Theoretical Study of Pressure-Induced Phase Transitions in Sb2S3, Bi2S3, and Sb2Se3

Abstract

We report an ab initio study of Sb2S3, Sb2Se3, and Bi2S3 sesquichalcogenides at hydrostatic pressures of up to 60 GPa. We explore the possibility that the C2/m, C2/c, the disordered Im-3m, and the I4/mmm phases observed in sesquichalcogenides with heavier cations, viz. Bi2Se3, Bi2Te3, and Sb2Te3, could also be formed in Sb2S3, Sb2Se3, and Bi2S3, as suggested from recent experiments. Our calculations show that the C2/c phase is not energetically favorable in any of the three compounds, up to 60 GPa. The C2/m system is also unfavorable for Sb2S3 and Bi2S3; however, it is energetically favorable with respect to the Pnma phase of Sb2Se3 above 10 GPa. Finally, the I4/mmm and the disordered body-centered cubic-type Im-3m structures are competitive in energy and are energetically more stable than the C2/m phase at pressures beyond 30 GPa. The dynamical stabilities of the Pnma, Im-3m, C2/m, and I4/mmm structural phases at high pressures are discussed for the three compounds.