This paper has been published in Bulletin of the Chemical Society of Japan, which can be viewed at the following URL: http://doi.org/10.1246/bcsj.20150110 Cs2SnI6, a variant of perovskite CsSnI3, is expected for a photovoltaic material. Based on a
simple ionic model, it is expected that Cs2SnI6 is composed of Cs+, I-, and Sn4+ ions and that the band gap is primarily made of occupied I- 5p6 valence band maximum (VBM) and unoccupied Sn4+ 5s conduction band minimum (CBM) similar to SnO2. In this work, we performed density functional theory (DFT) calculations and revealed that the real oxidation state of the Sn ion in Cs2SnI6 is +2 similar to CsSnI3. The +2 oxidation state of Sn originates from 2 ligand holes in the [SnI6]2- octahedron unit, where the ligand [I6] cluster has the apparent [I66-L+2]4- oxidation state, because the band gap is formed mainly by occupied I 5p VBM and unoccupied I 5p CBM. The +2 oxidation state of Sn and the band gap are originated from the intracluster hybridization and stabilized by the strong covalent interaction between Sn and I.
We report anistropy in superconducting and normal state of NiBi3 single crystals with Tc = 4.06 K. The magnetoresistance results indicate the absence of scattering usually associated with ferromagnetic metals, suggesting the absence of bulk long rang
e magnetic order below 300 K. However, the electron spin resonance results demonstrate that ferromagnetism fluctuations exist on the surface of the crystal below 150K.
Understanding iron based superconductors requires high quality impurity free single crystals. So far they have been elusive for beta-FeSe and extraction of intrinsic materials properties has been compromised by several magnetic impurity phases. Herei
n we report synchrotron - clean beta-FeSe superconducting single crystals grown via LiCl/CsCl flux method. Phase purity yields evidence for a defect induced weak ferromagnetism that coexists with superconductivity below Tc. In contrast to Fe1+yTe - based superconductors, our results reveal that the interstitial Fe(2) site is not occupied and that all contribution to density of states at the Fermi level must come from in-plane Fe(1).
We report the evolution of thermal transport properties of iron-based superconductor K$_x$Fe$_{2-y}$Se$_2$ with sulfur substitution at Se sites. Sulfur doping suppresses the superconducting $T_c$ as well as the Seebeck coefficient. The Seebeck coeffi
cient of all crystals in the low temperature range can be described very well by diffusive thermoelectric response model. The zero-temperature extrapolated value of Seebeck coefficient divided by temperature $S/T$ gradually decreases from $-0.48 mu V/K^2$ to a very small value $sim$ 0.03 $mu$V/K$^2$ where $T_c$ is completely suppressed. The normal state electron Sommerfeld term ($gamma_n$) of specific heat also decreases with the increase of sulfur content. The dcrease of $S/T$ and $gamma_n$ reflects a suppression of the density of states at the Fermi energy, or a change in the Fermi surface that would induce the suppression of correlation strength.
