Improved thermoelectric performance of solid solution Cu₄Sn_7.5S₁₆ through isoelectronic substitution of Se for S

Cu-Sn-S family of compounds have been considered as very competitive thermoelectric candidates in recent years due to their abundance and eco-friendliness. The first-principles calculation reveals that the density of states (DOS) increases in the vicinity of the Fermi level (E_f) upon an incorporation of Se in the Cu₄Sn_7.5S_16-xSe _x (x = 0-2.0) system, which indicates the occurrence of resonant states. Besides, the formation of Cu(Sn)-Se network upon the occupation of Se in S site reduces the Debye temperature from 395 K for Cu₄Sn₇S₁₆ (x = 0) to 180.8 K for Cu₄Sn_7.5S_16-xSe _x (x = 1.0). Although the point defects mainly impact the phonon scattering, an electron-phonon interaction also bears significance in the increase in phonon scattering and the further reducion of lattice thermal conductivity at high temperatures. As a consequence, the resultant TE figure of merit (ZT) reaches 0.5 at 873 K, which is 25% higher compared to 0.4 for Cu₄Sn_7.5S₁₆.