Preparation and thermoelectric properties of sintered type-I clathrates K8Ga(x)Sn(46-x).

Polycrystalline clathrate samples of nominal K(8)Ga(x)Sn(46-x) were prepared by the spark plasma sintering method to investigate their crystal structures, mobilities and thermoelectric properties. The samples almost had a single-phase type-I clathrate structure, and their relative densities reached as high as 98%. The room-temperature mobility of the K(8)Ga(8)Sn(38) sample was 25 cm(2) V(-1) s(-1), which substantially exceeded the reported mobilities of Rb- and Cs-containing Sn clathrates. Moreover, the mobility was larger than those of the type-I Ba(8)Ga(16)Sn(30), which had more Ga substituting atoms in unit cell. A higher mobility might accordingly be achieved in thermoelectric clathrates with a smaller number of substituting atoms. Their electrical conductivities and Seebeck coefficients in the temperature range 300-450 K were typical of n-type doped semiconductors in the extrinsic region while their room-temperature lattice thermal conductivities were as low as approximately 11 mW cm(-1) K(-1). The maximum dimensionless figure of merit ZT was estimated to be 0.27 at 490 K from the Seebeck coefficient of -262 microV K(-1) and the electrical conductivity of 96 S cm(-1) for the K(8)Ga(8)Sn(38) sample with a carrier concentration of 2.9 x 10(19) cm(-3).

Electron-phonon interactions of Si100 and Ge100 superconductors with Ba atoms inside.

The absolute density of states of isostructural Ba24Si100 and Ba24Ge100 near the Fermi level, which is very relevant for discussion on phonon-mediated superconductivity, is quantitatively evaluated to be 0.28 states eV⁻¹/Ge atom and 0.18 states eV⁻¹/Si   atom by combining soft x-ray photoelectron spectroscopy and magnetic susceptibility measurements. The energetics of the anharmonic motions of the endohedral Ba atoms are also discussed on the basis of the 4d-core-level spectra. The discussion based on these important physical parameters concludes that the unique electron-phonon interactions do not occur due to the local Jahn-Teller distortion of the fragile open cage structure in the phonon-mediated BCS formalism. Compounds with a rigid cage would be essential to give rise to anticipated unique interactions as a key ingredient favored for superconducting paring.

Soft x-ray photoelectron spectroscopy study of type-I clathrates.

Extensive soft x-ray photoelectron spectroscopy studies are performed on Ba8 Ga16 Ge30 (BGG) and Sr8Ga16Ge30 (SGG) single crystals ranging from Fermi to core levels, at a high-energy facility. Valence band x-ray photoelectron spectroscopy (XPS) experiments with theoretical calculations revealed that the valence band is mainly constructed by the Ge/Ga 4s and 4p wave functions with little contribution of the Ba/Sr atomic orbitals. Surprisingly, unexpected features evidencing the different shift for the 2a- and 6d- sites between Ba 4d and Sr 3d are observed. The detailed analyses including theoretical support by first-principles band-structure calculations lead to the conclusion that the component distributions of the larger tetrakaidecahedral cage are different depending on the endohedral atoms, which contrasts with the past consensus that BGG and SGG have the same framework structure. This may give thorough reconsiderations on earlier interpretations of experimental data.