Thermal and optical properties of Er-doped oxyfluorotellurite glasses

Er³⁺-doped oxyfluorotellurite glasses with four different concentrations of Er³⁺ ions have been prepared and investigated their thermal, optical absorption, excitation and luminescence properties. From the DSC spectra, glass transition and onset of crystallization temperatures have been found. Judd-Ofelt intensity parameters have been derived from the absorption spectrum and are in turn used to calculate radiative properties for the important luminescent levels of Er³⁺ ions. The calculated radiative properties are comparable to experimental values. The glasses show intense green and weak red emission under normal excitation with 451 nm. The decrease in emission intensities and lifetimes of the ⁴S_3/2 level with concentration of Er³⁺ ions has been explained as due to energy transfer processes between Er³⁺ ions. The stimulated emission cross-sections and quantum efficiencies of the green and infrared emissions have been determined. The results indicate that the glasses may be suitable for use as a laser medium in making solid-state green laser by normal pumping route and as laser medium and optical amplifier in the 1.5 μm region.     

Electrical conductivity improvement of strontium titanate doped lead vanadate glasses by nanocrystallization

The structural and electrical conductivity (σ) of annealed SrTiO₃–PbO₂–V₂O₅ glasses were studied. The annealing of initially glass samples leads to formation of nanocrystalline grains embedded in the glassy matrix. XRD patterns of the glass–ceramic samples show that nanocrystals were embedded in the glassy matrix with an average grain size of 32 nm. The glass–ceramic nanocrystals obtained by annealing at temperatures close to the crystallization temperature T_c exhibit enhancement of electrical conductivity up to four orders of magnitude than initially glasses. The enhancement of the electrical conductivity due to annealing was attributed to two interdependent factors: (i) an increase of concentration of V⁴⁺–V⁵⁺ pairs; and (ii) formation of defective, well-conducting regions along the glass–crystallites interfaces. From the conductivity temperature relation, it was found that small polaron hopping model was applicable at temperature above θ_D/2 (θ_D, the Debye temperature). The electrical conduction at T >θ_D/2 was due to non-adiabatic small polaron hopping (SPH) of electrons between vanadium ions. The parameters obtained from the fits of the experimental data to this model appear reasonable and are consistent with glass composition.     

Network structure of molybdenum lead phosphate glasses: Infrared spectra and constants of elasticity

Molybdenum lead phosphate glasses doped with La₂O₃ of the system xMoO₃-5La₂O₃-50P₂O₅-(45−x)PbO, with 0≤x≤25 mol%, have been synthesized and studied by FTIR, ultrasonic and differential scanning calorimetry (DSC) in order to investigate the role of MoO₃ content on their atomic structure. The constants of elasticity and Debye temperatures of the glasses have been investigated using sound velocity measurements at 4 MHz. According to the IR analysis, the vibrations of the phosphate structural units are shifted towards higher wavenumbers associated with the formation of bridging oxygens. The change in density with MoO₃ content reveals that the molybdate units are less dense than the lead units. The observed compositional dependence of the constants of elasticity is interpreted in terms of the effect of MoO₃ on the different phosphate bonds. It is assumed that MoO₃ plays the role of a former by increasing the ultrasonic velocity and the constants of elasticity of the phosphate glasses.     

Thermal properties of 3BaO–3TiO2–B2O3 glasses

Transparent glasses in the system 3BaO–3TiO₂–B₂O₃ (BTBO) were fabricated via the conventional melt-quenching technique. The as-quenched samples were confirmed to be non-crystalline by differential thermal analysis (DTA). Thermal parameters were evaluated using non-isothermal DTA experiments. The Kauzmann temperature was found to be 759 K based on heating-rate-dependent glass transition and crystallization temperatures. A theoretical relation for the temperature-dependent viscosity is proposed for these glasses and glass-ceramics.     

Elucidation of the crystallization kinetics for sodium-alumino-silicate glasses containing different amounts of manganese oxide

The glass samples [40SiO₂?+?5Al₂O₃?+?{55???x}Na₂O?+?xMnO₂] where x?=?0.05, 0.2, 0.4, 0.6, 0.8, and 1?mol% MnO₂ before and after being heat treated were subjected to X-ray diffraction. The diffraction lines provided clear evidence of the nucleation and growth, which are characteristic of sodium silicate phase. Crystallization studies were conducted using differential thermal analysis. Crystallization peak temperatures were identified and the transformed fractions were determined. Both the rate of growth, K ₀, and the activation energy, E, depend on the influence of manganese ions in the glass network as a modifier or as a former and the manganese content. The values of the Avrami parameter, n, were calculated using two methods and were in excellent agreement. The process of nucleation and growth rate depends on the manganese content.     

Nanoscale intrinsic heterogeneities in Ag-Ge-Se glasses and their correlation with physical properties

Ag-Ge-Se glass forming system is dominated by liquid immiscibility. Glasses in the Se-GeSe₂-Ag₂Se triangle may have different morphologies according to their composition. In this work inhomogeneous morphology is observed in Ag_x(Ge_ySe_1−y)_100−x bulk glasses with y = 0.20, 0.25 at.% fraction. Electron microscopy reveals that the scale of heterogeneity strongly depends on the sample composition. The physical properties of these glasses are also dependent on their composition and can be easily correlated to their morphology. Accordingly, the electric conductivity evolves from semiconducting to ionic conductivity whereas a percolation transition occurs in a narrow Ag concentration range.Mössbauer spectrometry let us to analyse the local order of these intrinsically heterogeneous glasses employing ⁵⁷Fe as a probe.     

Crystallization kinetics of the TeO2–BaO glass system

Tellurite glasses of the system (100–x)TeO₂–xBaO, with x = 05, 10, 15 and 20 wt%, have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions, applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC, using continuous-heating techniques. In addition, from the dependence of the glass-transition temperature (T _g) on heating rate, the activation energy for the glass transition was derived. Similarly, the activation energy of the crystallization process was determined and the crystallization mechanism characterized. The thermal stability of these glasses are considered in terms of the characteristic temperatures, T _g and T _in (the onset temperature of crystallization), via ΔT = T _in?T _g and a kinetic parameter K(T _g). The results confirm that thermal stability decreases with increasing BaO content. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of α-TeO₂, γ-TeO₂ and BaTeO₃ in the remaining amorphous matrix.     

Crystallization kinetics and thermal stability of Se98-x Zn2In x chalcogenide glasses

In this paper, we report on the non-isothermal crystallization kinetics of Se_{98 ?x} Zn₂In _x (0 ≤ x ≥ 10) chalcogenide glasses. The onset crystallization activation energy E _c, peak crystallization activation energy E _p and overall crystallization activation energy E have been determined by different approaches. The values of E _c, E _p and E have minima at a composition corresponding to 6 at% In. However the stability factor S and the crystallization rate constant stability factor K have a maximum and a minimum, respectively, at in the same composition. The nucleation and growth order parameter n, and the dimension order parameter m, are also determined and discussed for the present glasses.     

Synthesis and properties of MoO3–V2O5–PbO glasses

Lead vanadate glasses of the system xMoO₃–50V₂O₅–(50-x)PbO (0 ≤ x ≤ 25 mol. %) were synthesized and studied by FTIR and ultrasonic spectroscopy and differential scanning calorimetry to investigate the role of MoO₃ content on their atomic structure. The elastic properties and Debye temperatures of the glasses were investigated using sound velocity measurements at 4 MHz. The activation energy for the glass transition was derived from the dependence of the glass-transition temperature (T_g ) on the heating rate. Similarly, the activation energy of the crystallization process was also determined. According to the IR analysis, the vibrations of the vanadate structural units are shifted towards higher wavenumbers on the formation of bridging oxygens. The change of density and molar volume with MoO₃ content reveals that the molybdinate units are less dense than the lead oxide units. The observed compositional dependence of the elastic moduli is interpreted in terms of the effect of MoO₃ on the coordination number of the vanadate units. A good correlation was observed between the experimentally determined elastic moduli and those computed according to the Makishima–Mackenzie model. It is assumed that MoO₃ plays the role of a glass former by increasing the activation energy for the glass transition and the activation energy for crystallization and by increasing both the thermal stability and the glass formation range of the vanadate glasses.     

GeSe2-Sb2Se3-CsCl玻璃的光学性质与析晶动力学研究

采用熔融淬冷法制备了20GeSe₂-（80-x）Sb₂Se₃-xCsCl（x=2,4,8,10 mol%）硫卤玻璃系统,测试了样品在可见至中远红外区域的透过光谱,研究了硫卤玻璃中CsCl对玻璃短波吸收限的影响;并测试了典型的20GeSe₂-76Sb₂Se₃-4CsCl样品在不同升温速率下的DTA曲线,利用非等温方法研究了其析晶动力学; 关键词： 硫卤玻璃 非等温过程 析晶动力学     

Crystallization kinetics and thermal stability in Se85-xTe15Sbx chalcogenide glasses

Crystallization process of Se_85-xTe₁₅Sb_x (x = 2.7, 7.5, 10 and 15 at %) chalcogenide glasses has been studied by using differential scanning calorimetry (DSC) with different heating rates. These glasses are found to have a double glasses transition and overlapped crystalline phases for Se₇₀Te₁₅Sb₁₅ glass while single glasses transition and single crystallization stage for other glasses. Glass transition temperature, T_g, onset crystallization temperature, T_c, and peak crystallization temperature, T_p, are found to be dependent on composition and heating rates. Values of various kinetic parameters such as activation energy of glass transition, E_g, activation energy of crystallization, E_c, Hurby number, H_r, thermal stability, S_p, rate constant, K_p, and Avrami exponent, n, are determined for the present systems. Results indicate that rate of crystallization is dependent on thermal stability and glass-forming ability. Crystallization mechanism occurs in two dimensions for studied compositions. Crystalline phases resulting from DSC and scanning electron microscopy have been identified by using X-ray diffraction.     

Tb3+掺杂的氟氧碲酸盐玻璃发光性能

用高温熔融法制备了Tb³⁺掺杂的氟氧碲酸盐玻璃样品,测试了不同Tb³⁺和Gd³⁺浓度玻璃样品的密度、透过光谱、以及380 nm紫外光和X射线激发的发光光谱.着重研究了玻璃中不同Tb³⁺和Gd³⁺离子含量对玻璃性能的影响规律及机理.结果表明:氟氧碲酸盐玻璃具有较大的密度,ρ大于5 g/cm³;增加Tb³⁺离子的浓度,可以有效提高样品的闪烁发光 关键词： 铽离子 氟氧碲酸盐玻璃 闪烁玻璃 发光性能     

Optical properties of lithium barium haloborate glasses

Lithium haloborate glasses have been prepared according to the formula (70−y)B₂O₃-30BaF2-yLiX where y=0, 5, 10, 15 and 20 mol% and X=F, Cl and Br. The UV absorption spectra have been recorded at room temperature. The optical energy band gap E_opt and Urbach energy E_tail was determined. Increasing concentration of LiX in the glass shifts the UV cutoff to lower energy and decreases both E_opt and E_tail. The shift in UV cutoff and the decrease of E_opt and E_tail are maximum in the range 0-5 mol% LiX. The decrease of E_opt increases going from F, Cl to Br, whereas the decrease of E_tail increases going from Br, Cl to F. At higher LiX concentrations Urbach energy E_tail increases again. The behavior of E_opt has been correlated with the B-O bond length of the studied glasses. The decrease of E_opt and E_tail is due to the increase of nonbridging oxygen (NBO) concentration with increase of LiX content. The increase of E_tail at higher concentrations is attributed to the halide ion accumulation in the interstitial positions and to the formation of orthoborate groups. Refractive index, which is measured and calculated, molar refraction and polarizability are all correlated with the composition of the glasses.     

Role of Al coordination in barium phosphate glasses on the emission features of Ho ion in the visible and IR spectral ranges

The glasses of the composition (39−x)BaO-xAl₂O₃-60P₂O₅:1.0Ho₂O₃ (in mol%) with x value ranging from 1.0 to 4.0 have been synthesized. The IR spectral studies of these glasses have indicated that there is a gradual transformation of Al³⁺ ions from tetrahedral to octahedral with increase in the concentration of Al₂O₃ up to 3.0 mol%. Optical absorption and fluorescence spectra (in the visible and NIR regions) of these glasses have been recorded at room temperature. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of Ho³⁺ ions in these glasses. From the luminescence spectra, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and emission cross-section σ^E for various emission levels of these glasses have been evaluated. The radiative lifetime of the ⁵S₂→⁵I₈ (green emission) transition has also been measured. The variations observed in these parameters have been discussed in the light of varying co-ordinations (tetrahedral and octahedral positions) of Al³⁺ ions in the glass network. The influence of hydroxyl groups on the luminescence efficiency of the transition ⁵S₂→⁵I₈ has also been discussed. Finally the optimum concentration of Al₂O₃ for getting maximum luminescence output has also been identified and reported.     

AC conductivity and dielectric properties of sulphate glasses

AC conductivity and dielectric properties of sulphate glasses have been studied as a function of temperature, frequency and variation in interalkali concentration. AC conductivity at frequencies well beyond the dielectric loss peaks seems to arise from local motion of alkali ions within the neighbouring potential wells. Activation energies for AC conductivity were found to be very much lower than those for DC conductivity. Further, AC conductivity seems to be independent of interalkali variation, whereas ε′ and tan δ show a mild degree of mixed alkali effect. The observations made here have been explained on the basis of a structural model earlier proposed by us for these glasses. Communication No. 167 from Solid State and Structural Chemistry Unit.     

Glass forming regions and dielectric properties of new phosphate glasses

The glass forming regions have been determined in the systems P₂O₅-A₂O-MO (A = Li, Na; M = Cu, Cd), P₂O₅-Bi₂O₃-Li₂O and P₂O₅-Bi₂O₃-ZnO. The largest vitreous domain has been found in the ternary diagram P₂O₅-Bi₂O₃-ZnO. The variation of the dielectric constants has been followed inside the glass regions. ε'_r increases with increasing amount of alkaline oxides and substantially diminishes with increasing percentage of either CuO or CdO.     

Initial stage of physical ageing in network glasses

An atomistic view on Johari–Goldstein secondary β-relaxation processes responsible for structural relaxation far below the glass transition temperature (T_g ) in network glasses is developed for the archetypal chalcogenide glass, As₂₀Se₈₀, using positron annihilation lifetime, differential scanning calorimetry, Raman scattering and nuclear magnetic resonance techniques. Increased density fluctuations are shown to be responsible for the initial stage of physical ageing in these materials at the temperatures below T_g . They are correlated with changes in thermodynamic parameters of structural relaxation through the glass-to-supercooled liquid transition interval. General shrinkage, occurred during the next stage of physical ageing, is shown to be determined by the ability of system to release these redundant open volumes from the glass bulk through the densification process of glass network.     

荧光俘获效应对掺饵氧化物玻璃光谱性质的影响

测试了不同掺杂浓度和样品厚度下掺铒磷酸盐和碲酸盐玻璃的吸收光谱、荧光光谱和荧光寿 命，计算了Er³⁺离子在1.53 μm处的吸收截面(σ_a)、发射截面(σ _e)、自发辐射跃迁概率(A_rad)、辐射跃迁寿命(τ_rad) 、以及辐射跃迁量子效率(η)等光谱参数.讨论了荧光俘获效应对掺铒磷酸盐和碲酸盐玻璃 光谱性质及光谱参数的影响.结果表明即使在铒离子低掺杂浓度(0.1 mol% Er₂O ₃)下，荧光俘获效应也普遍存在于掺铒玻璃材料中，使得荧光寿命(τ_{f)和荧光半高宽(FWHM)随样品的厚度和铒离子掺杂浓度增加而增大，导致碲酸盐和磷酸 盐玻璃中τf分别增加11%—37％和6%—17%，FWHM分别增加15%—64%和11%—55% ，使得掺铒玻璃材料的放大品性参数(σe×FWHM) 也相应被估高.由于铒离子在 碲酸盐玻璃中在1.53 μm处吸收和发射截面重叠面积较大，加之铒离子在前者基质中的发射 截面高于后者，使得掺铒碲酸盐玻璃中的荧光俘获效应高于磷酸盐玻璃. 关键词： 荧光俘获 铒离子 碲酸盐玻璃 磷酸盐玻璃}     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃