Luminescence of Thin Bi2W2O9 Films

The luminescence spectra of thin Bi₂W₂O₉ films have been investigated. The spectra were separated into elementary components by the Alentsev–Fock method. The radiation band with a maximum at 2.43 eV in the luminescence spectrum of Bi₂W₂O₉ has been assigned to the Frenkel autolocalized excitons. The luminescence bands with maxima at 2.10 and 1.90 eV have been assigned to the emission of the centers whose energy levels are located in the forbidden band. The luminescence of the Bi₂W₂O₉ films is due to the emission of the WO₆ complex.     

Luminescence centers in bismuth-containing oxytungstate ceramics

We have studied the photoexcitation and luminescence spectra of Bi₂WO₆, Y₂WO₆ and Y₂WO₆:Bi ceramics. We used the Alentsev-Fock method to decompose the spectra into elementary components. The emission bands with maximum at 2.93 eV in the luminescence spectrum of Bi₂WO₆, 3.02 eV in the luminescence spectrum of Y₂WO₆, and 2.95 eV in the luminescence spectrum of Y₂WO₆:Bi are assigned to luminescence of self-localized Frenkel excitons. The bands with maxima at 2.35 eV and 1.90 eV in the spectrum of Bi₂WO₆, 2.25 eV and 1.75 eV in the spectrum of Y₂WO₆, and 2.35 eV and 1.85 eV in the spectrum of Y₂WO₆:Bi are connected with oxygen vacancies. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 688–691, September–October, 2007.     

Luminescence centers in Sc2O3

Sc₂O₃ luminescence spectra are studied. The spectra are separated into elementary bands by the Alentsev–Fock method. It is established that the luminescence spectra consist of a number of overlapping bands with maxima at 3.5; 3.05; 2.65; 2.35, and 2.05 eV. The band at 3.5 eV is interpreted as emission of self-localized excitons, and the other bands, as defect-center recombination. L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 776–778, November–December, 1997.     

Luminescence of Thin Bismuth Germanate Films Having the Structure of Eulitine and Benitoite

The luminescence and luminescence excitation spectra of thin films of Bi₄Ge₃O₁₂ and Bi₂Ge₃O₉ were investigated. The spectra were decomposed into elementary components by the Alentsev-Fok method. It has been established that the luminescence spectra of thin Bi₄Ge₃O₁₂ and Bi₂Ge₃O₉ films have a similar structure and that each contains three luminescence bands with maxima at 2.70, 2.40, and 2.05 eV and at 2.73, 2.40, and 1.95 eV, respectively. Comparison of the results obtained with the well-known results of investigation of the luminescence of Bi₁₂GeO₂₀ and Bi₂O₃ suggests that the luminescence in the compounds considered is caused by the radiation processes that proceed in structural complexes of similar configuration that contain the bismuth ion in the nearest oxygen environment. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 377–380, May–June, 2005.     

Luminescence centers in ceramics of yttrium, scandium, and bismuth oxytungstates

An investigation is made of the luminescence spectra of Me₂WO₆ ceramics (Me=Y, Sc, Bi). The spectra were decomposed into elementary components by the Alentsev—Fock method. Radiation hands with a maximum at 3.02 eV in the Y₂WO₆ luminescence spectrum, at 2.8 eV in the ScWO₆ spectrum, and at 2.93 eV in the Bi₂WO₆ spectrum are assigned to the light emission of self-localized Frenkel excitons. The bands with maxima at 2.25 and 1.75 eV in the Y₂WO₆ spectrum, at 2.36 and 1.9 eV in the Sc₂WO₆ spectrum, and at 2.35 and 1.9 eV in the Bi₂WO₆ spectrum are related to oxygen vacancies. Translated from Zhurnal Prikladnoi Spektroskopii, Vol 67, No. 2, pp. 273–275, March–April, 2000.     

Energy Levels in the Forbidden Band of the Bi4Ge3O12 Ceramics

Thermally stimulated luminescence in the Bi₄Ge₃O₁₂ ceramics and also in the ceramics of the parent components Bi₂O₃ and GeO₂ is investigated. The similarity of the curves of the thermally stimulated luminescence in bismuth germanate with the structure of eulytine Bi₄Ge₃O₁₂ and sillenite Bi₁₂GeO₂₀ is explained. The relation of the thermally stimulated luminescence band in Bi₄Ge₃O₁₂ (with a maximum at 143 K) to the disruptions in the germanium sublattice and of the thermally stimulated band (with a maximum at 187 K) to the recombination processes in the bismuth sublattice is shown. It has been established that the light sum in the Bi₄Ge₃O₁₂ ceramics is stored most effectively upon excitation by light in an energy region of 4.4 eV.     

Luminescence centers in thin films of lead and bismuth tungstates

Luminescence spectra of thin films of PbWO₄ and Bi₂WO₆ are invesigated. The Alentsev-Fock method is used to separate the spectra into elementary components. The emission bands with maxima at 2.8 eV in PbWO₄ and at 2.93 eV in Bi₂WO₆ luminescence spectra are interpreted as the emission of self-localized Frenkel excitons. The bands with maxima at 2.35 and 1.75 eV in PbWO₄ and at 2.35 and 1.9 eV in Bi₂WO₆ are related to oxygen vacancies. L’vov State University, 50, Dragomanov St., L'vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 143–145, January–February, 1998.     

Study of glasses and glass ceramics in Bi2O3-GeO2-Fe2O3 and Bi2O3-GeO2-Cr2O3 systems by optical spectroscopy

The ferroelectric Bi₂GeO₅ crystalline phase is synthesized by heat treatment of 1Bi₂O₃-1GeO₂-xFe₂O₃ and 1Bi₂O₃-1GeO₂-yCr₂O₃ glasses. The obtained glass ceramics and initial glasses are studied using X-ray diffraction analysis and optical spectroscopy. The dielectric characteristics are measured, and the Curie temperature is determined. The effect of chromium and iron ions on the absorption spectra and dielectric properties of glasses and glass ceramics is determined.     

Effect of excess Bi2O3 on the electrical properties and microstructure of (Bi1/2Na1/2)TiO3 ceramics

(Bi_1/2Na_1/2)TiO₃ ceramics (BNT) with 0–6 mol% of excess Bi₂O₃ are prepared by conventional solid-state sintering. The electrical properties of the samples are examined. The addition of excess Bi₂O₃ reduces the leakage current of BNT ceramics significantly, thus facilitating the poling process, and improves their piezoelectric properties slightly for certain amounts of added Bi₂O₃. BNT ceramics have very high dielectric constants and dissipation factors at low frequency and high temperature due to their high conductivity. Adding excess Bi₂O₃ to BNT ceramics affects their dielectric behavior and phase transition temperatures. Grain growth is suppressed by adding Bi₂O₃ and no second phase is observed for BNT ceramics with up to 6 mol% of excess Bi₂O₃ added.     

Influence of Oxygen Vacancies on the Luminescence Spectra of Thin Bi4Ge3O12 Films

Luminescence spectra of thin Bi₄Ge₃O₁₂ films annealed in air and in vacuum have been investigated. It has been established that the luminescence spectra for different forms of excitation consist of three bands with maxima at 2.70, 2.40, and 2.05 eV. The relation of the bands with maxima at 2.40 and 2.05 eV to the centers that incorporate an oxygen vacancy has been shown. The separated emission bands have been interpreted.     

Luminescence centers in α-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

Luminescence photoexcitation spectra of α-Bi₂O₃ ceramics are investigated. Luminescence spectra were deconvoluted into fundamental components using the Alentsev-Fok method. It is established that the luminescence spectra of α-Bi₂O₃ ceramics consist of three fundamental bands with maxima at 2.75, 2.40, and 1.97 eV. A comparison of the results with those from an investigation of luminescence of various modifications of bismuth oxide and bismuth germanates suggests that luminescence of these compounds is caused by radiation processes that occur in structural complexes that contain the bismuth ion in a nearest oxygen environment. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 672–676, September–October, 2008.     

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Thermally stimulated luminescence of bismuth germanate ceramics with the benitoite,eulitine, and sillenite structures

Thermally stimulated luminescence (TSL) of Bi₂Ge₃O₉, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀ and the primary components Bi₂O₃ and GeO₂ was studied under x-ray excitation. Thermal activation energies and frequency factors of trapping centers in the studied ceramics were determined. The relationships of TSL bands of the studied ceramics with maxima at 141–145 and 166–170 K and damage to the Ge sublattice and of TSL bands with maxima at 104–110 and 180–190 K and recombination processes in the Bi sublattice were demonstrated. Recombination processes causing luminescence upon nonequilibrium charge carrier release from trapping centers occur in structural complexes of similar configuration that contain the Bi ion in a nearest environment of O atoms. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 359–364, May–June, 2008.     

Magnetic,dielectric and optical properties of five-layered Aurivillius phase Bi6Fe2Ti3O18-based ceramics

The structural, magnetic, dielectric and optical properties of Aurivillius Bi₆Fe₂Ti₃O₁₈-based ceramics were investigated in detail. The replacement of Co for Fe/Ti ions obviously varies the grain morphology. Compared with Bi₆Fe₂Ti₃O₁₈ (BFTO) with antiferromagnetic ordering, a spin glass state can be observed in Bi_5.25La_0.75Fe₂Ti₃O₁₈ ceramic, while other samples exhibit the ferromagnetic behavior. The specimen Bi₆Fe₂Ti₂(NbCo)_0.5O₁₈ (BFTNCO) represents the largest remanent magnetization M_r of 0.93emu/g among all the samples, which can be attributed to the combination of a short lattice parameter c and a large lattice distortion as well as more magnetic ions in a unit cell. The room-temperature dc conductivity of BFTNCO is one order magnitude lower than that of BFTO. In addition, the band gaps of Co-doped samples are about 0.2eV smaller than these of Co-free samples. This work provides a promising path forward to tailor the multiferroic and optical properties in five-layered Aurivillius compounds.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Luminescence of Bismuth‐Activated Ceramics of Yttrium and Scandium Oxides

The luminescence spectra of Y₂O₃:Bi and Sc₂O₃:Bi ceramics have been investigated. The spectra have been resolved into elementary components by the Alentsev–Fock method. It has been established that the luminescence is attributed to emission centers of three types, two of which are due to the replacement of Y³⁺ (or Sc³⁺) by Bi³⁺ at the nodes of the crystal lattice of Y₂O₃ (or Sc₂O₃) with the point symmetry C ₂ and C _3i . The emission center Bi³⁺ in the position C_3i leads to the appearance of blue luminescence with maxima at 3.03 eV for Y₂O₃:Bi and at 3.05 eV for Sc₂O₃:Bi; this luminescence is attributed to the transition ³ P ₁–¹ S ₀. The emission center Bi³⁺ in the position C ₂ initiates green luminescence (which is also related to the ³ P ₁–¹ S ₀ transition in Bi³⁺) with a maximum in the region of 2.40 eV in Y₂O₃:Bi and in the region of 2.46 eV in Sc₂O₃:Bi. The red luminescence band with maxima at 1.85 eV in Y₂O₃:Bi and at 1.95 eV in Sc₂O₃:Bi is related to the presence of structural defects.     

Thermostimulated Luminescence of PbWO4, Bi2WO6, and Y2WO6 Ceramics

Thermostimulated luminescence (TSL) of PbWO₄, Bi₂WO₆, and Y₂WO₆ ceramics on x-ray excitation is investigated. The spectral luminosity of the thermostimulated luminescence is analyzed. The thermal activation energies conforming to the corresponding thermostimulated luminescence peaks are determined. It is established that on emptying trapping centers radiative recombination occurs at the intrinsic-luminescence centers associated with tungsten-oxygen complexes WO₄ ^2–.     

Bi4Cu0.2V1.8 O11–δ based membrane electrochemical reactors for propane oxidation at moderate temperaturesbased membrane electrochemical reactors for propane oxidation at moderate temperatures

Bi₄Cu_0.2V_1.8O_11–δ membrane material was synthesized by following the solid-state method. The oxygen permeation flux at 673 K was found to be 0.5 ml/cm² by the use of an external electric power source. The oxidation of propane was selected as the probe reaction using the Bi₄Cu_0.2V_1.8O_11–δ electrochemical membrane reactor. It was found that such electrochemical membrane reactors could have potential application in the area of alkanes selective oxidation at moderate temperatures. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

Study on structural, thermal, sintering and conductivity of Cu-Co doubly substituted Bi4V2O11

Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi₄V₂O₁₁, has led to the formation of the Bi₄V_1.8Cu_0.2−xCo_xO_10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form, is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10⁻² S·cm⁻¹ at 600 °C.