Purely Organic Room-Temperature Phosphorescence Molecule for High-Performance Non-Doped Organic Light-Emitting Diodes.

Purely organic molecules with room-temperature phosphorescence (RTP) are potential luminescent materials with high exciton utilization for organic light-emitting diodes (OLEDs), but those exhibiting superb electroluminescence (EL) performances are rarely explored, mainly due to their long phosphorescence lifetimes. Herein, a robust purely organic RTP molecule, 3,6-bis(5-phenylindolo[3,2-a]carbazol-12(5H)-yl)-xanthen-9-one (3,2-PIC-XT), is developed. The neat film of 3,2-PIC-XT shows strong green RTP with a very short lifetime (2.9 µs) and a high photoluminescence quantum yield (72 %), and behaviors balanced bipolar charge transport. The RTP nature of 3,2-PIC-XT is validated by steady-state and transient absorption and emission spectroscopies, and the working mechanism is deciphered by theoretical simulation. Non-doped multilayer OLEDs using thin neat films of 3,2-PIC-XT furnish an outstanding external quantum efficiency (EQE) of 24.91 % with an extremely low roll-off (1.6 %) at 1000 cd m-2. High-performance non-doped top-emitting and tandem OLEDs are also achieved, providing remarkable EQEs of 24.53 % and 42.50 %, respectively. Delightfully, non-doped simplified OLEDs employing thick neat films of 3,2-PIC-XT are also realized, furnishing an excellent EQE of 17.79 % and greatly enhanced operational lifetime. The temperature-dependent and transient EL spectroscopies demonstrate the electrophosphorescence attribute of 3,2-PIC-XT. These non-doped OLEDs are the best devices based on purely organic RTP materials reported so far.

Through-Space Conjugated Electron Transport Materials for Improving Efficiency and Lifetime of Organic Light-Emitting Diodes.

Thermally stable electron transport (ET) materials with high electron mobility and high triplet state energy level are highly desired for the fabrication of efficient and stable organic light-emitting diodes (OLEDs). Herein, a new design strategy of constructing through-space conjugated folded configuration is proposed to explore robust ET materials, opposite to the widely used planar configuration. By bonding two quinolines to the 9,10-positions of phenanthrene, two novel folded molecules with high thermal and morphological stabilities and high triplet state energy levels (>2.7 eV) are created. These folded molecules possess excellent ET ability with electron mobilities of three orders of magnitude higher than those of linear and planar counterparts. Theoretical calculation and crystallography analysis demonstrate the through-space conjugated folded configuration has not only reduced reorganization energy but also enlarged charge transfer integral at various dimensions, bringing about efficient multi-dimensional ET, independent of molecular orientation. By adopting the folded molecule as ET layers, OLEDs with no matter delayed fluorescence or phosphorescence emitters can achieve high external quantum efficiencies and long operational lifetimes simultaneously. This work paves a new avenue towards robust ET materials to improve efficiency and stability of OLEDs.

Stimuli-Responsive Aggregation-Induced Delayed Fluorescence Emitters Featuring the Asymmetric D-A Structure with a Novel Diarylketone Acceptor Toward Efficient OLEDs with Negligible Efficiency Roll-Off.

Multifunctional luminescent materials with aggregation-induced delayed fluorescence (AIDF) are capable of suppressing concentration-caused emission quenching and exciton annihilation when used as organic light-emitting diode (OLED) emitters. In this contribution, three stimuli-responsive AIDF luminogens, pipd-BZ-PXZ, pipd-BZ-PTZ, and pipd-BZ-DMAC, featuring a D-A asymmetric framework based on a fused N-heterocycle diarylketone acceptor (imid-azo[1,2-a]pyridin-2-yl(phenyl)methanone pipd) are designed and synthesized. Interestingly, pipd-BZ-PTZ forms two different kinds of crystals (G-crystal and O-crystal) with distinct intermolecular interactions between pipd moieties. The G-crystal with a looser packing mode presents significant morphology-dependent stimuli-responsive behavior with a shifted emission wavelength of 56 nm. Generated by a strong intramolecular charge transfer effect, pipd-BZ-PXZ and pipd-BZ-PTZ exhibit orange to red emission in solution and neat films. Both nondoped and doped devices are fabricated for comparison. Nondoped devices present moderate performance with external quantum efficiencies and current efficiency that reach 7.04% and 19.86 cd A-1, respectively, and the corresponding efficiency roll off at 1000 cd m-2 is as small as 2.3%, which is among the best records of AIDF-OLEDs with an emission wavelength over 570 nm. Doped devices show better performance with corresponding efficiencies of up to 55.41 cd A-1 and 15.77%.

Tuning molecular emission of organic emitters from fluorescence to phosphorescence through push-pull electronic effects.

Organic emitters with persistent phosphorescence have shown potential application in optoelectronic devices. However, rational design and phosphorescence tuning are still challenging. Here, a series of metal-free luminophores without heavy atoms and carbonyl groups from commercial/lab-synthesized carbazole and benzene were synthesized to realize tunable molecular emission from fluorescence to phosphorescence by simply substituent variation. All the molecules emit blue fluorescence in both solution and solid state. Upon removal of excitation source, the fluorinated luminophores show obvious phosphorescence. The lab-synthesized carbazole based molecules exhibit a huge lifetime difference to the commercially purchased ones due to the existence of isomer in the latter samples. The small energy gap between singlet and triplet state and low reorganization energy help enhance intersystem crossing to contribute to a more competitive radiative process from triplet to ground state. Blue and white organic light-emitting devices are fabricated by using fluorinated luminophore as emitting layer.

Universal Bipolar Host Materials for Blue, Green, and Red Phosphorescent OLEDs with Excellent Efficiencies and Small-Efficiency Roll-Off.

Host materials are indispensable for the fabrication of organic light-emitting diodes (OLEDs) with phosphorescent emitters, but high-quality host materials that can efficiently and simultaneously function in blue, green, and red phosphorescent OLEDs (PHOLEDs) are much rare. In this work, four bipolar materials are developed using carbazole and 9,9-dimethyl-9,10-dihydroacridine as hole-transporting groups, pyridine as electron-transporting groups, and biphenyl and m-methylbiphenyl as π-spacers. The crystal and electronic structures indicate that these materials have highly twisted conformations, which endow them with aggregation-induced emission features, intramolecular charge transfer processes, wide energy band gaps, and high triplet energies. The carrier transport ability and energy transfer property analyses show that these materials are able to achieve balanced hole and electron transports and can serve as bipolar host materials for PHOLEDs. A series of monochromatic PHOLEDs with different phosphorescent dopants, including blue-emissive FIrpic, green-emissive Ir(ppy)2(acac), and red-emissive Ir(piq)2(acac), are fabricated by employing these four host materials. The green PHOLEDs can provide an impressive luminance of up to 230 200 cd m-2. Based on an identical host material, excellent external quantum efficiencies as high as 25.12, 24.73, and 19.71%, as well as minor efficiency roll-off, are attained for blue, green, and red PHOLEDs, respectively, clearly demonstrating the promising applications as universal bipolar host materials in PHOLEDs with monochromatic light and white light.

New Aggregation-Induced Delayed Fluorescence Luminogens With Through-Space Charge Transfer for Efficient Non-doped OLEDs.

In this work, two tailor-made luminogens comprising of electron donors (acridine and phenoxazine) and acceptor (triazine) bridged by the through-space conjugated hexaphenylbenzene (HPB) are synthesized and characterized. Their thermal stability, electrochemical behaviors, crystal, and electronic structures, and photophysical properties are systematically investigated. The crystal and electronic structures reveal that the peripheral phenyls in HPB are closely aligned in a propeller-like fashion, rendering efficient through-space charge transfer between donor and electron moieties. These molecules display weak fluorescence with negligible delayed component in solutions but strong fluorescence with greatly increased delayed component upon aggregate formation, namely aggregation-induced delayed fluorescence (AIDF). Their neat films exhibit high photoluminescence quantum yields (PLQY), and prominent delayed fluorescence. The non-doped organic light-emitting diodes (OLEDs) based on these new luminogens exhibit excellent performance with maximum external quantum efficiency of 12.7% and very small efficiency roll-off of 2.7% at 1,000 cd m-2. Designing AIDF molecules with through-space charge transfer could be a promising strategy to explore robust luminescent materials for efficient non-doped OLEDs.

Mechanical Insights into Aggregation-Induced Delayed Fluorescence Materials with Anti-Kasha Behavior.

Organic materials with aggregation-induced delayed fluorescence (AIDF) have exhibited impressive merits for improving electroluminescence efficiency and decreasing efficiency roll-off of nondoped organic light-emitting diodes (OLEDs). However, the lack of comprehensive insights into the underlying mechanism may impede further development and application of AIDF materials. Herein, AIDF materials consisting of benzoyl serving as an electron acceptor, and phenoxazine and fluorene derivatives as electron donors are reported. They display greatly enhanced fluorescence with increased delayed component upon aggregate formation. Experimental and theoretical investigations reveal that this AIDF phenomenon can be rationally ascribed to the suppression of internal conversion and the promotion of intersystem crossing in solid. Moreover, the theoretical calculations disclose that the efficient solid-state delayed fluorescence originates from the higher energy electronic excited state (e.g., S2) rather than the lowest energy-excited state (S1), demonstrating an anti-Kasha behavior. The excellent AIDF property allows high exciton utilization and thus superb performance of OLEDs using these new materials as light-emitting layers.

Aggregation-Induced Delayed Fluorescence Luminogens for Efficient Organic Light-Emitting Diodes.

Aggregation-induced delayed fluorescence (AIDF) can be regarded as a special case of aggregation-induced emission (AIE). Luminogens with AIDF can simultaneously emit strongly in solid state and fully utilize the singlet and triplet excitons in organic light-emitting diodes (OLEDs). In this work, two new AIDF luminogens, DMF-BP-DMAC and DPF-BP-DMAC, with an asymmetric D-A-D' structure, are designed and synthesized. The characteristics of both luminogens are systematically investigated, including single crystal structures, theoretical calculations, photophysical properties and thermal stabilities. Inspired by their AIDF nature, the green-emission non-doped OLEDs based on them are fabricated, which afford good electroluminescence performances, with low turn-on voltages of 2.8 V, high luminance of 52560 cd m-2 , high efficiencies of up to 14.4 %, 42.3 cd A-1 and 30.2 lm W-1 , and very small efficiency roll-off. The results strongly indicate the bright future of non-doped OLEDs on the basis of robust AIDF luminogens.

High-Performance Non-doped OLEDs with Nearly 100 % Exciton Use and Negligible Efficiency Roll-Off.

Non-doped organic light-emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton use are generally unsuitable for non-doped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation-induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for non-doped OLEDs. By grafting 4-(phenoxazin-10-yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Non-doped OLEDs of these AIDF luminogens exhibit excellent luminance (ca. 100000 cd m-2 ), outstanding external quantum efficiencies (21.4-22.6 %), negligible efficiency roll-off and improved operational stability. To the best of our knowledge, these are the most efficient non-doped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of non-doped OLEDs.

Heavy Atom Effect of Bromine Significantly Enhances Exciton Utilization of Delayed Fluorescence Luminogens.

Raising triplet exciton utilization of pure organic luminescent materials is of significant importance for efficiency advancement of organic light-emitting diodes (OLEDs). Herein, by introducing bromine atom(s) onto a typical molecule (bis(carbazol-9-yl)-4,5-dicyanobenzene) with thermally activated delayed fluorescence, we demonstrate that the heavy atom effect of bromine can increase spin-orbit coupling and promote the reverse intersystem crossing, which endow the molecules with more distinct delayed fluorescence. In consequence, the triplet exciton utilization is improved greatly with the increase of bromine atoms, affording apparently advanced external quantum efficiencies of OLEDs. Utilizing the enhancement effect of bromine atoms on delayed fluorescence should be a simple and promising design concept for efficient organic luminogens with high exciton utilization.

Highly Efficient Nondoped OLEDs with Negligible Efficiency Roll-Off Fabricated from Aggregation-Induced Delayed Fluorescence Luminogens.

Purely organic emitters that can efficiently utilize triplet excitons are highly desired to cut the cost of organic light-emitting diodes (OLEDs), but most of them require complicated doping techniques for their fabrication and suffer from severe efficiency roll-off. Herein, we developed novel luminogens with weak emission and negligible delayed fluorescence in solution but strong emission with prominent delayed components upon aggregate formation, giving rise to aggregation-induced delayed fluorescence (AIDF). The concentration-caused emission quenching and exciton annihilation are well-suppressed, which leads to high emission efficiencies and efficient exciton utilization in neat films. Their nondoped OLEDs provide excellent electroluminescence efficiencies of 59.1 cd A-1 , 65.7 lm W-1 , and 18.4 %, and a negligible current efficiency roll-off of 1.2 % at 1000 cd m-2 . Exploring AIDF luminogens for the construction of nondoped OLEDs could be a promising strategy to advance device efficiency and stability.