Hydrogen on WO3(001)

Ultraviolet photoemission measurements of the (001) surface of WO₃ show that after exposure to atomic hydrogen new states appear in the energy gap region at 2.3 and 0.9 eV below the Fermi energy. A peak at 2.2 eV was also produced by hydrogen ion bombardment. To investigate whether these surface effects were due to the formation of hydrogen tungsten bronze H_xWO₃, comparison was made with spectra from the electronically similar sodium bronze. The form of the spectra were different both in the valence band and energy gap regions indicating that hydrogen adsorption or loss of oxygen from the surface rather than formation of H_xWO₃ is the major effect.     

Intrinsic polyatomic defects in Sc2(WO4)3

The intrinsic formation of polyatomic defects in Sc₂(WO₄)₃-type structures is studied by Mott Littleton calculations and Molecular Dynamics simulations. Defects involving the WO₄²⁻ tetrahedron are found to be energetically favorable when compared to isolated W and O defects. WO₄²⁻ Frenkel and (2Sc³⁺, 3WO₄²⁻) Schottky defects exhibit formation energies of 1.23 eV and 1.97 eV, respectively and therefore may occur as intrinsic defects in Sc₂(WO₄)₃ at elevated temperatures. WO₄²⁻ vacancy and interstitial migration processes have been simulated by classical Molecular Dynamics simulations. The interstitial defect exhibits a nearly 10 times higher mobility (with a migration energy of 0.68 eV), than the vacancy mechanism (with a slightly higher migration energy of 0.74 eV) and thus should dominate the overall ionic conduction. Still both models reproduce the experimental activation energy (0.67 eV) nearly within experimental uncertainty.     

Effect of WO3 on structural and optical properties of CeO2-PbO-B2O3 glasses

Pure and WO₃ doped CeO₂-PbO-B₂O₃ glasses are prepared by the melt-quench technique. The structural and optical analyses of glasses are carried out by XRD, FTIR, density and UV-vis spectroscopic measurement techniques. FTIR analysis indicates the transformation of structural units of BO₃ into BO₄ with W-O-W vibration and the presence of WO₄ and WO₆ units observed with increase in WO₃ contents. Decrease in band gap for CeO₂-PbO-B₂O₃ glasses from 2.89 to 2.30 eV and for WO₃ doped glasses from 2.89 to 1.95 eV has been observed and discussed. This decrease in band gap with WO₃ doping approaches to semiconductor behavior. It shows that the presence of WO₃ in the glass samples causes more compaction of the borate network due to the formation of BO₄ groups and the presence of WO₄ and WO₆ groups, which result in a decrease in the optical band gap energy and increase in the density.     

Luminescence of Thin Films of Lead and Bismuth Tungstates

The luminescence spectra of thin films of PbWO₄ and Bi₂WO₆ were investigated. It is shown that these spectra are similar and that they consist of three individual bands in the blue (2.80 eV PbWO₄ and 2.93 eV Bi₂WO₆), green (2.35 eV PbWO₄ and Bi₂WO₆), and red (1.75 eV PbWO₄ and 1.90 eV Bi₂WO₆) spectral regions. The differences in the nature of the absorption centers of excitation energy are established. The distinguishing features displayed by the temperature dependences of the individual emission bands in the PbWO₄ films are explained by energy migration between emission centers via transfer of free carriers through the conduction and valence bands.     

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.     

Driving force for the WO3(0 0 1) surface relaxation

The optimized structure of the WO₃(0 0 1) surface with various types of termination ((1 × 1)O, (1 × 1)WO₂, and c(2 × 2)O) has been simulated using density functional theory with the Perdew-Wang 91 gradient corrected exchange-correlation functional. While the energy of bulk WO₃ depends weakly on the distortions and tilting of the WO₆ octahedra, relaxation of the (0 0 1) surface results in a significant decrease of surface energy (from 10.2 × 10⁻² eV/Ų for the cubic ReO₃-like, c(2 × 2)O-terminated surface to 2.2 × 10⁻² eV/Ų for the relaxed surface). This feature illustrates a potential role of surface relaxation in formation of crystalline nano-size clusters of WO₃. The surface relaxation is accompanied by a dramatic redistribution of the density of states near the Fermi level, in particular a transformation of surface electronic states. This redistribution is responsible for the decrease of electronic energy and therefore is suggested to be the driving force for surface relaxation of the WO₃(0 0 1) surface and, presumably, similar surfaces of other transition metal oxides.     

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.     

Cooperative phenomena of random electric dipoles in an amorphous matrix

A ferroelectric phase transition has been observed for the first time in a series of glasses containing WO₆-octahedra. The techniques of thermally stimulated depolarization currents were used to observe the transition from independent dipole behavior to cooperative behavior in this amorphous system as a function of concentration. These measurements yielded the activation energy ΔE=1.2eV, the pre-exponential τ₀=2 × 10^-22sec, and the dipole moment p?=1.3 × 10^?15 esu cm for WO₃ in Li₂B₄O₇. A dipole moment bearing species due to Li₂B₄O₇ was observed with ΔE=0.44eV and pre-exponential τ₀=5 × 10^?8 sec. The depolarization peaks of WO₃ occur in the temperature range 265–275 K depending upon WO₃ concentration and are pressure dependent with an initial slope of 2 × 10^?5K dyne^?1 cm². A model was developed for a possible phase transition associated with a random “pseudo-spin” system in an amorphous matrix.     

Study of the x-ray photoelectron spectrum of tungsten—tungsten oxide as a function of thickness of the surface oxide layer

The photoelectron spectrum of tungsten metal using Al K_α X-rays has been studied as a function of a tungsten oxide layer on the surface. The photoelectron lines arising from the 4f shell of tungsten metal are clearly separated in energy from those coming from WO₃. The ratio of the intensities of these two sets of lines were measured for a series of metal samples which were anodized to a determined level of tungsten oxide. The data were shown to be consistent with a uniform deposition of oxide film. The escape depth, or thickness from which half the photoelectron intensity is derived, was found for a 1450 eV photoelectron to be 8.9 Å and 18.3 Å for W and WO₃, respectively.     

Photocatalytic ability of Bi<Subscript>6</Subscript>Ti<Subscript>3</Subscript>WO<Subscript>18</Subscript> nanoparticles with a mix-layered Aurivillius structure

Aurivillius phase layered perovskites Bi₆Ti₃WO₁₈ was prepared by the sol-gel citrate-complexation synthesis. The sample developed into the plate-like nanoparticles with the exposed (001) facets. The phase formation and structure have been verified via X-ray polycrystalline powder diffraction (XRD) Rietveld refinements. The nanoparticles were investigated via the measurements such as FE-SEM, TEM, EDS, and the surface analyses. UV–Vis absorption data revealed that the Aurivillius compound has a direct band characteristic with the band energy of 2.214 eV. The band structure of Bi₆Ti₃WO₁₈ nanoparticles was discussed on the base of the experiments and theoretical calculation. Bi³⁺-containing Aurivillius Bi₆Ti₃WO₁₈ shows efficient photocatalytic degradation for rhodamine B dye (RhB) with the visible light irradiation (λ?>?420 nm). Dynamic characteristic of the light-created excitons was measured by the luminescence and decay lifetime. The multivalent properties of W and Ti ions in the Aurivillius-like lattices of Bi₆Ti₃WO₁₈ photocatalyst were discussed.     

Fabrication and capacitive characteristics of conjugated polymer composite p-polyaniline/n-WO3 heterojunction

A nanocrystalline and porous p-polyaniline/n-WO₃ dissimilar heterojunction at ambient temperature is reported. The high-quality and well-reproducible conjugated polymer composite films have been fabricated by oxidative polymerization of anilinium ion on predeposited WO₃ thin film by chemical bath deposition followed by thermal annealing at 573 K for 1 h. Atomic force microscopy (AFM) analyses reveal a homogenous but irregular cluster of faceted spherically shaped grains with pores. The scanning electron microscopy confirms the porous network of grains, which is in good agreement with the AFM result. The optical absorption analysis of polyaniline/WO₃ hybrid films showed that direct optical transition exist in the photon energy range 3.50–4.00 eV with bandgap of 3.70 eV. The refractive index developed peak at 445 nm in the dispersion region while the high-frequency dielectric constant, ? _∞, and the carrier concentration to effective mass ratio, N/m^*, was found to be 1.58 and 1.10 × 10³⁹ cm^?3, respectively. The temperature dependence of electrical resistivity of the deposited films follows the semiconductor behavior while the C–V characteristics (Mott–Schottky plots) show that the flat band potential was ?791 and 830 meV/SCE for WO₃ and polyaniline.     

Analysis of the physical structure of nanometric WOx/ZrO2 using electrical measurements

The structure of WO_x/ZrO₂ was studied by X-ray diffraction, laser Raman spectroscopy and measurement of electrical properties using impedance spectroscopy. Results from classical analysis were consistent with a structure comprising nanometric ZrO₂ particles covered by a WO_x surface layer. Based on this information we modelled the impedance spectra as the superposition of two contributions. The values of the electrical properties estimated from our model indicated the presence of a dielectric and a semiconductor. The first phase had electrical properties closely matching the reported values for ZrO₂, whereas the semiconductor phase was assigned to a non-stoichiometric WO_x phase. The tungsten-bearing species had temperature-dependent properties and play an important role in the ac response of the studied system and also in oxidation–reduction processes. The activation energy is 1.3 eV for ZrO₂, whereas WO_x has two slightly different energy values (2.4 and 2.1 eV) in different temperature ranges. Use of impedance spectroscopy provides valuable information about the surface structure as well as the contribution of the bulk, which may be important in catalysis. PACS 68.35.Bs; 81.05.Ys; 82.65.Dp     

Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

Structural and optical properties of WO3-ZnO-PbO-B2O3 glasses

Glass samples of compositions 20PbO-80B₂O₃ and xWO₃—(20−x) ZnO-20PbO-60B₂O₃ with x varying from 0% to 10% mole fraction are prepared by the melt quench technique. Decrease in the band gap from 2.86 to 2.16 eV for ZnO-PbO-B₂O₃ glasses with an increase in the WO₃ content has been observed and discussed. The FTIR spectral studies have pointed out the conversion of structural units of BO₃ to BO₄ and WO₄ to WO₆ with the presence of W-O-W vibration of tungsten and incorporation of ZnO₄ structural units of zinc in these glasses. The increase in density from 2.75 to 4.03 gcm⁻³ for ZnO-PbO-B₂O₃ glasses is observed with an increase in WO₃ content. Due to the formation of WO₆, WO₄ and BO₄ units, changes in the atomic structure with WO₃ composition are observed and discussed.     

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.     

Electrical conductivity and amorphization of Sc2(WO4)3 at high pressures and temperatures

Impedance spectroscopy measurements and synchrotron X-ray diffraction studies of Sc₂(WO₄)₃ at 400°C have been carried out as a function of pressure up to 4.4 GPa. Ionic conductivity shows normal decrease with increase in pressure up to 2.9 GPa, but then increases at higher pressures. The XRD results show that Sc₂(WO₄)₃ undergoes pressure-induced amorphization at pressures coincident with the reversal in conductivity behavior. The loss of crystal structure at high pressure is consistent with growing evidence of pressure-induced amorphization in negative thermal expansion materials, such as Sc₂(WO₄)₃. The increase in conductivity in the amorphized state is interpreted as the result of an increase in structural entropy and a concomitant reduction of energy barriers for ionic transport.     

Low energy electron spectroscopy of N2 in the 11.8–13.8 eV energy range

In the 11.8–13.8 eV energy range differential threshold and energy loss spectra of electrons scattered by N₂ molecules have been obtained at an incident energy of 14.3 eV and with a 30 meV experimental resolution. The study of the angular behaviour of the observed peaks permits us to distinguish between singlet-singlet and singlet-triplet transitions. The predicted F³Π_u and G³Π_u Rydberg states are observed. Also some levels of unknown triplet states are seen at 13.155, 13.395 and 13.635 eV.     

Preparation and physical properties of CuxWO3

We report on the study of WO₃ doped with Cu using sol-gel (Cu_xWO₃^d) and impregnation (Cu_xWO₃ⁱ) methods. All materials are well crystallized and exhibit single phases whose crystallite size ranges from 17 to 100 nm depending on Cu amount and the preparation technique. The conductivity dependence on temperature demonstrates semiconductor behavior and follows the Arrhenius model, with activation energies, E_σ, commonly in the range 0.4-0.6 eV. Moreover, the thermopower study shows that Cu_xWO₃^d is mainly of p-type conductivity, whereas Cu_xWO₃ⁱ is n-type. The mechanism of conduction is attributed to a small polaron hopping. The doping process is found to decrease the interband transition down to 520 nm depending on the preparation conditions. The photoelectrochemical characterization confirms the conductivity type and demonstrates that the photocurrent J_ph increases with Cu-doping. Taking into consideration the activation energy, the flat band potential and the band gap energy, the band positions of each material are proposed according to the preparation method and Cu amount.     

Electrochromic properties of nanocrystalline WO3 thin films grown on flexible substrates by plasma-assisted evaporation technique

Thin films of Tungsten trioxide (WO₃) were deposited on ITO-coated flexible Kapton substrates by plasma-assisted activated reactive evaporation (ARE) technique. The influence of growth and microstructure on optoelectrochromic properties of WO₃ thin films was studied. The nanocrystalline WO₃ films grown at substrate temperature of 250°C were composed of vertically elongated cone-shaped grains of size 65 nm with relative density of 0.71. These WO₃ films demonstrated higher optical transmittance of 85% in the visible region with estimated optical band gap of 3.39 eV and exhibited better optical modulation of 66% and coloration efficiency of 52.8 cm²/C at the wavelength of 550 nm.     

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.