Cooperative Passivation Exciton Quenching Triggers Surpassing 30% External Quantum Efficiency for a Deep‐Blue Organic Light‐Emitting Diode.

Overcoming exciton quenching and improving electroluminescence (EL) performances continue to pose persistent challenges in the development of efficient deep blue thermally activated delayed fluorescence (TADF) emitters. Herein, an asymmetric multi‐donors strategy is employed that provides the potential of establishing multiple radiative transition channels for fluorescence emission and reverse intersystem crossing (RISC), while allowing flexible modulation of packing modes in single‐crystal state and optimization of morphology in films by modifying the substitution site of the donor units. As a result, intermolecular π–π interactions are effectively alleviated and a very smooth surface with a reduced defect density is simultaneously achieved, which can significantly reduce the density of triplet excitons, accelerate the charge transfer rate, and enhance carrier injection efficiency. Consequently, a super‐high photoluminescence quantum yield (PLQY) of 99% and fast kRISC of 1.1 × 105 s−1 are concurrently achieved for the proof‐of‐concept emitter 3,4‐Cz‐SF‐SFAC. The corresponding deep‐blue organic light‐emitting diode (OLED) demonstrates an exceptional external quantum efficiency (EQE) of 31.1%, accompanied by an emission peak at 457 nm, one of the preeminent TADF materials within the deep blue region, ranking among the most efficient OLEDs with an EL spectra below 460 nm on record. [ABSTRACT FROM AUTHOR]