Single-crystal structure of vanadium-doped La2Mo2O9

A high-precision X-ray diffraction study of single crystals of two compositions—La₂Mo_1.78V_0.22O_8.89 and La₂Mo_1.64V_0.36O_8.82—was performed. In the vanadium-doped compounds, as in the structure of the metastable β_ms phase of pure La₂Mo₂O₉, the La and Mo atoms and one of the three oxygen atoms are displaced from the threefold axis, on which they are located in the high-temperature β phase. The structure contains two partially occupied oxygen sites. It was shown that molybdenum atoms are partially replaced by vanadium atoms, which are not involved in the disordering, are located on the threefold axis, and are shifted toward one of the oxygen atoms. This is consistent with the temperature-induced changes in the structure of La₂Mo₂O₉ and the changes in the properties of these crystals caused by the introduction of vanadium atoms into the structure.     

Synthesis and properties of oxide ion conductor Pr2Mo2O9 with La2Mo2O9 structure

Polycrystalline Pr₂Mo₂O₉ samples have been prepared by solid-state synthesis and single crystals of this compound have been grown. Pr₂Mo₂O₉ is unstable in the temperature range 700–900°C and partially decomposes with the formation of Pr₂Mo₃O₁₂ at these temperatures, but upon further heating to 1000–1050°C, Pr₂Mo₂O₉ is recovered. At room temperature, the structure, polymorphism, and physical properties of Pr₂Mo₂O₉ are similar to those of the known oxide ion conductor La₂Mo₂O₉. Pr₂Mo₂O₉ exhibits a reversible first-order phase transition to the cubic phase in the temperature range 520–540°C. The electric conductivity of Pr₂Mo₂O₉ is close to that of La₂Mo₂O₉ and amounts to 3.5 × 10⁻² S/cm at 700°C. The conductivity of Pr₂Mo₂O₉ is described by the Arrhenius law in the low-temperature phase and by the Vogel-Fulcher-Tammann equation in the high-temperature phase.     

Structure and properties of antimony-doped lanthanum molybdate La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript>

Polycrystalline samples of the composition La₂Mo_{2 − x} Sb _x O_{9 − y} , where 0 ≤ x ≤ 0.05, were prepared by solid-phase synthesis. Single crystals of La₂Mo_1.96Sb_0.04O_8.17 were obtained by spontaneous crystallization from flux. The structure of the metastable β _ms phase of this compound was determined at room temperature by X-ray diffraction. It was found that the La, Mo, and O1 atoms are displaced from the threefold axis on which they are located in the high-temperature β phase. It was shown that molybdenum atoms in the crystal structure are partially replaced by antimony atoms, which are located on the threefold axis. In antimony-doped crystals, lanthanum atoms partially return to the site on the threefold axis and the coordination environment of molybdenum cations becomes more ordered, thus facilitating the stabilization of the cubic phase at room temperature. Calorimetric measurements (DSC) showed that the introduction of Sb as the dopant into the La₂Mo₂O₉ structure leads to a decrease in the temperature of the α → β phase transition from 570 to 520°C and to the partial suppression of this transition. The temperature behavior of the conductivity confirms the DSC data. Thus, doping with Sb contributes to the stabilization of the cubic phase at room temperature.     

Specific features of phase transitions and the conduction of La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> oxide-ion conducting compound doped with vanadium

The X-ray powder analysis, calorimetric studies, and conductivity measurements of a series of ceramic La₂Mo_2−x V _x O _y specimens with different vanadium content are performed with the aim of following the dynamics of phase formation of the low-temperature α, high-temperature β, and metastable β _ms phases. At x ≥ 0.06, the cubic phase becomes stable and the monoclinic phase vanishes; therefore, the main α → β transition is suppressed. According to the data of differential thermal analyses, a weak thermal anomaly is observed in the range 450–470°C at x ≥ 0.06. This anomaly is indicative of the β _ms → β transition due to the conversion of the cubic phase with statically disordered oxygen atoms into the cubic phase with dynamic disorder. The conductivity of the high-temperature β phase obeys the Vogel-Tammann-Fulcher law.     

Synthesis and phase transitions of oxide-ion conducting compound La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> doped with alkaline metals

The specific features of synthesis, polymorthism, and electric conductivity of oxide-ion conducting compounds La_{2 − x} Me _x Mo₂O_{9 − y} , where Me = Na, K, Rb, or Cs, have been studied. Ceramic samples were obtained by solid-state synthesis in the temperature range of 960–1100°C. The regions where solid solutions exist have been found to depend on the temperature of the sample firing. According to the calorimetric and electrophysical data, the phase transition from the monoclinic phase (α) to the cubic phase (β) in samples doped with potassium and rubidium disappears at x = 0.02 and 0.04, respectively. In these cases the only transition from the cubic β _ms phase to the high-temperature cubic β phase is observed near 450°C. Doping with sodium and cesium does not suppress the α → β phase transition.     

Crystal structure of La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystals doped with bismuth

Precision X-ray diffraction studies of La_{2 − x} Bi _x Mo₂O₉ (x = 0.04, 0.06, and 0.18) single crystals are performed. It is found that in the compounds doped with bismuth, analogously with the structure of the metastable β_ms phase of pure La₂Mo₂O₉ (LM), the La, Mo1, and O1 atoms deviate from the threefold axis on which they are located in the high-temperature β phase. It is shown that bismuth atoms substitute for part of lanthanum atoms and occupy a position at the threefold axis in the neighborhood of the split lanthanum position. The implantation of bismuth atoms in the LM structure results in the return of a part of the molybdenum atoms to the position at the threefold axis. The occupancy of this position is equal to the occupancy of the bismuth atomic position.     

Crystal structure of samarium hexamolybdoaluminate Sm[Al(OH)6Mo6O18] · 11H2O

The structure of a new complex of samarium(III) with a hexamolybdoaluminate ion, Sm[Al(OH)₆Mo₆O₁₈] · 11H₂O, was established by the methods of X-ray diffraction analysis. The crystallographic data are as follows: sp. gr. Pbc2₁, a = 10.927(4) Å, b = 11.757(5) Å, c = 22.327(9) Å, V = 2868(1) ų, Z = 4, ρ _calcd = 3.040 g/cm³, R = 0.084, R _W = 0.198. In the [Al(OH)₆Mo₆O₁₈ ^3? anion, an Al atom is surrounded by six Mo atoms with distorted octahedral coordination. The anions are linked into chains via Sm atoms. The coordination polyhedron of a Sm atom is a tricapped trigonal prism with the vertices being occupied by two terminal oxygen atoms of two adjacent anions and seven water molecules.     

Synthesis and electrical properties of Aurivillius phases in the Bi<Subscript>2</Subscript>MoO<Subscript>6</Subscript>-Bi<Subscript>2</Subscript>VO<Subscript>5.5</Subscript> system

To search for new oxygen conductive phases, a series of Bi₂V_{1 ? x} Mo_xO_{5.5 + x/2} ceramic samples have been synthesized in which the extreme compositions Bi₂VO_5.5 (x = 0) and Bi₂MoO₆ (x = 1) are single-layer Aurivillius phases having ferroelectric properties and high ionic oxide conductivity. It is established that single-layer Aurivillius phases exist in the composition ranges 0 ≤ x ≤ 0.1 and 0.9 ≤ x ≤ 1. Additional phases with BiVO₄ and Bi₆Mo₂O₁₅ structures are found in the range 0.2 ≤ x ≤ 0.8. The presence of molybdenum stabilizes the orthorhombic β-Bi₂VO_5.5 phase at room temperature. The conductivity of solid solutions based on Bi₂VO_5.5 differs only slightly from that of pure bismuth vanadate. Conductivity of solid solutions based on Bi₂MoO₆ is half an order of magnitude higher than that of pure bismuth molybdate.     

Crystal structure of the cubic β<Subscript>ms</Subscript>-phase of a La<Subscript>1.82</Subscript>Bi<Subscript>0.18</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystal at 33 K

Single crystals of the cubic β_ms-phase of La_1.82Bi_0.18Mo₂O₉ have been characterized for the first time by precision X-ray diffraction at 33 K. The structure of a crystal determined at T = 33 K is identical to the structure studied at room temperature. It is confirmed that the La, Mo1, and O1 atoms deviate from their positions on the threefold axis in the high-temperature β-phase; part of lanthanum atoms is substituted by bismuth atoms, which are located on the threefold axis; part of the molybdenum atoms return to the position on the threefold axis.     

Simulation of ion transport in layered cuprate La2SrCu2O6

Oxygen diffusion in layered cuprate La₂SrCu₂O₆ has been simulated by the molecular dynamics method in the temperature range of 300–2500 K. The lattice is found to transform at temperatures above 1550 K; this transformation is accompanied by a change in the pair correlation functions. The abrupt change in the oxygen diffusion coefficient in the range of 1500–1550 K may indicate the presence of a phase transition to the superionic state. The motion of oxygen anions could be traced at the microscopic level. It has been proven for the first time that the La₂SrCu₂O₆ crystal lattice allows, along with displacements of O1 ions within the CuO₂ layer, their migration from the crystallographic positions to the intermediate unoccupied O3 positions. The motion of O2 anions is also fairly complicated: they move not only in their layer over the O2 positions but they also jump to the neighboring layer to occupy the O1 positions. The oxygen diffusion coefficient in layered cuprate La₂SrCu₂O₆ exceeds that in cuprates with perovskite structure and structure of the K₂NiF₄ type (at the same temperatures), which indicates that this material has good prospects for electrodes with mixed ionic-electronic conductivity.     

Oxygen-conducting crystals of La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript>: Growth and main properties

Single crystals of the anionic conductor La₂Mo₂O₉ are grown by crystallization from a nonstoichiometric melt. Their polymorphism and domain structure, as well as the temperature dependences of conductivity and dielectric permittivity, are studied. In the temperature range 750–600°C, the conductivity of these crystals is as high as 10^?1–10^?2 Ω^?1 cm^?1.     

Structural phase transition in CuFe2O4 spinel

A structural transition with a reduction in symmetry of the high temperature cubic phase (sp. gr. Fd3m) to the tetragonal phase (sp. gr. I4₁/amd) and the appearance of a ferrimagnetic structure occur in CuFe₂O₄ copper ferrite at T ≈ 440°C. It is established by an experiment on a high-resolution neutron diffractometer that the temperature at which long-range magnetic order occurs is higher than that of tetragonal phase formation. When cooling CuFe₂O₄ spinel from 500°C, the equilibrium coexistence of both phases is observed in a fairly wide temperature range (～40°C). The composition studied is a completely inverse spinel in the cubic phase, and in the tetragonal phase the inversion parameter does not exceed few percent (x = 0.06 ± 0.04). At the same time, the phase formed upon cooling has a classical value of tetragonal distortion (γ ≈ 1.06). The character of temperature changes in the structural parameters during the transition from cubic to tetragonal phase indicates that this transition is based on the Jahn-Teller distortion of (Cu,Fe)O₆ octahedra rather than the mutual migration of copper and iron atoms.     

Epitaxial growth of β-Ga2O3 nanocolumns on MgO substrate

Crystal structure of Ga₂O₃ nanocolumns grown on MgO substrate is analyzed by electron microscopy and electron diffraction study. The nanocolumns have β-Ga₂O₃ structure and the growth direction is [0 0 1] directions. A thin γ-Ga₂O₃ layer grows on the substrate to relax the lattice misfit between MgO and β-Ga₂O₃. The bottom layer of the γ form layer is disordered by {1 1 0} stacking faults. Poly crystalline structure that consists of β-Ga₂O₃ and γ-Ga₂O₃ nanocrystals exists between the β form nanocolumns and the γ form layer. The γ form changes gradually to the β form growing up to the nanocolumn. Though various crystal forms appear in a specimen, oxygen cubic close-packed lattice in crystal structures has always the same orientation in all layers including the MgO substrate.     

Structure of the metastable cubic B<Subscript>1</Subscript> phase of the La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystal

The structure of the metastable B₁ phase of the La₂Mo₂O₉ single crystal is investigated using X-ray diffraction. It is established that the crystal structure of the compound under investigation is described by the cubic unit cell with the parameter a = 7.158(5) Å, which makes it possible to index approximately 84% of the reflections measured for this single crystal. The structure of the metastable cubic B₁ phase is characterized by a local lowering of the symmetry for the La and Mo atoms, which are displaced from their positions on the threefold axis, thus forming three sites around it with an occupancy of 0.333(2). The O(1) atom in the structure of the metastable cubic B₁ phase remains in the 4a position on the threefold axis but occupies it by only 86%. The O(2) and O(3) atoms located in a general position occupy their own sites with occupancies of 0.77(2) and 0.35(2), respectively. The final R factor of the refinement of this structural model is 2.52%.     

Synthesis and electrophysical properties of some rare-earth molybdates with fluorite-like structure of the Nd<Subscript>5</Subscript>Mo<Subscript>3</Subscript>O<Subscript>16</Subscript> type

Polycrystalline samples of PbLn ₄Mo₃O₁₆ (Ln = La, Pr, Nd, or Sm), CdLn ₄Mo₃O₁₆ (Ln = La, Nd, Sm, Eu, or Tm), and PbLa_4–xNd_xMo₃O₁₆ (0 ≤ x ≤ 3) with the cubic fluorite-like structure and sp. gr. Pn n have been obtained by solid-phase synthesis in air. The specific conductivity of lead compounds is established to reach 10^–2 S/cm (which is an order of magnitude higher than that for cadmium compounds). The conductivity value is shown to reach a maximum at a concentration ratio of rare-earth elements of Nd: La = 1: 1.     

Crystal structure of β′-Zn2V2O7

The crystal structure of the high-temperature modification of zinc pyrovanadate, namely, β′-Zn₂V₂O₇, is refined by the full-profile Rietveld method (GSAS) using the high-temperature X-ray diffraction data. The crystals are monoclinic (space group C2/m, Z = 2); the unit cell parameters are as follows: a = 6.9324(2) Å, b = 8.4394(2) Å, c = 5.0326(1) Å, and β = 108.272(2)°. Comparative analysis of the crystal structures of β′-Zn₂V₂O₇, β-Mn₂V₂O₇, and Cd₂V₂O₇ is performed.     

Synthesis and Electrical Properties of a Fluorite-Like Nd<Subscript>5</Subscript>Mo<Subscript>3</Subscript>O<Subscript>16</Subscript> Compound with Partial Substitution of Molybdenum by Tungsten,Niobium, or Vanadium

The phase formation of Nd₅Mo_{3 – x}W _x O_16.5, Nd₅Mo_{3 – x}Nb _x O_{16.5 – х/2}, and Nd₅Mo_{3 – x}V _x O_{16.5 – х/2} solid solutions based on a fluorite-like Nd₅Mo₃O_16.5 compound (mixed conductor with interstitial oxygen conductivity) has been studied. The electrical conductivity of doped compounds obeys the Arrhenius law and, at a low impurity content, is as high as 0.03–0.08 S/cm at 800°C. Substitution of Mo⁶⁺ cations by V⁵⁺ and Nb⁵⁺ cations reduces the interstitial oxygen content, which causes a decrease in the solid-solution electrical conductivity by 1–2 orders of magnitude and a decrease in the cubic unit-cell parameter. A wide diffuse anomaly with a maximum of about 1500–4000 has been observed in the temperature dependence of the permittivity for all single-crystal and polycrystalline samples in the range of 300–900°C.     

Crystal structure of the metastable cubic β<Subscript>ms</Subscript> phase of La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystal at <Emphasis Type="Italic">T</Emphasis> = 33 K

The structure of the cubic metastable β_ms phase of La₂Mo₂O₉ single crystal has been precisely investigated by X-ray diffraction at 33 K for the first time. The measurement of the unit-cell parameter of this crystal in the range from room temperature to 33 K showed that the unit-cell parameter and volume change continuously in this range. The crystal has a similar structure at T = 33 K and at room temperature. A local lowering of the symmetry for La and Mo atoms, caused by their displacement, is confirmed, and a similar displacement (which was not observed at room temperature) is revealed for O(1) atoms. The thermal parameters for O(2) and O(3) atoms do not change with a decrease in temperature, in contrast to the thermal parameters of Mo, La, and O(1) atoms. This fact indicates that the O(2) and O3 atoms in this crystal are statically disordered.     

Specific features of the flux growth of bulk crystals of high-temperature modification of BaB2O4

High-quality single crystals of the high-temperature phase of barium metaborate (α-BaB₂O₄) up to 100–120 g in weight are grown from a flux in the ternary system BaO-B₂O₃-Na₂O. The growth temperature is below the α → β phase transition temperature. The conditions necessary for growing α-BaB₂O₄ crystals under metastable conditions are determined and the morphology and optical quality of the crystals grown are investigated.     

Preparation and properties of La2O3–Ga2S3 glass-ceramics for IR materials

IR transmitting glass-ceramics were prepared by isothermal treatments of La₂O₃–Ga₂S₃ glasses. The glass-ceramics were characterized by crystalline phases, microstructure, Vickers hardness and mid (3–5 μm) IR transmittance. The Nd₂S₃-doped La₂O₃–Ga₂S₃ glass-ceramics consisting of a large numbers of (LaO)₄Ga_1.72S_4.58, α-(LaO)GaS₂ and α-Ga₂S₃ crystals with <1 μm in size exhibit a high hardness of 5.3 GPa and a mid IR transparency of >60%.