Superconductivity of structurally disordered Y5Ir6Sn18.

The structural and physical properties of Y5Ir6Sn18 grown from Sn-flux as large single crystals are studied. Y5Ir6Sn18 crystallizes with a unique structure [space group Fm3̄m, a = 13.7706(1) Å], which is characterized by a strong disorder. A transmission electron microscopy (TEM) study indicated that the structural model of Y5Ir6Sn18 obtained from X-ray diffraction methods is an average description of a complex intergrowth of domains with different structural arrangements. The studied stannide is a type-II superconductor with a critical temperature Tc = 2.1 K, a rather weak electron-phonon coupling and conventional s-wave BCS-like mechanisms. Performed theoretical electronic band structure calculations indicated the inconsistency of an idealized structural model earlier reported for Y5Ir6Sn18.

Composition dependent polymorphism and superconductivity in Y3+x{Rh,Ir}4Ge13-x.

Polymorphism is observed in the Y3+xRh4Ge13-x series. The decrease of Y-content leads to the transformation of the primitive cubic Y3.6Rh4Ge12.4 [x = 0.6, space group Pm3̄n, a = 8.96095(9) Å], revealing a strongly disordered structure of the Yb3Rh4Sn13 Remeika prototype, into a body-centred cubic structure [La3Rh4Sn13 structure type, space group I4132, a = 17.90876(6) Å] for x = 0.4 and further into a tetragonal arrangement (Lu3Ir4Ge13 structure type, space group I41/amd, a = 17.86453(4) Å, a = 17.91076(6) Å) for the stoichiometric (i.e. x = 0) Y3Rh4Ge13. Analogous symmetry lowering is found within the Y3+xIr4Ge13-x series, where the compound with Y-content x = 0.6 is crystallizing with La3Rh4Sn13 structure type [a = 17.90833(8) Å] and the stoichiometric Y3Ir4Ge13 is isostructural with the Rh-analogue [a = 17.89411(9) Å, a = 17.9353(1) Å]. The structural relationships of these derivatives of the Remeika prototype are discussed. Compounds from the Y3+xRh4Ge13-x series are found to be weakly-coupled BCS-like superconductors with Tc = 1.25, 0.43 and 0.6, for x = 0.6, 0.4 and 0, respectively. They also reveal low thermal conductivity (<1.5 W K-1 m-1 in the temperature range 1.8-350 K) and small Seebeck coefficients. The latter are common for metallic systems. Y3Rh4Ge13 undergoes a first-order phase transition at Tf = 177 K, with signatures compatible to a charge density wave scenario. The electronic structure calculations confirm the instability of the idealized Yb3Rh4Sn13-like structural arrangements for Y3Rh4Ge13 and Y3Ir4Ge13.

Valence fluctuations in the 3D + 3 modulated Yb3Co4Ge13 Remeika phase.

Yb3Co4Ge13 is the first example of a Remeika phase with a 3D + 3 [space group P4̄3n(α,0,0)000(0,α,0)000(0,0,α)000; a = 8.72328(1) Å, α = 0.4974(2)] modulated crystal structure. A slight shift of the composition towards higher Yb-content (i.e. Yb3.2Co4Ge12.8) leads to the disappearance of the satellite reflections and stabilization of the disordered primitive cubic [space group Pm3̄n, a = 8.74072(2) Å] Remeika prototype structure. The stoichiometric structurally modulated germanide is a metal with hole-like charge carriers, where Yb-ions are in a temperature-dependent intermediate valence state varying from +2.60 to +2.66 for the temperature range 85-293 K. The valence fluctuations have been investigated by means of temperature dependent X-ray absorption spectroscopy, magnetic susceptibility and thermopower measurements.

Crystal, electronic and magnetic structures of a novel series of intergrowth carbometalates R4Co2C3 (R = Y, Gd, Tb).

A series of new ternary isostructural R4Co2C3 (R = Y, Gd, Tb) carbides was synthesized by annealing of arc-melted stoichiometric samples. The crystal structure of Tb4Co2C3 [space group P2/m, Pearson symbol mP18, a = 12.754(2) Å, b = 3.6251(4) Å, c = 7.0731(9) Å, ß = 105.601(6)°] was solved by direct methods from neutron powder diffraction data collected at 100 K. The room temperature unit cell parameters of the new phases were determined by X-ray powder diffraction technique. The crystal structure of Tb4Co2C3 is characterized as an intergrowth structure resulting from the stacking of alternating TbCoC (YCoC-type) and Tb2C (anti-CdCl2 type) fragments with a 2 : 1 ratio. Tb4Co2C3 orders ferromagnetically at TC = 35(1) K, whereas the isostructural Gd4Co2C3 reveals two magnetic transitions at TC1 = 82(3) K and TC2 = 13(2) K. Density functional theory (DFT) calculations confirm that the magnetic moments of the R4Co2C3 (R = Gd, Tb) carbides are exclusively due to the rare-earth elements. Y4Co2C3 is shown to be a Pauli-paramagnet by experimental and theoretical studies.

Crystal structure and superconducting properties of Sc5Ir6Sn18.

Sc5Ir6Sn18 crystallizes with a split variant of the Tb5Rh6Sn18 structure type (space group I41/acd, [Formula: see text] [Formula: see text], [Formula: see text] [Formula: see text]). DFT calculations confirmed the instability of the structural arrangement with the fully occupied and unsplit crystallographic sites. High quality single crystals were grown from a Sn melt. Sc5Ir6Sn18 is a diamagnetic metal showing a superconducting transition at a critical temperature [Formula: see text] K. The relatively low critical magnetic field [Formula: see text] 3.2 T as well as the obtained values of the specific heat ratio [Formula: see text] and energy-gap ratio [Formula: see text] suggest this system to be a weakly coupled BCS-like superconductor.