Reproducible and High-Performance WOLEDs Based on Independent High-Efficiency Triplet Harvesting of Yellow Hot-Exciton ESIPT and Blue TADF Emitters.

Hot exciton organic light-emitting diode (OLED) emitters can balance the high performance of a device and reduce efficiency roll-off by fast reverse intersystem crossing from high-lying triplets (hRISC). In this study, an excited-state intramolecular proton transfer (ESIPT) fluorophore of 2-(benzo[d]thiazol-2-yl)-4-(pyren-1-yl)phenol (PyHBT) with the typical characteristic properties of a hot exciton is developed. With high efficiency of utilization of the exciton (91%), its yellow OLED exhibited high external quantum efficiency (EQE) of 5.6%, current efficiency (CE) of 16.8 cd A-1 , and power efficiency (PE) of 17.3 lm W-1 . The performance of the yellow emissive "hot exciton" ESIPT fluorophores is among the highest recorded. Due to the large Stokes shift of the ESIPT emitter, non-energy-transferred high-performance white OLEDs (WOLEDs) are developed, which are reproducible and highly efficient. This is possible because of the independent harvesting of most of the triplets in both complementary-color emitters without the interference of energy transfer. The PyHBT-based WOLEDs exhibit a maximum EQE of 14.3% and CE of 41.1 cd A-1 , which facilitates the high-yield mass production of inexpensive WOLEDs.

Creating Efficient Red Thermally Activated Delayed Fluorescence Materials with Cyano-Substituted 11,12-Diphenyldipyrido[3,2-a:2',3'-c]phenazine Acceptors.

Red luminescent materials are essential components for full color display and white lightening based on organic light-emitting diode (OLED) technology, but the extension of emission color towards red or deep red region generally leads to decreased photoluminescence and electroluminescence efficiencies. Herein, we wish to report two new luminescent molecules (2CNDPBPPr-TPA and 4CNDPBPPr-TPA) consisting of cyano-substituted 11,12-diphenyldipyrido[3,2-a:2',3'-c]phenazine acceptors and triphenylamine donors. As the increase of cyano substituents, the emission wavelength is greatly red-shifted and the reverse intersystem crossing process is promoted, resulting in strong red delayed fluorescence. Meanwhile, due to the formation of intramolecular hydrogen bonds, the molecular structures become rigidified and planarized, which brings about large horizontal dipole ratios. As a result, 2CNDPBPPr-TPA and 4CNDPBPPr-TPA can perform as emitters efficiently in OLEDs, furnishing excellent external quantum efficiencies of 28.8 % at 616 nm and 20.2 % at 648 nm, which are significantly improved in comparison with that of the control molecule without cyano substituents. The findings in this work demonstrate that the introduction of cyano substituents to the acceptors of delayed fluorescence molecules could be a facile and effective approach to explore high-efficiency red or deep red delayed fluorescence materials.

Tuning the Electronic and Optical Properties of Phenoxaborin Based Thermally Activated Delayed Fluorescent Materials: A DFT Study.

The electronic and optoelectronic properties of molecules constituted by benzene as linker, phenoxaborin as acceptor coupled with different types of donor moieties are investigated using the density functional theoretical method. The energy gap between the first excited singlet and triplet states (ΔEST) of the designed molecules (1-9) is found to be less than 0.5 eV suggesting them as ideal candidates for thermally activated delayed fluorescence (TADF) emitters. The analysis of frontier molecular orbitals of the molecules revealed a minimum spatial overlap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in favor of the small values of ΔEST. Among the molecules studied, the one in which dihydrophenazine acts as the donor has the lowest value of ΔEST. All designed molecules are good electron transporters. The non-linear optical properties of the molecules are also examined.

Development of an Organic Emitter Exhibiting Reverse Intersystem Crossing Faster than Intersystem Crossing.

In thermally activated delayed fluorescence (TADF)-based organic light-emitting diodes (OLEDs), acceleration of reverse intersystem crossing (RISC) and suppression of intersystem crossing (ISC) are demanded to shorten a lifetime of triplet excitons. As a system realizing RISC faster than ISC, inverted singlet-triplet excited states (iST) with a negative energy difference (ΔEST) between the lowest excited singlet and the lowest triplet states have been gathering much attention recently. Here, we have focused on an asymmetric hexa-azaphenalene (A6AP) core to obtain a new insight into iST. Based on A6AP, we have newly designed A6AP-Cz with the calculated ΔEST of -44 meV. The experimental studies of a synthesized A6AP-Cz revealed that the lifetime of delayed fluorescence (τDF) was only 54 ns, which was the shortest among all organic materials. The rate constant of RISC (kRISC=1.9×107 s-1) was greater than that of ISC (kISC=1.0×107 s-1). The negative ΔEST of A6AP-Cz was experimentally confirmed from 1) the kRISC and kISC (-45 meV) and 2) the temperature-dependent τDF. 3) The onsets of fluorescence and phosphorescence spectra at 77 K also supported the evidence of negative ΔEST (-73 meV). This study demonstrated the potential of A6AP as an iST core for the first time.

Synergetic Modulation of Steric Hindrance and Excited State for Anti-Quenching and Fast Spin-Flip Multi-Resonance Thermally Activated Delayed Fluorophore.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials hold great promise for advanced high-resolution organic light-emitting diode (OLED) displays. However, persistent challenges, such as severe aggregation-caused quenching (ACQ) and slow spin-flip, hinder their optimal performance. We propose a synergetic steric-hindrance and excited-state modulation strategy for MR-TADF emitters, which is demonstrated by two blue MR-TADF emitters, IDAD-BNCz and TIDAD-BNCz, bearing sterically demanding 8,8-diphenyl-8H-indolo[3,2,1-de]acridine (IDAD) and 3,6-di-tert-butyl-8,8-diphenyl-8H-indolo[3,2,1-de]acridine (TIDAD), respectively. These rigid and bulky IDAD/TIDAD moieties, with appropriate electron-donating capabilities, not only effectively mitigate ACQ, ensuring efficient luminescence across a broad range of dopant concentrations, but also induce high-lying charge-transfer excited states that facilitate triplet-to-singlet spin-flip without causing undesired emission redshift or spectral broadening. Consequently, implementation of a high doping level of IDAD-BNCz resulted in highly efficient narrowband electroluminescence, featuring a remarkable full-width at half-maximum of 34 nm and record-setting external quantum efficiencies of 34.3 % and 31.8 % at maximum and 100 cd m-2, respectively. The combined steric and electronic effects arising from the steric-hindered donor introduction offer a compelling molecular design strategy to overcome critical challenges in MR-TADF emitters.

Achieving the Reverse Intersystem Crossing in Chalcone Based Donor-Acceptor System through Down-Conversion of Triplet Exciton.

In recent years, understanding the mechanism of thermally activated delayed fluorescence (TADF) has become the primary choice for designing high-efficiency, low-cost, metal-free organic light emitting diodes (OLEDs). Herein, we propose a strategically designed chalcone based donor-acceptor system, where intensification of delayed fluorescence with decrease in temperature (300 K to 100 K) is observed; the theoretical investigations of electronic states and orbital characters uncovered a new cold rISC pathway in donor-acceptor system, where rISC occurs through the down-conversation of higher triplet exciton (from T3 ) to lowest singlet state (S1 ), having negative energy splitting, thus no thermal energy is required. The comprehensive research described herein might open-up new avenues in donor-acceptor system over the conventional up-convention of triplet exciton and demonstrates that not necessarily all delayed fluorescence are thermally activated (TADF).

Tuning of the Singlet-Triplet Energy Gap of Donor-Linker-Acceptor Based Thermally Activated Delayed Fluorescent Emitters.

Thermally activated delayed fluorescent emitters based on carbazole donor, benzonitrile acceptor with the linkers biphenyl, bipyridine and naphthalene are investigated using the density functional theoretical method. The molecule in which bipyridine acts as the linker with the least ΔEST is further selected for the designing of a series of D-L-A framework TADF molecules. Remarkably, the ΔEST is decreased successively by attaching the additional cyano groups at the acceptor site which is further reduced when the electron donating methoxy groups are attached at the donor site. To know the effect of substituents on ΔEST, the acceptor moiety of the D-L-A framework is modified with -F, -Cl and -CF3 substituents. The studies showed a relatively less decrement in the value of ΔEST compared to the cyano substituted molecules. However, ΔEST significantly reduced further on attaching methoxy groups at the donor site.

Regulation of Multiple Resonance Delayed Fluorescence via Through-Space Charge Transfer Excited State towards High-Efficiency and Stable Narrowband Electroluminescence.

B- and N-embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation-caused emission quenching. Here, we report the design of a sandwich structure by placing the B-N MR core between two electron-donating moieties, inducing through-space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10-fold higher RISC rate in comparison with the parent B-N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light-emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll-offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B-N core. A good operational stability with LT95 of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR-TADF emitters.

Cluster Light-Emitting Diodes Containing Copper Iodine Cube with 100 % Exciton Utilization Using Host-Cluster Synergy.

Clusters combine the advantages of organic molecules and inorganic nanomaterials, which are promising alternatives for optoelectronic applications. Nonetheless, recently emerged cluster light-emitting diodes require further excited state optimization of cluster emitters, especially to reduce population of the cluster-centered triplet quenching state (3 CC). Here we report that redox-active ligands enhance reverse intersystem crossing (RISC) of Cu4 I4 cluster for triplet-to-singlet conversion, and thermally activated delayed fluorescence (TADF) host can provide an external RISC channel. It indicates that the complementarity between TADF host and cluster in RISC transitions gives rise to 100 % triplet conversion efficiency and complete singlet exciton convergence, rendering 100-fold increased singlet radiation rate constant and tenfold decreased triplet non-radiation rate constant. We achieve a photoluminescence quantum yield of 99 % and a record external quantum efficiency of 29.4 %.

Reverse Intersystem Crossing of Single Deuterated Perylene Molecules in a Dibenzothiophene Matrix.

Intersystem crossing to the long-lived metastable triplet state is often a strong limitation on fluorescence brightness of single molecules, particularly for perylene in various matrices. In this paper, we report on a strong excitation-induced reverse intersystem crossing (rISC), a process where single perylene molecules in a dibenzothiophene matrix recover faster from the triplet state, turning into bright emitters at saturated excitation powers. With a detailed study of single-molecule fluorescence autocorrelations, we quantify the effect of rISC. The intrinsic lifetimes found for the two effective triplet states (8.5±0.4 ms and 64±12 ms) become significantly shorter, into the sub-millisecond range, as the excitation power increases and fluorescence brightness is ultimately enhanced at least fourfold. Our results are relevant for the understanding of triplet state manipulation of single-molecule quantum emitters and for markedly improving their brightness.

A Computational-Experimental Approach to Unravel the Excited State Landscape in Heavy-Atom Free BODIPY-Related Dyes.

We performed a time-gated laser-spectroscopy study in a set of heavy-atom free single BODIPY fluorophores, supported by accurate, excited-state computational simulations of the key low-lying excited states in these chromophores. Despite the strong fluorescence of these emitters, we observed a significant fraction of time-delayed (microseconds scale) emission associated with processes that involved passage through the triplet manifold. The accuracy of the predictions of the energy arrangement and electronic nature of the low-lying singlet and triplet excited states meant that an unambiguous assignment of the main deactivation pathways, including thermally activated delayed fluorescence and/or room temperature phosphorescence, was possible. The observation of triplet state formation indicates a breakthrough in the "classic" interpretation of the photophysical properties of the renowned BODIPY and its derivatives.

Highly Efficient Asymmetric Multiple Resonance Thermally Activated Delayed Fluorescence Emitter with EQE of 32.8 % and Extremely Low Efficiency Roll-Off.

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters show great potentials for high color purity organic light-emitting diodes (OLEDs). However, the simultaneous realization of high photoluminescence quantum yield (PLQY) and high reverse intersystem crossing rate (kRISC ) is still a formidable challenge. Herein, a novel asymmetric MR-TADF emitter (2Cz-PTZ-BN) is designed that fully inherits the high PLQY and large kRISC values of the properly selected parent molecules. The resonating extended π-skeleton with peripheral protection can achieve a high PLQY of 96 % and a fast kRISC of above 1.0×105  s-1 , and boost the performance of corresponding pure green devices with an outstanding external quantum efficiency (EQE) of up to 32.8 % without utilizing any sensitizing hosts. Remarkably, the device sufficiently maintains a high EQE exceeding 23 % at a high luminance of 1000 cd m-2 , representing the highest value for reported green MR-TADF materials at the same luminescence.

Robust Luminescent Molecules with High-Level Reverse Intersystem Crossing for Efficient Near Ultraviolet Organic Light-Emitting Diodes.

Organic light-emitting diodes (OLEDs) radiating near ultraviolet (NUV) light are of high importance but rarely reported due to the lack of robust organic short-wavelength emitters. Here, we report a short π-conjugated molecule (POPCN-2CP) with high thermal and morphological stabilities and strong NUV photoluminescence. Its neat film exhibits an electroluminescence (EL) peak at 404 nm with a maximum external quantum efficiency (ηext,max ) of 7.5 % and small efficiency roll-off. The doped films of POPCN-2CP in both non-polar and polar hosts at a wide doping concentration range (10-80 wt%) achieve high-purity NUV light (388-404 nm) and excellent ηext,max s of up to 8.2 %. The high-level reverse intersystem crossing improves exciton utilization and accounts for the superb ηext,max s. POPCN-2CP can also serve as an efficient host for blue fluorescence, thermally activated delayed fluorescence and phosphorescence emitters, providing excellent EL performance via Förster energy transfer.

Multiple-Resonance-Induced Thermally Activated Delayed Fluorescence Materials Based on Indolo[3,2,1-jk]carbazole with an Efficient Narrowband Pure-Green Electroluminescence.

Herein, we report two multiple-resonance thermally activated delayed fluorescence emitters (VTCzBN and TCz-VTCzBN) based on indolo[3,2,1-jk]carbazole unit and boron-nitrogen skeletons, whose emissions peaking at 496 and 521 nm with full width at half maximum of 34 and 29 nm, respectively. Meanwhile, fast rate constants of reverse intersystem crossing of above 106  s-1 are obtained due to small singlet-triplet energy gaps and large spin-orbital coupling values. Notably, planar molecular structures along the transition dipole moment direction endow them with high horizontal emitting dipole ratios of up to 94 %. Consequently, the corresponding organic light-emitting diodes (OLEDs) show the maximum external quantum efficiencies of 31.7 % and 32.2 %, respectively. Particularly, OLED with TCz-VTCzBN display ultra-pure green emission with Commission Internationale de l'Eclairage coordinates of (0.22, 0.71), consistent with the green display standard of the National Television System Committee.

Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule.

In the field of organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have achieved great performance. The key factor for this performance is the small energy gap (ΔEST ) between the lowest triplet (T1 ) and singlet excited (S1 ) states, which can be realized in a well-separated donor-acceptor system. Such systems are likely to possess similar charge transfer (CT)-type T1 and S1  states. Recent investigations have suggested that the intervention of other type-states, such as locally excited triplet state(s), is necessary for efficient reverse intersystem crossing (RISC). Here, we theoretically and experimentally demonstrate that our blue TADF material exhibits efficient RISC even between singlet CT and triplet CT states without any additional states. The key factor is dynamic flexibility of the torsion angle between the donor and acceptor, which enhances spin-orbit coupling even between the charge transfer-type T1 and S1  states, without sacrificing the small ΔEST . This results in excellent photoluminescence and electroluminescence performances in all the host materials we investigate, with sky-blue to deep-blue emissions. Among the hosts investigated, the deepest blue emission with CIE coordinates of (0.15, 0.16) and the highest EQEMAX of 23.9 % are achieved simultaneously.

High-Performance Ultraviolet Organic Light-Emitting Diode Enabled by High-Lying Reverse Intersystem Crossing.

Ultraviolet (UV) organic emitters that can open up applications for future organic light-emitting diodes (OLEDs) are of great value but rarely developed. Here, we report a high-quality UV emitter with hybridized local and charge-transfer (HLCT) excited state and its application in UV OLEDs. The UV emitter, 2BuCz-CNCz, shows the features of low-lying locally excited (LE) emissive state and high-lying reverse intersystem crossing (hRISC) process, which helps to balance the color purity and exciton utilization of UV OLED. Consequently, the OLED based on 2BuCz-CNCz exhibits not only a desired narrowband UV electroluminescent (EL) at 396 nm with satisfactory color purity (CIEx, y =0.161, 0.031), but also a record-high maximum external quantum efficiency (EQE) of 10.79 % with small efficiency roll-off. The state-of-the-art device performance can inspire the design of UV emitters, and pave a way for the further development of high-performance UV OLEDs.

Tetrabenzo[a,c]phenazine Backbone for Highly Efficient Orange-Red Thermally Activated Delayed Fluorescence with Completely Horizontal Molecular Orientation.

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.

Experimentally Observed Reverse Intersystem Crossing-Boosted Lasing.

Thermally activated delayed-fluorescent (TADF) materials are anticipated to overcome triplet-related losses towards electrically driven organic lasers. Thus far, contributions from triplets to lasing have not yet been experimentally demonstrated owing to the limited knowledge about the excited-state processes. Herein, we experimentally achieve reverse intersystem crossing (RISC)-boosted lasing in organic microspheres with uniformly dispersed TADF emitters. In these materials, triplets are continuously converted to radiative singlets through RISC, giving rise to reduced losses in stimulated emission. The involvement of regenerated singlets in population inversion results in a thermally activated lasing; that is, the lasing intensity increases with increasing temperature, accompanied by accelerated depletion of the excited-state population. Benefiting from the suppression of triplet accumulations by RISC processes, a high-repetition-rate microlaser was achieved.

Theoretical studies on thermally activated delayed fluorescence mechanism of a series of organic light-emitting diodes emitters comprising 2,7-diphenylamino-9,9-dimethylacridine as electron donor.

According to one experimentally reported thermally activated delayed fluorescence (TADF) emitter (AcDPA-2TP), two new molecules (AcDPA-2PP and AcDPA-TPP) have been designed theoretically to probe into the effect of different acceptor strengths on their TADF mechanisms. In this work, the rates of reverse intersystem crossing (kRISC ) of the three targeted molecules were calculated by the semiclassical Marcus rate expression. The present results demonstrate that the kRISC rate of AcDPA-2PP is estimated to be 5.56 × 106 s-1 , about twice larger than that of AcDPA-2TP (2.63 × 106 s-1 ), and especially AcDPA-TPP is found to exhibit the largest kRISC value (6.97 × 106 s-1 ) among the three molecules. Considering that AcDPA-2TP has been observed to be an efficient TADF emitter, our newly designed two molecules AcDPA-2PP and AcDPA-TPP are also expected to be potential TADF materials. © 2018 Wiley Periodicals, Inc.

The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules.

Factors influencing the rate of reverse intersystem crossing (krISC ) in thermally activated delayed fluorescence (TADF) emitters are critical for improving the efficiency and performance of third-generation heavy-metal-free organic light-emitting diodes (OLEDs). However, present understanding of the TADF mechanism does not extend far beyond a thermal equilibrium between the lowest singlet and triplet states and consequently research has focused almost exclusively on the energy gap between these two states. Herein, we use a model spin-vibronic Hamiltonian to reveal the crucial role of non-Born-Oppenheimer effects in determining krISC . We demonstrate that vibronic (nonadiabatic) coupling between the lowest local excitation triplet (3 LE) and lowest charge transfer triplet (3 CT) opens the possibility for significant second-order coupling effects and increases krISC by about four orders of magnitude. Crucially, these simulations reveal the dynamical mechanism for highly efficient TADF and opens design routes that go beyond the Born-Oppenheimer approximation for the future development of high-performing systems.