Tetragonality induced superconductivity in anti-ThCr2Si2-type RE2O2Bi (RE = rare earth) with Bi square nets.

We report a series of layered superconductors, anti-ThCr2Si2-type RE2O2Bi (RE = rare earth), composed of electrically conductive Bi square nets and magnetic insulating RE2O2 layers. Superconductivity was induced by separating the Bi square nets as a result of excess oxygen incorporation, irrespective of the presence of magnetic ordering in RE2O2 layers. Intriguingly, the transition temperature of all RE2O2Bi including nonmagnetic Y2O2Bi was approximately scaled by unit cell tetragonality (c/a), implying a key role in the relative separation of the Bi square nets to induce superconductivity.

Development of intra-operative assessment system for ossicular mobility and middle ear transfer function.

Objective measurements of the ossicular mobility have not been commonly performed during the surgery, and the assessment of ossicular mobility is made by palpation in most cases. Palpation is inherently subjective and may not always be reliable, especially in milder degrees of ossicular fixation and in the case of multiple fixation. Although several devices have been developed to quantitatively measure the ossicular mobility during surgery, they have not been widely used. In this study, a new system with a hand-held probe which enables intraoperative quantitative measurements of ossicular mobility has been developed. This system not only measures the ossicular mobility, but also investigates "local" transmission characteristics of the middle ear by directly applying vibration to the ossicles and measuring cochlear microphonic. The basic performance of this system was confirmed by measuring the mobility of artificial ossicles and cochlear microphonics in an animal experiment. Our system may contribute to selection of a better surgical method and reducing the risks of revision surgery.

Multiple-wavelength neutron holography with pulsed neutrons.

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering-that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique.

Crystal structures, magnetic properties, and DFT calculation of B-site defected 12L-perovskites Ba2La2MW2O12 (M = Mn, Co, Ni, Zn).

The synthesis, crystal structures and magnetic properties of Ba2La2MW2O12 (M = Mn, Co, Ni, Zn) were investigated. They crystallize in the 12-layer polytype of the perovskite structure with a regular cation defect in the B-site. The results of neutron diffraction measurements reveal that they adopt a rhombohedral structure with a space group R - 3 and have a cation ordering between Ba and La ions in the A-site. In these compounds, the magnetic M ions form the 2D triangular lattice. From the results of magnetic measurements, the ferromagnetic ordering of M2+ ions for M = Co (T C = 1.3 K) and Ni (6.2 K) and the paramagnetic behavior (T > 1.8 K) with an antiferromagnetic interaction for M = Mn are observed. From the DFT calculation, their band structures and magnetic interactions are discussed.

Crystallographic, Electronic, and Magnetic Properties of Rock Salt Superstructure Sulfide Lu2CrS4 with Jahn-Teller Distortion.

A new chromium(II) sulfide, Lu2CrS4, with a novel structure was prepared by a solid-state reaction. The powder X-ray diffraction pattern could be indexed as a tetragonal system, with a = 7.46373(2) Å, c = 22.6338(2) Å, and space group I4̅2d (No. 122). Rietveld analysis of the pattern provided the crystal structure consisting of CrS6 and LuS6 octahedra sharing edges and apexes and revealed a rock salt superstructure with new cation (vacancy) arrangements. The electrical resistivity indicates semiconducting behavior. The magnetic susceptibility and specific heat measurements showed that the Cr ions are in the high-spin d(4) configuration and that their magnetic moments ordered antiferromagnetically at 55 K. The basic antiferromagnetic structure was determined using powder neutron diffraction data at 10 K. The band structure calculations demonstrate that the densities of states of Cr 3d electrons split into two spin-up eg bands because of Jahn-Teller distortion.

Oxyhydrides of (Ca,Sr,Ba)TiO3 perovskite solid solutions.

The oxyhydride solid solutions (Ca,Sr)TiO(3-x)H(x) and (Sr,Ba)TiO(3-x)H(x) have been prepared by reducing the corresponding ATiO(3) oxides with calcium hydride. Under the reaction conditions examined, a hydride content of x = 0.1-0.3 was obtained for all compositions. Compared to our previous result with BaTiO(3-x)H(x), the larger particle size in this study (20-30 µm vs 170 nm) resulted in a somewhat lower hydride amount despite prolonged reaction times. We examined changes in cell volume, octahedral tilt angle, and site occupancy of different anion sites after conversion to oxyhydrides; it appears that these oxyhydrides fit the geometrical descriptions typical for regular ABO(3) perovskites quite well. The hydrogen release temperature, previously shown to be indicative of the hydride exchange temperature, however, does not scale linearly with the A-site composition, indicating a potential effect of chemical randomness.

(Sr(1-x)Ba(x))FeO2 (0.4 ≤ x ≤ 1): a new oxygen-deficient perovskite structure.

Topochemical reduction of (layered) perovskite iron oxides with metal hydrides has so far yielded stoichiometric compositions with ordered oxygen defects with iron solely in FeO(4) square planar coordination. Using this method, we have successfully obtained a new oxygen-deficient perovskite, (Sr(1-x)Ba(x))FeO(2) (0.4 ≤ x ≤ 1.0), revealing that square planar coordination can coexist with other 3-6-fold coordination geometries. This BaFeO(2) structure is analogous to the LaNiO(2.5) structure in that one-dimensional octahedral chains are linked by planar units, but differs in that one of the octahedral chains contains a significant amount of oxygen vacancies and that all the iron ions are exclusively divalent in the high-spin state. Mössbauer spectroscopy demonstrates, despite the presence of partial oxygen occupations and structural disorders, that the planar-coordinate Fe(2+) ions are bonded highly covalently, which accounts for the formation of the unique structure. At the same time, a rigid 3D Fe-O-Fe framework contributes to structural stabilization. Powder neutron diffraction measurements revealed a G-type magnetic order with a drastic decrease of the Néel temperature compared to that of SrFeO(2), presumably due to the effect of oxygen disorder/defects. We also performed La substitution at the Ba site and found that the oxygen vacancies act as a flexible sink to accommodate heterovalent doping without changing the Fe oxidation and spin state, demonstrating the robustness of this new structure against cation substitution.

Magnetic and neutron diffraction study on melilite-type oxides Sr2MGe2O7 (M = Mn, Co).

The crystal structures and magnetic properties of melilite-type oxides Sr(2)MGe(2)O(7) (M = Mn, Co) were investigated. These compounds crystallize in the melilite structure with space group P ̅42(1)m, in which the M and Ge ions occupy two kinds of tetrahedral sites in an ordered manner. The magnetic M ions form a square-planar lattice in the ab plane. Both compounds do not show the structural phase transition down to 2.5 K. The temperature dependence of magnetic susceptibility for Sr(2)MnGe(2)O(7) shows a broad peak at ~6.0 K because of a two-dimensional magnetic interaction between Mn ions in the ab plane. At 4.4 K, an antiferromagnetic transition was observed. The magnetic structure was determined by the neutron powder diffraction measurements at 2.5 K. It can be represented by the propagation vector k = (0, 0, 1/2), and the magnetic moments of Mn(2+) (3.99 µ(B)) ions order antiferromagnetically in a collinear manner along the c axis. On the other hand, Sr(2)CoGe(2)O(7) shows an antiferromagnetic transition at 6.5 K with divergence between zero-field-cooled and field-cooled susceptibilities. Its magnetic structure determined at 2.5 K has a magnetic propagation vector k = (0, 0, 0), and the ordered magnetic moment of Co(2+) (2.81 µ(B)) adopts a collinear arrangement lying on the ab plane.

Fe-site substitution effect on the structural and magnetic properties in SrFeO2.

We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mössbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mössbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction.

Orthogonal spin arrangement in quasi-two-dimensional La2Co2O3Se2.

The crystal, electronic, and magnetic structures of the cobalt oxyselenide La(2)Co(2)O(3)Se(2) were investigated through powder neutron diffraction measurements and band structure calculations. This oxyselenide crystallizes in a tetragonal layered structure with space group I4/mmm. The Co ion is sixfold-coordinated by two oxide ions and four selenide ions, and the face-sharing CoO(2)Se(4) octahedra form Co(2)OSe(2) layers. The band structure calculations revealed that the Co ion is in the divalent high-spin state. Rietveld analysis of the neutron diffraction profiles below 200 K demonstrated that the Co moments have a noncollinear antiferromagnetic structure with the propagation vector k = (½, ½, 0). The ordered magnetic moment was determined to be 3.5 µ(B) at 10 K, and the directions of the nearest-neighbor Co moments are orthogonal each other in the c plane.

Multimode hydriding/dehydriding reactions of CaPd.

Combined thermodynamical and structural studies have confirmed the occurrence of multimode hydriding/dehydriding reactions of CaPd that vary depending on temperature, and that these reactions proceed via hydrogen solution/dissolution in the temperature range 273-523 K and via phase decomposition/recombination in the temperature range 523-773 K.

Synthesis and thermal stability of the solid solution AFeO2 (A = Ba, Sr, Ca).

We have studied the A-site substitution effect on the structural, thermal, and magnetic properties of the infinite layer iron oxide AFeO(2) (A = alkali-earth elements) with an FeO(4) square-planar coordination. Together with the previous study showing a total substitution by Ca, Ba substitution is found to be tolerable up to 30%, presenting almost the same substitutional range as that found in ACuO(2) under high pressure. Notably, Ba substitution shows little influence on the magnetic properties, in contrast to expectations from first principles calculations. The temperature at which oxidation to an AFeO(2.5) phase occurs and its transformation rate show a wide variation tunable solely by the out-of-plane distance.

Structural studies of a mixed-valence state in the incommensurate composite crystal Sr1.261CoO3.

The incommensurate modulated crystal structure of the hexagonal cobalt oxide Sr1.261CoO3 has been studied using a four-dimensional (4D) superspace profile analysis of neutron powder diffraction data. Sr1.261CoO3 is a composite crystal that consists of the [CoO3] and [2Sr] subsystems. The [CoO3] subsystem forms 1D chains that run parallel to the c-axis and consist of face-sharing CoO6 polyhedra with octahedral (Oh) and trigonal prismatic (TP) coordinations. The structure analysis reveals that the [CoO3] chains contain 73.9% Oh and 26.1% TP sites, and that the TP sites have longer Co-O bonds than the Oh sites: dav. =2.039(4) Š(TP) and 1.895(3) Š(Oh). The averaged Co bond valences are Co3.56(3)+ in the Oh sites and Co2.45(3)+ in the TP sites, suggesting that a considerable amount of Co3+ ions are mixed with Co4+ions in the Oh sites and with Co2+ ions in the TP sites. The observed magnetic susceptibility can be well explained assuming that the compound has the Co mixed-valence state with the spin configurations of S=0 low-spin state for Co3+(dε6), S=1/2 low-spin state for Co4+(dε5) and S=3/2 high-spin state for Co2+(dε5dγ2). The Weiss temperature, approximately 0.8 K, implies that Sr1.261CoO3 naturally assumes a Curie paramagnetic state, probably owing to the obstruction of the intrachain magnetic interaction by the nonmagnetic Co3+ ions. These results suggest that the nonmagnetic Co3+ ions play an essential role in the magnetism of Sr2γCoO3 systems.

CaFeO2: a new type of layered structure with iron in a distorted square planar coordination.

CaFeO(2), a material exhibiting an unprecedented layered structure containing 3d(6) iron in a high-spin distorted square-planar coordination, is reported. The new phase, obtained through a low-temperature reduction procedure using calcium hydride, has been characterized through powder neutron diffraction, synchrotron X-ray diffraction, Mossbauer spectroscopy, XAS experiments as well as first-principles DFT calculations. The XAS spectra near the Fe-K edge for the whole solid solution (Sr(1-x)Ca(x))FeO(2) supports that iron is in a square-planar coordination for 0

Magnetic and neutron diffraction study on quaternary oxides MTeMoO(6) (M = Mn and Zn).

Crystal structures and magnetic properties of quaternary oxides MTeMoO(6) (M = Mn and Zn) were investigated. From the Rietveld analyses for the powder x-ray and neutron diffraction measurements, their detailed structures have been determined. Both compounds have orthorhombic structure with space group P 2(1)2(1)2 and a charge configuration of M(2+)Te(4+)Mo(6+)O(6). ZnTeMoO(6) shows diamagnetic behavior. In this structure, M ions are arranged in a square-planar manner. The temperature dependence of the magnetic susceptibility for MnTeMoO(6) shows a broad peak at ∼33 K, which is due to a two-dimensional characteristic of the magnetic interaction. In addition, this compound shows an antiferromagnetic transition at 20 K. The magnetic structure was determined by the powder neutron diffraction measurement at 3.3 K. The magnetic moments of Mn(2+) ions (4.45 µ(B)) order in a collinear antiferromagnetic arrangement along the b axis.

Experimental visualization of lithium diffusion in LixFePO4.

Chemical energy storage using batteries will become increasingly important for future environmentally friendly ('green') societies. The lithium-ion battery is the most advanced energy storage system, but its application has been limited to portable electronics devices owing to cost and safety issues. State-of-the-art LiFePO4 technology as a new cathode material with surprisingly high charge-discharge rate capability has opened the door for large-scale application of lithium-ion batteries such as in plug-in hybrid vehicles. The scientific community has raised the important question of why a facile redox reaction is possible in the insulating material. Geometric information on lithium diffusion is essential to understand the facile electrode reaction of LixFePO4 (0