ZnPSe₃ as ultrabright indirect band-gap system with microsecond excitonic lifetimes

ZnPSe₃ was identified as a two-dimensional material wherein valley and spin can be optically controlled in technologically relevant timescales. We report an optical characterization of ZnPSe₃ crystals that show indirect band-gap characteristics in combination with unusually strong photoluminescence. We found evidence of interband recombination from photoexcited electron-hole states with lifetimes in a microsecond timescale. Through a comparative analysis of photoluminescence and photoluminescence excitation spectra, we reconstructed the electronic band scheme relevant to fundamental processes of light absorption, carrier relaxation, and radiative recombination through interband pathways and annihilation of defect-bound excitons. The investigation of the radiative processes in the presence of a magnetic field revealed spin splitting of electronic states contributing to the ground excitonic states. Consequently, the magnetic field induces an imbalance in the number of excitons with the opposite angular momentum according to the thermal equilibrium as seen in the photoluminescence decay profiles resolved by circular polarization.