Transport processes in heavy metal fluoride glasses

Na self-diffusion, Li self-diffusion, Na⁺–Li⁺ ion exchange, electrical conductivity, and mechanical relaxation have been studied below T_g on glasses of the system ZrF₄–BaF₂–LaF₃–AF (A=Na, Li), with A=10, 20, 30 mol%. Compared to the transport mechanism in alkali-containing silicate glasses, the mechanisms in these non-oxide glasses are anomalous. Thus the self-diffusion coefficient of Na decreases with increasing NaF content, whereas that of Li increases with increasing LiF content. Both the electrical conductivity and the Na⁺–Li⁺ ion exchange reach a minimum at ≈ 20 mol% LiF, and the mechanical relaxation shows one peak for the 20 and 30 mol% LiF-glasses and two peaks for the glass with 10 mol% LiF, evidencing both a contribution of F⁻ and Li⁺ ions to the transport. Moreover, the presence of the three partially interacting mobile species F⁻, Na⁺, Li⁺ obviously leads to an anionic–cationic mixed ion effect. Applying the Nernst–Einstein equation to the Li⁺ transport in LiF-containing glasses shows that its mechanism is dissimilar to that in oxide glasses. Calculated short jump distances possibly can be interpreted as an Li⁺ movement via energetically suitable sites near F⁻ ions. Likewise the Nernst–Planck model, successfully applied to the ionic transport in mixed alkali silicate glasses, obviously does also not hold for the present heavy metal fluoride glasses.     

10BaF2:NaF, Na3AlF6/TiO2 composite as a novel visible-light-driven photocatalyst based on upconversion emission

A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.     

Exploration of fluoride glasses with faster fluoride-ion conduction

Electrical conductivity measurements by ac methods were made of various fluoride glasses to explore glasses with faster fluoride-ion conduction. One of the measurements was made on ZrF₄BaF₂CsF glasses in which some of the fluoride-ions were substituted by the chloride, bromide, iodide and oxide ions. All of these substitutions resulted in a decrease in conductivity. The magnitude of the decrease was in proportion to the substituted fluoride-ion concentration, regardless of the substituent species. This may be explained by a blocking effect of the introduced anions of the fluoride-ion motion. Other electrical conductivity measurements were made of ternary and/or quaternary glasses of the ZrF₄⁻, HfF₄⁻, ZnF₂⁻, ScF₃⁻, MnF₂⁻ GaF₃⁻, FeF₃⁻ and InF₃⁻based fluoride systems. Remarkably high conductivities were observed in the InF₃⁻, FeF₃⁻ and GaF₃⁻based glasses containing appreciable amounts of PbF₂ as one of the glass constituents. Among these highly conductive glasses 35InF₃·30SnF₂·35PbF₂ glass exhibited extremely high conductivity, e.g., 6.3×10⁻⁴ S cm⁻¹ at 150 °C. This conductivity value is about 10² times the highest conductivity value thus far reported for fluorozirconate glasses and is higher than that of a crystalline material with fast fluoride-ion condition, β-PbF₂.     

Mössbauer study of various fluoride glasses containing iron fluoride

(PbF₂, ZnF₂, AlF₃, or ZrF₄) - (BaF₂ and CaF₂) - FeF₃ glasses with 20 or 30 mol%FeF₃ contents were studied by ⁵⁷Fe Mössbauer spectroscopy. The Mössbauer spectrum at room temperature for the PbF₂-based glass is composed of one doublet due to Fe³⁺, whereas those for the ZnF₂?, AlF₃?, and ZrF₄-based glasses, two doublets due to Fe³⁺ and Fe²⁺. Both the iron ions have octahedral F coordination in the high spin states. The Fe²⁺/(Fe²⁺ + Fe³⁺) value in glass increases with the basicity of base glass.     

Ionic conductivity of ZrF4BaF2MX (M = Li,Na;X = F,Cl) glasses

Glasses were prepared in a wide range of compositions for the two systems oof mixed-cation, ZrF₄BaF₂LiFNaF, and mixed-anion, ZrF₄BaF₂LiFLiCl. Ionic conductivities were measured for these glasses and it was found that these glasses were not only cationic but also anionic conductors depending on the total alkali halide content. Four types of mixed-cation and mixed-anion effects on ionic conductivity were demonstrated for the cation-conducting and anion-conducting glasses. In cation conduction, the cation mixing caused the conductivity decline, whereas the anion mixing led to the conductivity enhancement. In anion conduction, on the other hand, the cation mixing led to the conductivity enhancement, whereas the anion mixing caused the conductivity decline.     

Controllable optical bistability and multistability in a rare-earth-ion-doped optical fiber

We investigated the optical bistability and multistability in an Er³⁺-doped ZrF₄–BaF₂–LaF₃–AlF₃–NaF optical fiber inside an optical ring cavity. It is found that the optical bistability and multistability can be easily controlled via adjusting properly the parameters of the corresponding system. Our scheme may provide some new possibilities for technological applications in optoelectronics and optical-fiber communication.     

Lead−barium fluoroborate glass ceramics doped with Nd<Superscript>3+</Superscript> or Er<Superscript>3+</Superscript>

Lead?barium fluoroborate glasses in the PbF₂–BaF₂–B₂O₃, PbF₂–BaO–B₂O₃, and PbO_– BaF₂–B₂O₃ systems doped with rare-earth ions (Nd³⁺ or Er³⁺) are synthesized and studied. It is shown that, based on these glasses, it is possible to produce transparent glass ceramics with fluoride crystalline phases, including ceramics with one crystalline phase of the fluorite structure. The spectral and luminescent properties of the doped glasses, glass ceramics, and polycrystalline complex fluorides containing Pb, Ba, and rare ions are studied.     

DC conductivity of new single and mixed alkali oxyfluorovanadate glasses

New glasses have been prepared according to these formulas (70-x)V₂O₅-30BaF₂-xAF, where AF=LiF or NaF and (60-x)V₂O₅-30BaF₂-10LiF-xAF, where AF=NaF and x=10, 15, 20, 25 and 30 mol%. Density of the glasses was measured and molar volume calculated and they correlated with the AF content. The dc conductivity has been measured in the temperature range from 302 to 453 K. The dc conductivity increases with temperature and V₂O₅ content, while it decreases with the alkali fluoride content. Conductivity has been correlated with the calculated polaron distance, R, and glass transition temperature, T_g. The activation energy, W, increases with the increase in the alkali fluoride, while it decreases with the V₂O₅ content. Some parameters like polaron distance, R, polaron radius, r_p, ion concentrations, n(V), n(Li) or n(Na), hopping energy, W_H, density of localized states at Fermi level, N(E_F), polaron coupling constant, γ_p, polaron band width, J, hopping mobility, μ, and carrier density for electronic conduction, N_c, were calculated to explain the conduction mechanism and behavior of the present glasses.     

Structural and photoluminescence properties of Dy3+ doped different modifier oxide-based lithium borate glasses

Structural and photoluminescence properties of Dy³⁺ doped lithium fluoro-borate glasses with the compositions Li₂B₄O₇–BaF₂–NaF–MO (where M=Mg, Ca, Cd and Pb), Li₂B₄O₇–BaF₂–NaF–MgO–CaO and Li₂B₄O₇–BaF₂–NaF–CdO–PbO have been investigated through XRD, FTIR, optical absorption, emission and decay measurements. From the optical absorption spectra, Judd–Ofelt intensity parameters (Ω_λ, λ=2, 4 and 6) have been evaluated and are in turn used to predict radiative properties such as radiative transition probabilities (A_T), branching ratios (β_r) and stimulated emission cross sections (σ_p) for all emission levels of Dy³⁺ ion in different lithium fluoro-borate glass matrices. From the emission spectra, chromaticity color coordinates have been calculated and indicated emission color for all glass matrices. The nature of decay profiles of ⁴F_9/2 state of Dy³⁺ in all the glass matrices are analyzed.     

Application of BaF2-B2O3-GeO2-SiO2 glasses to metal-oxide-silicon field-effect transistors

The capacitance and voltage characteristics of field effect transistors passivated by BaF₂-B₂O₃-GeO₂-SiO₂ glasses with various water contents were investigated. As the OH absorption coefficients of the glass increased, adverse effects on the recovery of hysteresisC-V curve shifts was seen. The water content is related to the fluoride content of the BaF₂–B₂O₃–GeO₂–SiO₂ glass. The viscous flow point of the glass was lowered with increasing ionic character obtained from Hannay's equation. The source-drain current and voltage (I-V) characteristics of typical enhancement and depletion mode field effect transistors passivated with these glasses were investigated.     

Transport numbers in the molten system NaF–KF–AlF3–Al2O3

Transport numbers in the molten system NaF–KF–AlF₃ (Al₂O₃, CaF₂) were investigated by the Hittorf method. It was confirmed that in molten cryolite, Na₃AlF₆, 1,010 °C, the current is transported almost exclusively by the Na⁺ cations (t(Na⁺)?=?0.99). When AlF₃ was added to a Na₃AlF₆ melt, the transport number of sodium cations decreased to 0.74 at the composition corresponding to NaAlF₄. In molten K₃AlF₆, the transport number of K⁺ cations equals 0.836 at 1,005 °C. In melts containing both Na⁺ and K⁺, the cations contribute to the charge transport approximately in the ratio of the squares of their ionic radii. When 5 mass % of CaF₂ was added to the molten NaF–KF–AlF₃ system, it remarkably influenced the transport numbers of potassium and fluoride anions.     

AlF3-K2NbOF5系统非晶态材料离子导体的结构与电性能

本文研究了AlF₃-K₂NbOF₅系列玻璃导电性。通过对AlF₃-K₂NbOF₅系列玻璃的Raman光谱研究,初步确认了玻璃的结构。根据结构随组成的变化情况,进一步讨论了玻璃的电导率。AlF₃-K₂NbOF₅二元系玻璃,当AlF₃的含量在21—29mol％范围内时,Al^{3+关键词：}     

UV absorption edge shift by doping alkali fluorides in fluoroaluminate glass

The effect on transmittance and reflectance in the vacuum ultraviolet (VUV) region by doping alkali fluorides (LiF, NaF and KF) has been investigated in a ternary fluoroaluminate (18BaF₂-37CaF₂-45AlF₃) glass. The absorption edge of the glass obeys the Urbach rule and was shifted monotonically towards higher energies by increasing the concentration of each alkali fluoride. The VUV reflection peak at 11.3 eV was not sensitive to the change of the concentration of dopants. The magnitude of the edge shift was 10-20 times larger than that expected from the additive law on the magnitude of absorption coefficients of the glass and alkali fluorides. An excitonic interaction similar to that observed in mixed crystals of alkali halides is suggested from the monotonic shift toward the absorption edges of the dopants. The weak sensitivity of the reflection peak upon doping supports that the excitonic state lies predominantly around the edge energies.     

Large refractive index with vanishing absorption in optical fibers

We propose and demonstrate a novel scheme for realizing large refractive index with vanishing absorption in a three-level quantum system consisting of the energy levels of Er³⁺-doped ZrF₄–BaF₂–LaF₃–AlF₃–NaF (ZBLAN) optical fiber. It is found that the refractive index of the probe field can be controlled via the coherent coupling field and incoherent pumping field. The switching from negative refractive index to positive refractive index and manipulation of the value of the index of refraction while maintaining vanishing absorption of the probe field can be achieved via tuning the detuning of the coherent coupling field. Our scheme may provide some new possibility for technological applications in fiber communication.     

Pulsed laser deposition of fluoride glass thin films

The development of integrated waveguide lasers for different applications such as marking, illumination or medical technology has become highly desirable. Diode pumped planar waveguide lasers emitting in the green visible spectral range, e.g. thin films from praseodymium doped fluorozirconate glass matrix (called ZBLAN, owing to the main components ZrF₄, BaF₂, LaF₃, AlF₃ and NaF) as the active material pumped by a blue laser diode, have aroused great interest. In this work we have investigated the deposition of Pr:ZBLAN thin films using pulsed laser radiation of λ = 193 and λ = 248 nm. The deposition has been carried out on MgF₂ single crystal substrates in a vacuum chamber by varying both processing gas pressure and energy fluence. The existence of an absorption line at 210 nm in Pr:ZBLAN leads to absorption and radiative relaxation of the absorbed laser energy of λ = 193 nm preventing the evaporation of target material. The deposited thin films consist of solidified and molten droplets and irregular particulates only. Furthermore, X-ray radiation has been applied to fluoride glass targets to enhance the absorption in the UV spectral region and to investigate the deposition of X-ray treated targets applying laser radiation of λ = 248 nm. It has been shown that induced F-centres near the target surface are not thermally stable and can be easily ablated. Therefore, λ = 248 nm is not suitable for evaporation of Pr:ZBLAN.     

氟化物材料在深紫外波段的光学常数

研究了紫外领域常用的6种大带隙的氟化物薄膜材料,在氟化镁单晶基底上用热舟蒸发镀制了三种高折射率材料薄膜LaF₃,NdF₃,GdF₃和三种低折射率材料薄膜MgF₂,AlF₃,Na₃AlF₆;用商用lambda900光谱仪测量了它们在190—500 nm范围的透射率光谱曲线;用包络法研究了它们的折射率和消光系数,研究了影响透射率和光学常数的主要因素,给出了6 关键词： 光学常数 包络法 氟化物材料 深紫外     

Fluoride glasses in the InF3-GaF3-YF3-PbF2-CaF2-ZnF2 system

New glasses have been synthesized in a multicomponent system based on indium fluoride. Samples of a few mm in thickness were obtained. They are transparent and homogeneous. Main physical properties such as density, characteristic temperatures, density, thermal expansion and refractive index have been measured. The evolution versus composition is reported for samples with the formula: (35−x) InF₃-xGaF₃-10YF₃-25PbF₂-15CaF₂-15ZnF₂. T_g lies between 260 and 296 °C while melting starts around 480 °C. Glass samples are stable at room temperature. By comparison with other standard fluoride glasses, they exhibit higher refractive index and density.     

Nanotechnology studies of layered fluoride superionic conductors

A computer simulation by a molecular dynamics method at constant volume has been performed on a model material that is composed of accumulating two different fluoride conductors: ⋯BaF₂–CaF₂–BaF₂–CaF₂⋯. The average value of CaF₂ and BaF₂ for the lattice constant of the new layered material is prepared to hold its mechanical strength. The CaF₂ region is compressed and the BaF₂ region is stretched along the c axis (z axis) in the thermal equilibrium state. It is obtained that the diffusion coefficient and ionic conductivity of F− ions in the layered fluoride conductors increases with decreasing periods, more specifically with the number of interfaces. The layer depth dependence on transport coefficients approximately coincides with the experiment.     

Fluorescence enhancement of oxide fluoride glass co-doped with TbF3 and SmF3

The fluorescence property of xTbF₃-BaF₂-AlF₃-GeO₂+ySmF₃ (x=0.01-40 mol%, y=0-5 wt%) glasses were investigated. The enhancement of Sm³⁺ fluorescence was recognized in the presence of Tb³⁺. Increasing Tb³⁺ content, the emission color changed from green to orange. When the intensity of fluorescence at 540 nm originated from Tb³⁺ is compared with that at 600 nm originated from Sm³⁺, the information about the concentration quenching of Tb³⁺ and Sm³⁺ was obtained. From these results, rare earth ions were dispersed identically in the glasses. After heating to 673 K or cooling to 77 K, the emission color of 20TbF₃-20BaF₂-10AlF₃-50GeO₂/mol%+0.05 wt% SmF₃ glass was reversibly changed from orange to green. In addition, while the emission from 10TbF₃-20BaF₂-10AlF₃-60GeO₂+0.01 wt% SmF₃ glass was green, its crystallized sample, prepared by annealing at 1073 K, exhibited an orange emission due to Sm³⁺ at room temperature.     

High upconversion optical gain of Er3+-doped tellurite glass

The upconversion technique of rare-earth-doped glasses or crystals is a potential route for achieving short-wavelength lasers (SWLs). The optical gain is an important parameter for evaluating lasing medium performance. Therefore, upconversion luminescence in glass with composition of 70TeO₂–9PbF₂–10AlF₃–10BaF₂–1Er₂O₃ was demonstrated, and the small-signal optical gain was measured via an amplified spontaneous emission technique when the sample was excited with a 980 nm laser. It was found that the optical gain was as large as 4.0 dB/cm, thus indicating that this glass may be a good medium for SWLs.