Optical characterization of the phosphate glasses containing pair transition ions

The paper deals with optical and electronic properties of the aluminophosphate glasses containing Fe–Mn and Fe–Cr ion pairs in different concentration. The influence of the mixed alkali ions over the electronic properties has been investigated. The optical behavior (optical transmission) of the glass samples has been studied by UV-VIS spectroscopy and the refractive index dependency on wavelength has been discussed. The transmission spectra show features specific for the doping transition ions (TM), revealing different oxidation states of iron (Fe²⁺/Fe³⁺), manganese (Mn²⁺/Mn³⁺) and chromium (Cr³⁺/Cr⁶⁺) in the vitreous network. Mössbauer spectroscopy offers information regarding the TM oxidation states, redox processes and the iron coordination symmetry in the vitreous network. In the case of Fe–Mn doped glasses, the percentage of Fe²⁺ is about 40% and a doubled iron content leads to an increasing of Fe²⁺ percentage up to 53%. The replacing of lithium ions by natrium ions (mixed alkali effect) provides an increasing of the Fe²⁺ percentage up to 56%. The occurrence of the tetrahedral or octahedral symmetry of Fe²⁺ ions bonded by O^2? ions depends on the transition ion nature and Li⁺/Na⁺ ratio. Infrared absorption spectra of the pair transition ions-doped aluminophosphate glasses reveal optical phonons specific for the phosphate glass matrix.     

Concentration-dependent luminescence of Tb ions in high calcium aluminosilicate glasses

This study deals with the results on the concentration-dependent fluorescence properties of Tb³⁺-doped calcium aluminosilicate (CAS) glasses of composition (100−x)(58SiO₂–23CaO–5Al₂O₃–4MgO–10NaF in mol%)-x Tb₂O₃ (x=0, 0.25, 0.5, 1, 2, 4, 8, 16, 24, 32, 40 in wt%). The FTIR reflectance spectra suggested the role of dopant ions as network modifiers in the glass network. The fluorescence spectra of low Tb³⁺-doped glasses have revealed prominent blue and green emissions from ⁵D₃ and ⁵D₄ excited levels to ⁷F_j ground state multiplet, respectively. The glass with 2 wt% of Tb₂O₃ has exhibited maximum intensity of blue emission from ⁵D₃ level, while green emission from ⁵D₄ level has increased linearly up to 24 wt% and showed reduction in the rate of increase for higher Tb₂O₃ concentrations. The concentration quenching of blue emission (⁵D₃→⁷F_j) is attributed mainly to the resonant energy transfer (RET) assisted cross-relaxation (CR) among the excited and nearest neighbour unexcited Tb³⁺ ions in the glass matrix. The decline in rate of increase of green emission (⁵D₄→⁷F_j) at higher concentrations has been explained due to a possible occurrence of cooperative energy transfers leading to 4f⁸→4f⁷5d transition interactions. The blue and green emission decay kinetics have been recorded to compute the excited level (⁵D₃ and ⁵D₄) lifetimes, which confirmed the Tb³⁺ concentration quenching of the blue emission in these glasses.     

Theoretical studies of the optical and EPR spectra for vanadyl ions in alkaline-earth aluminoborate glasses

The optical spectra and electron paramagnetic resonance (EPR) g and A factors of calcium aluminoborate glasses (CaAB) : VO²⁺ are calculated using a complete diagonalization (of the energy matrix) process (CDP). Good agreement between the theoretical values and experimental results indicates the effectiveness of the CDP method for theoretical studies of optical and EPR spectra of 3d¹ (or V⁴⁺) ions in glasses.     

Laser spectroscopy of Nd and Dy ions in lead borate glasses

The spectroscopic and laser properties of Nd³⁺ and Dy³⁺ ions in lead borate glass were studied. Luminescence spectra recorded in the near-infrared and visible ranges correspond to ⁴F_3/2-⁴I_J/2 (J=9, 11, 13) transitions of Nd³⁺ and ⁴F_9/2-⁶H_J/2 (J=11, 13, 15) transitions of Dy³⁺, respectively. Luminescence decay curves were analyzed as a function of activator concentration. Luminescence quenching is observed, which is due to Ln-Ln interaction increasing. Several spectroscopic parameters relevant to laser potential of Ln³⁺ ions (Ln=Nd, Dy) in lead borate glass were determined. The relatively large values of the quantum efficiency and the room-temperature emission cross-section for the ⁴F_3/2-⁴I_11/2 transition of Nd³⁺ at 1061 nm and the ⁴F_9/2-⁶H_13/2 transition of Dy³⁺ at 573 nm imply that Ln-doped lead borate glasses can be considered as promising solid-state materials for laser applications.     

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.     

Luminescent properties of Dy-doped and Dy–Tmco-doped phosphate glasses

Phosphate glasses doped with Dy³⁺ ions and co-doped with Dy³⁺–Tm³⁺ ions are successfully prepared in the present work. Their photoluminescence properties have been studied by absorption, excitation and emission spectra. A combination of blue and yellow emissions has emerged in the glasses, which allows the observation of white light when the glasses are excited by the ultraviolet light. The emission intensity of Dy³⁺ is influenced by the system ionicity, while the intensity ratio of yellow to blue emissions from Dy³⁺ can be tuned by varying both the concentration of Tm³⁺ ion and the glass matrix composition.     

Preparation and properties of Ce-doped Na–Gd phosphate glasses

Rare earth-doped sodium–gadolinium phosphate glasses with increased luminescence efficiency are promising materials for the detection of neutrons, γ- and X-rays. Their main advantages are low cost, high radioluminescence light output, high quality and chemical durability. The glasses were prepared by a rapid quenching technique in air. The radioluminescence intensity maximum was achieved for a Ce concentration of 3 mol% and that of Gd around 30%. Glass transition temperatures were above 300°C for the tested samples and this guarantees that the glass can be utilised in a sufficiently broad temperature range. The glass-forming ability of this glass system is high. However, until now high-quality glass has been only prepared with a Gd concentration of 40 mol% in the starting batch. The glasses containing at least 30 mol% Gd were moisture resistant, while those with lower Gd concentrations were slightly hygroscopic.     

荧光捕获效应对Yb3+磷酸盐玻璃光谱性质的影响

测试了不同掺杂浓度和不同厚度下Yb3+ 磷酸盐玻璃的吸收光谱、荧光光谱和荧光寿命 ,计算了积分吸收截面、吸收截面、受激发射截面、自发辐射寿命以及荧光有效线宽等光谱参数 ,讨论了荧光俘获效应对Yb3+ 磷酸盐玻璃光谱性质的影响 .结果表明荧光俘获效应随样品厚度和掺杂浓度的增加而增大 .由于荧光俘获效应的存在使得测量的Yb3+ 磷酸盐玻璃荧光寿命明显长于计算的荧光寿命 ,在 0 2mol%Yb2 O3低掺杂浓度下采用不同厚度 ( <4mm)的样品测量的荧光寿命之间误差为 3 0 %左右 ,高浓度 ( 6mol%Yb2 O3)掺杂下误差可达 43 % .荧光俘获还造成荧光谱线加宽 ,导致荧光有效线宽在低浓度 ( 0 2mol%Yb2 O3)时增加 14% ,在高掺杂浓度 ( 6mol%Yb2 O3)下增加 3 0 %以上     

Structural investigation of xAg2O·(100−x)·[2B2O3·As2O3] glasses doped with manganese ions

Structural analysis of x[(100−y)Ag₂O·yMnO]·(100−x)[2B₂O₃·As₂O₃] glasses, with x=10 mol% and 0≤y≤10 mol%, was performed by means of FT-IR and FT-Raman spectroscopies. The purpose of this work is to investigate the structural changes that appear in the xAg₂O·(100−x)·[2B₂O₃·As₂O₃] glasses with the addition and increase in manganese ions content. FT-IR measurements revealed the presence of pyro-, ortho-, di-, tri-, tetra- and penta-borate groups and structural units characteristic to As₂O₃ in the structure of the studied glasses. FT-IR spectroscopy measurements also show that BO₃ units are the main structural units of the glass system. The presence of structural units characteristic to Ag₂O were not directly evidenced by FT-IR spectroscopy. In addtition, the FT-Raman analysis evidenced the presence of boroxol rings in the structure of the studied glasses.     

Fluorophosphate glasses containing manganese

New fluorophosphate glasses based on MnF₂, NaPO₃ and MF_n (M=Zn²⁺, Sr²⁺, Mg²⁺, Ba²⁺, Li⁺, Na⁺ and K⁺) have been synthesised and characterized. Large vitreous areas were observed. Samples of 4 mm in thickness have been obtained. These glasses are easy to prepare and stable in ambient air. Depending on the composition and the nature of the M cation, glass transition temperature, T_g, lies between 230 and 314 °C, crystallisation temperature, T_x is between 320 and 475 °C. These glasses are pink coloured, and infrared transmission extends up to 4.5 μm with extrinsic OH⁻ absorption band at 3200 cm⁻¹ and other bands around 2200 and 1600 cm⁻¹ that relate to PO₄ tetrahedron vibration. Other physical properties including density, microhardness, Young modulus, thermal expansion and refractive index were investigated and correlated to composition.     

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.     

Nonlinear optical characterization of phosphate glasses based on ZnO using the Z-scan technique

The nonlinear optical properties of a phosphate vitreous system [(ZnO)_x-(MgO)_30-x-(P₂ O₅)₇₀], where x=8, 10, 15, 18, and 20 mol% synthesized through the melt-quenching technique have been investigated by using the Z-scan technique. In the experiment, a continuous-wave laser with a wavelength of 405 nm was utilized to determine the sign and value of the nonlinear refractive (NLR) index and the absorption coefficient with closed and opened apertures of the Z-scan setup. The NLR index was found to increase with the ZnO concentration in the glass samples by an order of 10^-10 cm²·W^-1. The real and imaginary parts of the third-order nonlinear susceptibility were calculated by referring to the NLR index (n₂) and absorption coefficient (β) of the samples. The value of the third-order nonlinear susceptibility was presented by nonlinear refractive or absorptive behavior of phosphate glasses for proper utilization in nonlinear optical devices. Based on the measurement, the positive sign of the NLR index shows a self-focusing phenomenon. The figures of merit for each sample were calculated to judge the potential of phosphate glasses for application in optical switching.     

荧光捕获效应对Yb3+磷酸盐玻璃光谱性质的影响

测试了不同掺杂浓度和不同厚度下Yb³⁺磷酸盐玻璃的吸收光谱、荧光光谱和荧 光寿命，计算了积分吸收截面、吸收截面、受激发射截面、自发辐射寿命以及荧光有效线宽等光谱参数，讨论了荧光俘获效应对Yb³⁺磷酸盐玻璃光谱性质的影响.结果表明荧光俘 获效应随样品厚度和掺杂浓度的增加而增大.由于荧光俘获效应的存在使得测量的Yb^{3+磷酸盐玻璃荧光寿命明显长于计算的荧光寿命，在0.2mol%Yb₂O₃低掺 杂浓度下 关键词： 荧光俘获 掺镱磷酸盐玻璃 荧光光谱}     

Silver-doped calcium phosphate nanopowders prepared by electrostatic spraying

Silver-doped calcium phosphate nanopowders were successfully prepared by the cost-effective electrostatic spray-pyrolysis process. The properties of the silver-doped nanopowder annealed at 500°C for 30 min were investigated through X-ray diffraction analysis, field emission scanning electron microscope, and Fourier transform infrared spectroscopy. The silver-doped nanopowders with 70–90 nm particle size showed an antibacterial performance against Escherichia coli.     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

Preparation and optical spectroscopy of phosphate glasses containing divalent europium ions

P2O5.BaO.Na2O.K2O glasses doped with various content of Eu2O3 were prepared using high temperature melting method, and the Eu2+ ions in the phosphate glasses were obtained with the aid of the reductive action of silicon powder. The fabricating conditions, fluorescence, excitation spectra of the glasses were then studied. The glasses containing europium show a broad emission band at 450 nm and sharp bands from 580 to 650 nm, and the co-existence of Eu2+ and Eu3+ is identified. Also, a good glass with a dominant proportion and large quantity of Eu2+ ions can be obtained by the reductive action of silicon powder and proper processing.     

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.