Quantifying the Energy Loss of Triplet Excitons on High‐Lying Triplet States to Develop High Efficiency Blue Fluorescence OLEDs Based on AIE Emitter

Abstract “Hot exciton” molecules that allow the transition of excitons from a high‐lying triplet state (T_n, n≥ 2) to singlet states (S_m, m≥1) by a reverse intersystem crossing (hRISC) process have become an effective strategy to achieve high efficiency fluorescence organic light emitting diodes (OLEDs). However, the understanding of the dynamic behavior of the “hot exciton” process is still very lacking. Herein, the exciton dynamics of an aggregation‐induced emission (AIE) molecule TPA‐An‐mPhCz with the “hot exciton” property are deeply investigated, and the proportion between hRISC and internal inversion (IC) of excitons on T_n is successfully quantified by in situ transient electroluminescent measurements and theoretical calculation. It is found that the IC process increases severe energy loss of T_n excitons. By introducing a triplet–triplet annihilation up‐conversion layer in the emissive layer to efficiently recapture the IC excitons and further doping a blue fluorescent emitter in the TPA‐An‐mPhCz layer to achieve high photoluminescence quantum yield (PLQY), the resulting OLED achieves a maximum external quantum efficiency of 12.5% with negligible efficiency roll‐off. More impressively, the operational lifetime LT₇₅ (lifetime to 75% of the initial luminance) of the device with efficient triplets utilization performs a remarkable 116 h under 1000 cd m⁻². This work provides the fundamentals for the design of hot exciton materials with efficient exciton utilization to develop efficient blue fluorescence OLEDs.