Superconducting transition temperatures in the electronic and magnetic phase diagrams of Sr2VFeAsO3-δ , a superconductor.

We elucidate the magnetic phases and superconducting (SC) transition temperatures (T c) in Sr2VFeAsO3-δ (21113V), an iron-based superconductor with a thick-blocking layer fabricated from a perovskite-related transition metal oxide. At low temperatures (T < 37.1 K), 21113V exhibited a SC phase in the range 0.031 ⩽ δ ⩽ 0.145 and an antiferromagnetic (AFM) iron sublattice in the range 0.267 ⩽ δ ⩽ 0.664. Mixed-valent vanadium exhibited a dominant AFM phase in 0.031 ⩽ δ ⩽ 0.088, and a partial ferrimagnetic (Ferri.) phase in the range 0.124 ⩽ δ ⩽ 0.664. The Ferri. phase was the most dominant at a δ value of 0.267, showing an AFM phase of Fe at T < 20 K. Increasing the spontaneous magnetic moments reduced the magnetic shielding volume fraction due to the SC phase. This result was attributed to the magnetic phase of vanadium, which dominates the superconductivity of Fe in 21113V. The T c-δ curve showed two maxima. The smaller and larger of T c maxima occurred at δ = 0.073 and δ = 0.145, respectively; the latter resides on the phase boundary between AFM and the partial Ferri. phases of vanadium. 21113V is a useful platform for verifing new mechanisms of T c enhancement in iron-based superconductors.

Discovery of the Pt-Based Superconductor LaPt5As.

A novel superconductor, LaPt5As, which exhibits a new crystal structure was discovered by high-pressure synthesis using a Kawai-type apparatus. A superconducting transition temperature was observed at 2.6 K. Depending on the sintering pressure, LaPt5As has superconducting and non-superconducting phases with different crystal structures. A sintering pressure of around 10 GPa is effective to form single-phase superconducting LaPt5As. This material has a very unique crystal structure with an extremely long c lattice parameter of over 60 Å and corner-sharing tetrahedrons composed of network-like Pt layers. Density functional theory calculations have suggested that the superconducting current flows through these Pt layers. Also, this unique layered structure characteristic of LaPt5As is thought to play a key role in the emergence of superconductivity. Furthermore, due to a stacking structure which makes up layers, various structural modifications for the LaPt5As family are conceivable. Since such a high-pressure synthesis using a Kawai-type apparatus is not common in the field of materials science, there is large room for further exploration of unknown phases which are induced by high pressure in various materials.

Crystal Structure, Electronic Structure, and Photocatalytic Activity of Oxysulfides: La2Ta2ZrS2O8, La2Ta2TiS2O8, and La2Nb2TiS2O8.

The novel oxysulfides La2Ta2ZrS2O8 (LTZSO), La2Ta2TiS2O8 (LTTSO), and La2Nb2TiS2O8 (LNTSO) were synthesized, and their crystal structures, electronic structures, and photocatalytic activities for water splitting under visible light were investigated. Density functional theory calculations showed that these compounds are direct-band-gap semiconductors. Close to the conduction band minimum, the main contribution to the band structure comes from the d orbitals of Zr or Ti ions, while the region near the valence band maximum is associated with the 3p orbitals of S ions. The absorption-edge wavelength was determined to be 540 nm for LTZSO and 700 nm for LTTSO and LNTSO. An analysis of the crystal structure using synchrotron X-ray diffraction revealed that these compounds contained antisite defects at transition metal ion sites, and these were considered to be the origin of the broad absorption at wavelengths longer than that corresponding to band-gap excitation. LTZSO was revealed to be active in the oxygen evolution reaction from aqueous solution containing a sacrificial electron acceptor under visible-light illumination. This result was supported by the band alignment and flat-band potential determined by photoelectron spectroscopy and Mott-Schottky plots.

Enhanced thermoelectric figure of merit in stannite-kuramite solid solutions Cu(2+x)Fe(1-x)SnS(4-y) (x = 0-1) with anisotropy lowering.

In this Article, we elucidate the structural and thermoelectric properties of stannite-kuramite solid solutions, Cu(2+x)Fe(1-x)SnS(4-y) (x = 0-1), with sulfur defects (y) ≤ 0.4. Structural analysis revealed that anisotropy decreases and Cu/Sn disorder increases with an increase in x. The samples with x = 0.8-1 exhibit degenerate conduction, whereas the Seebeck coefficient (S) remains relatively high, S ≈ 100 µV K(-1) for x = 0.8 at 300 K. Thermal conductivities (κ) of the solid solutions are in the range 10(-3)-10(-2) W cm(-1) K(-1), which is close to the κ value of silicon dioxide. The dimensionless figure of merit (ZT) reaches 0.044 for x = 0.8 at 300 K. The ZT is enhanced significantly by an increase in temperature and is doubly larger than that of x = 0 at 300 K. These findings allow us to attain higher ZT values through optimization of chemical composition.

Spin dynamics in iron-based layered superconductor (La0.87Ca0.13)FePO revealed by 31P and 139La NMR studies.

We report 31P and 139La NMR studies of (La0.87Ca0.13)FePO, which is a family member of the recently discovered superconductor LaFeAs(O1-xFx). In the normal state, Knight shift and nuclear spin-lattice relaxation rate divided by T (1/T1T) show that a Fermi-liquid state with moderate ferromagnetic fluctuations emerges below 30 K. From 1/T1T of 31P and 139La, a quasi-two- dimensional electronic structure is suggested, in which the FeP layer is more conductive than the LaO layer. In the superconducting (SC) state, although a clear Meissner signal was observed, 1/T1T increases below Tc, in contrast to a decrease of 1/T1T due to the opening of a SC gap, suggesting that novel low-energy spin dynamics develop in the SC state.

Superconductivity at 43 K in an iron-based layered compound LaO(1-x)F(x)FeAs.

The iron- and nickel-based layered compounds LaOFeP (refs 1, 2) and LaONiP (ref. 3) have recently been reported to exhibit low-temperature superconducting phases with transition temperatures T(c) of 3 and 5 K, respectively. Furthermore, a large increase in the midpoint T(c) of up to approximately 26 K has been realized in the isocrystalline compound LaOFeAs on doping of fluoride ions at the O2- sites (LaO(1-x)F(x)FeAs). Experimental observations and theoretical studies suggest that these transitions are related to a magnetic instability, as is the case for most superconductors based on transition metals. In the copper-based high-temperature superconductors, as well as in LaOFeAs, an increase in T(c) is often observed as a result of carrier doping in the two-dimensional electronic structure through ion substitution in the surrounding insulating layers, suggesting that the application of external pressure should further increase T(c) by enhancing charge transfer between the insulating and conducting layers. The effects of pressure on these iron oxypnictide superconductors may be more prominent than those in the copper-based systems, because the As ion has a greater electronic polarizability, owing to the covalency of the Fe-As chemical bond, and, thus, is more compressible than the divalent O2- ion. Here we report that increasing the pressure causes a steep increase in the onset T(c) of F-doped LaOFeAs, to a maximum of approximately 43 K at approximately 4 GPa. With the exception of the copper-based high-T(c) superconductors, this is the highest T(c) reported to date. The present result, together with the great freedom available in selecting the constituents of isocrystalline materials with the general formula LnOTMPn (Ln, Y or rare-earth metal; TM, transition metal; Pn, group-V, 'pnicogen', element), indicates that the layered iron oxypnictides are promising as a new material platform for further exploration of high-temperature superconductivity.

Nickel-based oxyphosphide superconductor with a layered crystal structure, LaNiOP.

A layered oxyphosphide, LaNiOP, was synthesized by solid-state reactions. This crystal was confirmed to have a layered structure composed of an alternating stack of (La(3+)O(2-))(+) and (Ni(2+)P(3-))(-). We found that the resulting LaNiOP shows a superconducting transition at approximately 3 K. This material exhibited metallic conduction and Pauli paramagnetism in the temperature range of 4-300 K. The resistivity sharply dropped to zero and the magnetic susceptibility became negative at <4 K, indicating that a superconducting transition occurs. The volume fraction of the superconducting phase estimated from the diamagnetic susceptibility reached approximately 40 vol % at 1.8 K, substantiating that LaNiOP is a bulk superconductor.

Iron-based layered superconductor: LaOFeP.

We report superconductivity in an iron-based layered oxy-pnictide LaOFeP. LaOFeP is composed of an alternate stack of lanthanum oxide (La3+O2-) and iron pnictide (Fe2+P3-) layers. Magnetic and electrical resistivity measurements verify the occurrence of the superconducting transition at approximately 4 K.