Efficient organic emitters in the deep-red region are rare due to the "energy gap law". Herein, multiple boron (B)- and nitrogen (N)-atoms embedded polycyclic heteroaromatics featuring hybridized π-bonding/ non-bonding molecular orbitals are constructed, providing a way to overcome the above luminescent boundary. The introduction of B-phenyl-B and N-phenyl-N structures enhances the electronic coupling of those para-positioned atoms, forming restricted π-bonds on the phenyl-core for delocalized excited states and thus a narrow energy gap. The mutually ortho-positioned B- and N-atoms also induce a multi-resonance effect on the peripheral skeleton for the non-bonding orbitals, creating shallow potential energy surfaces to eliminate the high-frequency vibrational quenching. The corresponding deep-red emitters with peaks at 662 and 692 nm exhibit narrow full-width at half-maximums of 38 nm, high radiative decay rates of ca. 108  s-1 , ≈100 % photo-luminescence quantum yields and record-high maximum external quantum efficiencies of ca. 28 % in a normal planar organic light-emitting diode structure, simultaneously.

Multi-Resonance Deep-Red Emitters with Shallow Potential-Energy Surfaces to Surpass Energy-Gap Law**

Carbazole-based DABNA analogues (CzDABNAs) were synthesized from triarylamine by regioselective one-shot single and double borylation. The reaction proceeded selectively at the ortho position of the carbazolyl group, where the highest occupied molecular orbital is mainly localized owing to the difference in the electron-donating abilities of the diarylamino and carbazolyl groups. The facile and scalable method enabled synthesis of CzDABNAs, exhibiting narrowband thermally activated delayed fluorescence with emission spectra ranging from deep blue to green. The organic light-emitting diode devices employing these products as emitters exhibited deep-blue, sky-blue, and green emission with high external quantum efficiencies of 19.5, 21.8, and 26.7 %, respectively.

Carbazole-Based DABNA Analogues as Highly Efficient Thermally Activated Delayed Fluorescence Materials for Narrowband Organic Light-Emitting Diodes

The International Telecommunication Union announced a new color gamut standard of broadcast service television (BT 2020) for ultra-high-definition TV in 2012. To satisfy the wide-color gamut standard of BT 2020, monochromatic red (R), green (G), and blue (B) emissions require a small full width at half-maximum, which is an important property for improving color purity. Although organic light-emitting diode (OLED) displays are currently one of the main types of display technologies, their broad emission via strong vibronic coupling between ground and excited states is a major hurdle to overcome in the development of next-generation wide-color gamut displays. Thus, the development of OLED emitters with narrowband R–G–B emissions is of great significance. In this review, the recent progress in the development of OLED materials with narrowband emission is summarized by grouping them into fluorescent, phosphorescent, and thermally activated delayed fluorescent emitters to reveal the correlation between molecular structures, optical properties, and device characteristics. We discuss rational molecular design strategies to achieve narrow photoluminescence and electroluminescence and the underlying mechanisms for controlling the emission bandwidth. Finally, the challenges in the realization of wide-color gamut OLED displays and the future prospects of such devices are discussed. Organic light-emitting diodes (OLEDs) with high color purity could be used in the next generation of high-definition televisions. The most widely used semiconductor, silicon, is an inorganic material but a wide range of organic alternatives are now emerging. These alternatives are especially in demand for light-emitting applications, where the performance of silicon is poor. Ji-Eun Jeong, Han Young Woo and colleagues from Korea University in Seoul, South Korea, reviewed recent progress in the development of OLEDs. An OLED tends to emit light over a relatively broad spectrum. This lack of color purity limits the device’s use in future ultra-high-definition TVs. The team presented an overview of the various molecular design strategies that have been used to reduce emission bandwidth and the physical mechanisms forming the basis of these strategies. With a growing demand for new emitters to realize ultra-high-definition displays, various types of organic emitters with narrow emission and high luminescent efficiency have been extensively studied. In this review, we summarized the recent developments of organic emitters (fluorescent, phosphorescent, and thermally activated delayed fluorescent) which show narrowband emission spectra with full-width half-maximum smaller than 50 nm.

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Recent advances in organic luminescent materials with narrowband emission

Multiresonance thermally activated delayed fluorescence (MR-TADF) emitters manifest great potential for organic light-emitting diodes (OLEDs) due to their high exciton-utilization efficiency and narrowband emission. Nonetheless, their tendency toward self-quenching caused by strong interchromophore interactions would induce doping sensitivity and deteriorate the device performances, and effective strategy to construct quenching-resistant emitters without sacrifycing color purity is still to be developed. By segregating the planar MR-TADF skeleton using two bulky carbazolyl units, herein a highly emissive molecule with enhanced quenching resistance is reported. The steric effect largely removes the formation of detrimental excimers/aggregates, and boosts the performance of the corresponding devices with a maximum external quantum efficiency (EQEmax ) up to 40.0% and full width at half maximum (FWHM) of 25 nm, representative of the only example of single OLED that can concurrently achieve narrow bandwidth and high EL efficiency surpassing 40% to date. Even at doping ratio of 30 wt%, the EQEmax is retained to be 33.3% with nearly unchanged emission spectrum. This work provides a viable approach to realize doping-insensitive MR-TADF devices with extreme EL efficiency and color purity for high-end OLED displays.

Quenching-Resistant Multiresonance TADF Emitter Realizes 40% External Quantum Efficiency in Narrowband Electroluminescence at High Doping Level.

The establishment of a simple molecular design strategy to realize red-shifted emission while maintaining good color purity for multi-resonance induced thermally activated delayed fluorescent (MR-TADF) materials remains an appealing yet challenging task. Herein, we demonstrate that the attachment of a cyano (CN) functionality at the lowest unoccupied molecular orbital location of the MR-TADF skeleton can promote attractive red-shifted emission due to the exceptional electron-withdrawing capacity of the CN group, which represents the first example of orange–red MR-TADF emitters. Meanwhile, the linear CN group adopts a coplanar conformation with the MR-framework to restrict structure relaxation associated with rotation, which is beneficial to maintain a small full-width at half-maximum and thus a good color purity. The CNCz-BNCz-based OLED device, which utilizes a TADF sensitized mechanism to accelerate the up-conversion process of triplet excitons in the emitting layer, exhibits an outstanding external quantum efficiency (EQE) as high as 33.7%, representing the state-of-the-art performance for orange–red TADF-OLEDs.

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Molecular design of thermally activated delayed fluorescent emitters for narrowband orange–red OLEDs boosted by a cyano-functionalization strategy

Pure green emitters are essential for realizing an ultrawide color gamut in next-generation displays. Herein, by fusing the difficult-to-access aza-aromatics onto B (boron)-N (nitrogen) skeleton, a hybridized multi-resonance and charge transfer (HMCT) molecule AZA-BN was successfully synthesized through an effective one-shot multiple cyclization method. AZA-BN shows pure green fluorescence with photoluminance quantum yield of 99.7 %. The corresponding green device exhibits a maximum external quantum efficiency and power efficiency of 28.2 % and 121.7 lm W-1 , respectively, with a full width half maximum (FWHM) of merely 30 nm and Commission Internationale de l'Eclairage (CIE) coordinate y of 0.69, representing the purest green bottom-emitting organic light-emitting diode.

Achieving Pure Green Electroluminescence with CIEy of 0.69 and EQE of 28.2% from an Aza-Fused Multi-Resonance Emitter

The first example of luminescent monosubstituted polyacetylenes (mono-PAs) is presented, based on a contracted cis-cisoid polyene backbone. It has an excellent circularly polarized luminescence (CPL) performance with a high dissymmetric factor (up to the order of 10-1 ). The luminescence stems from the helical cis-cisoid PA backbone, which is tightly fixed by the strong intramolecular hydrogen bonds, thereby reversing the energy order of excited states and enabling an emissive energy dissipation. CPL switches are facilely achieved by the solvent and temperature through reversible conformational transition. By taking advantages of fast response and high sensitivity, the thin film of mono-PAs could be used as a CPL-based probe for quantitative detection of trifluoroacetic acid with a wider linear dynamic range than those of photoluminescence and circular dichroism. This work opens a new avenue to develop novel smart CPL materials through modulating conformational transition.

Brightening up Circularly Polarized Luminescence of Monosubstituted Polyacetylene by Conformation Control: Mechanism, Switching, and Sensing

Achieving high exciton utilization is a long-cherished goal in the development of organic light-emitting diode materials. Herein, a three-step mechanism is proposed to achieve 200% exciton utilization: (i) hot triplet exciton (T2) conversion to singlet S1; (ii) singlet fission from S1 into two T1; (iii) and then a Dexter energy transfer to phosphors. The requirement is that S1 should lie slightly lower than or close to T2 and twice as high as T1 in energy. For this, a scenario is put forward to design a series of donor-bridge-acceptor (DBA) type molecules with 2E(T1) ≤ E(S1) < E(T2), in which the Baird-type aromatic pyrazoline ring is used as a bridge owing to its stabilized T1 (1.30-1.74 eV) and different kinds of donors and acceptors are linked to the bridge for regulating S1 (2.35-3.87 eV) and T2 (2.44-3.96 eV). The ultrafast spectroscopy and sensitization measurements for one compound (TPA-DBPrz) fully confirm the theoretical predictions.

Deping Hu

Papers

Achieving Pure Green Electroluminescence with CIEy of 0.69 and EQE of 28.2% from an Aza-Fused Multi-Resonance Emitter

Brightening up Circularly Polarized Luminescence of Monosubstituted Polyacetylene by Conformation Control: Mechanism, Switching, and Sensing

Molecular design of DBA-type five-membered heterocyclic rings to achieve 200% exciton utilization for electroluminescence.