Atomic-scale phonon scatterers in thermoelectric colusites with a tetrahedral framework structureElectronic supplementary information (ESI) available. See DOI: 10.1039/c8ta08248k

Copper-based chalcogenides with tetrahedral framework structures have been attracting increasing attention as environmentally friendly thermoelectric materials. A representative group of such thermoelectric chalcogenides is the Cu 26 A 2 M 6 S 32 (A = V, Nb, Ta; M = Ge, Sn) family of colusites, which exhibit low electrical resistivity, a large Seebeck coefficient, and low thermal conductivity; these properties are necessary for efficient thermal-to-electronic energy conversion. Here, we show the impact of crystal structure on the lattice thermal conductivity of colusite with A = Nb, M = Sn. The crystal structure can be modified by controlling the cationic compositions and the deficiency in the sulfur content as Cu 26− x Nb 2 Sn 6+ x S 32− δ . The Cu/Sn ratio is found to be the key parameter for exsolution into distinct phases with ordered and disordered arrangements of cations. For the ordered-structure phase, sulfur sublimation induces atomic-scale defects/disordered states including interstitial defects, anti-site defects, and site splitting, which function as strong phonon scatterers, and the lowest lattice thermal conductivity of ∼0.5 W K −1 m −1 is achieved for the modified ordered structure. This finding provides a simple approach to modifying the crystal structure of thermoelectric chalcogenides via the loss of anions to reduce their lattice thermal conductivity. Atomic-scale defects/disorded states induced by sulfur sublimation are responsible for reduced lattice thermal conductivity of thermoelectric colusite.