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The present study reports the effect of Sn substitution on the structural and thermoelectric properties of synthetic tetrahedrite (Cu 12 Sb 4 S 13 ) system. The samples were prepared with the intended compositions of Cu 12 Sb 4- x Sn x S 13 ( 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/mK 2 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 (Cu 12 Sb 4 S 13 ), primarily because of reduced electronic thermal conductivity. Due to an optimum power factor (1.3 mW/mK 2 ) 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 (Cu 12 Sb 4 S 13 ) sample.

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite