Mingke Li, Yulong Li, Yue Yu, Yichao Chen, Jianhui Pan, Feng Peng, Dezhi Yang, DongGe Ma, Lei Ying, Yuguang Ma
ABSTRACT Host–guest doping is the mainstream technology for organic light-emitting diodes (OLEDs). Non-doped OLEDs, using a single material for both electron migration and exciton luminescence, promise simplified preparation, but lack efficient emitting-layer materials due to the concentration quenching of excitons (especially long-lifetime triplet excitons). This study compares two novel isomeric emitters (pTCN and mTCN) based on the hot-exciton mechanism. It shows that thermodynamically favorable excited-state alignments enable efficient high-lying reverse intersystem crossing (hRISC) from high-lying triplet states (Tn, n ≥ 2) to singlet states (S1) with ΔETn−S1 > 0. The pTCN-based non-doped device exhibited an unprecedented maximum external quantum efficiency (EQEmax) of 20.3% with CIE coordinates of (0.15, 0.07), while mTCN (unfavorable ΔETn−S1 < 0) only has 5.3% EQEmax. Photophysical and excited-state dynamics studies confirm that the difference between the rates of the hRISC processes (∼1 × 108 vs. 0.7 × 108 s–1) gives rise to this performance gap.