Hybridization of short-range and long-range charge transfer excited states in multiple resonance emitter.

Multiple resonance (MR) thermally activated delayed fluorescence emitters have been actively studied as pure blue dopants for organic light-emitting diodes (OLEDs) because of excellent color purity and high efficiency. However, the reported MR emitter, 2,5,13,16-tetra-tert-butylindolo[3,2,1-jk]indolo[1',2',3':1,7]indolo[2,3-b]carbazole (tDIDCz) based on bis-fused indolocarbazole framework could not demonstrate efficient triplet-to-singlet spin crossover. In this work, we report two isomeric MR emitters designed to promote triplet exciton harvesting by reconstructing the electronic structure of tDIDCz. To manage excited states, strong electron donors were introduced at the 2,5-/1,6-position of tDIDCz. As a result, 2,5-positions managed tDIDCz shows long-range charge transfer characteristics while preserving the MR nature. Quantum chemical calculation demonstrates direct spin-orbit coupling by long-range charge transfer and spin-vibronic coupling assisted reverse intersystem crossing by short-range charge transfer simultaneously contribute to triplet-to-singlet spin crossover. Consequently, high performance blue OLED recorded a high external quantum efficiency of 30.8% at a color coordinate of (0.13, 0.13).

Color Stable Deep Blue Multi-Resonance Organic Emitters with Narrow Emission and High Efficiency.

The development of highly efficient and deep blue emitters satisfying the color specification of the commercial products has been a challenging hurdle in the organic light-emitting diodes (OLEDs). Here, deep blue OLEDs with a narrow emission spectrum with good color stability and spin-vibronic coupling assisted thermally activated delayed fluorescence are reported using a novel multi-resonance (MR) emitter built on a pure organic-based molecular platform of fused indolo[3,2,1-jk]carbazole structure. Two emitters derived from 2,5,11,14-tetrakis(1,1-dimethylethyl)indolo[3,2,1-jk]indolo[1',2',3':1,7]indolo[3,2-b]carbazole (tBisICz) core are synthesized as the MR type thermally activated delayed fluorescence emitters realizing a very narrow emission spectrum with a full-width-at-half-maximum (FWHM) of 16 nm with suppressed broadening at high doping concentration. The tBisICz core is substituted with a diphenylamine or 9-phenylcarbazole blocking group to manage the intermolecular interaction for high efficiency and narrow emission. The deep blue OLEDs achieve high external quantum efficiency (EQE) of 24.9%, small FWHM of 19 nm, and deep blue color coordinate of (0.16, 0.04) with good color stability with increase in doping concentration. To the authors' knowledge, the EQE in this work is one of the highest values reported for the deep blue OLEDs that achieve the BT.2020 standard.

Multiple-Resonance Extension and Spin-Vibronic-Coupling-Based Narrowband Blue Organic Fluorescence Emitters with Over 30% Quantum Efficiency.

Achieving narrow-bandwidth emission and high external quantum efficiency (EQE) simultaneously is a challenge for next-generation blue-emitting organic light-emitting diodes (OLEDs). In this study, novel multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters are developed by fusing an indolocarbazole unit with two carbazole skeletons using para-oriented nitrogen atoms. The resulting rigid and planar π-system without electron-accepting atoms exhibits pure blue photoluminescence at 470 nm, reaching a 100% quantum yield with a full-width-at-half-maximum (FWHM) of 25 nm. Higher-level quantum chemistry calculations confirm an MR effect within the extended π-conjugation and an enhanced triplet-to-singlet crossover (104 s-1 ) through a reduced energy gap (ΔEST ) coupled with large spin-vibronic coupling mediated by low-lying triplet excited states. An OLED fabricated using the MR-TADF emitter with CIE color coordinates of (0.12, 0.16) exhibits a record high EQE of 30.9% and a small FWHM of 23 nm. With further optimization of the device structure, a high EQE of 33.8% is achieved without additional outcoupling enhancements owing to the near-perfect horizontal alignment of the emitting dipoles.

Dipole Moment- and Molecular Orbital-Engineered Phosphine Oxide-Free Host Materials for Efficient and Stable Blue Thermally Activated Delayed Fluorescence.

To utilize thermally activated delayed fluorescence (TADF) technology for future displays, it is necessary to develop host materials which harness the full potential of blue TADF emitters. However, no publication has reported such hosts yet. Although the most popular host for blue TADF, bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO) guarantees high-maximum external quantum efficiency (EQEmax ) TADF devices, they exhibit very short operational lifetimes. In contrast, long-lifespan blue TADF devices employing stable hosts such as 3',5-di(9H-carbazol-9-yl)-[1,1'-biphenyl]-3-carbonitrile (mCBP-CN) exhibit much lower EQEmax than the DPEPO-employed devices. Here, an elaborative approach for designing host molecules is suggested to achieve simultaneously stable and efficient blue TADF devices. The approach is based on engineering the molecular geometry, ground- and excited-state dipole moments of host molecules. The engineered hosts significantly enhance delayed fluorescence quantum yields of TADF emitters, as stabilizing the charge-transfer excited states of the TADF emitters and suppressing exciton quenching, and improve the charge balance. Moreover, they exhibit both photochemical and electrochemical stabilities. The best device employing one of the engineered hosts exhibits 79% increase in EQEmax compared to the mCBP-CN-employed device, together with 140% and 92-fold increases in operational lifetime compared to the respective mCBP-CN- and the DPEPO-based devices.

Three States Involving Vibronic Resonance is a Key to Enhancing Reverse Intersystem Crossing Dynamics of an Organoboron-Based Ultrapure Blue Emitter.

The recently developed narrow-band blue-emitting organoboron chromophores based on the multiple-resonance (MR) effect have now become one of the most important components for constructing efficient organic light emitting diodes (OLEDs). While they basically emit through fluorescence, they are also known for showing substantial thermally activated delayed fluorescence (TADF) even with a relatively large singlet-triplet gap (ΔE ST). Indeed, understanding the reverse intersystem crossing (RISC) dynamics behind this peculiar TADF will allow judicious molecular designs toward achieving better performing OLEDs. Explaining the underlying nonadiabatic spin-flip mechanism, however, has often been equivocal, and how the sufficiently fast RISC takes place even with the sizable ΔE ST and vanishingly small spin-orbit coupling is not well understood. Here, we show that a vibronic resonance, namely the frequency matching condition between the vibration and the electronic energy gap, orchestrates three electronic states together and this effect plays a major role in enhancing RISC in a typical organoboron emitter. Interestingly, the mediating upper electronic state is quite high in energy to an extent that its thermal population is vanishingly small. Through semiclassical quantum dynamics simulations, we further show that the geometry dependent non-Condon coupling to the upper triplet state that oscillates with the frequency ΔE ST/ℏ is the main driving force behind the peculiar resonance enhancement. The existence of an array of vibrational modes with strong vibronic rate enhancements provides the ability to sustain efficient RISC over a range of ΔE ST in defiance of the energy gap law, which can render the MR-emitters peculiar in comparison with more conventional donor-acceptor type emitters. Our investigation may provide a new guide for future blue emitting molecule developments.

Purely Spin-Vibronic Coupling Assisted Triplet to Singlet Up-Conversion for Real Deep Blue Organic Light-Emitting Diodes with Over 20% Efficiency and y Color Coordinate of 0.05.

Finding narrow-band, ultrapure blue thermally activated delayed fluorescence (TADF) materials is extremely important for developing highly efficient organic light-emitting diodes (OLEDs). Here, spin-vibronic coupling (SVC)-assisted ultrapure blue emitters obtained by joining two carbazole-derived moieties at a para position of a phenyl unit and performing substitutions using several blocking groups are presented. Despite a relatively large singlet-triplet gap (∆EST ) of >0.2 eV, efficient triplet-to-singlet crossover can be realized, with assistance from resonant SVC. To enhance the spin crossover, electronic energy levels are fine-tuned, thereby causing ∆EST to be in resonance with a triplet-triplet gap (∆ETT ). A sizable population transfer between spin multiplicities (>103 s-1 ) is achieved, and this result agrees well with theoretical predictions. An OLED fabricated using a multiple-resonance-type SVC-TADF emitter with CIE color coordinates of (0.15, 0.05) exhibits ultrapure blue emissions, with a narrow full-width-at-half-maximum of 21 nm and a high external quantum efficiency of 23.1%.

Holistic Approach to the Mechanism Study of Thermal Degradation of Organic Light-Emitting Diode Materials.

The design of stable organic light-emitting diode materials is the key to long lifetime displays under various stressful conditions. Elucidating the degradation mechanism of the materials at the molecular level provides useful information for securing high stability. Previous works based on experiments or computations disclosed only a part of the whole degradation process. Here, we propose a holistic approach to the systematic analysis of the degradation mechanism by combining experimental mass analysis and computation in a semi-automated fashion. The mass analysis identifies molecular weights of feasible products from degradation reactions. Then, the computational analysis goes through initiation, propagation, and termination phases. The initiation phase determines radical fragments and reactive sites, triggering the propagation process. In the propagation phase, we subsequently perform intermediate sampling, reaction network construction, and kinetic analysis. As a proof of concept, this approach was applied to the thermal degradation problem during the sublimation purification process. Two major pathways were successfully elucidated with full atomistic details.

Spin-Vibronic Model for Quantitative Prediction of Reverse Intersystem Crossing Rate in Thermally Activated Delayed Fluorescence Systems.

Computationally predicting reverse intersystem crossing (RISC) rates is important for designing new thermally activated delayed fluorescence (TADF) materials. We report a method that can quantitatively predict RISC rates by explicitly considering the spin-vibronic coupling mechanism. The coupling element of the spin-vibronic Hamiltonian is obtained by expanding the spin-orbit and the non-Born-Oppenheimer terms to second order and is then brought into the Golden Rule rate under the Condon approximation. The rate equation is solved directly in the time domain using a correlation function approach. The contributions of the first-order direct spin-orbit coupling and the second-order spin-vibronic coupling to an RISC rate can be quantitatively analyzed in a separate manner. We demonstrate the utility of the method by applying it to a representative TADF system, where we observe that the spin-vibronic portion is substantial but not dominant especially with a relatively small triplet-singlet energy gap. Likewise, our method may elucidate the physical background of efficient nonradiative transitions from the lowest triplet to a higher lying singlet in other purely organic TADF systems, and it will be of great utility toward designing new such molecules.

A Novel Design Strategy for Suppressing Efficiency Roll-Off of Blue Thermally Activated Delayed Fluorescence Molecules through Donor-Acceptor Interlocking by C-C Bonds.

The short material lifetime of thermally activated delayed fluorescence (TADF) technology is a major obstacle to the development of economically feasible, highly efficient, and durable devices for commercial applications. TADF devices are also hampered by insufficient operational stability. In this paper, we report the design, synthesis, and evaluation of new TADF molecules possessing a sterically twisted skeleton by interlocking donor and acceptor moieties through a C-C bond. Compared to C-N-bond TADF molecules, such as CPT2, the C-C-bond TADF molecules showed a large dihedral angle increase by more than 30 times and a singlet-triplet energy-gap decrease to less than 0.22 eV because of the steric hindrance caused by the direct C-C bond connection. With the introduction of a dibenzofuran core structure, devices comprising BMK-T317 and BMK-T318 exhibited a magnificent display performance, especially their external quantum efficiencies, which were as high as 19.9% and 18.8%, respectively. Moreover, the efficiency roll-off of BMK-T318 improved significantly (26.7%). These results indicate that stability of the material can be expected through the reduction of their singlet-triplet splitting and the precise adjustment of dihedral angles between the donor-acceptor skeletons.

An Alternative Host Material for Long-Lifespan Blue Organic Light-Emitting Diodes Using Thermally Activated Delayed Fluorescence.

It has been challenging to find stable blue organic light emitting diodes (OLEDs) that rely on thermally activated delayed fluorescence (TADF). Lack of stable host materials well-fitted to the TADF emitters is one of the critical reasons. The most popular host for blue TADF, bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), leads to unrealistically high maximum external quantum efficiency. DPEPO is however an unstable material and has a poor charge transporting ability, which in turn induces an intrinsic short OLED operating lifespan. Here, an alternative host material is introduced which educes the potential efficiency and device lifespan of given TADF emitters with the appropriateness of replacing the most popular host material, DPEPO, in developing blue TADF emitters. It simultaneously provides much longer device lifespan and higher external quantum efficiency at a practical brightness due to its high material stability and electron-transport-type character well-fitted for hole-transport-type TADF emitters.

Highly efficient blue organic light-emitting diodes based on 2-(diphenylamino)fluoren-7-ylvinylarene derivatives that bear a tert-butyl group.

Blue fluorescent materials with a 2-(diphenylamino)fluoren-7-ylvinylarene emitting unit and tert-butyl-based blocking units were synthesized. The photophysical properties of these materials, including UV/Vis absorption, photoluminescent properties, and HOMO-LUMO energy levels, were characterized and rationalized with quantum-mechanical DFT calculations. The electroluminescent properties of these molecules were examined through the fabrication of multilayer devices with a structure of indium-tin oxide, 4,4'-bis{N-[4-(N,N-di-m-tolylamino)phenyl]-N-phenylamino}biphenyl, 4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, and blue materials doped in 2-methyl-9,10-di(2-naphthyl)anthracene/tris(8-quinolinolato)aluminum/LiF/Al. All devices exhibit highly efficient blue electroluminescence with high external quantum efficiency (3.20-7.72 % at 20 mA cm(-2)). A deep-blue device with Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.11) that uses 7-[2-(3',5'-di-tert-butylbiphenyl-4-yl)vinyl]-9,9-diethyl-2-N-(3,5-di-tert-butylphenyl)-2,4-difluorobenzenamino-9H-fluorene as a dopant in the emitting layer showed a luminous efficiency and external quantum efficiency of 3.95 cd A(-1) and 4.23 % at 20 mA cm(-2), respectively. Furthermore, a highly efficient sky-blue device that uses the dopant 7-{2-[2-(3,5-di-tert-butylphenyl)-9,9'-spirobifluorene-7-yl]vinyl}-9,9-diethyl-2-N,N-diphenylamino-9H-fluorene exhibited a luminous efficiency and high quantum efficiency of 10.3 cd A(-1) and 7.7 % at 20 mA cm(-2), respectively, with CIE coordinates of (0.15, 0.20).

Synthesis of titania embedded silica hollow nanospheres via sonication mediated etching and re-deposition.

Titania embedded silica hollow nanospheres were synthesized from sonication-mediated etching and re-deposition of silica/titania core/shell nanospheres. The designed structure of the hollow nanospheres was proved to be a key factor for the charge trapping/detrapping and resulting bistability in non-volatile organic bistable memory devices (OBDs).

Highly efficient single-layer phosphorescent white organic light-emitting diodes using a spirofluorene-based host material.

Highly efficient phosphorescent white organic light-emitting diodes (PHWOLEDs) were developed by the doping of phosphorescent blue and red dopants in a spirofluorene-based phosphine oxide host material. A high quantum efficiency of 18.3% and a current efficiency of 34.2 cd/A at 100 cd/m(2) were obtained from the PHWOLED with the spirofluorene-based phosphine oxide host material. In addition, a high power efficiency of 28.3 lm/W was achieved in the PHWOLED. The wide triplet bandgap of host and charge balance in the light-emititng layer were responsible for the high efficiency.