Annealing Time Dependence on the Phase Equilibria and Thermoelectric Property of Type-I Ba8Cu6Ag2Si38 Clathrate

Poly-crystalline Ba8Cu6Ag2Si38 clathrates were synthesized by the arc-melting method and a subsequent annealing treatment. The main phase of all the samples was type-I clathrate. However, there were some precipitates which rich in Cu, Ag or Si in the grain boundary of the as-synthesized sample and the precipitates gradually reduced with the increase of annealing time. The transition metal content in the clathrate increased with the annealing time because of the diffusion of the Cu and Ag atoms from precipitates phase into clathrates phase. The as-synthesized sample was n-type material. For the 576 hours annealed sample, the carrier type changed from n-type to p-type because of the increase of Cu and Ag content in the clathrate.