Daigorou Hirai

Superconductivity in Layered Pnictides BaRh2P2 and BaIr2P2

Bulk superconductivity was discovered in BaRh2P2 (Tc = 1.0 K) and BaIr2P2 (Tc = 2.1 K), which are isostructural to (Ba,K)Fe2As2, indicative of the appearance of superconductivity over a wide variety of layered transition metal pnictides. The electronic specific heat coefficient gamma in the normal state, 9.75 and 6.86 mJ/mol K2 for BaRh2P2 and BaIr2P2 respectively, indicate that the electronic density of states of these two compounds are moderately large but smaller than those of Fe pnictide superconductors. The Wilson ratio close to 1 indeed implies the absence of strong electron correlations and magnetic fluctuations unlike Fe pnictides.

Emergence of superconductivity in BaNi[subscript 2](Ge[subscript 1-x]P[subscript x])[subscript 2] at a structural instability

The physical properties and structural evolution of the 122-type solid solution BaNi2(Ge1-xPx)2 are reported. The in-plane X-X (X = Ge1-xPx) dimer formation present in the end member BaNi2Ge2, which results in a structural transition to orthorhombic symmetry, is completely suppressed to zero temperature on P substitution near x = 0.7, and a dome-shape superconducting phase with a maximum Tc = 2.9 K emerges. Clear indications of phonon softening and enhanced electron-phonon coupling are observed at the composition of the structural instability. Our findings show that dimer breaking offers new possibilities as a tuning parameter of superconductivity.

Fabrication of (111)-oriented Ca0.5Sr0.5IrO3/SrTiO3 superlattices—A designed playground for honeycomb physics

We report the fabrication of (111)-oriented superlattice structures with alternating 2m-layers (m = 1, 2, and 3) of Ca0.5Sr0.5IrO3 perovskite and two layers of SrTiO3 perovskite on SrTiO3(111) substrates. In the case of m = 1 bilayer films, the Ir sub-lattice is a buckled honeycomb, where a topological state may be anticipated. The successful growth of superlattice structures on an atomic level along the [111] direction was clearly demonstrated by superlattice reflections in x-ray diffraction patterns and by atomically resolved transmission electron microscope images. The ground states of the superlattice films were found to be magnetic insulators, which may suggest the importance of electron correlations in Ir perovskites in addition to the much discussed topological effects.

Spin and orbital contributions to magnetically ordered moments in 5d layered perovskite Sr2IrO4.

The ratio of orbital (L) and spin (S) contributions to the magnetically ordered moments of a 5d transition metal oxide, Sr2IrO4 was evaluated by nonresonant magnetic x-ray diffraction. We applied an improved experimental setting that minimized the experimental error, in which we varied only the linear polarization of incident x ray at a fixed scattering angle. Strong polarization dependence of the intensity of magnetic diffraction was observed, from which we conclude that the ordered moments contain substantial contribution from the orbital degree of freedom with the ratio of /∼5.0, evidencing the pronounced effect of spin-orbit coupling. The obtained ratio is close to, but slightly larger than the expected value for the ideal J(eff) = 1/2 moment of a spin-orbital Mott insulator, ||/|| = 4, which cannot be accounted for by the redistribution of orbital components within the t(2g) bands associated with the elongation of the IrO6 octahedra.

Semimetallic transport properties of epitaxially stabilized perovskite CaIrO3 films

We report on the synthesis and transport properties of perovskite (Pv) CaIrO3 thin films. The Pv phase of CaIrO3 was stabilized by epitaxial growth on SrTiO3, (LaAlO3)0.3(Sr2AlTaO6)0.7, and LaAlO3 substrates with strong tensile, weak tensile, and compressive strains, respectively. The resistivity of these films showed a poorly metallic behavior. The Hall resistivity exhibited a sign change as a function of temperature and a nonlinear magnetic-field dependence, which clearly indicated the coexistence of electrons and holes and hence supported that Pv CaIrO3 films are semimetallic. The observed robustness of the semimetallic ground state against tensile and compressive strains is consistent with the presence of symmetry-protected Dirac points (nodes) around the Fermi level that prohibits the system from becoming a band insulator.

Superconductivity at 3.7 K in Ternary Silicide Li2IrSi3

We report the discovery of superconductivity at Tc = 3.7 K in the new ternary lithium silicide Li2IrSi3. The crystal structure of Li2IrSi3 consists of IrSi6 antiprisms connected by Si triangles, giving rise to a three dimensional framework of covalent Si–Si and Si–Ir bonds. The electronic specific heat in the superconducting phase suggests that Li2IrSi3 is a BCS weak-coupling superconductor.

Destabilization of the 6H-SrIrO3 polymorph through partial substitution of zinc and lithium

We report on the destabilization of the 6H-SrIrO3 polymorph through partial substitutions of zinc and lithium for iridium to form perovskites. The perovskites crystallize in the orthorhombic space group Pbnm: SrIr1−xZnxO3 is found for 0.25 ≤ x ≤ 0.33, while SrIr1−xLixO3 is found only for x = 0.25. The Zn and Li ions are randomly distributed in the B-site lattice. Analysis shows that the perovskite stabilization is not driven by changes in average ionic size but rather is due to destabilization of the face-sharing octahedra that are present in 6H-type SrIrO3. Magnetic susceptibility measurements show Curie–Weiss behavior, with relatively large temperature independent contributions, and that the iridium atoms have low effective moments, 0.52 to 1.08 μB per Ir. The resistivity of SrIr0.67Zn0.33O3, characterized by Mott variable range hopping type semiconducting behavior, indicates that substituted Zn ions introduce significant disorder into the system. SrIr0.75Li0.25O3 has a significant linear contribution to the specific heat at low temperatures.

Superconductivity in the Cu(Ir1-xPtx)2Se4 spinel

We report the observation of superconductivity in the CuIr2Se4 spinel induced by partial substitution of Pt for Ir. The optimal doping level for superconductivity in Cu(Ir1-xPtx)2Se4 is x = 0.2, where Tc is 1.76 K. A superconducting Tc vs. composition dome is established between the metallic, normal conductor CuIr2Se4 and semiconducting CuIrPtSe4. Electronic structure calculations show that the optimal Tc occurs near the electron count of a large peak in the calculated electronic density of states and that CuIrPtSe4 is a band-filled insulator. Characterization of the superconducting state in this heavy metal spinel through determination of {\Delta}C/{\gamma}Tc, indicates that it is BCS-like. The relatively high upper critical field at the optimal superconducting composition (Hc2(0) = 3.2 T) is much larger than that reported for analogous rhodium spinels and is comparable to or exceeds the Pauli field (mu0Hp), suggesting that strong spin orbit coupling may influence the superconducting state. Further, comparison to doped CuIr2S4 suggests that superconductivity in iridium spinels is not necessarily associated with the destabilization of a charge-ordered spin-paired state through doping.

Strong Electron–Phonon Coupling Superconductivity Induced by a Low-Lying Phonon in IrGe

The physical properties of the previously reported superconductor IrGe and the Rh1-xIrxGe solid solution are investigated. IrGe has an exceptionally high superconducting transition temperature (Tc = 4.7 K) among the isostructural 1:1 late-metal germanides MGe (M = Rh, Pd, Ir and Pt). Specific-heat measurements reveal that IrGe has an anomalously low Debye temperature, originating from a low-lying phonon, compared to the other MGe phases. A large jump at Tc in the specific-heat data clearly indicates that IrGe is a strong coupling superconductor. In the Rh1-xIrxGe solid solution, a relationship between an anomalous change in lattice constants and the Debye temperature is observed. We conclude that the unusually high Tc for IrGe is likely due to strong electron-phonon coupling derived from the presence of a low-lying phonon.

Superconducting phase diagram of InxWO3 synthesized by indium deintercalation

We report the superconducting phase diagram of the hexagonal tungsten bronze (HTB) InxWO3. The InxWO3 samples were prepared by indium deintercalation of the thermodynamically stable parent phase In0.33WO3. By employing this technique, a lowest indium content in the HTB phase of was achieved, which cannot be obtained by conventional solid-state reaction. In addition, accurately and reproducibly controlled indium content and homogeneous samples enable us to perform a systematic study of the physical properties of InxWO3. Most of the InxWO3 samples exhibit a superconducting transition and the highest transition temperature in InxWO3 was observed at . The indium content dependence of shows remarkable similarities to other MxWO3 ( and Rb) HTBs. Our results reveal the universality of physical properties in the HTB family and give a strategy to achieve higher in HTBs.