Synthesis of a bismuth germanium oxide source material for Bi4Ge3O12 crystal growth

A technique has been developed for the preparation of a modified source material for the crystal growth of bismuth orthogermanate, Bi₄Ge₃O₁₂ (BGO). It includes dispersion of molten bismuth through mixing with germanium oxide (GeO₂) powder in a rotating reactor, followed by oxidation with oxygen. The source material thus prepared contains, in addition to bismuth and germanium oxides, considerable proportions of germanates (Bi₂GeO₅, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀), which improve the reactivity of the components of the source material during homogenization before the crystal growth process. After sintering at 880°C, the density of the modified source material (3.9 g/cm³) is a factor of 1.5 higher than that of a source material prepared from Bi₂O₃ and GeO₂ powders. BGO crystals grown using the synthesized source material possess good scintillation characteristics.     

Dynamics of energy absorption versus crystallization in Bi4Ge3O12 (BGO) amorphous materials

Theoretical and experimental determinations show that the intrinsic luminescence of BGO materials is strongly influenced by GeO₄⁻ tetrahedra around Bi³⁺ ions. Besides Bi³⁺ transitions, the excitonic spectra mask the BGO bandgap. Theoretical computations give the bandgap at 5.19 eV compared with the experimental one at 5.17 eV in BGO crystals and a significant decrease at 3.26 eV in the amorphous materials. This is due to the high disordering of the GeO₄⁻ tetrahedral which also reduces the refractive index of the amorphous materials. Formation of excitonic states and their overlap with the Bi³⁺ transitions suggests that the energy absorption takes place via the p-electrons of the O₂⁻ ions and is then transferred to the Bi³⁺p-electrons (excited states) close to the conduction band. Light emission appears after de-excitation to the ground state.     

Scintillating properties of pure and doped BGO ceramics

The ceramic processing and characterization of Bi₄Ge₃O₁₂ pure and doped with Eu³⁺ and Nd³⁺ was performed in order to investigate its potential use in radiation detector devices. Single phase Bi₄Ge₃O₁₂ in pure state and containing 1% of the dopands Nd³⁺ and Eu³⁺ were produced via a solid state route and their photoluminescent and radioluminescent properties were investigated. When excited at 200–230 nm, pure BGO ceramics presented a wide photoluminescent band emission centered at 450 nm, assigned to the Bi³⁺ internal transitions. For the doped samples under the same excitation, this wide band was superposed by the emission peaks of the rare earth dopands, at around 600 nm for BGO:Eu³⁺ and at 350 nm, 430 and 600 nm for BGO:Nd³⁺. Radioluminescence measurements presented similar results and allowed the determination of the light output efficiency of the three scintillators. The values determined were 4 × 10³ photons/MeV for BGO:Nd and 5.9 × 10³ photons/MeV for BGO:Eu, which are higher than the value 3.9 × 10³ photons/MeV determined previously for the pure ceramic. A selective sensibility of the BGO:Eu ceramics to the nature and energy of the radiation, which is not observed in pure samples, was also presented and discussed.     

Direct atomic emission analysis of bismuth and germanium oxides and bismuth orthogermanate crystals using two-jet arc plasma

Simple, high-speed procedures have been proposed for direct analysis of Bi₂O₃, GeO₂, and crystals of bismuth orthogermanate (BGO) by atomic emission spectroscopy with a high-power two-jet arc plasma as an excitation source. The detection limits for 36 impurities have been shown to lie in the ranges of 0.008–2 (Bi₂O₃), 0.006–4 (GeO₂), and 0.008–3.5 μg/g (BGO).     

A TEM study and non-isothermal crystallization kinetic of tellurite glass-ceramics

The glass transition temperature was studied via differential thermal analysis of glasses in the system (100 − x)TeO₂–5Bi₂O₃–xZnO and (100 − x)TeO₂–10Bi₂O₃–xZnO where x = 15, 20, 25 in mol%. The crystallization behavior and microstructure development of the 0.7TeO₂/0.1Bi₂O₃/0.2ZnO glass during annealing were investigated by non-isothermal differential thermal analysis (DTA), X-ray diffractometry, and transmission electron microscopy. The glass transition temperature, crystallization temperature, and the nature of crystalline phases formed were determined. From the heating rate dependence of the glass transition temperature, the glass transition activation energy was derived. From variation of DTA peak maximum temperature with heating rate, the activation energies of crystallization were calculated to be 305.8 and 197 kJ mol⁻¹ for first and second crystallization exotherms, respectively. Moreover, synthesized crystalline Bi_3.2Te_0.8O_6.4, Bi₂Te₄O₁₁, and Zn₂Te₃O₈ were investigated. In addition, the change in particle size with increasing annealing time was observed by high-polarized optical microscope.     

Non-isothermal crystallization kinetics of niobium-doped BGO70 glasses

Niobium-doped BGO glass of composition 85[3Bi₂O₃–7GeO₂ (BGO70)]–Nb15 was investigated for its kinetic parameters n and activation energies E _i : i = 1, 2, g of transformations via available models. Two crystallization exothermal peaks were observed for all heating histograms exploiting 5, 10, 15, and 20 K/min heating rates following the glass transition in non-isothermal DTA curves. An exothermal shoulder prior to first crystallization peak P₁ was identified as thermally favorable crystallizing metastable phase Bi₂GeO₅. P₁ was assigned to thermally stable crystal phase Bi₄Ge₃O₁₂. T _g lied between 729 and 731 K ± 4 K; T _p1 varied from 835–855 K ± 2 K, and T _p2 had values 965–986 K ± 2 K. Independent of the model exploited, activation energies E _g, E _p1, and E _p2 were 32.89 ± 3.1, 47.33 ± 0.72, and 62.74 ± 0.72 kcal/mol, respectively. P₁ corresponds to crystalline disks of Bi₄Ge₃O₁₂, and P₂ identified stable phase BGO crystal rods growing inward from the surface imbedded in glass matrix. Niobium doping modified the transformation kinetic parameters n and E _a of the composition by providing a control on growth mechanism for BGO platelets or rods.     

Compositional dependence of the structural and dielectric properties of Li<Subscript>2</Subscript>O–GeO<Subscript>2</Subscript>–ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

(10Li₂O–20GeO₂–30ZnO–(40-x)Bi₂O₃–xFe₂O₃ where x = 0.0, 3, 6, and 9 mol%) glasses were prepared. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, DC and AC conductivities, and dielectric properties (constant ε′, loss tan δ, AC conductivity, σ _ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of iron ion concentration. The analysis of the results indicate that, the density and molar volume decrease with an increasing of iron content indicates structural changes of the glass matrix. The glass transition temperature T _g and onset of crystallization temperature T _x increase with the variation of concentration of Fe₂O₃ referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter ΔT decrease with increase Fe₂O₃ content, indicates an increasing concentration of iron ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BiO₃, BiO₆, ZnO₄, GeO₄, and GeO₆. The structural changes observed by varying the Fe₂O₃ content in these glasses and evidenced by FTIR investigation suggest that the iron ions play a network modifier role in these glasses while Bi₂O₃, GeO₂, and ZnO play the role of network formers. The temperature dependence of DC and AC conductivities at different frequencies was analyzed using Mott’s small polaron hopping model and, the high temperature activation energies have been estimated and discussed. The dielectric constant and dielectric loss increased with increase in temperature and Fe₂O₃ content.     

Spectral Absorptivity and Thermal Conductivity of BGO and BSO Melts and Single Crystals

The present work describes the results of spectral absorptivity, α, and thermal conductivity, λ, studies for compound oxides Bi₄Ge₃O_12, Bi₁₂GeO_20, Bi₄Si₃O_12, and Bi₁₂SiO₂₀ in molten and monocrystalline states. The data for the spectral absorptivity were obtained by placing the sample onto a mirror and using the transmission method. To obtain the data on the thermal conductivity of crystals, the stationary method of two identical samples was used. The data for the thermal conductivity of melts were obtained by a new stationary relative method in which the thermal conductivity of the crystal is used as a reference. Special attention is focused on numerical and experimental error analysis at high temperature. The studies have shown that α in the range of a transmission band strongly depends on crystal purity. It varies from 0.0005 cm⁻¹ to 0.03 cm⁻¹ for Bi₄Ge₃O₁₂ and reaches 0.15 cm⁻¹ for Bi₄Si₃O₁₂. It was found that α is significantly greater for melts than for crystals, reaching (150 to 200) cm⁻¹ for the Bi₄Ge₃O₁₂ melt. The thermal conductivity of the melts under investigation was found to be much smaller than that of the corresponding crystals.     

Depolymerization of GeO2 and GeO2 · Sb2O3 glasses by Bi2O3

Glasses that contain at least 60 mol% GeO₂ were prepared in the Bi₂O₃ · GeO₂ and Bi₂O₃ · Sb₂O₃ · GeO₂ systems. Their densities, refractive indices, and infra-red spectra were recorded. Negative molar volume deviations and positive refraction deviations occur for all of the binary glasses. These create deviations for the 60 to 80 mol % GeO₂ ternary glasses that indicate non-ideal mixing when Sb³⁺ substitutes for Bi³⁺. Also, the main Ge-O stretching vibration shifts to as low as 695 cm^?1 for the Bi₂O₃-rich binary and ternary glasses. All of these findings show that Bi₂O₃ more effectively depolymerizes GeO₂ than does Sb₂O₃. The probable structural reasons for this behaviour are discussed.     

Effects of glass components on crystallization and dielectric properties of BST glass–ceramics

Crystallization behavior was studied for glass powders in which some portions of AlF₃ in the net composition of 60(Ba_0.7Sr_0.3)TiO₃–25SiO₂–15AlF₃ were replaced with Ga₂O₃ or Bi₂O₃. The replacement with Ga₂O₃ resulted in a progressive increase in crystallization temperature, which effectively assisted the viscous sintering of glass powders to produce densified BST glass–ceramics at relatively lower temperatures. For the Bi₂O₃-replaced glass powders, an increasing amount of Bi₂O₃ replacement lowered the crystallization temperature and yielded less densified glass–ceramics containing a considerable amount of glassy phase. The temperature dependence of permittivity was estimated for the Ga₂O₃- and Bi₂O₃-replaced glass–ceramics as a function of sintering conditions and the amount of replacement, respectively.     

Silver Diffusion and Clustering in Oxyfluoride Glasses Investigated by Molecular Dynamics Simulations

Glasses with compositions (97 – x)[PbF₂:GeO₂]–3Al₂O₃–xAg₂O, with the PbF₂:GeO₂ ratio equals to 1.5 and x varying from 0 to 3%, form silver surface films after thermal treatment near the glass transition temperature. The NPT molecular dynamics simulations of a glass composition 56.4PbF₂–37.6GeO₂–3Al₂O₃–3Ag₂O have been performed, where 0, 20, 40, 60, and 100% of the Ag⁺ ions were reduced to Ag by the fluoride ions. The simulations showed that the silver atoms aggregate into clusters of increasing numbers and sizes as the silver atoms content increases. In addition, the silver atoms diffusion coefficients are at least one order of magnitude larger than the fastest ion in the matrix. These results are consistent with the rapid formation of the metallic surface film observed experimentally.     

Raman spectra of Bi–Sr–Ca–Cu–O high temperature superconductors

Two high-temperature superconducting BiSrCaCuO compounds were fabricated as Bi_2.1Sr₄Ca₄Cu₃O_10+δ and Bi₂Sr₂Ca₂Cu₃O_10+δ. The X-ray diffraction patterns of both the compounds show that Bi_2.1Sr₄Ca₄Cu₃O_10+δ contains predominantly the high T_c 2223 phase, and Bi₂Sr₂Ca₂Cu₃O_10+δ the low T_c 2212 and high T_c 2223 phases, in equal amounts. The Raman spectra of these samples exhibit broad bands in the 430–512 cm^-1 region, as in the lead-substituted 2212 phase. Change in configuration due to the presence of the 2223 phase in the sample is indicated by the broadening of the 465 cm^-1 line. New bands at 611 and 678 cm^-1 are observed. Peaks in the 430–512 cm^-1 region exhibit a softening when the temperature is reduced to 93 K. This revised version was published online in November 2006 with corrections to the Cover Date.     

Study of structure and properties of ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the ternary system ZnO–Bi₂O₃–P₂O₅ were prepared and studied in two compositional series 50ZnO–xBi₂O₃–(50 − x)P₂O₅ and (50 − y)ZnO–yBi₂O₃–50P₂O₅. Two distinct glass-forming regions were found in the 50ZnO–xBi₂O₃–(50 − x)P₂O₅ glass series with x = 0–10 and 20–35 mol.% Bi₂O₃. All prepared Bi₂O₃-containing glasses reveal a high chemical durability. Small additions of Bi₂O₃ (∼5 mol.%) improve thermal stability of glasses. All glasses crystallize on heating within the temperature range of 505–583 °C. Structural studies by Raman and ³¹P MAS NMR spectroscopies showed the rapid depolymerisation of phosphate chains within the first region with x = 0–15 and the presence of isolated Q⁰ phosphate units within the second region with x = 20–35. Raman studies showed that bismuth is incorporated in the glass structure in BiO₆ units and their vibrational bands were observed within the spectral region of 350–700 cm⁻¹. The evolution of properties and the spectroscopic data are both in accordance with a network former effect of Bi₂O₃.     

Preparation,characterization and photocatalytic activity of Bi2O3–MgO composites

A series of Bi₂O₃–MgO composites were synthesized by solvent-thermal method. It was found that the Bi₂O₃–MgO composites perform much better than TiO₂ (P25), Bi₂O₃ and MgO in the photocatalytic degradation of rhodamine B (RhB) in the presence of HCl and under irradiation of visible light (λ > 400 nm). The effects of Bi/Mg molar ratio, crystallization temperature of Bi₂O₃–MgO and reaction conditions on photocatalytic activity were studied. The best performance was observed over the composite with Bi:Mg molar ratio equal to 2:1 that had been subject to crystallization at 120 °C for 20 h. In addition, the photocatalytic efficiency of the composite can be significantly enhanced by the presence of hydrochloric acid. The prepared samples were characterized by XRD and UV–vis DRS techniques. The relationships between the structure and photocatalytic performance of the as-prepared Bi₂O₃–MgO samples were also investigated.     

Influence of different synthesizing steps on the multiferroic properties of Bi5Fe1Ti3O15 and Bi5Fe0.5Co0.5Ti3O15 ceramics

The compounds Bi₅FeTi₃O₁₅ (BFTO) and Bi₅Fe_0.5Co_0.5Ti₃O₁₅ (BFCT) were prepared by incorporating BiFeO₃ (BFO) and BiFe_0.5Co_0.5O₃ (BFCO) into the host Bi₄Ti₃O₁₂ (abbreviated as BFTO-1 and BFCT-1) and by the conventional solid-state reaction method (abbreviated as BFTO-2 and BFCT-2). X-ray analysis indicates a four-layer Aurivillius phases with an orthorhombic symmetry. At room temperature, the remnant polarization (2P _r) of BFTO-1, BFTO-2, BFCT-1, and BFCT-2 samples are measured to be 11.0, 3.5, 13, and 6.3 μC/cm², respectively, and the corresponding remnant magnetization (2M _r) are about 2.72 × 10⁻³ memu/g, 1.51 × 10⁻³ memu/g, 7.6 and 2.1 memu/g, respectively. Both BFTO-1 and BFCT-1 samples exhibit the dielectric peaks at around 755 and 772 °C in their ε–T curves, respectively.     

Spectroscopic properties of B2O3–PbO–Bi2O3–GeO2 glass doped with Sm3+ and gold nanoparticles

Heavy metal oxide B₂O₃–PbO–Bi₂O₃–GeO₂ transparent glass doped with Sm³⁺ was synthesized and implanted with Au⁺ using energy of 300 keV and fluence of 1 × 10¹⁶ cm⁻². The annealing of the implanted glass at moderate temperature below the glass transition temperature induced the nucleation of gold nanoparticles, confirmed by the characteristic absorption band in the visible range and by transmission electron microscopy. Using Miés and Doylés theories for the surface plasmon resonance, the average size of the gold nanoparticles was about 4.6 nm, similar to the values observed by transmission electron microscopy. It was also observed the crystallization of a thin layer of the glass at the implanted surface after annealing, detected by X-ray diffraction and scanning electron microscope. Visible and near-infrared emission of Sm³⁺ was enhanced after annealing of the glass implanted with gold. Judd–Ofelt parameters and radiative parameters were calculated for the glass doped with Sm³⁺ with and without gold nanoparticles.     

Luminescent properties of Eu, Tb or Bi activated yttrium germanates

Preliminary studies were conducted on Eu³⁺, Tb³⁺ or Bi³⁺ doped Y₂Ge₂O₇, Y₂GeO₅ and Y₄GeO₈ phosphors. Both photoluminescence and cathodoluminescent properties of the materials were measured. Among these materials, the luminescent intensities of Y₂Ge₂O₇:Eu, Y₂GeO₅:Tb and Y₂Ge₂O₇:Bi are relatively high and the luminescent colors of them are red, green and blue, respectively. In order to improve the luminescent properties for field emission display applications, further optimization is necessary. In addition, X-ray powder diffraction results indicate that Y₄GeO₈ phase forms in an orthorhombic unit cell, the parameters of which are: a=1.4976(5) nm, b=0.9357(6) nm, c=0.5885(3) nm, V_cell=0.82467(2) nm³.     

Alteration of amorphous Bi4Ge3O12 by Tl2O and Na2O

Ternary thallium and sodium bismuth germanate glasses were prepared and their densities refractive indices, and infra-red spectra obtained. The effect of univalent cations on the stability of the arrangement of decoupled GeO₄ tetrahedra in amorphous Bi₄Ge₃O₁₂ was compared with the effect of divalent cations. The molar volumes of glasses with the nominal mol% composition 20 M₂O(MO).20 Bi₂O₃.60 GeO₂ are directly related to the size and charge type of M^z+. However, the molar volumes of such glasses are inversely related to the ionic potential (z/r) of M^z+. The infra-red spectra of these ternary glasses exhibitv _Ge?O shifts that reflect the presence of both isolated and small clusters of GeO₄ tetrahedra compared to amorphous Bi₄Ge₃O₁₂. This slight increase in the degree of polymerization appears to be directly related to the ionic potential of M^z+.     

Spectroscopic properties of red Bi4Ge3O12 by vertical Bridgman method

Red Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by vertical Bridgman (VB) method. The structure of this crystal was determined by XRD. The absorption and emission spectra of the red BGO in visible and near infrared region (NIR) were measured at room temperature. The emission intensity of the red BGO is weaker than that of ordinary BGO at about 500 nm. Interestingly, the red BGO shows a significant emission band centered at about 1495 nm. The red BGO faded and its properties recovered after ultraviolet (UV) irradiation or annealing.     

Effect of some VA group modifiers on R2O3 (R = Sb,Bi)–ZnF2–GeO2 glasses doped with CuO by means of spectroscopic and dielectric investigations

Transparent glasses 40Sb₂O₃–20ZnF₂–(40 − x)GeO₂:xCuO, and 40Bi₂O₃–20ZnF₂–(40 − y)GeO₂:yCuO with x = 0, 0.6 and 0 ≤ y ≤ 1 wt% were prepared by melt quenching technique and were characterized by XRD and differential thermal analysis. Spectroscopic studies like optical absorption, FTIR, Raman, EPR and dielectric parameters (such as ?′, loss(tan δ), and σ_ac) were carried out to examine the modifier and dopant effect on zinc germanate glass network. Optical absorption and EPR data have revealed that the environment of Cu²⁺ ions is more ionic in bismuth series rather than antimony glasses. Reduced bismuth ions have been found in pure and at lower concentration of dopant in Bi₂O₃ mixed glasses, which are useful for IR amplifications. FTIR and Raman spectra have indicated the conversion of GeO₄ to GeO₆ structural units by forming cross linking bonds like Bi–O–Ge, Ge–O–Cu, etc., and open the glass network with integration of Bi₂O₃ and CuO doping. It is also confirmed by decreasing T_g and E_g values. The temperature dependence of dielectric parameters at different frequencies was interpreted in terms of structural changes in the glass network.