First-principles investigation of structural phase transitions and electronic properties of CuGaSe2 up to 100 GPa

First-principles calculations based on density functional theory have been carried out for the photovoltaic material CuGaSe2 up to 100 GPa to clarify its possible structural phase transitions and electronic properties. Energy–Volume analysis confirms that CuGaSe2 transforms from the tetragonal I4¯2d structure to the cubic Fm3¯m structure at 11.87 GPa with a volume reduction of 13.33%, which are in fair agreement with the experimental results of 13 GPa and 13%, respectively. We also predict another phase transformation of CuGaSe2 from the cubic Fm3¯m structure to the orthorhombic Cmcm structure at 51.4 GPa with a volume reduction of 0.49%. By using the HSE functional for Gap–Pressure   analysis, we find that the energy gap of I4¯2d structure broadens at a rate of 52.3 meV/GPa. By the band structure and the density of states calculation, we predict the metallic nature of the Fm3¯m and Cmcm phases and discuss the original reason of metallic nature under high pressure by the calculation of bond lengths and the charge redistribution.

► The structural phase transitions and electronic properties of CuGaSe2 are investigated under pressure. ► The phase transition from the tetragonal I4¯2d structure to the cubic Fm3¯m structure is confirmed. ► A new phase transformation for CuGaSe2 is found at 51.4 GPa with a volume reduction of 0.49%. ► The energy gap of I4¯2d structure for CuGaSe2 broadens at a rate of 52.3 meV/GPa. ► CuGaSe2 undergoes a transition from semiconductor to metal under the application of pressure.