Synthesis,physical properties,and atomic structure of niobium-doped RbTiOPO<Subscript>4</Subscript> crystals

Single crystals of solid solutions Rb_1?xTi_1?xNb_xOPO₄(RTP: Nb) were grown and the temperature dependences of their dielectric and nonlinear optical properties and electric conductivity were studied. The maximum possible niobium content in these crystals is close to x = 0.1. The niobium impurities decelerate growth of {100} faces, and crystals take a plate-like habit. With increasing doping level, ferroelectric phase transitions diffuse and their temperature decreases. A specific feature of the dielectric properties of RTP: Nb crystals is the appearance of a broad relaxation maximum ε₃₃ in the temperature range 200–600°C caused by the formation of vacancies in the rubidium cation sublattice. The intensity of second-harmonic generation under laser irradiation decreases with increasing niobium content. The atomic structure of a crystal with x = 0.01 is studied and it is established that niobium substitutes for titanium only in Ti(1) positions.     

On the effect of structural and symmetrical features of potassium titanyl phosphate crystals with different contents of niobium,antimony, and zirconium on the second-harmonic intensity

A model is proposed, which shows that, at small deviations from the centrosymmetric state of the atomic structure, the quadratic nonlinear susceptibility of a crystal monotonically decreases with approach of the degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] of the electric potential function of the crystal structure to unity. The quadratic nonlinear susceptibility of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.02, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals has been measured. The degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] has been calculated for the structures of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals. It is shown that, at \(\eta _{\overline 1 } \)[φ(r)] > 0.7, the relationship between the quadratic nonlinear susceptibility of the investigated crystals and the degree of their central symmetry \(\eta _{\overline 1 } \)[φ(r)] is in qualitative agreement with the proposed model.     

Synthesis and properties of zirconium-doped RbTiOPO<Subscript>4</Subscript> single crystals

Single crystals of the solid solutions RbTi_{1 ? x} Zr _x OPO₄ (0.015 < x < 0.034) were grown and their physical properties were studied. In the presence of zirconium in the crystals with the maximum content x = 0.034, the ferroelectric phase transition and the high-temperature transition from the orthorhombic to the cubic phase are shifted to lower temperatures by 100 and 50°C, respectively. In the temperature range from 700°C to room temperature, the conductivity of doped crystals decreases compared to that of the undoped crystals. It is of particular interest that the intensity of the second-harmonic generation of the doped crystals is substantially higher than that of RbTiOPO₄.     

The Changes of Thermal,Dielectric, and Optical Properties at Insertion of Small Concentrations of Ammonium to K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Crystals

The structure of (K_1–x(NH₄)_x)₃H(SO₄)₂ crystals with a low ammonium concentration and the behavior of their thermal, optical, and dielectric properties in a temperature range of 275–500 K have been investigated to clarify the influence of doping on the phase transition kinetics. An examination of unit-cell parameters of (K_{1 – x}(NH₄)_x)₃H(SO₄)₂ single crystals has confirmed the existence of a superprotonic phase transition at a temperature of ≈450K. The conducting properties of single-crystal and polycrystalline samples have been studied.     

Ti/Zr isomorphism in wadeite: The crystal structure of the titanium-dominant K<Subscript>2</Subscript>(Ti<Subscript>0.55</Subscript>Zr<Subscript>0.45</Subscript>)Si<Subscript>3</Subscript>O<Subscript>9</Subscript> member of the series

The crystal structure of the titanium-rich mineral wadeite K₂(Ti_0.55Zr_0.45)Si₃O₉ from rischorrites of the Khibiny Alkaline Massif (Kola Peninsula, Russia) is studied by X-ray diffraction (XCalibur-S diffractometer, R = 0.0459): a = 6.8611(6) Å and c = 10.0611(9) Å; space group P6₃/m, Z = 6, D _x = 3.03 g/cm³. It is shown that the unit-cell parameters and volume of the mineral of mixed (Ti/Zr) composition are naturally intermediate between those of the terminal members of the isomorphous wadeite-based K₂ZrSi₃O₉–K₂(Ti_0.55Zr_0.45)Si₃O₉–K₂TiSi₃O₉ series. The expected correlation is due to the ionic radii of Zr⁴⁺ and Ti⁴⁺ which determine the lengths of Zr/Ti–O bonds in octahedra. The data of field observations and microscopic studies show that the Ti-dominant wadeite is formed on the basis of primary zirconium mineral in the course of a late imposed process under unique geochemical conditions.     

Structural study of K<Subscript>0.93</Subscript>Ti<Subscript>0.93</Subscript>Nb<Subscript>0.07</Subscript>OPO<Subscript>4</Subscript> single crystals at 30 K

The structure of a K_0.93Ti_0.93Nb_0.07OPO₄ single crystal is studied at the temperature 30 K. The measurements are performed on a four-circle HUBER-5042 diffractometer with a DISPLEX DE-202 cryostat. Processing of the diffraction data and the preliminary refinement of the model are performed using the ASTRA program package. The final refinement of the structure model is made using the JANA2000 program complex. The refinement shows that the structure of a K_0.93Ti_0.93Nb_0.07OPO₄ crystal at T = 30 K is similar to its structure at room temperature. No phase transitions are revealed. Slight temperature-induced displacements of the potassium positions in the large cavities of the mixed framework are established.     

Synthesis and an X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The synthesis and X-ray diffraction study of compound Rb₂[(UO₂)₂(C₂O₄)₃], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) Å, b = 8.8259(8) Å, c = 11.3220(7) Å, β = 105.394(2)°, and V = 770.7(1) ų; space group P2₁/n, Z = 2, and R ₁ = 0.0271. [(UO₂)₂(C₂O₄)₃]^2? layers belonging to the AK _0.5 ⁰² T ¹¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and T ¹¹ = C₂O ₄ ^2? ) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.     

High-pressure synthesis and magnetic properties of Bi<Subscript>0.5</Subscript>D<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> (<Emphasis Type="Italic">D</Emphasis> = Pb,Ba) solid solutions

Perovskites Bi_0.5D_0.5MnO₃(D = Pb, Ba) were prepared under high pressure (4 GPa) at 1200–1300°C. According to the X-ray diffraction data, crystalline Bi_0.5Pb_0.5MnO₃ has a tetragonal unit cell with the parameters a = 3.940 Å and c = 3.800 Å, whereas Bi_0.5Ba_0.5MnO₃ crystals are cubic with a = 3.940 Å. It is concluded from magnetic studies that lead-containing manganite is an antiferromagnet with T_N = 120 K, whereas Bi_0.5Ba_0.5MnO₃ is a spin glass with spin-freezing temperature T _f = 38 K. Both compounds are decomposed upon heating in air at temperatures above 500°C. With the use of synthesis in air, Bi_0.5Ca_{0.5 ? x}D _x MnO₃ solid solutions with x as high as 0.25 were obtained.     

Birefringence of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals under the action of uniaxial pressures

The influence of uniaxial mechanical pressure σ _m ≤ 150 bar on the spectral (300–800 nm) dependence of the birefringence Δn _i of (NH₄)₂SO₄ crystals is studied. The dispersion Δn _i (λ) is shown to be normal and greatly increases when approaching the absorption edge. Uniaxial pressure changes the value of dispersion dΔn _i /dλ but not its character. It is found that the simultaneous action of pressures σ _x ～ σ y ～ 560 bar results in the occurrence of a uniaxial isotropic state. Piezoelectric constants of the crystals are estimated.     

The Influence of Cation Substitution on the Kinetics of Phase Transitions in Crystals of (K,NH<Subscript>4</Subscript>)<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Solid Solutions

The structure of (K_0.967(NH₄)_0.033)₃H(SO₄)₂ crystals, belonging to the K₃H(SO₄)₂–(NH₄)₃H(SO₄)₂–H₂O salt system, has been investigated by X-ray structural analysis. The room-temperature characteristics of the atomic structure of these crystals are found to be as follows: sp. gr. C2/c, Z = 4, a = 14.7025(4) Å, b = 5.6859(2) Å, c = 9.7885(3) Å, and R/wR = 0.021/0.030%. The thermal and optical properties of (K,NH₄)₃H(SO₄)₂ and K₃H(SO₄)₂ single crystals have been investigated and compared in a temperature range of 295–500 K.     

Growth and structure of La<Subscript>3</Subscript>Zr<Subscript>0.5</Subscript>Ga<Subscript>5</Subscript>Si<Subscript>0.5</Subscript>O<Subscript>14</Subscript> crystals

The complete X-ray structure determination of Czochralski grown La₃Zr_0.5Ga₅Si_0.5O₁₄ single crystals with the Ca₃Ga₂Ge₄O₁₄ structure is performed (sp. gr. P321, a = 8.226(1) Å, c = 5.1374(6) Å, Z = 1, Mo K_α1 radiation, 1920 crystallographically independent reflections, R = 0.0166, R_w = 0.0192). The absolute structure is determined. It is shown that possible transition of some of La atoms (～1.2%) from the 3e to 6g position may give rise to the formation of structural defects.     

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.     

Investigation of zirconium phosphate Zr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>4</Subscript> during heating

Zirconium phosphate Zr₃(PO₄)₄ has been synthesized by the sol-gel technique and investigated using X-ray powder diffraction, IR spectroscopy, and differential scanning calorimetry. It has been established that the symmetry of the unit cell, R \(\bar 3\) c, which is characteristic of the NaZr₂(PO₄)₃ (NZP) family, is lowered to P \(\bar 3\) c. The behavior of the zirconium phosphate during heating has been examined using high-temperature X-ray diffraction at temperatures ranging from 25 to 575°C. It has been revealed that the structure of the zirconium phosphate is hardly subjected to expansion due to heating in the temperature ranges 25–125°C (α _a < 1 × 10^?6 K^?1, α _c < 1 × 10^?6 K^?1, Δα < 1 × 10^?6 K^?1) and 325–575°C (α _a = ?1.4 × 10^?6 K^?1, α _c < 1 × 10^?6 K^?1, Δα < ?2.4 × 10^?6 K^?1). In the temperature range 125–325°C, the synthesized compound undergoes a second-order phase transition (upon heating), which is accompanied by the contraction of the structure along all crystallographic directions. Upon cooling in the range from 75 to 25°C, the phase transition is accompanied by the expansion of the structure.     

Growth and crystal structure of binary molybdate CsFe(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>

CsFe(MoO₄)₂ single crystals have been grown by solution-melt crystallization with a charge-to-solvent ratio of 1: 3 (with Cs₂Mo₃O₁₀ used as a solvent). The crystal structure of this compound has been refined by X-ray diffraction (X8 APEX automatic diffractometer, MoK _α radiation, 356 F(hkl), R = 0.0178). The trigonal unit cell has the following parameters: a = b = 5.6051(2) Å, c = 8.0118(4) Å, V = 217.985(15) ų, Z = 1, ρ_calc = 3.875 g/cm³, and sp. gr. P \(\bar 3\) m1. The structure is composed of alternating layers of FeO₆ octahedra (with MoO₄ tetrahedra attached by sharing vertices) and CsO₁₂ icosahedra.     

Magnetization,paramagnetic susceptibility,and electrical conductivity of layered TIMnS<Subscript>2</Subscript> and TIMnSe<Subscript>2</Subscript> antiferromagnets

TlMnS₂ and TlMnSe₂ crystals have been synthesized by the method of solid-state reaction from chemical elements weighted in the stoichiometric ratio. X-ray, magnetic, and electric studies have been performed. It is established that the TlMnS₂ compound crystallizes in the tetragonal structure with the unit-cell parameters a = 7.74 Å, c = 30.60 Å, Z = 20, and ρ_x = 6.40 g/cm³; TlMnSe₂ crystallizes in the hexagonal structure with the unit-cell parameters a = 6.53 Å, c = 23.96 Å, Z = 8, and ρ_x = 6.71 g/cm³. TlMnS₂ and TlMnSe₂ are semiconductors and exhibit an antiferromagnetic character of exchange interaction.     

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.     

Dispersion of the polarization processes in Ca<Subscript>0.32</Subscript>Ba<Subscript>0.68</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystals

The switching processes in calcium barium niobate crystals CaxBa_1–x Nb₂O₆ with x = 0.32 have been investigated. The dielectric hysteresis loops observed in the samples exposed to alternating fields of different frequencies and constant amplitude have been analyzed. It is shown that the loop formation is caused by the sample heating. The sample temperature increases due to the dielectric loss energy release only up to a certain frequency, above which complete switching becomes impossible.     

Crystal structure and microtwinning of monoclinic La<Subscript>3</Subscript>SbZn<Subscript>3</Subscript>Ge<Subscript>2</Subscript>O<Subscript>14</Subscript> crystals of the langasite family

The crystal structure of monoclinic La₃SbZn₃Ge₂O₁₄ crystals from the langasite family is determined by X-ray diffraction analysis [a = 5.202(1) Å, b = 8.312(1) Å, c = 14.394(2) Å, β = 90.02(1)°, sp. gr. A2, Z = 2, and R/R _w = (5.2/4.6)%]. The structure is a derivative of the Ca₃Ga₂Ge₄O₁₄-type structure (a = 8.069 Å, c = 4.967 Å, sp. gr. P321, Z = 1). The crystal studied is a polysynthetic twin with the twin index n = 2, whose monoclinic components are related by pseudomerohedry by a threefold rotation axis of the supergroup P321.     

Crystal structure of the Ca<Subscript>3</Subscript>TaGa<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> compound

The absolute crystal structure of the Ca₃TaGa₃Si₂O₁₄ piezoelectric compound is refined using X-ray diffraction analysis. The unit cell parameters and final R factors are as follows: a = 8.112(1) Å, c = 4.9862(6) Å, space group P321, Z = 1, R = 0.98%, and R _w = 1.42%. It is shown that the configuration of the absolute crystal structure inherited from the seed material determines the positive sense of the optical activity of the crystal under investigation. The structural and acoustical characteristics of the Ca₃TaGa₃Si₂O₁₄ crystals are compared with those of the La₃Ga₅SiO₁₄ crystals.     

Novel Polyoxovanadate K<Subscript>2</Subscript>ZnV<Subscript>5</Subscript>O<Subscript>14</Subscript>: Crystal Structure and Peculiarities of Crystal Chemistry

A novel structure type has been established as a result of studying a non-merohedral microtwin of polyoxovanadate (K₂ZnV₅O₁₄) by X-ray diffractometry (R = 0.0595). The new compound, synthesized under hydrothermal conditions in the ZnCl₂–K₂CO₃–V₂O₅–H₂O system, is characterized as follows: a = 8.066(5) Å, b = 8.117(5) Å, c = 9.236(5) Å, β = 105.287(5)°, sp. P2₁/m, Z = 2, ρ_calcd = 3.54 g/cm³. Edge-shared five-core “clusters” consisting of vanadium octahedra, between which ZnO₄ tetrahedra (sharing vertices with octahedra) are located, form two-dimensional two-layer anion packets of the (ZnV₅O₁₄)^2– composition, alternating along the c axis with layers of potassium atoms. Structural peculiarities determine the morphology and color of new-phase crystals.