A combined metal-halide/metal flux synthetic route towards type-I clathrates: crystal structures and thermoelectric properties of A8Al8Si38 (A = K, Rb, and Cs).

Single-phase samples of the compounds K8Al8Si38 (1), Rb8Al8Si38 (2), and Cs7.9Al7.9Si38.1 (3) were obtained with high crystallinity and in good quantities by using a novel flux method with two different flux materials, such as Al and the respective alkali-metal halide salt (KBr, RbCl, and CsCl). This approach facilitates the removal of the product mixture from the container and also allows convenient extraction of the flux media due to the good solubility of the halide salts in water. The products were analyzed by means of single-crystal X-ray structure determination, powder X-ray and neutron diffraction experiments, (27)Al-MAS NMR spectroscopy measurements, quantum chemical calculations, as well as magnetic and transport measurements (thermal conductivity, electrical resistivity, and Seebeck coefficient). Due to the excellent quality of the neutron diffraction data, the difference between the nuclear scattering factors of silicon and aluminum atoms was sufficient to refine their mixed occupancy at specific sites. The role of variable-range hopping for the interpretation of the resistivity and the Seebeck coefficient is discussed.