Atomic-scale phonon scatterers in thermoelectric colusites with a tetrahedral framework structure

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 Cu26-xNb2Sn6+xS32-. 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 approximate to 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.