Tunable Negative Thermal Expansion in Layered Perovskite Ba3Zr2S7

Abstract

We simulated the thermal expansion coefficient (TEC) of the layered perovskite sulfide Ba₃Zr₂S₇ (P4₂/mnm symmetry) from first principles. The calculated ambient pressure and room-temperature volumetric TEC is 38 × 10^–6 K^–1, which makes the material suitable for use in conventional PV devices. We further predicted low-temperature, pressure-tunable negative thermal expansion (NTE) in Ba₃Zr₂S₇ that arises from a quasi-2D vibration mechanism shared by other n = 2 Ruddlesden–Popper oxides Ca₃Ti₂O₇, Ca₃Zr₂O₇, and Sr₃Zr₂O₇. We computationally found a pressure-induced phase transition to a structure in the monoclinic crystal system. Experimental investigation of this system as a function of pressure supported by in situ diffraction studies in a diamond anvil cell confirmed a phase change at high pressures to a new polymorph that likely exhibits P2/c symmetry. Our simulations show that the quasi-2D mechanism and proximity to a mechanochemical transition enhance the NTE response. These features may be used to design NTE in other layered perovskites.