Structural and Thermoelectric Properties of Cu Substituted Type I Clathrates Ba8CuxSi~32−xGa~14

Abstract

With an attempt to improve the thermoelectric properties of type I clathrates in the Ba-Ga-Si system, we introduce Cu into the framework of the crystal structure. Single crystals are prepared in Ga-flux and characterized by X-ray diffraction techniques and transport measurements for the structural and thermoelectric properties. Our composition analyses show that only a small amount of Cu is determined in the clathrates. The single crystal X-ray diffraction data refinements confirm that Ga atoms prefer the 6c and 24k sites and avoid the 16i sites in the crystal structure. The small amount of Cu affects the crystal structure by compressing the tetrakaidecahedral cage along the direction perpendicular to the six-atom-ring plane. This could be the reason for the high charge carrier concentration, and low electrical resistivity and Seebeck coefficient. We analyze the principal mechanism for our observation and conclude that the Cu substitution can adjust some subtle details of the structure, maintaining the Zintl rule in the type I clathrates.