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Development of white organic light-emitting diodes based on purely thermally activated delayed fluorescence with a single-emissive-layer configuration has been a formidable challenge. Here, we report the rational design of a donor-acceptor energy-relaying exciplex and its utility in fabricating single-emissive-layer, thermally activated delayed fluorescence-based white organic light-emitting diodes that exhibit 100% internal quantum efficiency, 108.2 lm W −1  power efficiency, and 32.7% external quantum efficiency. This strategy enables thin-film fabrication of an 8 cm × 8 cm thermally activated delayed fluorescence white organic light-emitting diodes (10 inch 2 ) prototype with 82.7 lm W −1  power efficiency and 25.0% external quantum efficiency. Introduction of a phosphine oxide-based acceptor with a steric group to the exciplex limits donor-acceptor triplet coupling, providing dual levels of high-lying and low-lying triplet energy. Transient spectroscopic characterizations confirm that a ladder-like energy relaying occurs from the high-lying triplet level of the exciplex to a blue emitter, then to the low-lying triplet level of the phosphine oxide acceptor, and ultimately to the yellow emitter. Our results demonstrate the broad applicability of energy relaying in multicomponent systems for exciton harvesting, providing opportunities for the development of third-generation white organic light-emitting diode light sources.

Ladder-like energy-relaying exciplex enables 100% internal quantum efficiency of white TADF-based diodes in a single emissive layer