Pressure-induced structural changes and insulator-metal transition in layered bismuth triiodide, BiI₃: a combined experimental and theoretical study

Noting that BiI3 and the well-known topological insulator (TI) Bi2Se3 have the same high symmetry parent structures, and that it is desirable to find a wide-band gap TI, we determine here the effects of pressure on the structure, phonons and electronic properties of rhombohedral BiI3. We report a pressure-induced insulator-metal transition near 1.5 GPa, using high pressure electrical resistivity and Raman measurements. X-ray diffraction studies, as a function of pressure, reveal a structural peculiarity of the BiI3 crystal, with a drastic drop in c/a ratio at 1.5 GPa, and a structural phase transition from rhombohedral to monoclinic structure at 8.8 GPa. Interestingly, the metallic phase, at relatively low pressures, exhibits minimal resistivity at low temperatures, similar to that in Bi2Se3. We corroborate these findings with first-principles calculations and suggest that the drop in the resistivity of BiI3 in the 1–3 GPa range of pressure arises possibly from the appearance of an intermediate crystal phase with a lower band-gap and hexagonal crystal structure. Calculated Born effective charges reveal the presence of metallic states in the structural vicinity of rhombohedral BiI3. Changes in the topology of the electronic bands of BiI3 with pressure, and a sharp decrease in the c/a ratio below 2 GPa, are shown to give rise to changes in the slope of phonon frequencies near that pressure.