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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) materials are attractive for the fabrication of high‐efficiency organic light‐emitting diodes (OLEDs) owing to the "hot exciton" process by reverse intersystem crossing (hRISC) and high photoluminescence quantum yields (PLQY). However, the internal conversion (IC) from the high‐lying triplet excitation states (Tn, n≥2) to the lower excited triplet state (Tn‐1) is inevitable, resulting in severe exciton losses. Herein, an effective device structure is designed that reuses the lost triplet excitons caused by IC and realizes the breakthrough in the efficiency of blue fluorescence OLEDs based on AIE molecule as an emitter. The maximum external quantum efficiency reached as high as 14.8% and is kept at 14.4% at the luminance of 1000 cd m−2. In the designed device, a triplet–triplet annihilation (TTA) up‐conversion material 1‐[2,5‐dimethyl‐4‐(1‐pyrenyl)phenyl]pyrene (DMPPP) is introduced into the AIE emitter as a triplet sensitizer to receive the lost triplet excitons, and a thin TTA up‐conversion layer 9‐[4‐(10‐phenyl‐9‐anthryl)phenyl]‐9H‐carbazole (CzPA) is introduced in the middle of the doped layer to form the emissive layer (EML). It is found that the hRISC process of iTPB‐2AC greatly enhances the utilization efficiency of TTA intermediate state ([TT]*) excitons on CzPA to iTPB‐2AC so that the utilization of the lost excitons is maximized. This work establishes physical insights into the AIE emission materials and device fabrication of high‐efficiency blue fluorescence OLEDs. [ABSTRACT FROM AUTHOR]