Enhanced Upconversion of Triplet Excitons for Conjugated Polymeric Thermally Activated Delayed Fluorescence Emitters by Employing an Intramolecular Sensitization Strategy.

Endowed by a thermally activated delayed fluorescence (TADF) sensitizer with a high constant rate of reverse intersystem crossing, the singlet excitons could be accumulated and then delivered to emitting states through favorable Förster resonance energy transfer, bypassing the inefficient intersystem transition processes of emitters. However, the conventional intermolecular sensitization strategies suffer from inherent aggregation-induced quenching and inevitable phase segregation of TADF sensitizers and emitters. In this context, we proposed a novel intramolecular sensitization strategy by covalently incorporating the TADF sensitizer into conjugated polymeric emitters. After rationally regulating the proportions of sensitizer and emitter units in polymers, the intramolecular sensitized conjugated TADF polymers with anticipated photophysical properties and stable device performance were obtained. A superior kRISC value over 106 s-1 accompanied by a suppressed nonradiative transition of the triplet exciton could be gained; therefore, the photoluminescence quantum yield (PLQY) could reach nearly 90%. In accord with the superior PLQY values enhanced by our intramolecular sensitization strategy, the solution-processed organic light-emitting diodes (OLEDs) can achieve a maximum external quantum efficiency (EQE) value of 17.8% while still maintaining 16.0% at 1000 cd/m2 with extremely low efficiency roll-off. These results convincingly manifest the significance of an intramolecular sensitization strategy for designing high-efficiency polymeric TADF emitters.