Termoelektrické vlastnosti tuhých roztoků tetraedritu a tenantitu Cu₁₂Sb_4−xAs_xS₁₃ and Cu₁₀Co₂Sb_4−yAs_yS₁₃ (0 ≤ x, y ≤ 4)

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Tetrahedrites, a class of copper- and sulfur-rich minerals, exhibit inherently very low lattice thermal conductivity and adjustable electronic properties that make them interesting candidates for thermoelectric applications. Here, we investigate the influence of isovalent As substitution on the Sb site on the structural and transport properties (5–700 K) of the two solid solutions Cu₁₂Sb_4−xAs_xS₁₃ and Cu₁₀Co₂Sb_4−yAs_yS₁₃ (0 ≤ x, y ≤ 4). Electronic band structure calculations predict that As has only a weak influence on the valence bands and hence, on the p-type metallic character of Cu₁₂Sb₄S₁₃. In agreement with these predictions, all the samples of the series Cu₁₂Sb_4−xAs_xS₁₃ exhibit p-type metallic behavior with relatively low electrical resistivity and moderate thermopower values that only slightly evolve with the As content. In contrast, the substitution of Co for Cu in As-rich samples seems less favorable as suggested by a decrease in the Co concentration with increasing the As content. This trend leads to a concomitant increase in the electrical resistivity and thermopower leaving the ZT values practically unchanged with respect to purely Cu-based samples. As a result, peak ZT values ranging between 0.60 and 0.75 are achieved at 700 K for both series. The lack of significant variations in the ZT values confirms the robustness of the thermoelectric performances of tetrahedrites with respect to variations in the Sb-to-As ratio.