Efficient OLEDs with Alleviated Efficiency Roll‐Off Based on MR‐TADF Materials Containing Indolo[3,2,1‐jk]carbazole

Abstract The multiple resonance thermally activated delayed fluorescence (MR‐TADF) materials can meet the requirement of a high color gamut of displays due to their narrowband emission. However, most reported organic light‐emitting diodes (OLEDs) based on MR‐TADF materials suffer from severe efficiency roll‐off. Herein, three green MR‐TADF emitters, p‐ICz‐BNCz, m‐ICz‐BNCz, and dm‐ICz‐BNCz, are obtained by introducing bulky indolo[3,2,1‐jk]carbazole (ICz) units into the classical DtBuCzB skeleton at the para or meta positions relative to the boron‐substituted phenyl ring. Compared with the para‐substitution of ICz, the meta‐substitution not only increases the reverse intersystem crossing rate constants of m‐ICz‐BNCz and dm‐ICz‐BNCz by nearly three times, but also makes their configurations more twisted. The two factors work together to improve the utilization of triplet excitons of the emitters, showing photoluminescence quantum yields exceeding 90%. As a result, the two corresponding OLEDs exhibit maximum external quantum efficiency (EQE_max) values of 28% and 32.9%, respectively, with low‐efficiency roll‐off. At the high brightness of 1000 cd m⁻², the EQE values of the two devices still maintain at 19.3% and 25.0%, respectively. In addition, green emissions with Commission Internationale de l'Eclairage coordinates of (0.20, 0.70) and (0.30, 0.67) are also observed.