We prepared the type-I Ba8AuxSi46-x (x=5.5, 5.4 and 5.33) clathrates with p-type conduction by arc-melting and subsequent annealing. The Seebeck coefficients of all as-synthesized samples were negative. After annealing, in the case of x=5.4 and 5.5, the Seebeck coefficients changed to positive, and in the case of x=5.33, this value was negative for the annealed sample. The chemical composition revealed that Au content in the Ba8AuxSi46-x clathrates increased after the annealing process. The backscattered electron images showed that there were many Au-excess regions which were not clathrate structure in the as-synthesized samples, and these regions decreased and even disappeared after the annealing process. The disappearing of Au-excess regions can be explained by the diffusion of Au atoms from the Au-excess regions into the clathrates. Based on these results, annealing treatment can be used to tune the carrier conduction by controlling the content of Au for type-I Ba8AuxSi46-xclathrates.

We have synthesized single crystalline Ba8AlxSix-46 clathrates by using the flux Czochralski (CZ) method with Al-rich melt. The specific electric resistivity, the Seebeck coefficient and the power factor of single crystalline Ba8Al14Si32 were 0.73 mΩcm,70.0μV/K and 6.8×10-4 V2/K2Ωm, respectively. These values are higher than that of single crystalline Ba8Al12Si34 clathrate because of the reduced carrier concentration. It is indicated that Al contents and the carrier concentration of single crystalline Ba8AlxSi46-x can be controlled by using the flux Czochralski method.