Spectrally resolved luminescence lifetime detection for measuring the energy splitting of the long-lived excited states.

Molecular motion plays an important role in the reverse intersystem crossing of thermally activated delayed fluorescence (TADF) materials, since the conformation varies as the molecule vibrates, leading to potential changes in the energies of excited states. Although many theoretical simulations have researched the relationship between the excited states and the molecular conformations, there are still few experimental results showing the energy level difference between different long-lived excited states. Herein, a novel method for measuring spectrally resolved luminescence lifetimes is proposed to detect the energy splitting of the long-lived excited states of a classical TADF molecule, BTZ-DMAC. A set of the time-gated luminescence spectra with different delay times were captured by a spectrograph equipped on an auto-phase-locked system, and then used for lifetime analysis at each wavelength. Unlike traditional measurement techniques, the proposed novel method does not require ultrafast laser, high-speed detector and any phase matching circuitry, thus significantly reducing the cost. This method revealed a definite energy gap between the two excited states of BTZ-DMAC with different lifetimes, indicating different conformations caused by molecular vibration. This low-cost method could be also used to detect many other luminescence materials for investigating the detail mechanisms of multiple excited states.