Achieving Hybridized Local and Charge‐Transfer Excited State and Excellent OLED Performance Through Facile Doping

Abstract Hybridized local and charge‐transfer (HLCT) excited states provide a new avenue for achieving high yields of singlet excitons (>25%) and outstanding electroluminescence (EL) performance in organic light‐emitting diodes (OLEDs). In this contribution, donor–acceptor (D–A) structured (Z)‐2,3‐bis[4‐(diphenylamino)phenyl]acrylonitrile (BDPACS) with aggregation‐induced emission (AIE) characteristics is demonstrated to possess HLCT excited states in low‐polarity solvents and in vacuum‐deposited neat films. However, undoped OLED devices of the same material show unexpectedly poor performances with external quantum efficiencies (EQE_max) of at most 0.41%, due to the formation of exciplexes or excimers. To alleviate this, doped devices are fabricated using low‐polarity 2‐methyl‐9,10‐di(2‐naphthyl)anthracene (MADN), which has the appropriate energy levels to serve as a host in the emissive layer and can eradicate exciplexes/excimers and moreover help achieve the HLCT state through the solid‐state solvation effect. Such devices exhibit strikingly improved EQE_max of 6.8%, as well as singlet utilization yields exceeding the theoretical limit of 25%. Furthermore, all doped devices exhibit extremely low efficiency roll‐off. These results may have significant implications for the future fabrication of high‐performance OLEDs based on AIE luminogens and HLCT emitters.