Synthesis and Superconductivity of a Strontium Digermanide SrGe2-δ with ThSi2 Structure.

We have succeeded in crystallizing a new strontium digermanide (SrGe2-δ) with the ThSi2-type structure (tetragonal SrGe2), which is theoretically predicted to compete with the EuGe2-type one (trigonal SrGe2) under pressure. The tetragonal SrGe2 appeared as a metastable phase in samples at approximately 900 °C under a pressure of 2 GPa. X-ray diffraction studies show that the tetragonal SrGe2 is formed by the reaction between trigonal SrGe2 and excess Sr. The composition of the tetragonal SrGe2 was analyzed to be SrGe1.66(4). Lattice parameters for the tetragonal SrGe2 are determined to be a = 4.559(4) Å and c = 14.42(1) Å. The tetragonal SrGe2 shows metallic resistivity behavior and exhibits superconductivity with a critical temperature (Tc) of 7.3 K, which is the highest among compounds with the ThSi2-type structure. Superconducting properties of the tetragonal SrGe2, such as the upper critical field, and the effect of pressure on Tc, are presented and superconductivity is discussed on the basis of electronic band structure calculations.

Crystal structure and superconductivity of BaIr2Ge7 and Ba3Ir4Ge16 with two-dimensional Ba-Ge networks.

The Ba-Ir-Ge ternary compounds BaIr2Ge7 and Ba3Ir4Ge16 exhibit superconductivity (SC) at 2.5 and 5.2 K, respectively. Detailed single-crystal structural analysis revealed that these compounds share unique quasi-two-dimensional networks composed of crown-shaped Ge rings that accommodate Ba atoms at the center, referred to as "edge-shared crown-shaped BaGe16 polyhedra". The layered Ba-Ge network yielded a modest anisotropy of 1.3-1.4 in the upper critical field, which is in good agreement with the band structure calculations. The Ba-Ge structural unit is similar to cage structures seen in various clathrates in which the anharmonic vibration of the central atoms, the so-called "rattling" behavior, brings about strong-coupling SC. However, each Ba-Ge unit is relatively small compared to these materials, which likely excludes the possibility of unconventional SC.

Emergence of superconductivity in "32522" structure of (Ca3Al2O(5-y))(Fe2Pn2) (Pn = As and P).

Using a high-pressure technique, we have successfully synthesized (Ca(3)Al(2)O(5-y))(Fe(2)Pn(2)) (Pn = As and P), the first iron-based superconductors with the perovskite-based "32522" structure to be reported. The transition temperature (T(c)) is 30.2 K for Pn = As and 16.6 K for Pn = P. The emergence of superconductivity is ascribed to the small tetragonal a-axis lattice constant of the materials. From these results, an empirical relationship is established between the a-axis lattice constant and T(c) in iron-based superconductors, which offers a practical guideline for exploring new superconductors with higher T(c).

Cyclotron resonance and mass enhancement by electron correlation in KFe2As2.

Cyclotron resonance (CR) measurements for the Fe-based superconductor KFe(2)As(2) are performed. One signal for CR is observed, and is attributed to the two-dimensional α Fermi surface at the Γ point. We found a large discrepancy in the effective masses of CR [(3.4±0.05)m(e) (m(e) is the free-electron mass)] and de Haas-van Alphen results, a direct evidence of mass enhancement due to electronic correlation. A comparison of the CR and de Haas-van Alphen results shows that both intra- and interband electronic correlations contribute to the mass enhancement in KFe(2)As(2).

Ferroelectricity from iron valence ordering in the charge-frustrated system LuFe2O4.

Ferroelectric materials are widely used in modern electric devices such as memory elements, filtering devices and high-performance insulators. Ferroelectric crystals have a spontaneous electric polarization arising from the coherent arrangement of electric dipoles (specifically, a polar displacement of anions and cations). First-principles calculations and electron density analysis of ferroelectric materials have revealed that the covalent bond between the anions and cations, or the orbital hybridization of electrons on both ions, plays a key role in establishing the dipolar arrangement. However, an alternative model-electronic ferroelectricity-has been proposed in which the electric dipole depends on electron correlations, rather than the covalency. This would offer the attractive possibility of ferroelectric materials that could be controlled by the charge, spin and orbital degrees of freedom of the electron. Here we report experimental evidence for ferroelectricity arising from electron correlations in the triangular mixed valence oxide, LuFe(2)O(4). Using resonant X-ray scattering measurements, we determine the ordering of the Fe(2+) and Fe(3+) ions. They form a superstructure that supports an electric polarization consisting of distributed electrons of polar symmetry. The polar ordering arises from the repulsive property of electrons-electron correlations-acting on a frustrated geometry.

Absence of an appreciable iron isotope effect on the transition temperature of the optimally doped SmFeAsO(1-y) Superconductor.

We report the iron (Fe) isotope effect on the transition temperature (T(c)) in oxygen-deficient SmFeAsO(1-y), a 50-K-class, Fe-based superconductor. For the optimally doped samples with T(c) = 54 K, a change of the average atomic mass of Fe (M(Fe)) causes a negligibly small shift in T(c), with the Fe isotope coefficient (α(Fe)) as small as -0.024 ± 0.015 (where α(Fe)=-d lnT(c)/dlnM(Fe)). This result contrasts with the finite, inverse isotope shift observed in optimally doped (Ba,K)Fe2As2, indicating that the contribution of the electron-phonon interaction markedly differs between these two Fe-based high-T(c) superconductors.

Inverse iron isotope effect on the transition temperature of the (Ba,K)Fe2As2 superconductor.

We report that the (Ba,K)Fe(2)As(2) superconductor (transition temperature, T(c) approximately 38 K) has an inverse iron isotope coefficient alpha(Fe) = -0.18(3) (where T(c) approximately M(-alphaFe) and M is the iron isotope mass); i.e., the sample containing the large iron isotope mass depicts a higher T(c). Systematic inverse shifts in T(c) were clearly observed between the samples using three types of Fe isotopes ((54)Fe, natural Fe, and (57)Fe). This indicates the first evidence of the inverse isotope effect in high-T(c) superconductors. This anomalous mass dependence on T(c) implies an exotic coupling mechanism in Fe-based superconductors.

Large enhancement of superconducting transition temperature of SrBi3 induced by Na substitution for Sr.

The Matthias rule, which is an empirical correlation between the superconducting transition temperature (Tc) and the average number of valence electrons per atom (n) in alloys and intermetallic compounds, has been used in the past as a guiding principle to search for new superconductors with higher Tc. The intermetallic compound SrBi3 (AuCu3 structure) exhibits a Tc of 5.6 K. An ab-initio electronic band structure calculation for SrBi3 predicted that Tc increases on decreasing the Fermi energy, i.e., on decreasing n, because of a steep increase in the density of states. In this study, we demonstrated that high-pressure (~ 3 GPa) and low-temperature ( < 350 °C) synthesis conditions enables the substitution of Na for about 40 at.% of Sr. With a consequent decrease in n, the Tc of (Sr,Na)Bi3 increases to 9.0 K. A new high-Tc peak is observed in the oscillatory dependence of Tc on n in compounds with the AuCu3 structure. We have shown that the oscillatory dependence of Tc is in good agreement with the band structure calculation. Our experiments reaffirm the importance of controlling the number of electrons in intermetallic compounds.