Mechanism of Intersystem Crossing of Thermally Activated Delayed Fluorescence Molecules

Abstract

The spin sublevel dynamics of the excited triplet state in thermally activated delayed fluorescence (TADF) molecules have not been investigated for high-intensity organic light-emitting diode materials. Understanding the mechanism for intersystem crossing (ISC) is thus important for designing novel TADF materials. We report the first study on the ISC dynamics of the lowest excited triplet state from the lowest excited singlet state with charge-transfer (CT) character of TADF molecules with different external quantum efficiencies (EQEs) using time-resolved electron paramagnetic resonance methods. Analysis of the observed spin polarization indicates a strong correlation of the EQE with the population rate due to ISC induced by hyperfine coupling with the magnetic nuclei. It is concluded that molecules with high EQE have an extremely small energy gap between the ¹CT and ³CT states, which allows an additional ISC channel due to the hyperfine interactions.