Crystallographic and optical properties and band structures of CuInSe2, CuIn3Se5, and CuIn5Se8 phases in Cu-poor Cu2Se-In2Se3 pseudo-binary system

Abstract

We prepared CuInSe2 and Cu-poor Cu-In-Se (CIS) phases such as CuIn3Se5 and CuIn5Se8 in the composition of (1 % x)Cu2Se-(x)In2Se3 with 0.5 : x : 1.0. The crystal structure of the sample changed from chalcopyrite-type CuInSe2 to hexagonal CuIn5Se8 through stannite-type CuIn3Se5 with increasing x (decreasing Cu/In ratio). The band-gap energies of Cu-poor CIS samples, i.e., CuIn3Se5 (1.17 eV) and CuIn5Se8 (1.22-1.24 eV), are larger than that of chalcopyrite-type CuInSe2 (0.99 eV). The energy levels of the valence band maxima (VBMs) were estimated from the ionization energy by photoemission yield spectroscopy (PYS) measurements. The energy levels of the VBMs of the Cu-poor CIS samples decrease rapidly with decreasing Cu/In ratio. The ionization energy of stannite-type CuIn3Se5 is 0.4 eV larger than that of chalcopyrite-type CuInSe2. The ionization energy of CuIn5Se8 is 0.1-0.3 eV larger than that of CuIn3Se5. These results show that the energy position of the VBM from the vacuum level of Cu-poor CIS phases, such as CuIn3Se5 and CuIn5Se8, is deeper than that of CuInSe2. To understand the electronic structure of Cu-poor CIS compounds, we performed first-principles band structure calculations on stannite-type CuIn5Se8 and a reference compound, tetragonal chalcopyrite-type CuInSe2, using the HSE06 nonlocal screened hybrid density functional. The calculated band-gap energy of tetragonal stannite-type CuIn5Se8 (1.19 eV) is larger than that of chalcopyrite-type CuInSe2 (0.94 eV).