Hydride-Reduced EuSrFeO: A T-to-T' Conversion Enabling Fe in Square-Planar Coordination.

Low-temperature reaction of A-site-ordered layered perovskite EuSrFeO (T structure) with CaH induces a shift in the EuO slabs to form EuSrFeO with a T' structure (4/ space group) in which only the Fe cation is reduced. Contrary to the previously reported T' structures with Jahn-Teller-active d cations (Cu and Ni), stabilization of EuSrFeO with the Fe (d) cation reflects the stability of the FeO square-planar unit. The stability of T'-type EuSrFeO over a T-type polymorph is confirmed by density functional theory calculations, revealing the d occupancy for the T' structure.

Soft Magnetic Switching in a FeSrYCuO Superconductor with Unusually High Iron Valence.

Ozone oxidation has allowed the stabilization of a very high iron oxidation state in the FeSrYCuO cuprate, in which a long-range magnetic ordering of the high valent iron cations coexists with the superconducting interactions ( = 110 K > = 70 K). The somewhat unexpected A-type AFM structure, with a μ(Fe) ∼ 2 μ magnetic saturation moment associated with the hypervalent iron sublattice, suggests an unusual low spin state for the iron cations, while the low dimensionality of the magnetic structure results in a soft switching toward ferromagnetism under small external magnetic fields. The role of the crystal structure and of the high charge concentration in the stabilization of this unusual electronic configuration for the iron cations is discussed.

Influence of Structural (Cation and Anion) Order in the Superconducting Properties of Ozone-Oxidized MoCuSrRECuO (RE = Yb, Tm, Gd, Nd, and Pr).

The influence of rare earth (RE) elements on superconducting properties of the transition element (TE)-substituted TE CuSrRECuO cuprates has not been sufficiently emphasized so far. In the case of molibdo-cuprates with the general formula MoCuSrRECuO , all the RE element containing compounds except La, Ce, and Lu can be prepared at room pressure. The influence of the crystal structure on the superconducting properties after ozone oxidation of the present system is reported selecting three groups of RE elements attending to their different atom sizes: small (Yb and Tm), medium (Gd), and big (Nd and Pr).

Particle size effect on the superconducting properties of YBaCuO particles.

YBCO samples with different microstructures were prepared after the thermal treatment of a precursor previously obtained by autocombustion. A drastic influence of the particle size on the magnetic behavior of the samples was observed. Thus, particles smaller than 110 nm do not exhibit superconducting properties and for those ranging around 200 nm the diamagnetic signal characteristic of the superconductivity at low temperature disappears in a large applied magnetic field.

Long- and Short-Range Structure of Ferrimagnetic Iron-Chromium Maghemites.

Maghemite-like materials containing Fe(3+) and Cr(3+) in comparable amounts have been prepared by solution-combustion synthesis. The conditions of synthesis and the magnetic properties are described. These materials are ferrimagnetic and are much more stable than pure iron maghemite since their maghemite-hematite transformation takes place at about ∼ 700 °C instead of ∼ 300 °C, as usually reported.

Core-level photoemission spectra of Mo0.3Cu0.7Sr2ErCu2Oy, a superconducting perovskite derivative. Unconventional structure-property relationships.

Detailed studies of the electronic states for Mo(0.3)Cu(0.7)Sr(2)ErCu(2)Oy samples with different oxygen contents are presented here.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.

Spin-glass behavior and incommensurate modulation in high-pressure perovskite BiCr0.5Ni0.5O3.

The BiCr(0.5)Ni(0.5)O(3) perovskite has been obtained at high pressure.

High-pressure synthesis, structural and complex magnetic properties of the ordered double perovskite Pb2NiReO6.

The ordered double perovskite Pb2NiReO6 has been prepared at 6 GPa and temperatures ranging from 1273 to 1373 K. Its crystal structure determined by X-ray powder diffraction and selected area electron diffraction shows monoclinic symmetry with centrosymmetric space group I2/m (a = 5.6021(1) Å, b = 5.

Spin glass to superconducting phase transformation by oxidation of a molybdo-cuprate: Mo0.3Cu0.7Sr2TmCu2Oy.

A detailed study of the structure and properties for the as-prepared and oxygen annealed Mo0.3Cu0.7Sr2TmCu2Oy material is reported.

Driving Curie temperature towards room temperature in the half-metallic ferromagnet K2Cr8O16 by soft redox chemistry.

The half-metallic ferromagnet K(2)Cr(8)O(16) with the hollandite structure has been chemically modified using soft chemistry methods to increase the average oxidation state of chromium. The synthesis of the parent material has been performed under high pressure/high temperature conditions. Following this, different redox reactions have been carried out on K(2)Cr(8)O(16).

Structural percolation in the PbM(1-x)M(x)'O(3) (M, M' =Ti, Cr, and V) perovskites.

Structural properties and the influence of d electrons' insertion in PbTiO(3) have been determined in the study of PbM(1-x)M(x)'O(3) (M, M' = Ti, Cr, and V) solid solutions by means of X-ray diffraction, high-resolution transmission electron microscopy, magnetization measurements, and strain mapping analysis. PbTi(1-x)V(x)O(3) is the only system that preserves the same space group (P4mm) for all x, whereas PbTi(1-x)Cr(x)O(3) and PbV(1-x)Cr(x)O(3) change to cubic (Pm ̅3m) at x = 0.30 and 0.

Highly stable cooperative distortion in a weak Jahn-Teller d2 cation: perovskite-type ScVO3 obtained by high-pressure and high-temperature transformation from bixbyite.

A novel ScVO(3) perovskite phase has been synthesized at 8 GPa and 1073 K from the cation-disordered bixbyite-type ScVO(3). The new perovskite has orthorhombic symmetry at room temperature, space group Pnma, and lattice parameters a = 5.4006(2) Å, b = 7.

High-pressure synthesis and local structure of corundum-type In(2-2x)Zn(x)Sn(x)O(3) (x ≤ 0.7).

The corundum-type In(2-2x)Zn(x)Sn(x)O(3) solid solution (cor-ZITO, x ≤ 0.7) was synthesized at 1000 °C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In(2-2x)Zn(x)Sn(x)O(3) (x ≤ 0.

Spinel to CaFe2O4 transformation: mechanism and properties of beta-CdCr2O4.

The CdCr(2)O(4) spinel transforms to a 10.6% denser new polymorph of the CaFe(2)O(4)-type structure at 10 GPa and 1100 degrees C. This new polymorph has a honeycomb-like structure because of double rutile-type chains formed by [Cr-O(6)] edge-shared octehedra.

Reliable method for determining the oxidation state in chromium oxides.

We show that an appropriate analysis of the electron energy loss spectra in relation to the Cr-O bonds gives a reliable methodology to obtain the oxidation state in chromium oxides. It is based on the energy difference between the Cr L(3) and O K edges, which acts as a measure of the binding energy difference between the Cr 2p(3/2) and O 1s core levels.

Antiferromagnetism and spin reorientation in "PbCrO3".

The perovskite "PbCrO(3)" was synthesized at high pressure and high temperature. Its magnetic properties have been investigated by means of magnetization, specific heat, and resistivity measurements. Earlier workers had concluded it to have a G-type antiferromagnetic structure.

Increasing the structural complexity of chromium(IV) oxides by high-pressure and high-temperature reactions of CrO2.

This work presents an overview of a series of increasingly complex oxides synthesized from CrO 2, under high-pressure and high-temperature conditions, having Cr (4+) in octahedral coordination. Although the emphasis is on the structure and microstructure of the compounds as obtained from X-ray diffraction and transmission electron microscopy and diffraction, attention is also given to their interesting electronic and magnetic properties. The study is complemented with an electron energy loss spectroscopic analysis of the different phases.

Ahead of the lanthanide contraction; pressure and ionic size in the synthesis of MSr2RECu2O8 (RE = Rare Earth, M = Ru, Cr, Ir): a Gaussian relation.

We have been working for sometime on the synthesis at high pressure (P < or = 12.5 Gpa) and high temperature (T < or = 1400 K) of new materials of the type MSr2RECu2O8 (RE = Rare Earth), which formally derive from YBCO (i.e.

Beyond the structure-property relationship paradigm: influence of the crystal structure and microstructure on the Li+ conductivity of La2/3Li(x)Ti(1-x)Al(x)O3 Oxides.

The crystal structures of several oxides of the La(2/3)Li(x)Ti(1-x)Al(x)O(3) system have been studied by selected-area electron diffraction, high-resolution transmission electron microscopy, and powder neutron diffraction, and their lithium conductivity has been by complex impedance spectroscopy. The compounds have a perovskite-related structure with a unit cell radical2 a(p)x2 a(p)x radical2 a(p) (a(p)=perovskite lattice parameter) due to the tilting of the (Ti/Al)O(6) octahedra and the ordering of lanthanum and lithium ions and vacancies along the 2 a(p) axis. The Li(+) ions present a distorted square-planar coordination and are located in interstitial positions of the structure, which could explain the very high ionic conductivity of this type of material.

New Materials Derived from Ybco: CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, Lu).

Eleven new oxides, derived from yttrium barium copper oxide by replacing the square-planar copper [Cu-O4] of the basal plane of the triple perovskite-based structure with octahedral Cr(IV), have been prepared at high pressure and temperature. Their crystal structures have been determined, and their complex microstructure has been established by means of high-resolution electron microscopy and electron diffraction. The materials have a general formula of CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, and Lu); they are tetragonal, show the symmetry of space group P4/mmm, and do not appear to be superconducting.

Crystal structure and microstructure of some La(2/3-x)Li 3xTiO3 oxides: an example of the complementary use of electron diffraction and microscopy and synchrotron X-ray diffraction to study complex materials.

Three representative oxides of the La(2/3)(-)(x)()Li(3)(x)()TiO(3) system have been studied by selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and powder synchrotron X-ray diffraction. HRTEM showed that the materials have a complex microstructure. The SAED and HRTEM results have allowed us to propose a model to refine the crystal structure of these oxides that also accounts for their microstructure.