Observation of Structural Transition and Metallization in a van der Waals Diamagnet ZnPS 3 via Pressure Manipulation

High Resolution Image Download MS PowerPoint Slide Zinc phosphorus trisulfide (ZnPS 3 ), one of the prototypical examples of diamagnetic metal phosphorus trichalcogenides (MPTs), has recently ignited extensive research into next-generation photocatalysis and energy storage. In this paper, the structural evolution and electrical transport properties of ZnPS 3 have been systematically investigated using Raman scattering spectroscopy and electrical conductivity coupled with first-principles calculations at high pressures up to 52.8 GPa under different pressure conditions. Upon application of nonhydrostatic pressure, ZnPS 3 may undergo a C 2/ m -to- P 3̅1 m structural modification at 5.5 GPa arising from the prominent contraction in interlayer distance as well as the P–Zn–P and P–S–P bond angles. Upon further pressurization to 36.8 GPa, ZnPS 3 experienced a semiconductor-to-metal transition evidenced by the high conductivity value and the positive-to-negative conversion in temperature-dependent electrical conductivity relations. Nevertheless, the comparable C 2/ m -to- P 3̅1 m structural transition pressure and an approximate 6.0 GPa pressure delay in metallization under hydrostatic conditions were due to the impact of deviatoric stress. On decompression, a reversible phase transition was demonstrated by the resumable Raman spectra and electrical conductivity magnitudes under different pressure conditions. Our research on ZnPS 3 not only offers an insightful perspective on the fundamental physics of MPTs under extreme conditions but also establishes a basis for further investigation into its potential applications.