Efficiency Breakthrough of Fluorescence OLEDs by the Strategic Management of “Hot Excitons” at Highly Lying Excitation Triplet Energy Levels

Abstract 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 (T n , n ≥ 2). Nonetheless, the efficiency of the resulting OLEDs did not meet expectations due to the possible loss of T n →T n −1 . Herein, experimental results and theoretical calculations demonstrate the “hot exciton” process between the high‐lying triplet state T 3 and the lowest excited singlet state S 1 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 T 3 →T 2 loss by doping a blue fluorescent emitter in TPB‐PAPC. Finally, the doped TPB‐PAPC blue OLEDs achieve a maximum external quantum efficiency (EQE max ) of 9.0% with a small efficiency roll‐off. Furthermore, doping the blue fluorescent emitter in a HLCT material 2‐(4‐(10‐(3‐(9 H ‐carbazol‐9‐yl)phenyl)anthracen‐9‐yl)phenyl)‐1‐phenyl‐1 H ‐phenanthro[9,10‐ d ] imidazole (PAC) is used as the emission layer, and the resulting blue OLEDs exhibit an EQE max 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.