Investigation of new phases in the Ba–Si phase diagram under high pressure using ab initio structural search

Abstract

Barium silicides are versatile materials that have attracted attention for a variety of applications in electronics and optoelectronics. Using an unbiased structural search based on a particle-swarm optimization algorithm combined with density functional theory calculations, we investigate systematically the ground-state phase stability and the structural diversity of Ba–Si binaries under high pressure. The phase diagram turns out to be quite intricate, with several compositions stabilizing/destabilizing as a function of pressure. In particular, we identify novel phases of BaSi, BaSi₂, BaSi₃, and BaSi₅ that might be synthesizable experimentally over a wide range of pressures. Our results not only clarify and complete the previously known structural phase diagram, but also provide new insights for understanding the Ba–Si binary system.