Nitrogen-Embedding Strategy for Short-Range Charge Transfer Excited States and Efficient Narrowband Deep-Blue Organic Light Emitting Diodes.

The development of deep-blue organic light-emitting diodes (OLEDs) featuring high efficiency and narrowband emission is of great importance for ultrahigh-definition displays with wide color gamut. Herein, based on the nitrogen-embedding strategy for modifying the short range charge transfer excited state energies of multi-resonance (MR) thermally activated delayed fluorescence (TADF) emitters, we introduce one or two nitrogen atoms into the central benzene ring of a versatile boron-embedded 1,3-bis(carbazol-9-yl)benzene skeleton. This approach resulted in the stabilization of the highest occupied molecular orbital energy levels and the formation of intramolecular hydrogen bonds, and thus systematic hypsochromic shifts and narrowing spectra. In toluene solution, two heterocyclic-based MR-TADF molecules, Py-BN and Pm-BN, exhibit deep-blue emissions with high photoluminescence quantum yields of 93% and 94%, and narrow full width at half maximum of 14 and 13 nm, respectively. A deep-blue hyperfluorescent OLED based on Py-BN exhibited a maximum external quantum efficiency of 27.7% and desired color purity with Commission Internationale de L'Eclairage (CIE) coordinates of (0.150, 0.052). These results demonstrate the significant potential for the development of deep blue narrowband MR-TADF emitters.

Frontier Molecular Orbital Engineering: Constructing Highly Efficient Narrowband Organic Electroluminescent Materials.

It is of great strategic significance to develop highly efficient narrowband organic electroluminescent materials that can be utilized to manufacture ultra-high-definition (UHD) displays and meet or approach the requirements of Broadcast Television 2020 (B.T.2020) color gamut standards. This motif poses challenges for molecular design and synthesis, especially for developing generality, diversity, scalability, and robustness of molecular structures. The emergence of multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters has ingeniously solved the problems and demonstrated bright application prospects in the field of UHD displays, sparking a research boom. This Minireview summarizes the research endeavors of narrowband organic electroluminescent materials, with emphasis on the tremendous contribution of frontier molecular orbital engineering (FMOE) strategy. It combines the outstanding advantages of MR framework and donor-acceptor (D-A) structure, and can achieve red-shift and narrowband emission simultaneously, which is of great significance in the development of long-wavelength narrowband emitters with emission maxima especially exceeding 500 nm. We hope that this Minireview would provide some inspiration for what could transpire in the future.

Multi-Resonance Building-Block-Based Electroluminescent Material: Lengthening Emission Maximum and Shortening Delayed Fluorescence Lifetime.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials are considered a class of organic materials with exceptional electronic and optical properties, which make them promising for the applications in organic light-emitting diodes (OLEDs). In this study, we improved, synthesized, and characterized a multiple-resonance type emitter based on the assembly of MR-building blocks (MR-BBs). By optimizing the geometric arrangement of MR-BBs, we were able to generate narrowband emission in the longer wavelength region and shorten the delayed excited-state lifetime, resulting in improved emission efficiency compared to the parent molecule. Our proof-of-concept molecule, m-DBCz, exhibited narrowband yellowish-green TADF emission with a full width at half-maximum of 32 nm and a small singlet-triplet energy gap of 0.04 eV. The OLED developed using m-DBCz as the emitter demonstrated electroluminescence at 548 nm and achieved a high external quantum efficiency (EQE) of 34.9 %. Further optimization of the device resulted in a high external quantum efficiency of 36.3 % and extremely low efficiency roll-off, with EQE values of 30.1 % and 27.7 % obtained even at high luminance levels of 50 000 and 100 000 cd m-2 . These results demonstrate the full potential of MR-TADF materials for applications on ultrahigh-luminance OLEDs.

Solution-Processable Pure-Red Multiple Resonance-induced Thermally Activated Delayed Fluorescence Emitter for Organic Light-Emitting Diode with External Quantum Efficiency over 20 .

Developing solution-processable red organic light-emitting diodes (OLEDs) with high color purity and efficiency based on multiple resonance thermally activated delayed fluorescence (MR-TADF) is a formidable challenge. Herein, by introducing auxiliary electron donor and acceptor moieties into the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) distributed positions of multiple resonance skeleton simultaneously, an effective strategy to obtain red MR-TADF emitters was represented. The proof-of-the-concept molecule BN-R exhibits a narrowband pure-red emission at 624 nm, with a high luminous efficiency of 94 % and a narrow bandwidth of 46 nm. Notably, the fabricated solution-processable pure-red OLED based on BN-R exhibits a state-of-the-art external quantum efficiency over 20 % with the Commission Internationale de I'Éclairage coordinates of (0.663, 0.337) and a long operational lifetime (LT50 ) of 1088 hours at an initial luminance of 1000 cd m-2 .

Achieving 37.1% Green Electroluminescent Efficiency and 0.09 eV Full Width at Half Maximum Based on a Ternary Boron-Oxygen-Nitrogen Embedded Polycyclic Aromatic System.

Herein, a ternary boron-oxygen-nitrogen embedded polycyclic aromatic hydrocarbon with multiple resonance thermally activated delayed fluorescence (MR-TADF), namely DBNO, is developed by adopting the para boron-π-boron and para oxygen-π-oxygen strategy. The designed molecule presents a vivid green emission with a high photoluminescence quantum yield (96 %) and an extremely narrow full width at half maximum (FWHM) of 19 nm/0.09 eV, which surpasses all previously reported green TADF emitters to date. In addition, the long molecular structure along the transition dipole moment direction endows it with a high horizontal emitting dipole ratio of 96 %. The organic light-emitting diode (OLED) based on DBNO reveals a narrowband green emission with a peak at 504 nm and a FWHM of 24 nm/0.12 eV. Particularly, a significantly improved device performance is achieved by the TADF-sensitization (hyperfluorescence) mechanism, presenting a FWHM of 27 nm and a maximum external quantum efficiency (EQE) of 37.1 %.

Highly Efficient Electroluminescence from Narrowband Green Circularly Polarized Multiple Resonance Thermally Activated Delayed Fluorescence Enantiomers.

Purely organic fluorescent materials that concurrently exhibit high efficiency, narrowband emission, and circularly polarized luminescence (CPL) remain an unaddressed issue despite their promising applications in wide color gamut- and 3D-display. Herein, the CPL optical property and multiple resonance (MR) effect induced thermally activated delayed fluorescence (MR-TADF) emission are integrated with high color purity and luminous efficiency together. Two pairs of highly efficient green CP-MR-TADF enantiomers, namely, (R/S)-OBN-2CN-BN and (R/S)-OBN-4CN-BN, are developed. The enantiomer-based organic light-emitting diodes (OLEDs) exhibit pure green emission with narrow full-width at half-maximums (FWHMs) of 30 and 33 nm, high maximum external quantum efficiencies (EQEs) of 29.4% and 24.5%, and clear circularly polarized electroluminescence (CPEL) signals with electroluminescence dissymmetry factors (gEL ) of +1.43 × 10-3 /-1.27 × 10-3 and +4.60 × 10-4 /-4.76 × 10-4 , respectively. This is the first example of a highly efficient OLED that exhibits CPEL signal, narrowband emission, and TADF concurrently.

Constructing Charge-Transfer Excited States Based on Frontier Molecular Orbital Engineering: Narrowband Green Electroluminescence with High Color Purity and Efficiency.

The design and synthesis of organic materials with a narrow emission band in the longer wavelength region beyond 510 nm remain a great challenge. For constructing narrowband green emitters, we propose a unique molecular design strategy based on frontier molecular orbital engineering (FMOE), which can integrate the advantages of a twisted donor-acceptor (D-A) structure and a multiple resonance (MR) delayed fluorescence skeleton. Attaching an auxiliary donor to a MR skeleton leads to a novel molecule with twisted D-A and MR structure characteristics. Importantly, a remarkable red-shift of the emission maximum and a narrowband spectrum are achieved simultaneously. The target molecule has been employed as an emitter to fabricate green organic light-emitting diodes (OLEDs) with Commission Internationale de L'Eclairage (CIE) coordinates of (0.23, 0.69) and a maximum external quantum efficiency (EQE) of 27.0 %.