Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn1-x Fe x O2.5+δ, x = 0.25, 0.50, and 0.75. Local and Average Structures.

The series BaIn1-x Fe x O2.5+δ, x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba2In2O5 (BaInO2.5) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba2Fe2O5 (BaFeO2.5) crystallizes in a complex monoclinic structure, P21/c, showing seven Fe3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm3̅m, with long-range disorder on the small cation and oxygen sites. 57Fe Mössbauer studies indicate a mixed valency, Fe4+/Fe3+, for both the air-fired and argon-fired samples. The increased Fe3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm3̅m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ∼6 K [5 K] for x = 0.50 and at ∼22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe3+-Fe3+ antiferromagnetic exchange and ferromagnetic Fe3+-Fe4+ exchange. The PDF and 57Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm3̅m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe3+ sites are largely fourfold-coordinated and Fe4+ sites are fivefold- or sixfold-coordinated.

Synthesis, crystal structure, and magnetic properties of Li3Mg2OsO6, a geometrically frustrated osmium(V) oxide with an ordered rock salt structure: comparison with isostructural Li3Mg2RuO6.

The novel osmium-based oxide Li(3)Mg(2)OsO(6) was synthesized in polycrystalline form by reducing Li(5)OsO(6) by osmium metal and osmium(IV) oxide in the presence of stoichiometric amounts of magnesium oxide. The crystal structure was refined using powder X-ray diffraction data in the orthorhombic Fddd space group with a = 5.88982(5) Å, b = 8.46873(6) Å, and c = 17.6825(2) Å. This compound is isostructural and isoelectronic with the ruthenium-based system Li(3)Mg(2)RuO(6). The magnetic ion sublattice Os(5+) (S = 3/2) consists of chains of interconnected corner- and edge-shared triangles, which brings about the potential for geometric magnetic frustration. The Curie-Weiss law holds over the range 80-300 K with C = 1.42(3) emu·K/mol [µ(eff) = 3.37(2) µ(B)] and θ(C) = -105.8(2) K. Below 80 K, there are three anomalies at 75, 30, and 8 K. Those at 75 and 30 K are suggestive of short-range antiferromagnetic correlations, while that at 8 K is a somewhat sharper maximum showing a zero-field-cooled/field-cooled divergence suggestive of perhaps spin freezing. The absence of magnetic Bragg peaks at 3.9 K in the neutron diffraction pattern supports this characterization, as does the absence of a sharp peak in the heat capacity, which instead shows only a very broad maximum at ∼12 K. A frustration index of f = 106/8 = 13 indicates a high degree of frustration. The magnetic properties of the osmium phase differ markedly from those of the isostructural ruthenium material, which shows long-range antiferromagnetic order below 17 K, f = 6, and no unusual features at higher temperatures. Estimates of the magnetic exchange interactions at the level of spin-dimer analysis for both the ruthenium and osmium materials support a more frustrated picture for the latter. Errors in the calculation and assignment of the exchange pathways in the previous report on Li(3)Mg(2)RuO(6) are identified and corrected.

Topotactic oxidation pathway of ScTiO3 and high-temperature structure evolution of ScTiO3.5 and Sc4Ti3O12-type phases.

The novel oxide defect fluorite phase ScTiO(3.5) is formed during the topotactic oxidation of ScTiO(3) bixbyite. We report the oxidation pathway of ScTiO(3) and structure evolution of ScTiO(3.5), Sc(4)Ti(3)O(12), and related scandium-deficient phases as well as high-temperature phase transitions between room temperature and 1300 °Cusing in-situ X-ray diffraction. We provide the first detailed powder neutron diffraction study for ScTiO(3). ScTiO(3) crystallizes in the cubic bixbyite structure in space group Ia3 (206) with a = 9.7099(4) Å. The topotactic oxidation product ScTiO(3.5) crystallizes in an oxide defect fluorite structure in space group Fm3m (225) with a = 4.89199(5) Å. Thermogravimetric and differential thermal analysis experiments combined with in-situ X-ray powder diffraction studies illustrate a complex sequence of a topotactic oxidation pathway, phase segregation, and ion ordering at high temperatures. The optimized bulk synthesis for phase pure ScTiO(3.5) is presented. In contrast to the vanadium-based defect fluorite phases AVO(3.5+x) (A = Sc, In) the novel titanium analogue ScTiO(3.5) is stable over a wide temperature range. Above 950 °C ScTiO(3.5) undergoes decomposition with the final products being Sc(4)Ti(3)O(12) and TiO(2). Simultaneous Rietveld refinements against powder X-ray and neutron diffraction data showed that Sc(4)Ti(3)O(12) also exists in the defect fluorite structure in space group Fm3m (225) with a = 4.90077(4) Å. Sc(4)Ti(3)O(12) undergoes partial reduction in CO/Ar atmosphere to form Sc(4)Ti(3)O(11.69(2)).

Systematic study of compositional and synthetic control of vacancy and magnetic ordering in oxygen-deficient perovskites Ca2Fe(2-x)Mn(x)O(5+y)and CaSrFe(2-x)Mn(x)O(5+y) (x = 1/2, 2/3, and 1; y = 0-1/2).

Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 Å. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca. Long-range magnetic order is also lost, giving way to spin glass or cluster-glass-like behavior below ~50 K. For the x = 0.5 phase, neutron pair distribution function (NPDF) studies show a local structure related to brownmillerite ordering of oxygen vacancies. Neutron diffraction data at 3.8 K show a broad magnetic feature, incommensurate with any multiple of the chemical lattice, and with a correlation length (magnetic domain) of 6.7(4) Å.

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 = 7.5011(2) Å, and c = 5.0706(1) Å with Sc(3+) and V(3+) ions fully ordered on the A and B sites of the perovskite cell. The vanadium oxygen octahedra [V-O(6)] display cooperative Jahn-Teller (JT) type distortions, with predominance of the tetragonal Q(3) over the orthorhombic Q(2) JT modes. The orthorhombic perovskite shows Arrhenius-type electrical conductivity and undergoes a transition to triclinic symmetry space group P-1 close to 90 K. Below 60 K, the magnetic moments of the 4 nonequivalent vanadium ions undergo magnetic long-range ordering, resulting in a magnetic superstructure of the perovskite cell with propagation vector (0.5, 0, 0.5). The magnetic moments are confined to the xz plane and establish a close to zigzag antiferromagnetic mode.

Composition, structure, bonding and thermoelectric properties of "CuT2P3" and "CuT4P3", members of the T(1-x)(CuP3)x series with T being Si and Ge.

Through electron microprobe analysis, X-ray and neutron diffraction, it has been established that "CuT(2)P(3)" and "CuT(4)P(3)" (T = Si, Ge) adopt the cubic or tetragonally distorted zinc blende structures in which two element mixtures are present on both atomic sites. One site contains the Cu/T mixture while the other site is occupied by T and P. The structure of "CuT(2)P(3)" and "CuT(4)P(3)" can be derived from that of silicon or germanium, in which the single Si or Ge site is broken into two independent sites by the preferential Cu and P substitution. The phases appear to be members of the extended series with a general formula of T(1-x)(CuP(3))(x). The Cu-P ratio of 1 : 3 provides 4 e(-) per atom and optimizes the atomic interactions. Thermoelectric performance of "CuSi(2)P(3)", "CuGe(2)P(3)" and "CuGe(4)P(3)" was evaluated from low temperatures to 400 K through resistivity, Seebeck coefficient and thermal conductivity measurements. The Ge-containing phases show a metallic-type behaviour and "CuSi(2)P(3)" is semiconducting with a narrow band gap. The ZT values are bigger for the Ge-containing phases and reach values of 8.49 x 10(-3) for "CuGe(2)P(3)" and 1.09 x 10(-2) for "CuGe(4)P(3)" at room temperature.

In situ powder X-ray diffraction, synthesis, and magnetic properties of the defect zircon structure ScVO(4-x).

We report the formation pathway of ScVO(4) zircon from ScVO(3) bixbyite with emphasis on the synthesis and stability of the novel intermediate defect zircon phase ScVO(4-x) (0.0 < x