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"Hot exciton" molecules that allow the transition of excitons from a high‐lying triplet state (Tn, n≥ 2) to singlet states (Sm, 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 Tn is successfully quantified by in situ transient electroluminescent measurements and theoretical calculation. It is found that the IC process increases severe energy loss of Tn 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. [ABSTRACT FROM AUTHOR]

Aggregation‐induced emission (AIE) and hybridized local and charge‐transfer (HLCT) materials are two kinds of promising electroluminescence systems for the fabrication of high‐efficiency organic light‐emitting diodes (OLEDs) by harnessing "hot excitons" at the high‐lying triplet exciton states (Tn, n ≥ 2). Nonetheless, the efficiency of the resulting OLEDs did not meet expectations due to the possible loss of Tn→Tn−1. Herein, experimental results and theoretical calculations demonstrate the "hot exciton" process between the high‐lying triplet state T3 and the lowest excited singlet state S1 in an AIE material 4⁗‐(diphenylamino)‐2″,5″‐diphenyl‐[1,1″:4′,1″:4″,1′″:4′″,1⁗‐quinquephenyl]‐4‐carbonitrile (TPB‐PAPC) and it is found that the Förster resonance energy transfer (FRET) between two molecules can facilitate the "hot exciton" process and inhibit the T3→T2 loss by doping a blue fluorescent emitter in TPB‐PAPC. Finally, the doped TPB‐PAPC blue OLEDs achieve a maximum external quantum efficiency (EQEmax) of 9.0% with a small efficiency roll‐off. Furthermore, doping the blue fluorescent emitter in a HLCT material 2‐(4‐(10‐(3‐(9H‐carbazol‐9‐yl)phenyl)anthracen‐9‐yl)phenyl)‐1‐phenyl‐1H‐phenanthro[9,10‐d] imidazole (PAC) is used as the emission layer, and the resulting blue OLEDs exhibit an EQEmax of 17.4%, realizing the efficiency breakthrough of blue fluorescence OLEDs. This work establishes a physical insight in the design of high‐performance "hot exciton" molecules and the fabrication of high‐performance blue fluorescence OLEDs. [ABSTRACT FROM AUTHOR]