic light-emitting diodes. Here, Moon et al. reveal the mechanism responsible for the preferred orientation of iridium complexes in an organic host and highlight the interaction between phosphor and host molecules at play.

Highly Efficient, Conventional, Fluorescent Organic Light-Emitting Diodes with Extended Lifetime.

Highly efficient, yellow-fluorescent organic light-emitting diodes with a maximum external quantum efficiency exceeding 25.0% and extended lifetime are reported using iridium-complex sensitizers doped in an exciplex host. Energy transfer processes reduce the lifetime of the exciplex and excitons on the Ir complexes and enable an excited state to exist in a conventional fluorescent emitter, thereby increasing device lifetime. The device stability depends on the location of the excited state.