Satoru Matsuishi

Light-induced conversion of an insulating refractory oxide into a persistent electronic conductor

Materials that are good electrical conductors are not in general optically transparent, yet a combination of high conductivity and transparency is desirable for many emerging opto-electronic applications. To this end, various transparent oxides composed of transition or post-transition metals (such as indium tin oxide) are rendered electrically conducting by ion doping. But such an approach does not work for the abundant transparent oxides of the main-group metals. Here we demonstrate a process by which the transparent insulating oxide 12CaO·7Al2O3 (refs 7–13) can be converted into an electrical conductor. H- ions are incorporated into the subnanometre-sized cages of the oxide by a thermal treatment in a hydrogen atmosphere; subsequent irradiation of the material with ultraviolet light results in a conductive state that persists after irradiation ceases. The photo-activated material exhibits moderate electrical conductivity (∼0.3 S cm-1) at room temperature, with visible light absorption losses of only one per cent for 200-nm-thick films. We suggest that this concept can be applied to other main-group metal oxides, for the direct optical writing of conducting wires in insulating transparent media and the formation of a high-density optical memory.

Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store

Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber-Bosch process, but this process requires high temperatures and pressures, and consumes more than 1% of the worlds power production. Therefore the search is on for a more environmentally benign process that occurs under milder conditions. Here, we report that a Ru-loaded electride [Ca(24)Al(28)O(64)](4+)(e(-))(4) (Ru/C12A7:e(-)), which has high electron-donating power and chemical stability, works as an efficient catalyst for ammonia synthesis. Highly efficient ammonia synthesis is achieved with a catalytic activity that is an order of magnitude greater than those of other previously reported Ru-loaded catalysts and with almost half the reaction activation energy. Kinetic analysis with infrared spectroscopy reveals that C12A7:e(-) markedly enhances N(2) dissociation on Ru by the back donation of electrons and that the poisoning of ruthenium surfaces by hydrogen adatoms can be suppressed effectively because of the ability of C12A7:e(-) to store hydrogen reversibly.

A novel phosphor for glareless white light-emitting diodes

The luminous efficiency of white light-emitting diodes, which are used as light sources for next-generation illumination, is continuously improving. Presently available white light-emitting diodes emit with extremely high luminance because their emission areas are much smaller than those of conventional light sources. Consequently, white light-emitting diodes produce a glare that is uncomfortable to the human eye. Here we report a yellow-emitting phosphor, the Eu(2+)-doped chlorometasilicate (Ca(1-x-y,)Sr(x,)Eu(y))(7)(SiO(3))(6)Cl(2), which can be used to create glareless white light-emitting diodes. The (Ca(1-x-y,)Sr(x,)Eu(y))(7)(SiO(3))(6)Cl(2) exhibits a large Stokes shift, efficiently converting violet excitation light to yellow luminescence, and phosphors based on this host material have much less blue absorption than other phosphors. We used crystal structure analysis to determine the origin of the desired luminescence, and we used (Ca(1-x-y,)Sr(x,)Eu(y))(7)(SiO(3))(6)Cl(2) and a blue-emitting phosphor in combination with a violet chip to fabricate glareless white light-emitting diodes that have large emission areas and are suitable for general illumination.

Superconductivity Induced by Co-Doping in Quaternary Fluoroarsenide CaFeAsF

A new quaternary fluoroarsenide CaFeAsF with the tetragonal ZrCuSiAs-type structure composed of alternate stacking of (FeAs)delta- and (CaF)delta+ layers was synthesized. CaFeAsF is a poor metal and shows the anomaly at approximately 120 K in temperature dependence of electrical conductivity. The electron doping by the partial replacement of the iron with cobalt suppresses the anomaly and induces the bulk superconductivity (optimal Tc = 22 K for CaFe0.9Co0.1AsF), analogous to recently discovered FeAs-based superconductors. The present results suggest that CaFeAsF is a promising candidate as a parent compound for high Tc superconductors.

Dicalcium nitride as a two-dimensional electride with an anionic electron layer

Recent studies suggest that electrides—ionic crystals in which electrons serve as anions—are not exceptional materials but rather a generalized form, particularly under high pressure. The topology of the cavities confining anionic electrons determines their physical properties. At present, reported confining sites consist only of zero-dimensional cavities or weakly linked channels. Here we report a layered-structure electride of dicalcium nitride, Ca2N, which possesses two-dimensionally confined anionic electrons whose concentration agrees well with that for the chemical formula of [Ca2N]+·e−. Two-dimensional transport characteristics are demonstrated by a high electron mobility (520 cm2 V−1 s−1) and long mean scattering time (0.6 picoseconds) with a mean free path of 0.12 micrometres. The quadratic temperature dependence of the resistivity up to 120 Kelvin indicates the presence of an electron–electron interaction. A striking anisotropic magnetoresistance behaviour with respect to the direction of magnetic field (negative for the field perpendicular to the conducting plane and positive for the field parallel to it) is observed, confirming diffusive two-dimensional transport in dense electron layers. Additionally, band calculations support confinement of anionic electrons within the interlayer space, and photoemission measurements confirm anisotropic low work functions of 3.5 and 2.6 electronvolts, revealing the loosely bound nature of the anionic electrons. We conclude that Ca2N is a two-dimensional electride in terms of [Ca2N]+·e−.

Two-dome structure in electron-doped iron arsenide superconductors

Iron arsenide superconductors based on the material LaFeAsO(1-x)F(x) are characterized by a two-dimensional Fermi surface (FS) consisting of hole and electron pockets yielding structural and antiferromagnetic transitions at x=0. Electron doping by substituting O(2-) with F(-) suppresses these transitions and gives rise to superconductivity with a maximum T(c) of 26 K at x=0.1. However, the over-doped region cannot be accessed due to the poor solubility of F(-) above x=0.2. Here we overcome this problem by doping LaFeAsO with hydrogen. We report the phase diagram of LaFeAsO(1-x)H(x) (x<0.53) and, in addition to the conventional superconducting dome seen in LaFeAsO(1-x)F(x), we find a second dome in the range 0.21<x<0.53, with a maximum T(c) of 36 K at x=0.3. Density functional theory calculations reveal that the three Fe 3d bands (xy, yz and zx) become degenerate at x=0.36, whereas the FS nesting is weakened monotonically with x. These results imply that the band degeneracy has an important role to induce high T(c).

Hydrogen in layered iron arsenides: Indirect electron doping to induce superconductivity

Utilizing the high stability of calcium and rare-earth hydrides, CaFeAsF

A germanate transparent conductive oxide

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Pressure-Induced Superconductivity in Iron Pnictide Compound SrFe2As2

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Hydrogen Ordering and New Polymorph of Layered Perovskite Oxyhydrides: Sr2VO4–xHx

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