Hexacarbazolylbenzene: An Excellent Host Molecule Causing Strong Guest Molecular Orientation and the High-Performance OLEDs.

Hexacarbazolylbenzene (6CzPh), which is benzene substituted by six carbazole rings, is a simple and attractive compound. Despite the success of a wide variety of carbazole derivatives in organic light-emitting diodes (OLEDs), 6CzPh has not received attention so far. Here, excellent performances of 6CzPh are revealed as a host material in OLEDs regarding conventional host materials. Various strategies are implemented to improve the performance of OLEDs, e.g., triplet utilization by thermally activated delayed fluorescence (TADF) and phosphorescence emitters for maximizing internal quantum efficiency, and molecular orientation control for increasing outcoupling efficiency. The present host material is suited for both criteria. Robustness of the structure and sufficiently high triplet energy enables a high external quantum efficiency with a long device lifetime. Besides, the host material boosts the horizontal molecular orientations of several guest emitters. It is noteworthy that disk-shaped 4CzIPN marks the complete horizontal molecular orientations (Θh = 100%, S = -0.50). These results provide an effective way of improving efficiencies without sacrificing device durability for future OLEDs.

Highly efficient light harvesting of a Eu(iii) complex in a host-guest film by triplet sensitization.

Trivalent lanthanide complexes are attractive light emitters owing to their ideal high color purity. Sensitization using ligands with high absorption efficiency is a powerful approach to enhancing photoluminescence intensity. However, the development of antenna ligands that can be used for sensitization is limited due to difficulties in controlling the coordination structures of lanthanides. When compared to conventional luminescent Eu(iii) complexes, a system composed of triazine-based host molecules and Eu(hfa)3(TPPO)2 (hfa: hexafluoroacetylacetonato and TPPO: triphenylphosphine oxide) significantly increased total photoluminescence intensity. Energy transfer from the host molecules to the Eu(iii) ion occurs via triplet states over several molecules, according to time-resolved spectroscopic studies, with nearly 100% efficiency. Our discovery paves the way for efficient light harvesting of Eu(iii) complexes with simple fabrication using a solution process.

Multiple donor-acceptor design for highly luminescent and stable thermally activated delayed fluorescence emitters.

A considerable variety of donor-acceptor (D-A) combinations offers the potential for realizing highly efficient thermally activated delayed fluorescence (TADF) materials. Multiple D-A type compounds are one of the promising families of TADF materials in terms of stability as well as efficiencies. However, those emitters are always composed of carbazole-based donors despite a wide choice of moieties used in linearly linked single D-A molecules. Herein, we developed a multiple D-A type TADF compound with two distinct donor units of 9,10-dihydro-9,9-dimethylacridine (DMAC) and carbazole as the hetero-donor design. The new emitter exhibits high photoluminescence quantum yield (PLQY) in various conditions including polar media blend and high concentrations. Organic light-emitting diodes (OLEDs) showed a reasonably high external quantum efficiency (EQE). In addition, we revealed that the multiple-D-A type molecules showed better photostability than the single D-A type molecules, while the operational stability in OLEDs involves dominant other factors.

Organic Binary and Ternary Cocrystal Engineering Based on Halogen Bonding Aimed at Room-Temperature Phosphorescence.

Recently, there has been intense interest in pure organic room-temperature phosphorescence (ORTP) from cocrystals composed of 1,4-diiodotetrafluorobenzene (DITFB) and a variety of polycyclic aromatic hydrocarbons (PAHs) or their derivatives. To expand the possibility of halogen bonding-based cocrystals, the relationship between the crystal packing motifs and ORTP characteristics in binary cocrystals composed of DITFB and PAHs of phenanthrene (Phen), chrysene (Chry), and pyrene (Pyr), respectively, is investigated. The σ-hole···π and π-hole···π interactions determine not only the crystal packing motifs but also photoluminescence quantum yields (PLQYs). The Phen-DITFB and Chry-DITFB binary cocrystals with σ-hole···π interactions show higher PLQY compared with the Pyr-DITFB binary cocrystal with π-hole···π interaction. Further, to clarify the effect of crystal structures on PLQY, ternary cocrystals are prepared by partially doping Pyr into Phen-DITFB. The crystal packing motif of the ternary cocrystal originates from a Phen-DITFB cocrystal with σ-hole···π interaction, and some of the Phen sites are randomly replaced with Pyr molecules. The ORTP emission is derived from Pyr. The maximum PLQY is >20% due to suppressing nonradiative decay by changing the crystal packing motif.

Carbazole-2-carbonitrile as an acceptor in deep-blue thermally activated delayed fluorescence emitters for narrowing charge-transfer emissions.

This work reports a new acceptor for constructing donor-acceptor type (D-A type) blue thermally activated delayed fluorescence (TADF) emitters with narrowed charge-transfer (CT) emissions. A new acceptor core, carbazole-2-carbonitrile (CCN), is formed by the fusion of carbazole and benzonitrile. Three D-A type TADF emitters based on the CCN acceptor, namely 3CzCCN, 3MeCzCCN, and 3PhCzCCN, have been successfully synthesized and characterized. These emitters show deep-blue emissions from 439 to 457 nm with high photoluminescence quantum yields of up to 85% in degassed toluene solutions. Interestingly, all CCN-based deep-blue TADF emitters result in narrow CT emissions with full-width at half-maximums (FWHMs) of less than 50 nm in toluene solutions, which are pretty narrower compared with those of typical D-A type TADF emitters. Devices based on these emitters show high maximum external quantum efficiencies of up to 17.5%.

Numerical Study of Triplet Dynamics in Organic Semiconductors Aimed for the Active Utilization of Triplets by TADF under Continuous-Wave Lasing.

The limitation of lasing duration less than nanosecond order has been a major problem for realizing organic solid-state continues-wave (CW) lasers and organic semiconductor laser diodes. Triplets accumulation under CW excitation has been well recognized as a critical inhibiting factor. To overcome this issue, the utilization of thermally activated delayed fluorescence (TADF) emitters is a promising mechanism because of efficient reverse intersystem crossing. Herein, we model the triplet accumulation processes under lasing and propose the active utilization of TADF for lasing based on our simulation analysis. We used the rate constants experimentally determined from the optical properties of a boron difluoride curcuminoid fluorophore showing both TADF and lasing. We demonstrate that the intersystem crossing efficiency is gradually increased after the convergence of relaxation oscillation, i.e., terminating laser oscillation. In addition, we found that when the reverse intersystem crossing rate is close to the intersystem crossing rate, CW lasing becomes dominant.

Hot exciplexes in U-shaped TADF molecules with emission from locally excited states.

Fast emission and high color purity are essential characteristics of modern opto-electronic devices, such as organic light emitting diodes (OLEDs). These properties are currently not met by the latest generation of thermally activated delayed fluorescence (TADF) emitters. Here, we present an approach, called "hot exciplexes" that enables access to both attributes at the same time. Hot exciplexes are produced by coupling facing donor and acceptor moieties to an anthracene bridge, yielding an exciplex with large T1 to T2 spacing. The hot exciplex model is investigated using optical spectroscopy and quantum chemical simulations. Reverse intersystem crossing is found to occur preferentially from the T3 to the S1 state within only a few nanoseconds. Application and practicality of the model are shown by fabrication of organic light-emitting diodes with up to 32 % hot exciplex contribution and low efficiency roll-off.

Suppression of external quantum efficiency rolloff in organic light emitting diodes by scavenging triplet excitons.

Large external quantum efficiency rolloff at high current densities in organic light-emitting diodes (OLEDs) is frequently caused by the quenching of radiative singlet excitons by long-lived triplet excitons [singlet-triplet annihilation (STA)]. In this study, we adopted a triplet scavenging strategy to overcome the aforementioned STA issue. To construct a model system for the triplet scavenging, we selected 2,6-dicyano-1,1-diphenyl-λ5σ4-phosphinine (DCNP) as the emitter and 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) as the host material by considering their singlet and triplet energy levels. In this system, the DCNP's triplets are effectively scavenged by BSBCz while the DCNP's singlets are intact, resulting in the suppressed STA under electrical excitation. Therefore, OLEDs with a 1 wt.%-DCNP-doped BSBCz emitting layer demonstrated the greatly suppressed efficiency rolloff even at higher current densities. This finding favourably provides the advanced light-emitting performance for OLEDs and organic semiconductor laser diodes from the aspect of the suppressed efficiency rolloff.

Observation of Nonradiative Deactivation Behavior from Singlet and Triplet States of Thermally Activated Delayed Fluorescence Emitters in Solution.

Excited states of emissive organic molecules undergo various kinds of quenching phenomena such as vibration-coupled quenching depending on their environmental conditions. Because bright singlet excitons in purely organic molecules exhibiting thermally activated delayed fluorescence (TADF) can access dark triplet excited states, photogenerated singlet excitons can decay nonradiatively through both singlet and triplet excited states. Here, we investigated nonradiative decay behavior, including internal and external exciton quenching processes, of various types of TADF materials in solution. Under air-saturated conditions, both the lowest singlet and triplet excited states of almost all of the TADF materials showed oxygen quenching. We considered the effect of oxygen quenching for both spin states to develop a method for determination of the triplet contribution to the total photoluminescence quantum yield from the transient photoluminescence profiles. Furthermore, we observed a clear energy gap law for the internal nonradiative processes.

Triplet-triplet upconversion enhanced by spin-orbit coupling in organic light-emitting diodes.

Triplet-triplet upconversion, in which two triplet excitons are converted to one singlet exciton, is a well-known approach to exceed the limit of electroluminescence quantum efficiency in conventional fluorescence-based organic light-emitting diodes. Considering the spin multiplicity of triplet pairs, upconversion efficiency is usually limited to 20%. Although this limit can be exceeded when the energy of a triplet pair is lower than that of a second triplet excited state, such as for rubrene, it is generally difficult to engineer the energy levels of higher triplet excited states. Here, we investigate the upconversion efficiency of a series of new anthracene derivatives with different substituents. Some of these derivatives show upconversion efficiencies close to 50% even though the calculated energy levels of the second triplet excited states are lower than twice the lowest triplet energy. A possible upconversion mechanism is proposed based on the molecular structures and quantum chemical calculations.

Enhanced Electroluminescence from Organic Light-Emitting Diodes with an Organic-Inorganic Perovskite Host Layer.

The development of host materials with high performance is essential for fabrication of efficient and stable organic light-emitting diodes (OLEDs). Although host materials used in OLEDs are typically organics, in this study, it is shown that the organic-inorganic perovskite CH3 NH3 PbCl3 (MAPbCl3 ) can be used as a host layer for OLEDs. Vacuum-evaporated MAPbCl3 films have a wide band gap of about 3 eV and very high and relatively balanced hole and electron mobilities, which are suitable for the host material. Photoluminescence and electroluminescence take place through energy transfer from MAPbCl3 to an organic emitter in films. Incorporation of an MAPbCl3 host layer into OLEDs leads to a reduction of driving voltage and enhancement of external quantum efficiency as compared to devices with a conventional organic host layer. Additionally, OLEDs with an MAPbCl3 host layer demonstrate very good operational stability under continuous current operation. These results can be extensively applied to organic- and perovskite-based optoelectronics.

Toward continuous-wave operation of organic semiconductor lasers.

The demonstration of continuous-wave lasing from organic semiconductor films is highly desirable for practical applications in the areas of spectroscopy, data communication, and sensing, but it still remains a challenging objective. We report low-threshold surface-emitting organic distributed feedback lasers operating in the quasi-continuous-wave regime at 80 MHz as well as under long-pulse photoexcitation of 30 ms. This outstanding performance was achieved using an organic semiconductor thin film with high optical gain, high photoluminescence quantum yield, and no triplet absorption losses at the lasing wavelength combined with a mixed-order distributed feedback grating to achieve a low lasing threshold. A simple encapsulation technique greatly reduced the laser-induced thermal degradation and suppressed the ablation of the gain medium otherwise taking place under intense continuous-wave photoexcitation. Overall, this study provides evidence that the development of a continuous-wave organic semiconductor laser technology is possible via the engineering of the gain medium and the device architecture.

Control of the Singlet-Triplet Energy Gap in a Thermally Activated Delayed Fluorescence Emitter by Using a Polar Host Matrix.

The photoluminescence properties of a thermally activated delayed fluorescence emitter, 1,2-bis(carbazol-9-yl)-4,5-dicyanobenzene (2CzPN), doped in a host matrix consisting of 1,3-bis(9-carbazolyl)benzene and a polar inert molecule, camphoric anhydride (CA), in various concentrations have been investigated. It is found that the addition of CA stabilizes only the lowest singlet excited state (S1) of 2CzPN without changing the energy level of the lowest triplet excited state (T1), leading to a reduction in the energy gap between S1 and T1. The maximum reduction of energy gap achieved in this work has been determined to be around 65 meV from the shift of the fluorescence spectrum and the temperature dependence of the photoluminescence decay rate.

Highly efficient organic light-emitting diodes from delayed fluorescence.

The inherent flexibility afforded by molecular design has accelerated the development of a wide variety of organic semiconductors over the past two decades. In particular, great advances have been made in the development of materials for organic light-emitting diodes (OLEDs), from early devices based on fluorescent molecules to those using phosphorescent molecules. In OLEDs, electrically injected charge carriers recombine to form singlet and triplet excitons in a 1:3 ratio; the use of phosphorescent metal-organic complexes exploits the normally non-radiative triplet excitons and so enhances the overall electroluminescence efficiency. Here we report a class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates, of more than 10(6) decays per second. In other words, these molecules harness both singlet and triplet excitons for light emission through fluorescence decay channels, leading to an intrinsic fluorescence efficiency in excess of 90 per cent and a very high external electroluminescence efficiency, of more than 19 per cent, which is comparable to that achieved in high-efficiency phosphorescence-based OLEDs.

Organic field effect transistor using pentacene single crystals grown by a liquid-phase crystallization process.

Nearly perfect pentacene single crystals with wide terraces several micrometers in width were grown by crystallization from a pentacene-containing trichlorobenzene solution. Organic field-effect transistors (OFETs) were fabricated with the pentacene single crystals and characterized for their electrical properties. The field effect mobility was found to be in the range of 0.4-0.6 cm(2)/V x s, which is comparable to that of OFETs fabricated with pentacene single crystals prepared by a physical vapor-phase growth method. The results described in this paper clearly demonstrate that the crystallization of organic semiconductors from solution is a promising chemical method for device processing of OFETs.