Square coordinated MnO(2)-units in BiMn(7)O(12).

Room temperature high-resolution synchrotron X-ray diffraction (HRSXRD) measurements were carried out on polycrystalline samples of BiMn(7)O(12) and LaMn(7)O(12). Rietveld refinements of HRSXRD data describe the crystal structures of both compounds in the monoclinic space group I2/m. The maximum entropy method-based pattern fitting (MPF) method inversion of HRSXRD data was utilized to obtain the spatial electron density (ED) distribution. Obtained results show clear differences in ED distributions around Mn-O bonds between isomorphic BiMn(7)O(12) and LaMn(7)O(12). The scheme of ED distributions in BiMn(7)O(12) indicates the presence of orbital ordering in the MnO(2) planar arrangement that appears as prominent features in very distorted MnO(12) and MnO(6) polyhedrons in the perovskite related structure of [BiMn(3)](A-site)[Mn(4)](B-site)O(12).

Electronic structures, hole-doping, and superconductivity of the s = 1, 2, 3, and 4 members of the (Cu,Mo)-12s2 homologous series of superconductive copper oxides.

We demonstrate that the T(c) value of superconductive copper oxides does not depend on the distance between two adjacent CuO(2) planes as long as the hole-doping level and the immediate (crystal) chemical surroundings of the planes are kept the same. Experimental evidence is accomplished for the homologous series of (Cu,Mo)-12s2, the member phases of which differ from each other by the number (s) of cation layers in the fluorite-structured (Ce,Y)-[O(2)-(Ce,Y)](s-1) block between the CuO(2) planes. X-ray absorption near-edge structure spectroscopy is employed as a probe for the hole states of these phases. The s = 1 member appears to be more strongly doped with holes than other phases of the series and accordingly to possess the highest T(c) value of 87 K. For s > or = 2, unexpectedly, both the CuO(2) plane hole concentration and the value of T(c) (approximately 55 K) remain constant, being independent of s.

Oxygen ordering and mobility in YBaCo(4)O(7+delta).

Extraordinary oxygen ordering and mobility have been found in an oxygen-nonstoichiometric mixed-valence cobalt oxide, YBaCo(4)O(8.5). The excess oxygen atoms appear to be incorporated in an orderly way into the YBaCo(4)O(7) parent lattice with different configurations as the oxygen content varies. Intense electron-beam irradiation was used to observe recurrent oxygen migration in the lattice, causing reversible structural modulation transitions. The oxygen migration can be attributed mainly to the electron-beam heating effect. This study highlights the high degree of freedom of surplus oxygen within the investigated structure and advances our understanding of the oxygen diffusion process in related transition-metal oxide systems.

Positive and negative magnetodielectric effects in A-site ordered (BiMn3)Mn4O12 perovskite.

A-site ordered perovskite (BiMn3)Mn4O12 was synthesized through a high-pressure synthesis route at 5 GPa and found to exhibit two magnetic transitions and to show either a positive or a negative magnetodielectric effect depending on the temperature range/magnetic state.

Layer-engineering of high-Tc superconductors: (Cu,Mo)Sr2(Ce,Y)4Cu2O13+delta with a quadruple-fluorite-layer block between CuO2 planes.

Among high-Tc superconductive copper oxides, there have been known phases that contain fluorite-structured layers as an additional "blocking block" between adjacent CuO2 planes. Here, we report that even a phase with the CuO2 planes separated by a 12-A thick quadruple-fluorite-layer block can be synthesized in a single phase and strongly oxygenated form to exhibit superconductivity with a Tc value as high as 55 K. The new phase is the fourth member of the (Cu,Mo)Sr2(Ce,Y)sCu2O(5+2s+delta) or (Cu,Mo)-12s2 homologous series. Comparison with the previously known s = 1, 2, and 3 members of the series reveals the amazing conclusion that Tc remains essentially unaffected upon inserting additional fluorite-structured layers between the two CuO2 planes as long as the hole-doping level of the planes is kept constant.

Electron microscope studies of nano-domain structures in Ru-based magneto-superconductors: RuSr(2)Gd(1.5)Ce(0.5)Cu(2)O(10-delta) (Ru-1222) and RuSr(2)GdCu(2)O(8) (Ru-1212).

Microstructures of the RuSr(2)Gd(1.5)Ce(0.5)Cu(2)O(10-delta) (Ru-1222) and RuSr(2)GdCu(2)O(8) (Ru-1212) magneto-superconductors have been investigated by using selected-area electron diffraction, convergent-beam electron diffraction, dark-field electron microscopy and high-resolution electron microscopy at room temperature. Both Ru-1212 and Ru-1222 consist of nm-size domains stacked along the [Formula: see text] direction, where the domains are formed by two types of superstructures due to ordering of rotated RuO(6) octahedra about the c-axis. In Ru-1212, both primitive-and body-centered tetragonal superstructures (the possible space groups: P4/mbm and I4/mcm) are derived to form the corresponding nm-domains. It is of great interest that Ru-1212 consists of domains of two crystallographically different superstructures, while the similar domains observed in Ru-1222 have crystallographically identical superstructure with an orthorhombic symmetry (possible space group: Aeam), related by 90 degrees rotation around the c-axis (Yokosawa et al., 2003, submitted for publication).