The role of modifier’s cation valence in structural properties of TeO2-based glasses

The compositional invariance of the Raman spectra of (1 ? x)TeO₂–xM_nO_m glasses (M = Ti, Nb) is analyzed and interpreted as evidence for the conservatism of a framework-type constitution inherent to such glasses. This is assigned to the chemical similarity of cations in the X–O–Y bridges (X, Y = Te⁴⁺, Ti⁴⁺, Nb⁵⁺) considered as the framework building blocks. It is concluded that the atoms of metals having valence IV and V can be placed into the category of such cations, to which certain of the atoms with valence III can be added.     

Optical spectroscopy and local structure of Er3+ luminescence centres in СaO–Ga2O3–GeO2 glasses

Optical absorption, luminescence excitation and emission spectra of Er³⁺ centres in Ca₃Ga₂Ge₃O₁₂:Er glass with Er content of 1.46 wt% are presented and analysed. Luminescence kinetics for the main Er³⁺ transitions was satisfactorily described by single exponential decays with characteristic lifetimes. Oscillator strengths, phenomenological Judd–Ofelt intensity parameters, radiative decay rates (emission probabilities of transitions), branching ratios and radiative lifetimes for Er³⁺ centres in Ca₃Ga₂Ge₃O₁₂:Er glass are calculated and compared with the corresponding parameters of the Ca₃Sc₂Ge₃O₁₂:Er³⁺ garnet and other crystals and glasses. Quantum efficiency, η, of the ⁴I_13/2 → ⁴I_15/2 Er³⁺ transition is determined. Incorporation peculiarities and local structure of Er³⁺ luminescence centres in Ca₃Ga₂Ge₃O₁₂:Er³⁺ glass are discussed in comparison with garnet crystals and oxide glasses. On the basis of the presented results and referenced EXAFS data for Er, Eu and Ho impurities (L₃-edge) it has been shown that Er³⁺ centres in Ca₃Ga₂Ge₃O₁₂ glass occupy network sites with the coordination number to oxygen of N = 6.     

Ab initio calculation of vibrational frequencies of GexSe1−x glass

We have used the density functional theory to make the models of Ge_xSe_1?x glass for which the energy is a minimum. The clusters, Ge₂Se₂, Ge₂Se₃, Ge₃Se, Ge₃Se₂, Ge₄Se, GeSe₃, GeSe₄, chain mode zig-zag Ge₄Se₃, corner sharing GeSe₄, and edge sharing Ge₂Se₆, have been made successfully and their vibrational spectra have been calculated from the first principles. We are able to optimize the bond distances as well as the bond angles. The calculated values of the frequencies of vibrations of the various clusters have been compared with those obtained from the experimental Raman spectra of actual glasses, Ge_xSe_1?x(0 < x < 0.3). The local concentration, x within 0.25 nm is nonuniform in the amorphous material. When the same cluster occurs in two stable configurations, low frequency vibrations of frequency, ν < 100 cm^?1, are found. The corner sharing GeSe₄ has low frequency modes at 54 cm^?1 and 93 cm^?1 whereas these modes disappear in the pyramidal configuration. The low frequency modes are therefore associated with the breaking of C₄ symmetry of the pyramidal configuration. The computed vibrational frequencies of clusters Ge₃, Ge₄Se₃, Ge₂Se₃, GeSe₃ and Ge₃Se₂ are actually present in the Raman spectra of the glass, Ge_xSe_1?x(0 < x < 0.3).     

Emission properties and local structure of Tm3+ in Ge–Ga–S–Br glass

Spectroscopic properties of Tm³⁺ in (1 − x) (Ge_0.25Ga_0.10S_0.65)–xBr (or CsBr) glasses (x = 0.0 and 0.1) were investigated. Emission properties of Tm³⁺ in 0.9(Ge_0.25Ga_0.10S_0.65)–0.1Br glass were similar to those in Ge_0.25Ga_0.10S_0.65 glass, while there was significant improvement when doped into 0.9(Ge_0.25Ga_0.10S_0.65)–0.1CsBr glass. The lifetime of the Tm³⁺:³H₄ level increased from 0.23 to 1.22 msec with 10 mol% CsBr addition. The presence of Cs⁺ facilitated the formation of [GaS_3/2Br]⁻ units by donating an electron to the Ga tetrahedron, resulting in the homogeneous distribution of Br. In this way, Tm³⁺ ions have their local environment made of Br only. When Br ions were added instead of CsBr, [GaS_(4−x)/2Br]⁻ units with x > 1 were formed and Tm³⁺ ions were surrounded by both S and Br, producing a high phonon environment.     

Preparation and characterization of telluride glasses

Chalcogenide bulk glasses Ge₂₀Se_80?xTe_x for x ∈ (0, 10) have been prepared by systematic replacement of Se by Te. Selected glasses have been doped with Er and Pr, and all systems have been characterized by transmission spectroscopy, measurements of dc electrical conductivity and low-temperature photoluminescence. Absorption coefficient has been derived from measured transmittance and estimated reflectance. Both absorption and low-temperature photoluminescence spectra reveal shifts of absorption edge and/or dominant luminescence band to longer wavelength due to Te → Se substitution. Arrhenius plots of dc electrical conductivity, in the temperature range 300–450 K, are characterized by activation energies roughly equal to the half of the optical gap. Arrhenius plots for temperatures below 300 K yield much lower activation energies. The dominant low-temperature luminescence band centered at about half the band gap energy starts to quench above 200 K and a new band appears at 900 nm. The band at 900 nm, due to band to band transitions, overwhelms the spectra at room temperature. Systems doped with Er exhibit a strong luminescence due to ⁴I_13/2 → I_15/2 transition of Er³⁺ ion at 1539 nm, and Pr doped samples exhibit a relatively weak luminescence peak at 1590 nm, which we tentatively assign to ³F₃ → ³H₄ transition of Pr³⁺ ion.     

Molecular dynamics,diffraction and EXAFS of rare earth phosphate glasses compared with predictions based on bond valence

Rare earth (RE) phosphate glasses, (R₂O₃)_x(P₂O₅)_1−x, commonly form with x < 0.3. As previously discussed by Hoppe, in this composition range Q² groups provide 6 O_nb (non-bridging oxygens) per RE, but higher RE coordinations can occur if RE are bonded to O_nb on Q³ groups, or if RE–O_nb–RE configurations occur (where Qⁿ refers to a PO₄ tetrahedra with connectivity of n). The values of N_RO and R_RO from the majority of the previous diffraction and EXAFS studies of RE phosphate glasses have been surveyed. Overall, the experimental results for 0.18 ⩽ x ⩽ 0.28 indicate RE coordination is from 6.5 to 7.0 for large RE, and slightly lower for small RE. For x ⩾ 0.23 this implies the occurrence of RE–O_nb–RE configurations, as observed in recent diffraction studies. The experimental results for x ⩽ 0.15 indicate RE coordination is from 7.5 to 8, which can be attributed to RE bonding to O_nb on Q³ groups. RE coordination of 8 for x ∼ 0.15 requires 2 Q³ groups (per RE) to be connected to Q² groups. Comparison with estimated connectivities between Q² and Q³ groups indicate that chemically ordered Q²–Q³ linkages are required. A recent MD model of a Tb metaphosphate glass has N_RO = 6, but includes Tb bonded to O_nb on Q³ groups and Tb–O_nb–Tb configurations, because it has a broad Qⁿ distribution.     

Structural impact of iron ions on BaBiBO4 glasses: Spectroscopic and dielectric investigations

Transparent glasses of composition 10BaO.20Bi₂O₃.(70 ? x)B₂O₃.xFe₂O₃ (wt.%) where 0 ≤ x ≤ 2.0, were characterized by XRD and SEM. Physical, spectroscopic and dielectric properties were investigated. At higher dopant of Fe₂O₃, EPR results revealed that, the number of Fe³⁺ ions participate in the resonance is decreased by forming a new signal at g ≈ 3.015 due to increase of antiferromagnetic interaction of Fe³⁺ ions and/or formation of low spin Fe³⁺ ions in the glass matrix. With initial 0.5 wt.% doping of Fe₂O₃, less dense glass is formed with colloids of metallic Bi⁰ atoms. The absorption bands at 604 and 712 nm in F5 glass are ascribed to Bi⁰ and Bi⁺ radicals respectively. No characteristic Fe³⁺ absorption bands (spin-forbidden) are found. Fe²⁺ ions are increased at higher concentration of Fe₂O₃. Higher concentration of Fe₂O₃ is favorable for BO₂O^?, BO₃, BiO₆ and FeO₆ symmetry unit leads to low band gap and high Urbach energy. By doping of Fe₂O₃ the dielectric parameters like dielectric constant (ε′), loss (tanδ and ac electrical conductivity (σ_ac) are found to increase.     

Structure and properties of the 70Li2S · (30 − x)P2S5 · xP2O5 oxysulfide glasses and glass–ceramics

The 70Li₂S · (30 ? x)P₂S₅ · xP₂O₅ (mol%) oxysulfide glasses were prepared by the melt quenching method. The glasses were prepared in the composition range 0 ≦ x ≦ 10. The glass–ceramics were prepared by heating the glasses over crystallization temperatures. The PO_nS_3?n (n = 1–3) oxysulfide units were produced in the glasses and glass–ceramics by partial substituting P₂O₅ for P₂S₅. In particular, the P₂OS₆^4? unit would be produced by substituting a small amount of P₂O₅ for P₂S₅. The oxygen atoms were incorporated into the Li₇P₃S₁₁ crystal structure because the diffraction peaks of the oxysulfide glass–ceramic shifted to the higher angle side. The glass–ceramic with 3 mol% of P₂O₅ exhibited the highest conductivity of 3.0 × 10^?3 S cm^?1 and the lowest activation energy for conduction of 16 kJ mol^?1. The P₂OS₆^4? dimer units in the oxygen-incorporated Li₇P₃S₁₁ crystal would improve conductive behavior of the Li₂S–P₂S₅ glass–ceramics.     

Spectral studies of Sm3+ and Dy3+ doped lithium cesium mixed alkali borate glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Sm³⁺ and Dy³⁺ has been studied in mixed alkali borate glasses of the type 67B₂O₃ · xLi₂O · (32 − x)Cs₂O (x = 8, 12, 16, 20 and 24). The Judd–Ofelt intensity parameters (Ω₂, Ω₄ and Ω₆) are calculated. The radiative transition probabilities (A), radiative lifetimes (τ_R), branching ratios (β) and integrated absorption cross-sections (Σ) are computed for certain excited states of Sm³⁺ and Dy³⁺ ions for different x values in the glass matrix. Stimulated emission cross-sections (σ_p) are obtained for certain emission transitions of two ions in these mixed alkali borate glasses. These parameters are compared for different x values in the glass matrix. Variation of these parameters with x in the glass matrix has been studied.     

EPR and magnetic susceptibility studies of B2O3–Bi2O3–Gd2O3 glasses

Glasses of the xGd₂O₃ · (100 − x)[B₂O₃ · Bi₂O₃] system with 0.5 ⩽ x ⩽ 10 mol% were studied by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. Data obtained show that for low gadolinium oxide contents of the samples (x ⩽ 3 mol%) the Gd³⁺ ions are randomly distributed in the host glass matrix and are present as isolated and dipole–dipole coupled species. For higher gadolinium oxide contents of the samples (x > 3 mol%) the Gd³⁺ ions appear as both isolated and antiferromagnetically coupled species. The EPR spectra of the glasses reveal resonance sites with an unexpected high crystalline field in addition to the ‘U’ spectrum, typical for Gd³⁺ ions in disordered systems. This absorption line is due to Gd³⁺ ions that replace Bi³⁺ ions from the host glass matrix and could play the network unconventional former role in the studied glasses.     

The effect of fluoride on the Fe2+/Fe3+-redox equilibrium in glass melts in the system Na2O/NaF/CaO/Al2O3/SiO2

Liquids with the base compositions (16 − x/2)Na₂O · xNaF · 10CaO · 74SiO₂ (x = 0, 1, 3, and 4) and (10 − x/2) · Na₂O · xNaF · 10CaO · yAl₂O₃ · (80 − y)SiO₂ (x = 0, 1, 3, 5 and y = 5 and 15) doped with 0.25 mol% Fe₂O₃ were studied by means of square-wave voltammetry in the temperature range from 1000 to 1500 °C. With increasing temperature, the redox equilibria were shifted to the reduced state. Also while increasing the alumina concentration, the Fe²⁺/Fe³⁺-redox equilibrium is shifted to the reduced state. In the soda-lime–silica melt the addition of fluoride shifts the equilibrium to the oxidized state, while in the aluminosilicate melts with 15 mol% Al₂O₃, the equilibrium is shifted to the reduced state. In the aluminosilicate melts with 5 mol% Al₂O₃, the equilibrium was not affected by the fluoride concentration. This is explained by the structure of the respective glass compositions.     

Chemical co-precipitation of hybrid precursors to synthesize Eu3+/Dy3+ activated YNbxP1−xO4 and YNbxV1−xO4 microcrystalline phosphors

A modified wet-chemical synthesis technology was put forward to fabricate Eu³⁺/Dy³⁺ doped with YNb_xP_1−xO₄ and YNb_xV_1−xO₄ phosphors with varying x from the assembly of multicomponent hybrid precursors. The morphologies have been found to be 1–2 μm crystalline spheres using XRD and SEM. The red photoluminescence intensity reaches the strongest in YNb_0.8P_0.2O₄:Eu³⁺ and YNb_0.1V_0.9O₄:Eu³⁺ phosphors and the red to orange intensity ratio (RO) values decrease with the content of P(V) increasing. Besides this, the optimum concentration for Dy³⁺ luminescence in YNb_0.5P_0.5O₄ is 1 mol%, while that in YNb_0.5V_0.5O₄ is 0.5 mol% or lower than 0.5 mol%. The yellow to blue intensity ratio (YB) value of Dy³⁺ increases when the Dy³⁺ concentration increases from 0.5 to 8 mol% in YNb_0.5P_0.5O₄; however, that of Dy³⁺ does not vary much in YNb_0.5V_0.5O₄ matrix.     

Bismuth-activated luminescent materials for broadband optical amplifier in WDM system

New broadband near infrared luminescence covering the whole work windows (1260–1625 nm) of the current wavelength division multiplexing (WDM) system was found from bismuth-activated M₂O–Al₂O₃–SiO₂ (M = Li, Na) and Li₂O–Ta₂O₅–SiO₂ glasses at room temperature in the case of 808 nm-laser excitation. But the near infrared luminescence mechanism of the bismuth-activated glasses is not well understood up to now. The figure-of-merits of bandwidth and gain of the glasses are better than those of Er³⁺-doped silicate glasses and Ti³⁺ doped sapphire, implying they are the promising gain-medium candidates for the broadband amplifiers and the widely tunable laser sources.     

Influence of valence and coordination of manganese ions on spectral and dielectric features of Na2SO4–B2O3–P2O5 glasses

Sodiumsulpho borophosphate glasses with composition (40 ? x)Na₂SO₄–30B₂O₃–30P₂O₅: xMnO with x ranging from 0 to 5.0 mol% were manufactures. Dielectric spectra have been studied over a wide frequency range of 10²–10⁵ Hz and in the temperature range within 30–250 °C. The valance states of manganese ions and their ligand coordination in the glass network have been investigated using optical absorption, luminescence and ESR spectroscopy. The analysis of the these results has indicated that the manganese ions exist both in Mn²⁺ as well as in Mn³⁺ states and occupy prevailingly octahedral positions and serve as modifiers similarly to Na⁺ ions The values of dielectric parameters (dielectric constant, ε′(ω), loss tan δ and ac conductivity, σ_ac) were found to increase with increasing MnO content. They play a role of modifiers similarly to Na⁺ ions, create bonding defects and free ions viz., [SO₄]^2?, [POO_1/2O₂]^2?, [POO_0/2O₃]^3–, Na⁺ and (NaSO₄)^?. The migration of these charge carriers would build up space charge polarization and may be responsible for the enhanced dielectric parameters. The ac conductivity also is enhanced with increasing MnO content. The mechanism responsible for such increase is well explained based on the modifying action of Mn²⁺ ions.     

Square-wave voltammetry and impedance spectroscopy in iron-doped melts of the system Li2O/Al2O3/SiO2

Glass melts with the basic compositions xLi₂O · 15Al₂O₃ · (85 − x)SiO₂ (x = 8.5, 11, 13.5, 16 and 18.5) doped with 0.25 mol% Fe₂O₃ were studied by square-wave voltammetry and impedance spectroscopy at temperatures in the range from 1100 to 1600 °C. The square-wave voltammograms show a pronounced peak attributed to the reduction of Fe³⁺ to Fe²⁺. The attributed peak potentials which are equal to the standard potentials of the redox pair decrease linearly with the temperature. Impedance spectra measured could be simulated using an equivalent circuit attributed to a simple electron transfer reaction controlled by diffusion.     

Effect of OH− content on emission properties in Er3+-doped tellurite glasses

A series of tellurite glasses of composition, 75TeO₂–20ZnO–(5 ? x)La₂O₃–xEr₂O₃ (x = 0.05, 0.1, 0.3, 0.6, 1.0, 2.0, and 3.0 mol%) with different hydroxl content were prepared. The effect of Er³⁺ and OH^? groups concentration on the emission properties of Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition in tellurite glasses was investigated. The constant K_OH–Er for Er³⁺ in tellurite glasses, which represents the strength of interaction between Er³⁺ and OH^? groups in the case of energy migration, was about 14 × 10^?19 cm⁴ s^?1. The interaction parameter C_Er,Er for the migration rate of Er³⁺: ⁴I_13/2 → ⁴I_13/2 transition in tellurite glass was 46 × 10^?40 cm², which indicates that concentration quenching in Er³⁺-doped modified tellurite glass for a given Er³⁺ concentration is much stronger than in silicate and phosphate glasses.     

Effect of heat treatment on Er3+ containing multicomponent oxyfluoride lead borate glass system

Effect of heat treatment on Er³⁺ containing multicomponent oxyfluoride lead borate glasses in (72 ? x)PbO–xPbF₂–18B₂O₃–6Al₂O₃–3WO₃–1ErF₃ (where x = 9 or 72) system have been studied. The samples with low and high PbF₂ concentrations were analyzed using X-ray diffraction and luminescence spectroscopy. Several narrowed and relatively intense diffraction lines have been formed after heat treatment attributed to the orthorhombic PbF₂ phase. Luminescence spectroscopy revealed bands due to ⁴I_13/2–⁴I_15/2 and ⁴S_3/2–⁴I_15/2 transitions of Er³⁺ ions. This observation makes these glasses candidates for NIR laser active media and up-conversion applications.     

Transport behavior of yttrium substituted polycrystalline La0.7Pb0.3MnO3

The transport properties in La_0.7?xY_xPb_0.3MnO₃ (0.0 ? x ? 0.2) is investigated. The substitution of La³⁺ ions by smaller nonmagnetic Y³⁺ leads to greater spin disorder and induces variations in the magnetotransport behavior. From resistivity versus temperature curves a metal–insulator transition phenomenon is observed at the transition temperature, T_P, decreases as the Y content increases. The resistivity is well fitted using the equation ρ(T) = ρ_nexp[(T¹/T)ⁿ] with n = 1/4 and n = 1/2 at high and intermediate temperatures, respectively. The characteristic temperature T¹ varies with Y content in a manner consistent with the localization model of variable range hopping. Below T_P, resistivity varies as a function of power law contributions, ρ = ρ₀ + ρ₂T² + ρ_5/2T^5/2, corresponding to the electron scattering processes in the ferromagnetic phase.     

Intense luminescence of amorphous Eu2O3 prepared by aqueous sol–gel method

Amorphous Eu₂O₃ was prepared by an aqueous sol–gel method. Emission due to the ⁵D₀ → ⁷F_J (J = 0, 1, 2) transitions of Eu³⁺ ions were observed. The dominant transition was the ⁵D₀ → ⁷F₂ red emission of Eu³⁺. The properties of the as-prepared samples were different with changes in the annealing temperature. To investigate the luminescence properties of the amorphous Eu₂O₃, the temperature-dependent photoluminescence (PL) spectra of samples annealed at 600 °C were measured in the temperature range 77–300 K. PL peak positions were unchanged with the change of temperature.     

Thermally reversing window in Ge15Te85 − xInx glasses: Nanoindentation and micro-Raman studies

Nanoindentation studies on Ge₁₅Te_85 ? xIn_x glasses indicate that the hardness and elastic modulus of these glasses increase with indium concentration. While a pronounced plateau is seen in the elastic modulus in the composition range 3 ≤ x ≤ 7, the hardness exhibits a change in slope at compositions x = 3 and x = 7. Also, the density exhibits a broad maximum in this composition range. The observed changes in the mechanical properties and density are clearly associated with the thermally reversing window in Ge₁₅Te_85 ? xIn_x glasses in the composition range 3 ≤ x ≤ 7. In addition, a local minimum is seen in density and hardness around x = 9, the chemical threshold of the system. Further, micro-Raman studies reveal that as-quenched Ge₁₅Te_85 ? xIn_x samples exhibit two prominent peaks, at 123 cm^? 1 and 155 cm^? 1. In thermally annealed samples, the peaks at 120 cm^? 1 and 140 cm^? 1, which are due to crystalline Te, emerge as the strongest peaks. The Raman spectra of polished samples are similar to those of annealed samples, with strong peaks at 123 cm^? 1 and 141 cm^? 1. The spectra of lightly polished samples outside the thermally reversing window resemble those of thermally annealed samples; however, the spectra of glasses with compositions in the thermally reversing window resemble those of as-quenched samples. This observation confirms the earlier idea that compositions in the thermally reversing window are non-aging and are more stable.