Octahedral tilt-driven phase transitions in BaZrS3 chalcogenide perovskite

Chalcogenide perovskites are lead-free materials for potential photovoltaic or thermoelectric applications. BaZrS₃ is the most studied member of this family due to its superior thermal and chemical stability, desirable optoelectronic properties, and low thermal conductivity. Phase transitions of the BaZrS₃ perovskite are under-explored in literature as most experimental characterization is performed at ambient conditions where the orthorhombic Pnma phase is reported to be stable. In this work, we study the dynamics of BaZrS₃ across a range of temperatures and pressures using an accurate machine-learned interatomic potential trained with data from hybrid density functional theory calculations. At 0 Pa, we find a first-order phase transition from the orthorhombic to tetragonal I4/mcm phase at 610 K, and a second-order transition from the tetragonal to the cubic Pm-3m phase at 880 K. The tetragonal phase is stable over a larger temperature range at higher pressures. To confirm the validity of our model we report the static structure factor as a function of temperature and compare our results with published experimental data.