Three thermally activated delayed fluorescence (TADF) molecules, namely PQ1, PQ2, and PQ3, are composed of electron‐accepting (A) tetrabenzo[a,c]phenazine (TBPZ) and electron‐donating (D) phenoxazine (PXZ) units are designed and characterized. The combined effects of planar acceptor manipulation and high steric hindrance between D and A units endow high molecular rigidity that suppresses nonradiative decay of the excitons with improved photoluminescence quantum yields (PLQYs). Particularly, the well‐aligned excited states involving a singlet and a triplet charge‐transfer excited states and a localized excited triplet state in PQ3 enhances the reverse intersystem crossing rate constant (kRISC) with a short delay lifetime (τd). The orange–red OLED based on PQ3 displays a maximum external EL quantum efficiency (EQE) of 27.4 % with a well‐suppressed EL efficiency roll‐off owing to a completely horizontal orientation of the transition dipole moment in the film state.

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.

Quenching of singlets by long-lived triplets is a serious issue for lasing from organic laser dyes, especially under long pulse excitation duration. As a strategy to scavenge or manage unnecessary triplets, an organic laser dye is dispersed into a host material having high singlet and low triplet energy levels [a large singlet-triplet energy gap (ΔE ST )]. However, finding such a host material having a triplet scavenging capability is limited. In this study, we synthesized an organic laser dye, 2,6-dicyano-1,1-diphenyl-λ 5 σ 4 -phosphinine (DCNP), having a small ΔE ST of ~0.44 eV, and thus we were able to employ 4-4΄-bis[(N-carbazole)styryl] biphenyl (BSBCz) as a triplet scavenging host, i.e., the triplets formed on DCNP are easily transferred to BSBCz. A 1 wt.%-DCNP-doped BSBCz film was formed on a mixed-order distributed feedback grating, showed lasing with a low threshold value of ~0.86 µJ cm −2 and a FWHM of ~0.5 nm. Because of the suppressed singlet-triplet annihilation, we demonstrated DCNP-based laser devices operating under continuous-wave operation, with a low threshold of 72 W cm −2 and a long laser half-lifetime of ~3 min. Our results This article is protected by copyright. All rights reserved.3 demonstrated a possibility of the wider selection of host materials, easing a material design strategy of fabricating high-performance laser devices in future.Received: ((will be filled in by the editorial staff))Revised: ((will be filled in by the editorial staff)) Published online: ((will be filled in by the editorial staff))

Continuous-wave (CW) lasing is still difficult to realize in organic laser dyes, one reason being the thermal degradation caused by intense photoexcitation. A decrease in laser threshold suppresses the thermal degradation and, therefore, leads to long-lasting lasing from organic laser dyes. Here, we show that it is possible to decrease the laser thresholds by combining the organic laser dye 4,4-bis­[(N-carbazole)­styryl]­biphenyl, which has a small spectral overlap between the laser emission and the excited-state triplet absorption, with two-dimensional (2D) distributed-feedback (DFB) gratings. We used second-order 2D cross double and square lattice DFB gratings, which offer light feedback in two orthogonal directions, and second-order and mixed-order circular DFB gratings, which offer light feedback in radial directions. Among these grating structures, the mixed-order circular DFB grating structure led to the lowest lasing threshold of ∼0.015 μJ cm–2 under short-pulse photoexcitation because of the excellent optical feedback. Moreover, a low average-power threshold of 10 W cm–2 (a peak-power threshold of 1 kW cm–2) was obtained when laser devices with this grating structure were operated under 1 s of long-pulse photoexcitation with a repetition rate of 0.01 Hz. Additionally, using the mixed-order circular DFB grating structure improved the laser stability under CW photoexcitation since shorter exciton lifetimes in the optical resonator suppress the chemical decomposition. These results demonstrate the importance of choosing an optical resonator structure for improving organic laser performance.