Exciton Structure and Recombination Dynamics in GaSe Crystals

At present, the available experimental data on the optical properties of layered III–VI monochalcogenide compounds are scattered and somewhat contradictory, although they are the parent materials for promising two-dimensional (2D) structures. This work is devoted to optical studies of bulk GaSe crystals, whose perfect structural properties are confirmed by Raman studies, observation of singlet-triplet splitting of 1.5 meV, and the polarized photoluminescence measurements from the sample edge. We analyze the band structure of GaSe, namely the sequence and energies of direct and indirect exciton transitions, using cw and time-resolved micro-photoluminescence measurements with variation of temperature. It turns out that the direct band gap in bulk GaSe is at 2.13 eV, close to calculated values. The indirect exciton transition is located ∼15 meV below the direct exciton (2.11 eV). Its intensity quickly quenches and characteristic decay time strongly shortens with increasing temperature, while the contribution of the direct exciton is relatively enhanced.