Inorganic Chemistry, Vol.52, No.14, 8272-8279, 2013
Cationic Clathrate of Type-III Ge172-xPxTey (y approximate to 21.5, x approximate to 2y): Synthesis, Crystal Structure and Thermoelectric Properties
A first germanium-based cationic clathrate of type-III, Ge129.3P42.7Te21.53, was synthesized and structurally characterized (space group P4(2)/mnm, a = 19.948(3) angstrom, c = 10.440(2) angstrom, Z = 1). In its crystal structure, germanium and phosphorus atoms form three types of polyhedral cages centered with Te atoms. The polyhedra share pentagonal and hexagonal faces to form a 3D framework. Despite the complexity of the crystal structure, the Ge129.3P42.7Te21.53 composition corresponds to the Zintl counting scheme with a good accuracy. Ge129.3P42.7Te21.53 demonstrates semiconducting/insulating behavior of electric resistivity, high positive Seebeck coefficient (500 mu V K-1 at 300 K), and low thermal conductivity (<0.92 m(-1) K-1) within the measured temperature range.