Atomic and electronic structures evolution of the narrow band gap semiconductor Ag2Se under high pressure

Non-trivial electronic properties of silver telluride and other chalcogenides, such as the presence of a topological insulator state, electronic topological transitions, metallization, and the possible emergence of superconductivity under pressure have attracted attention in recent years. In this work, we studied the electronic properties of silver selenide (Ag2Se). We performed direct current electrical resistivity measurements, in situ Raman spectroscopy, and synchrotron x-ray diffraction accompanied by ab initio calculations to explore pressure-induced changes to the atomic and electronic structure of Ag2Se. The temperature dependence of the electrical resistivity was measured up to 30 GPa in the 4–300 K temperature interval. Resistivity data showed an unusual increase in the thermal energy gap of phase I, which is a semiconductor under ambient conditions. Recently, a similar effect was reported for the 3D topological insulator Bi2Se3. Raman spectroscopy studies revealed lattice instability in phase I indicated by the softening of observed vibrational modes with pressure. Our hybrid functional band structure calculations predicted that phase I of Ag2Se would be a narrow band gap semiconductor, in accordance with experimental results. At a pressure of ~7.5 GPa, Ag2Se underwent a structural transition to phase II with an orthorhombic Pnma structure. The temperature dependence of the resistivity of Ag2Se phase II demonstrated its metallic character. Ag2Se phase III, which is stable above 16.5 GPa, is also metallic according to the resistivity data. No indication of the superconducting transition is found above 4 K in the studied pressure range.