Thermoelectric Properties of Bi Doped Tetrahedrite

Bi doped tetrahedrites with nominal compositions of Cu12Sb4-x Bi (x) S-13 (x = 0, 0.2, 0.4, 0.6, 0.8) were synthesized by the solid state reaction method. Powder x-ray diffraction patterns confirmed that Cu12Sb4S13 (tetrahedrite structure) was the main phase, along with Cu3SbS4 and Cu3SbS3 as the secondary phases. Electron probe microanalysis provided the elemental composition of all the samples. It was confirmed that the main phase is the tetrahedrite phase with slight deviations in the stoichiometry. All the transport properties were measured between 423 K and 673 K. The electrical resistivity increased with an increase in Bi content for all the samples, possibly induced by the variation in the carrier concentration, which may be due to the influence of impurity phases. The increase in electrical resistivity with an increase in temperature indicates the degenerate semiconducting nature of the samples. The absolute Seebeck coefficient is positive throughout the temperature range indicating the p-type nature of the samples. The Seebeck coefficient for all the samples increased with an increase in Bi content as electrical resistivity. The variation of electrical resistivity and the Seebeck coefficient with doping can be attributed to the changes in the carrier concentration of the samples. The total thermal conductivity increases with an increase in temperature and decreases with an increase in the Bi content that could be due to the reduction in carrier thermal conductivity. The highest thermoelectric figure of merit (zT) similar to 0.84 at 673 K was obtained for the sample with x = 0.2 due to lower thermal conductivity (1.17 W/m K).