First principles study of electronic structure and thermoelectric transport in tin selenide and phase separated tin selenide–copper selenide alloy

Abstract

The electronic structure and thermoelectric transport in SnSe and its alloy with Cu2Se have been studied using the first principles technique and semi classical Boltzmann transport theory. Our study reveals that SnSe is p-type with indirect band gap of 0.66 eV, while the alloy is phase separated and n-type with negligible indirect band gap of 0.064 eV. In both cases, two fold degeneracy in band extrema have been observed within the range of 25 meV. Delocalization of Se lone pair has been observed due to Cu substitution in Sn sites, which is supposed to lower its lattice thermal conductivity. A chemical potential map has been generated obeying thermodynamic restrictions to predict the possible existence of secondary phases. Our study shows the existence of SnSe2 as a secondary phase, while the possibility of Cu2Se as a secondary phase is negligible due to its higher formation energy. We calculated the transport coefficients as a function of carrier concentration and temperature to understand the range of optimized thermoelectric performance. The transport coefficients are similar along in plane direction whereas significant deviation is observed along the cross plane direction due to anisotropy in effective masses in SnSe. The effective masses are more isotropic in alloy than SnSe, thus transport properties show less anisotropy along three directions. Significant contribution of bipolar transport is observed in SnSe, while that is not noticed in the alloy. The behaviors of the Seebeck coefficients in both cases are discussed in terms of Mott’s theory and density of states modification near Fermi energy. Electron mobilities limited by acoustic phonon, ionized impurities, alloy scattering and inter carrier scattering have been examined relying on deformation potential approach and effective mass theory. The results indicate that acoustic phonon scattering is dominant scattering mechanism in SnSe over inter carrier scattering, whereas for the alloy the former contribute very weakly. Ionized impurity scattering and inter carrier scattering are most dominant in the alloy. Alloy scattering with U = 2 eV also contribute significantly.