Development of methods of X-ray diffraction analysis for determining the composition and structure of sillenite-family crystals

A methodology for refining the crystal structure of sillenites of nominal composition Bi₂₄ M ₂O₄₀ based on the choice of the correct initial model and thermal atomic parameters is reported. The validity of the approach proposed is demonstrated by examples of crystals with M = Si, Fe, or V, for which the real composition is found with allowance for the composition of each structural site. Individual structural details are confirmed by IR and Raman spectroscopy data.     

Growth and characterization of photorefractive Bi12TiO20 single crystals

Photorefractive Bi₁₂TiO₂₀ single crystals of high optical quality were grown in a resistive heating furnace from high temperature nonstoichiometric (10:1) solutions of Bi₂O₃ and TiO₂ at pulling rates 0.3–0.8 mm/h at rotation 20–30 rpm along the <001> and <011> axis. Powder X-ray analysis, Laue method, and electron-probe microanalysis were used for characterization. BTO crystals have the bcc structure of sillenite type with a₀ = 10.178(8) Å. The chemical composition of the crystals can be written down as Bi_{12.1 ± 0.2}Tio_{0.96 ± 0.09}O_20.1. Natural optical activity ρ of BTO crystals is 6.3 ± 0.2 deg/mm at λ = 0.633 μm and 11.9 ± 0.2 deg/mm at λ = 0.5145 μm, optical absorption coefficient α = 0.42 ± 0.04 cm⁻¹ at λ = 0.633 μm and linear electro-optic coefficient r₄₁ = r₅₂ = r₆₃ = 5.3 pm/V. Fanning effect in the “fiber-like” BTO sample was studied and double phase conjugation with conversion efficiency up to 8% was observed in a wide range of incidence angles of the pump at λ = 0.633 μm for 2 × 3 mW input light power.     

Improved Single Crystal Growth of the Boron Sillenite “Bi24B2O39” and Investigation of the Crystal Structure

The boron sillenite, up to now known as the 12:1 compound Bi₂₄B₂O₃₉ in the system Bi₂O₃ – B₂O₃ andcrystallizing in the space group I23, melts incongruently at 655 °C only about 25 K above the eutectic tie line and corresponding to a steep liquidus line. Single crystals with dimensions larger then 1 cm ³ have been successfully grown in [100], [110], and [111] direction by an improved Top Seeded Solution Growth (TSSG) technique equipped with crucible weighing, accelerated crystal rotation technique and air‐cooled pulling rod. The structure of the boron sillenite was analyzed by X‐ray diffraction method, which was possible due to the high crystalline quality achieved. A defect‐free sublattice corresponding to a Bi‐O framework is isostructural with all sillenites, but a 2 Å environment around the origin is occupied by different cations with different population coefficients. The best calculation results in the formula Bi_24.5BO_38.25 which is more Bi‐rich than the 12:1 assumption.     

Structural investigation of bismuth borate glasses and crystalline phases

Glasses of the system: xBi₂O₃-(100−x)B₂O₃ (x = 20 to 66 mol%) were prepared and characterized by density, DSC, UV-visible absorption and ¹¹B MAS-NMR spectroscopy. Glass molar volume increases while the glass transition temperature decreases with Bi₂O₃ concentration. Densities of some bismuth borate glasses are found to be greater or very close to those of single crystal phases with equal composition. B¹¹ MAS-NMR studies determined that the fraction of tetrahedrally coordinated borons (N₄) is maximum at 42 mol% of Bi₂O₃ and that there is a local maxima in N₄ at Bi₂O₃ concentration of 50 mol%. Glasses containing Bi₂O₃ concentration of 33 mol% and higher show an unusual, intense absorption band just below the optical band gap. Two crystalline phases: Bi₃B₅O₁₂ and Bi₄B₂O₉ were prepared by devitrification of glasses and characterized by X-ray diffraction, FTIR and ¹¹B MAS-NMR studies. Both crystalline phases contained significantly lower N₄ than glasses with equal composition.     

Effect of Bi2O3 proportion on physical, structural and electrical properties of zinc bismuth phosphate glasses

The variation in physical, structural and electrical properties has been studied as a function of Bi₂O₃ content in 20ZnF₂-(10 + x) Bi₂O₃-(70-x) P₂O₅, 0 ≤ x ≤ 10 mol% glasses, which were prepared by melt quenching technique and characterized by differential thermal analysis (DTA). Colorless samples, which have no absorption peaks, are obtained for 10 and 12 mol% of Bi₂O₃ and the glasses are slowly becoming brownish from 15 to 20 mol% of Bi₂O₃ which exhibit two absorption peaks at ~ 370 nm, ~ 450 nm correspond to Bi° transitions ⁴S_3/2 → ²P_3/2 and ⁴S_3/2 → ²P_1/2 respectively. The decrease in ³P₁ → ¹S₀ transition of Bi³⁺ photo luminescence emission for 18 and 20 mol% of Bi₂O₃ and increase in optical absorption area shows the reduction of Bi³⁺ to Bi°. From FTIR studies it is observed that an addition of Bi₂O₃ decreases the P―O―P covalent bond by forming P―O―Bi bonds due to high polarizing nature of Bi³⁺ ions. Dielectric parameters like ε', tan δ and a.c. conductivity σ_ac are found to increase and activation energy for a.c. conduction is found to decrease with the increase in the concentration of Bi₂O₃. Density of defect energy states is found to increase for higher concentration of Bi₂O₃ and is discussed according to quantum mechanical tunneling (QMT) model.     

Structure of phases of the sillenite family in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

X-ray diffraction studies of sillenite Bi₂₄V₂O₄₀ single crystals grown by the hydrothermal method are performed for a separate crystal and powdered crystals. It is found that the composition of the two specimens is described by the (Bi_{24 − x} ▭ _x )[Bi _y ³⁺V_1−y ⁵⁺]₂ O₄₀ general formula with completely populated oxygen sites but differs in the content of vacancies at the bismuth site (this was established for the first time) and the Bi: V ratio at the tetrahedral site. The structural models of all the vanadium-containing sillenites reported in the literature are considered, and the possibility that Bi atoms are located at the centers of BiO₄ tetrahedra is established.     

Effects of tantalum doping on microstructure and ferroelectric properties of Bi4Ti3O12 thin films prepared by a sol–gel method

Tantalum-substituted Bi₄Ti₃O₁₂ (Bi₄Ti_3-x/5Ta_x/5O₁₂, BTTO) thin films were fabricated on Pt(111)/Ti/SiO₂/Si(100) substrates by sol–gel technology. The effects of various processing parameters, including Ta content (x=0～0.08) and annealing temperature (500～800 °C), on the growth and properties of thin films were investigated. X-ray diffraction analysis shows that the BTTO thin films have a bismuth-layered perovskite structure with preferred (117) orientation. With the increase of Ta content, the grain size of film decreased slightly, and highly (117)-oriented BTTO films were obtained in the composition of x=0.06. Ta doping on the B-site of Bi₄Ti₃O₁₂ could induce the distortion of oxygen octahedral and decrease the oxygen vacancy concentration by a compensating effect. The highly (117)-oriented BTTO thin films with x=0.06 exhibits the maximum remanent polarization (2P_r) of 50 μC/cm² and a low coercive field (2E_c) of 104 kV/cm, fatigue free characteristics up to ≧ 10⁸ switching cycles.     

Correlation Between the Impurity Content,the Average Charge State of Chromium Cations and Optical Absorption in Sillenite Crystals Doped by Chromium in Wide Range of Concentrations

Single crystals of sillenites (Bi₁₂SiO₂₀, Bi₁₂TiO₂₀) doped with chromium in a wide range of concentrations from 1 x 10^‐5 up to 1.8 x 10^‐2 wt. % were grown by the Czochralski and top‐seed solution growth (TSSG) techniques. To estimate the content and the average charge state of chromium in the grown crystals the chemical analysis by the modified diphenylcarbazide method was applied. The dependencies of the chromium distribution coefficient, the average charge state of Cr cations, and optical absorption on the Cr concentration were found. Both the shift of the absorption edge toward lower frequencies and the appearance of an additional absorption band in the near IR were observed when the chromium concentration in the crystals was increased. The experimental data suggest that chromium has at least two charge states and occupies probably different positions in the sillenite unit cell.     

The influence of low-temperature annealings on the structural and superconducting properties of Bi 2212 and Bi 2201 whiskers

The influence of post-growth short-term low-temperature annealings (O₂, 400°C, 5–15 min) on the composition, crystal structure, and superconductivity of Bi₂Sr₂CaCu₂O_{8 + δ} and Bi₂Sr₂CuO_{6 + δ} oxycuprate whiskers freely grown in gas cavities has been investigated. The optimal conditions for growth in closed gas cavities in a flux and post-growth annealing in oxygen were found, making it possible to obtain high-quality superconducting Bi 2212 and Bi 2201 whiskers in a wide doping range (from heavily underdoped to optimally doped) with a small rocking curve half-width (～0.1^°–0.2^°) and narrow superconducting transition (ΔT = 1.5–2 K).     

Substitution effects on ferroelectric,leakage current and anti‐fatigue characteristic of Bi4‐xSbxTi3O12 thin films

Bi_4‐xSb_xTi₃O₁₂ (BSTO) (x = 0, 0.03, 0.04, 0.05, 0.06 and 0.07) thin films have been fabricated on Pt/Ti/SiO₂/Si substrates by sol‐gel method. The effects of various Sb³⁺ content on microstructure and ferroelectric properties of systems are investigated. XRD show that Bi_4‐xSb_xTi₃O₁₂ (x≠0) thin films prefer (117) orientation. The substitution Sb³⁺ for Bi³⁺ reduces the grain size of the film surface. Compared to the BTO (x = 0) film, Bi_4‐xSb_xTi₃O₁₂ films display exciting electric properties. Especially when x = 0.04, the film Bi_3.96Sb_0.04Ti₃O₁₂ has achieved the max 2Pr value of 87μC/cm². This film also has a better anti‐fatigue characteristic, which can be up to 10¹⁰ switching cycles without fatigue. The leakage current density improved with J = 8×10⁻⁸ A/cm².     

Glass composition dependence of luminescence due to Ge2+ center in germanate glasses

Germanate glasses were prepared by the melt-quenching method using an assembled hot-thermocoupler equipped in a sample chamber of a fluorescence spectrometer, and subsequently their luminescence and excitation spectra were measured. In the GeO₂ glass, luminescence bands due to the Ge²⁺ center appeared at the central wavelengths of 300 and 395 nm, their excitation bands being at 250 and 330 nm, respectively. In the (100 − x)GeO₂ − xM_mO_n glasses, for M_mO_n = B₂O₃ (x ≦ 50), SiO₂ (x ≦ 40), and Al₂O₃ (x ≦ 2), the luminescence intensity and therefore the amount of the Ge²⁺ center increased with increasing the content of M_mO_n, where M^(2n/m)+ ions (B³⁺, Si⁴⁺, and Al³⁺) have lower basicities than a Ge⁴⁺ ion. Contrarily, for M_mO_n = Li₂O (x ≦ 30), Na₂O (x ≦ 20), K₂O (x ≦ 20), CaO (x ≦ 20), SrO (x ≦ 3), BaO (x ≦ 15), ZnO (x ≦ 20), Ga₂O₃ (x ≦ 10), Sb₂O₃ (x ≦ 20), Bi₂O₃ (15 ≦ x ≦ 25), TiO₂ (x ≦ 3), and Nb₂O₅ (x ≦ 10), the luminescence intensity and the amount of the Ge²⁺ center rapidly decreased with increasing the amount of additives and disappeared, where M^(2n/m)+ ions (Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Ga³⁺, Sb³⁺, Bi³⁺, Ti⁴⁺, and Nb⁵⁺) have higher basicities than a Ge⁴⁺ ion.     

FTIR and ultrasonic investigations on modified bismuth borate glasses

Studies on xRO · 30Bi₂O₃ · (70−x)B₂O₃ glasses have been carried out (0 ? x ? 30 mol%, R = Zn, Ba). Elastic properties and Debye temperature have been investigated using sound velocity measurements at 4 MHz. The ultrasonic parameters along with the IR spectroscopic studies have been employed to explore the role of divalent cations in the structure of the studied glasses. Analysis of infrared spectra indicates that RO is preferentially incorporated into the borate network, forming BO₄ units. It is assumed that Bi₂O₃ enters the structure in the form of BiO₆ only. The change of density and molar volume with RO content reveals that BO₄ units linked to R²⁺ cations are denser than those linked to positive sites in the Bi₂O₃ network. Predicted values of four co-ordinated boron put forward questions about the reliability of assignment of structural units that Bi₂O₃ may form.     

Synthesis and crystal growth of sillenite phases in the Bi2O3 ‐ TiO2 ‐ Nb2O5 system

The synthesis of Bi₂O₃‐Nb₂O₅ sillenite phase (BNbO) and the solubility of this phase with Bi₁₂TiO₂₀ was investigated by solid‐state reaction synthesis and niobium doped Bi₁₂TiO₂₀ (BTO:Nb) crystals were grown by the Top Seeded Solution Growth (TSSG) technique. The structures of polycrystalline compounds were checked by X‐ray powder diffraction method at room temperature. The correct composition of the sillenite phase stabilized with niobium was determined as Bi₁₂[Nb_0.17Bi_0.83]O_19.7 (BNbO) with unit cell parameter a = 10.261(2) Å. The system BTO‐BNbO is poorly soluble, but niobium doped BTO crystals were grown from the liquid composition 10Bi₂O₃ : xTiO₂ : (1‐x)/2 Nb₂O₅, with x = 0.95 and 0.90. A niobium concentration limit in the liquid phase is established in order to grow BTO:Nb with good crystalline quality. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and refinement of the composition of Bi-Sr-Ca-Cu oxide crystals

The composite structure of the red phase, which accompanies the 2212 and 2201 superconducting phases prepared upon cooling of a melt in the Bi-Sr-Ca-Cu-O system, is revealed by scanning electron microscopy and X-ray diffraction analysis. The matrix component in two crystals I and II under investigation has a monoclinic structure with space group C2/m and the unit cell parameters a = 21.832(2) and 21.8142(9) Å, b = 4.3809(4) and 4.3771(2) Å, c = 12.9430(12) and 12.9378(6) Å, β = 102.832(2)° and 102.839(1)°, and V = 1207.0(2) and 1204.45(9) ų, respectively. The composition is described by the general formula Bi₄(Ca_2?x Sr_1.5+x )O_9.5 with x = 0.13(2) for crystal I and x = 0.19(2) for crystal II. The matrix contains intergrowing clusters of the composition Cu₂O. It is demonstrated that the presence of the second component is structurally justified by the commensurability of the systems of body-centered subcells of cations in the host matrix and anion sublattices in the structure of the Cu₂O oxide.     

Ionic conductivity of Bi12(V,Bi)O20 + δ single crystal (δ = 0.27) with a sillenite-type structure

The ionic conductivity of nonstoichiometric Bi₁₂(V_0.89Bi_0.03)O_20.27 single crystal with a sillenite-type structure has been investigated by impedance spectroscopy; its conductivity at 673 K is 2 × 10^?3 S/cm, which is about two orders of magnitude higher than the conductivity of oxide superionic conductor single crystal Zr_0.88Y_0.12O_1.94. As follows from crystallochemical analysis, ion transport in Bi₁₂(V_0.89Bi_0.03)O_20.27 is due to additional O^2? ions, which arise due to oxygen nonstoichiometry.     

Raman and luminescence studies of alkali borate tungstate glasses

Raman and luminescence spectroscopy were used to determine the structure of alkali borate tungstate glasses: M₂O(B₂O₃)₂·xWO₃, M = Li or Na (0 < x < 1). Raman scattering results showed the dominant tungstate species in these photochromic glasses to be tetrahedral WO₄⁼. At high concentrations of WO₃, WO₃·H₂O, and W₂O₇⁼ are also present. Luminescence measurements provided evidence for an octahedral WO₃ structure not identified by the Raman results. The results also revealed a possible change in the structure of the glasses similar to that observed in alkali borate glasses and associated with the “borate anomaly”. In addition, preliminary measurements are reported on the variation of the band gap, density, index of refraction, and the elastic coefficient C₁₁ determined by Brillouin scattering with composition.     

A new nonlinear optical crystal: Bi2O2(OH)(NO3)

The nonlinear optical (NLO) properties of Bi₂O₂(OH)(NO₃) crystals have been reported for the first time. Bi₂O₂(OH)(NO₃) crystals with dimensions of 1.3×1.2×0.1 mm³ have been grown by hydrothermal method, and the crystals characterized by X‐ray powder diffraction (XRD), SEM and IR. The measured second harmonic generation (SHG) effect of Bi₂O₂(OH)(NO₃) was about 7 times that of KDP. The mechanism responsible for the large SHG of Bi₂O₂(OH)(NO₃) was explained according to its structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and characterization of CuO doped Bi2O3–B2O3–BaO–ZnO glass system for transparent dielectric layer

The electrical, thermal, optical, and morphological properties of CUO doped Bi₂O₃–B₂O₃–BaO–ZnO glasses were studied as a PbO-free, low firing transparent dielectric layer for plasma display panels (PDP). CuO improved the transmittance of Bi₂O₃–B₂O₃–BaO–ZnO by up to 84% in the visible region, eliminating a yellowish color typical of Bi₂O₃–B₂O₃–BaO–ZnO. A slight absorption within the near infrared (NIR) region was also observed. The glass transition temperature (T_g), thermal coefficient of expansion (TCE), and root-mean square (rms) roughness of 0.005 wt% CuO doped Bi₂O₃–B₂O₃–BaO–ZnO were found to be 455 °C, 81.4 × 10⁻⁷/K, respectively, and 162 ± 14 Å, which satisfied the requirements for a transparent dielectric layer for PDP application.     

Crystallization of bismuth oxide nano-crystallites in a SiO2–PbO–Bi2O3 glass matrix

SiO₂–PbO–Bi₂O₃ glasses having the composition of 35SiO₂–xPbO–(65 ? x)Bi₂O₃ (where x = 5, 20 and 45; in mol%) have been prepared using the conventional melting and annealing method. Differential scanning calorimetry (DSC) was employed to characterize the thermal behavior of the prepared glasses in order to determine their crystallization temperatures (T_cr). It has been found that T_cr decreases with the decrease of Bi₂O₃ content. The amorphous nature of the prepared glasses as well as the crystallinity of the produced glass–ceramics were confirmed by X-ray powder diffraction (XRD) analysis. SiPbBi₂O₆ glass nano-composites, comprising bismuth oxides nano-crystallites, were obtained by controlled heat-treatment of the glasses at their (T_cr) for 10 h. Transmission electron microscopy (TEM) of the glass nano-crystal composites demonstrates the presence of cubic Bi₂O₃ nano-crystallites in the SiPbBi₂O₆ glass matrix. Nano-crystallites mean size has been determined from XRD line width analysis using Scherrer's equation as well as from TEM; and the sizes obtained from both analyses are in good agreement. These sizes varied from about 15 to 170 nm depending on the chemical compositions of parent glasses and, consequently, their structure. Interestingly, replacement of the Bi₂O₃ by PbO in the glass compositions has pronounced effect on the nature, morphology and size of the formed nano-crystallites. Decrease of the Bi₂O₃ content increases the size of the nano-crystallites, and at the lowest Bi₂O₃ extreme, namely 20 mol%, introduces minority of the monoclinic Bi₂O₄ in addition to the cubic Bi₂O₃. The crystallization mechanism is suggested to involve a diffusion controlled growth of the bismuth oxide nano-crystallites in the SiPbBi₂O₆ glass matrix with the zero nucleation rate.     

Computer modeling of the local structure, mixing properties, and stability of binary oxide solid solutions with corundum structure

An original technique of computer modeling of substitutional solid solutions has been applied to Al₂O₃-Cr₂O₃, Al₂O₃-Fe₂O₃, and Fe₂O₃-Cr₂O₃ binary systems. The parameters of semiempirical interatomic potentials were optimized using the experimentally studied structural, elastic, and thermodynamic properties of pure components. Among point defects, the most energetically favorable ones for all three oxides are Schottky vacancy quintets. To model (M _x ¹ M _{1 ? x} ² )₂O₃ solid solutions, 4 × 4 × 1 disordered supercells with M ¹: M ² cation ratios of 1: 5, 1: 2, 1: 1, 2: 1, and 5: 1 have been constructed in the cation sublattice containing 192 atoms. The mixing enthalpy and volume, interaction parameters, bulk moduli, and vibrational entropy were found by minimizing the interatomic interaction energy in supercells with the symmetry P1. Calculations of the Gibbs energy made it possible to estimate the fields of stability of the Al₂O₃-Cr₂O₃ and Al₂O₃-Fe₂O₃ solid solutions; these estimates were compared with the experimental data. Histograms of M-M, M-O, and O-O interatomic distances were constructed and the local structure was analyzed for the Al_1.0Cr_1.0O₃, Al_1.0Fe_1.0O₃, and Fe_1.0Cr_1.0O₃ compositions.