Luminescence mechanism analysis of a TADF molecule showing peculiar thermal behavior

Abstract

In recent years, much attention has been paid to the development of thermally activated delayed fluorescence (TADF) materials with short delayed-fluorescence lifetimes to improve the device performances of OLEDs. In principle, by reducing the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) overlap, while the energy difference between S₁–T₁ (ΔE_ST) and activation energy (E_a) can be reduced, and the reverse intersystem crossing rate constant (k_RISC) can be accelerated, a decrease in the radiative rate constant happens, necessitating an advanced molecular design. Furthermore, a molecule based on heptazine as a parent skeleton has recently been found to have a peculiar temperature dependence of luminescence decay, suggesting a negative gap (NG) material. In this report, we show that 9-[1,4]benzoxaborino[2,3,4-kl]phenoxaborine-7-yl-1,3,6,8-tetramethyl-9H-carbazole (TMCz-BO), a donor–acceptor linked TADF molecule with a very short delay lifetime of 750 ns, exhibits a peculiar thermal behavior similar to that of NG materials based on the temperature dependence of its luminescence decay in solution.