Effect of Sn substitution on the thermoelectric properties of synthetic tetrahedrite

Abstract

The present study reports the effect of Sn substitution on the structural and thermoelectric properties of synthetic tetrahedrite (Cu₁₂Sb₄S₁₃) system. The samples were prepared with the intended compositions of Cu₁₂Sb_4–xSn_xS₁₃ (x = 0.25, 0.35, 0.5, 1) and sintered using spark plasma sintering. A detailed structural characterization of the samples revealed tetrahedrite phase as the main phase with Sn substituting at both Cu and Sb sites instead of only Sb site. The theoretical calculations using density functional theory revealed that Sn at Cu(1) 12d or Cu(2) 12e site moves the Fermi level (E_F) toward the band gap, whereas Sn at Sb 8c site introduces hybridized hole states near E_F. Consequently, a relatively high optimum power factor of 1.3 mW/mK² was achieved by the x = 0.35 sample. The Sn-substituted samples exhibited a significant decrease in the total thermal conductivity (κ_T) compared to the pristine composition (Cu₁₂Sb₄S₁₃), primarily because of reduced electronic thermal conductivity. Due to an optimum power factor (1.3 mW/mK₂) and reduced thermal conductivity (0.9 W/mK), a maximum zT of 0.96 at 673 K was achieved for x = 0.35 sample, which is nearly 40% increment compared to that of the pristine (Cu₁₂Sb₄S₁₃) sample.