Highly Horizontal Oriented Tricomponent Exciplex Host with Multiple Reverse Intersystem Crossing Channels for High‐Performance Narrowband Electroluminescence and Eye‐Protection White Organic Light‐emitting Diodes

Abstract Despite multiple‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters with small full‐width at half maximum are attractive for wide color‐gamut display and eye‐protection lighting applications, their inefficient reverse intersystem crossing (RISC) process and long exciton lifetime induce serious efficiency roll‐off, which significantly limits their development. Herein, a novel device concept of building highly efficient tricomponent exciplex with multiple RISC channels is proposed to realize reduced exciton quenching and enhanced upconversion of nonradiative triplet excitons, and subsequently used as a host for high‐performance MR‐TADF organic light‐emitting diodes (OLEDs). Compared with traditional binary exciplex, the tricomponent exciplex exhibits obviously improved photoluminescence quantum yield, emitting dipole orientation and RISC rate constant, and a record‐breaking external quantum efficiency (EQE) of 30.4% is achieved for tricomponent exciplex p‐PhBCzPh: PO‐T2T: DspiroAc‐TRZ (50: 20: 30) based OLED. Remarkably, maximum EQEs of 36.2% and 40.3% and ultralow efficiency roll‐off with EQEs of 26.1% and 30.0% at 1000 cd m −2 are respectively achieved for its sky‐blue and pure‐green MR‐TADF doped OLEDs. Additionally, the blue emission unit hosted by tricomponent exciplex is combined with an orange‐red TADF emission unit to achieve a double‐emission‐layer blue‐hazard‐free warm white OLED with an EQE max of 30.3% and stable electroluminescence spectra over a wide brightness range.