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We have synthesized a new superconducting perovskite bismuth oxide by a facile hydrothermal route at 220 °C. The choice of starting materials, their mixing ratios, and the hydrothermal reaction temperature was crucial for obtaining products with superior superconducting properties. The structure of the powder sample was investigated using laboratory X-ray diffraction, high-resolution synchrotron X-ray diffraction (SXRD) data, and electron diffraction (ED) patterns [transmission electron microscopy (TEM) analysis]. The refinement of SXRD data confirmed a simple perovskite-type structure with a cubic cell of a = 4.27864(2) Å [space group Pm3̅m (No. 221)]. Elemental analysis detected magnesium in the final products, and a refinement based on SXRD and inductively coupled plasma data yielded an ideal undistorted simple cubic perovskite-type structure, with the chemical composition (Ba 0.62 K 0.38 )(Bi 0.92 Mg 0.08 )O 3 . ED patterns also confirmed the simple cubic perovskite structure; the cube-shaped microstructures and compositional homogeneity on the nanoscale were verified by scanning electron microscopy and TEM analyses, respectively. The fabricated compound exhibited a large shielding volume fraction of about 98% with a maximum T c mag of ∼30 K, which was supported by the measured bismuth valence as well. Its electrical resistivity dropped at ∼21 K, and zero resistivity was observed below 7 K. The compound underwent thermal decomposition above 400 °C. Finally, the calculated band structure showed a metallic behavior for this hydrothermally synthesized bismuth oxide.

A low-temperature topochemical reduction strategy is used herein to prepare unconventional phosphors with luminescence covering the biological and/or telecommunications optical windows. This approach is demonstrated by using Bi(III)-doped Y2O3 (Y(2-x)Bi(x)O3) as a model system. Experimental results suggest that topochemical treatment of Y(2-x)Bi(x)O3 using CaH2 creates randomly distributed oxygen vacancies in the matrix, resulting in the change of the oxidation states of Bi to lower oxidation states. The change of the Bi coordination environments from the [BiO6] octahedra in Y(2-x)Bi(x)O3 to the oxygen-deficient [BiO(6-z)] polyhedra in reduced phases leads to a shift of the emission maximum from the visible to the near-infrared region. The generality of this approach was further demonstrated with other phosphors. Our findings suggest that this strategy can be used to explore Bi-doped or other classes of luminescent systems, thus opening up new avenues to develop novel optical materials., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The relationship between the structure and superconductivity of Bi4O4S3 powders synthesized by heating under ambient and high pressures was investigated using synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy (TEM) observation. The Bi4O4S3 powders synthesized under ambient pressure exhibited a strong superconductivity (diamagnetic) signal and zero resistivity below ∼4.5 K, while the Bi4O4S3 powder synthesized by the high-pressure method exhibited a low-intensity signal down to 2 K. Further annealing of the latter Bi4O4S3 powder under ambient pressure led to the development of a strong signal and zero resistivity. The crystal structures of all Bi4O4S3 phases consisted of Bi4O4Bi2S4 blocks including a Bi-S layer and anion(s) sandwiched between Bi4O4Bi2S4 blocks, but minor structural differences were detected. A comparison of the structures of the superconductive and nonsuperconductive Bi4O4S3 samples suggested that the superconductive Bi4O4S3 phases had slightly smaller lattice parameters. The average structures of the superconductive Bi4O4S3 phases were characterized by a slightly shorter and less bent Bi-S plane. Raman spectroscopy detected vibration of the S-O bonds, which can be attributed to sandwiched anion(s) such as SO4(2-). TEM observation showed stacking faults in the superconductive Bi4O4S3 phases, which indicated local fluctuation of the average structures. The observed superconductivity of Bi4O4S3 was discussed based on impurity phases, enhanced hybridization of the px and py orbitals of the Bi-S plane within Bi4O4Bi2S4 blocks, local fluctuation of the average structures, compositional deviation related to suspicious anion(s) sandwiched between Bi4O4Bi2S4 blocks, and the possibility of suppression of the charge-density-wave state by enriched carrier concentrations.

BiCh2-based compounds (Ch: S, Se) are a new series of layered superconductors, and the mechanisms for the emergence of superconductivity in these materials have not yet been elucidated. In this study, we investigate the relationship between crystal structure and superconducting properties of the BiCh2-based superconductor family, specifically, optimally doped Ce1-xNdxO0.5F0.5BiS2 and LaO0.5F0.5Bi(S1-ySey)2. We use powder synchrotron X-ray diffraction to determine the crystal structures. We show that the structure parameter essential for the emergence of bulk superconductivity in both systems is the in-plane chemical pressure, rather than Bi-Ch bond lengths or in-plane Ch-Bi-Ch bond angle. Furthermore, we show that the superconducting transition temperature for all REO0.5F0.5BiCh2 superconductors can be determined from the in-plane chemical pressure.

Hexagonal Lu1-xScxFeO3 (0 ≤ x ≤ 0.8) was directly solidified from an undercooled melt by containerless processing with an aerodynamic levitation furnace. The hexagonal phase-forming region was considerably extended compared to that of the conventional solid-state reaction (x ∼ 0.5). Synchrotron X-ray diffraction measurements revealed that the crystal structure of the hexagonal phase was isomorphous to hexagonal ferroelectric RMnO3 (R = a rare earth ion) with a polar space group of P63cm. As x increased, the a-axis lattice constant decreased linearly, strengthening the antiferromagnetic interaction between the Fe(3+) ions on the a-b plane. Accordingly, the weak ferromagnetic transition temperature increased from 150 K for x = 0 to 175 K for x = 0.7. These transition temperatures were much higher than those of hexagonal Lu1-xScxMnO3. The results indicate that hexagonal Lu1-xScxFeO3 is a suitable alternative magnetic dielectric for use at higher temperatures.

Oxygen vacancy (VO) strongly affects the properties of oxides. In this study, we used X-ray diffraction (XRD) to study changes in the VO concentration as a function of the Co-doping level of ZnO. Rietveld refinement yielded a different result from that determined via X-ray photoelectron spectroscopy (XPS), but additional maximum entropy method (MEM) analysis led it to compensate for the difference. VO tended to gradually decrease with increased Co doping, and ferromagnetic behavior was not observed regardless of the Co-doping concentration. MEM analysis demonstrated that reliable information related to the defects in the ZnO-based system can be obtained using X-ray diffraction alone.

Perovskite-type structures (ABO3) have received significant attention because of their crystallographic aspects and physical properties, but there has been no clear evidence of a superconductor with a double-perovskite-type structure, whose different elements occupy A and/or B sites in ordered ways. In this report, hydrothermal synthesis at 220 °C produced a new superconductor with an A-site-ordered double perovskite structure, (Na(0.25)K(0.45))(Ba(1.00))3(Bi(1.00))4O12, with a maximum T(c) of about 27 K., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The thermal stability and dielectric and structural properties of ferroelectric Ba1-xCaxTi2O5 (0 ≤ x ≤ 0.30) prepared by crystallization from glass are investigated. The Ba1-xCaxTi2O5 compounds with x < 0.10 are thermally stable phases, while those with x ≥ 0.10 are metastable phases. The ferroelectric transition temperature drastically decreases from 470 to 220°C with increasing x. Crystal structure analyses reveal that one of two possible Ba sites is occupied by Ca in the stable phase region, while Ca-site selectivity is broken in the metastable phase region. The Ca-site selectivity introduces local distortion and makes the crystal lattice unstable. However, the local distortion is suppressed by the occupancy of Ca into both Ba sites. Accordingly, the metastable ferroelectric phase can be obtained beyond the substitution limit of Ca by crystallization from the glassy state. The stabilization mechanism provides possible wide control of the functionality of materials by expanding the composition range.

Lu1-xScxFeO3 (0 ≤ x ≤ 1) was synthesized by a conventional solid-state reaction. The hexagonal phase appeared at 0.4 ≤ x ≤ 0.6, between the perovskite phase (0 ≤ x ≤ 0.3) and the bixbyite phase (0.7 ≤ x ≤ 1). Structural, magnetic, and dielectric properties of hexagonal Lu0.5Sc0.5FeO3 were investigated. Synchrotron X-ray diffraction measurements revealed that the crystal structure of Lu0.5Sc0.5FeO3 is isomorphic to hexagonal ferroelectrics RMnO3 (R = rare earth ion) with a polar space group of P63cm. A weak ferromagnetic transition with a dielectric anomaly occurred at a much higher temperature (162 K) than those in hexagonal RMnO3. Although remanent magnetization was observed below the transition temperature, it decreased to almost zero at 10 K. These results indicate a strong antiferromagnetic interaction between ground-state Fe(3+) ions on the triangular lattice.

Carbon, nitrogen, and oxygen are essential components in solid-state materials. However, understanding their preference on the bonding to metals has not been straightforward. Here, niobium carbide, nitride, and oxide with simple rock-salt-based structures were analyzed by first-principles calculations and synchrotron X-ray diffraction. We found that an increase in the atomic number from carbon to oxygen formed fewer and shorter bonds to metals with better hybridization of atomic orbitals. This can provide a simple guiding principle for understanding the bonding and designing carbides, nitrides, oxides, and mixed-anion compounds.

The dielectric property of relaxor ferroelectric 0.93Pb(Zn₁/₃Nb₂/₃)O₃-0.07PbTiO₃ single crystals (PZN-0.07PT) is studied to investigate the ferroelectric phase transition. The temperature dependence of the susceptibility of the central peak in the light scattering shows a very similar behavior to the real part of the dielectric constant, indicating that the diffuse peak in the temperature dependence of the dielectric constant is induced by relaxation of the polarization. We suggest that the origin of the relaxation above T(m) is the non-180° polarization flipping of a small polar nanoregion (PNR). Additionally, the behavior of the PNRs is interpreted through both the Brillouin spectra and high-energy synchrotron-radiation powder diffraction patterns. Our results reveal that T*~ 499K is the temperature below which the growth rate of the dynamic polarization fluctuation is suppressed by the additional random electric field induced by the generation of the static PNRs.