HLCT-Type Acceptor Molecule-Based Exciplex System for Highly Efficient Solution-Processable OLEDs with Suppressed Efficiency Roll-Offs

Exciplex systems are promising candidates for thermally activated delayed fluorescence (TADF) molecules because of the small energy difference between the lowest singlet and triplet excited states (ΔE_ST). However, realizing high-efficiency and low-external-quantum-efficiency (EQE) roll-off in solution-processed organic light-emitting diodes (OLEDs) using an exciplex system remains a formidable challenge. In this study, two (HLCT)-type isomers with a spiro skeleton, 2-^tBuspoCz-TRZ and 10-^tBuspoCz-TRZ, are designed and synthesized as acceptors of exciplexes, where tert-butylspirofluorene indole is regarded as a donor and the triazine unit as an acceptor. Green exciplex emissions are observed for the 2-^tBuspoCz-TRZ:TAPC and 10-^tBuspoCz-TRZ:TAPC exciplexes, indicating distinct TADF characteristics with a very small ΔE_ST of 35 ± 5 meV. By using the TADF exciplex system based on the HLCT acceptor as an emitter, solution-processable OLEDs achieve a maximum external quantum efficiency (EQE_max) of 20.8%. Furthermore, a high EQE_max > 25% with a very low-efficiency roll-off (≈3.5% at 1000 cd m⁻²) is obtained for solution-processable phosphorescent devices using HLCT-based exciplexes as the host matrix of phosphors. This study paves the way for a novel strategy for designing acceptor exciplex molecules for effective TADF molecules and host matrices in solution-processable OLEDs.