Effects of Sn and In Double-Doping on the Thermoelectric Performance of Cu3Sb1-x-ySnxInyS4 Famatinites

Abstract

Famatinite (Cu3SbS4 ) is a promising p-type thermoelectric material because of its low lattice thermal conductivity and high Seebeck coefficient. In this study, famatinite powders, double-doped with Sn (a BIV group element) and In (a BIII group element) to give Cu3Sb1-x-ySnxInyS4 (0.02 ≤ x ≤ 0.12 and 0.06 ≤ y ≤ 0.10), were synthesized by mechanical alloying and then consolidated by hot pressing. Phase analysis and microstructure observations were conducted over a range of doping levels, and the charge transport parameters and thermoelectric properties were evaluated. Except for the specimen with y = 0.10, in which the secondary phase CuInS2 was found, all the specimens exhibited a tetragonal famatinite phase without secondary phases. The Sn/In double doping increased the unit cell a-axis to 0.5387–0.5389 nm and changed the c-axis to 1.0744–1.0752 nm. As the temperature increased, the electrical conductivity decreased while the Seebeck coefficient increased, which indicates that the Sn/In double-doped famatinites have degenerate semiconductor characteristics. With increasing Sn and In content, the carrier concentration increased, so that the electrical conductivity increased and the Seebeck coefficient decreased. Cu3Sb0.80Sn0.12In0.08S4 exhibited the highest power factor, 0.87 mW m-1 K-2 at 623 K, with greatly increased thermal conductivity. Cu3Sb0.86Sn0.08In0.06S4 showed the highest value for the dimensionless figure of merit, ZT = 0.53 at 623 K, with a power factor of 0.78 mW m-1 K-2 and thermal conductivity of 0.90 W m-1 K-1.