Understanding Spin-Orbit-Coupling-Induced Reverse Intersystem Crossing in DMAC-TRZ-Doped Organic Light-Emitting...

An efficient reverse intersystem crossing (RISC) process in thermally activated delayed fluorescence (TADF) material is a common way to obtain high-performance organic light-emitting diodes (OLEDs), but the physical mechanism for the spin flipping of the RISC remains vague. Here, using magneto-electroluminescence (MEL) as an effective tool, we found that the RISC (CT₃ → CT₁) from a triplet charge transfer (CT₃) to the singlet charge transfer (CT₁) state is decided by spin-orbit coupling (SOC) in metal-free OLEDs based on a typical TADF emitter DMAC-TRZ. By fitting and analyzing the current and concentration-dependent MEL data, it is found that the characteristic magnetic field of the SOC-induced RISC process is approximately 65-85 mT, which is obviously larger than that (several mT) of the hyperfine-interaction-induced RISC process. Simultaneously, the dissociation effect of the electric field on the CT₃ state causes the SOC-induced RISC process to decrease with increasing bias current. The different formation methods of excited states lead to the nonmonotonic change of SOC-induced RISC process with the increase of dopant concentration. Furthermore, considering the orbital polarization of dipoles, the SOC mechanism is further verified by the measurement of magneto-photoluminescence to be the responsible for achieving the spin flipping in TADF molecules. Therefore, this work clarifies the underlying dynamic mechanism of the RISC process in TADF-OLEDs.