Secondary Acceptor Optimization for Full‐Exciton Radiation: Toward Sky‐Blue Thermally Activated Delayed Fluorescence Diodes with External Quantum Efficiency of ≈30%

Efficient blue emitters are indispensable for organic light-emitting diodes (OLEDs) with respect to display and lighting applications. Because of their high-energy excited states, both radiation enhancement and non-radiation suppression should be simultaneously optimized to realize 100% exciton utilization. Here, it is shown that the excited-state characteristics of blue thermally activated delayed fluorescence emitters can be precisely controlled by a secondary acceptor having moderate electronic effects on increasing the singlet charge-transfer component and preserving the triplet locally excited-state component. In addition of planar configuration between the donor and the primary acceptor, the radiative transition improvement and non-radiative transition suppression can be simultaneously achieved for "full-exciton radiation". A molecule using diphenylphosphine oxide as the secondary acceptor exhibits ≈100% photoluminescence quantum yield on the basis of its tenfold increased singlet radiative rate constant, fivefold decreased singlet and triplet non-radiative rate constants, and ≈100% reverse intersystem crossing efficiency, which further endows ≈100% exciton utilization efficiency to its sky-blue OLEDs.