UV–visible and infrared absorption spectra of transition metals-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and transition metals (TM 3d)-doped lead phosphate glasses were prepared. Ultraviolet–visible absorption spectra were measured in the range 200–1100 nm before and after successive gamma irradiation. Experimental results indicate that the undoped lead phosphate glass reveals before irradiation strong and broad ultraviolet absorption which is related to the co-sharing of absorption due to both trace iron impurities and lead ions (Pb²⁺). In the TM-doped glasses, characteristic absorption bands are obtained in both the UV and/or visible regions due to each respective TM ion in addition to that observed by the base undoped UV absorption. Gamma irradiation produces with the undoped glass a prominent induced ultraviolet broad band centered at about 300 nm originating mostly from the contribution of trace iron impurities and the visible spectra reveal markedly high shielding behavior towards successive gamma irradiation, due to the presence of both high content of heavy Pb²⁺ ions and the sharing of phosphate as a partner. With TM-doped samples, the observed induced bands are virtually varying and related to the type of the sharing TM ions. Infrared absorption spectra reveal in the undoped and TM-doped glasses characteristic structural phosphate groups mainly consisting of metaphosphate and pyrophosphate units. Transition metals are assumed to cause depolymerization of the phosphate glass network with different ratios but the changes in IR spectral data are limited due to the low doping level. Gamma irradiation of the samples is assumed to cause changes in the bond angles or bond lengths of the structural phosphate units within network as evident in the variation of the intensities of the IR bands.     

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd–PSS films were processed using the acid of poly(styrene sulfonate) – H–PSS and neodymium nitrate – Nd(NO₃)₃; the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV–Vis–NIR spectral region presents typical electronic transitions of Nd³⁺ ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N–O groups in the range of 1400–720 cm^?1, prove the permanence of Nd(NO₃)_x, with x = 1, 2 and/or 3, in the H–PSS matrix. UV–Vis site selective photoluminescence data indicate that the incorporation of Nd³⁺ introduces a blue shift in PSS emission (325–800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd³⁺ reabsorption and energy transfer effects between the PSS matrix and Nd³⁺ were also observed. The IR emission of Nd–PSS films at 1076 nm (⁴F_3/2 → ⁴I_11/2) present constant efficiency, independent on Nd³⁺ concentration. The Judd–Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd³⁺. Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix.     

Effect of alkali and alkaline-earth cations on the neodymium environment in a rare-earth rich aluminoborosilicate glass

The local structure around neodymium in an aluminoborosilicate glass bearing 3.6 mol% Nd₂O₃ is studied by optical absorption spectroscopy and EXAFS at the Nd L_III- and K-edges. The influence of the nature of alkalis (M⁺ = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and alkaline-earths (M²⁺ = Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺) on the coordination sphere of Nd³⁺ ions in the glass is particularly investigated. The Nd³⁺ sites are well-defined with NdO mean distances of 2.46 ± 0.03 Å, whatever the alkali and alkaline-earth ion type except Li⁺ and Mg²⁺, for which glasses exhibit slightly more disordered Nd sites and longer NdO distances (2.49 ± 0.03 Å). Using bond valence considerations, a model is proposed for the Nd site, and consists in 7–8 non-bridging oxygens (NBO), every NBO being charge compensated by 2–3 alkalis and alkaline-earths. The NdO mean distance is adjusted according to the mean field strength of these cations, to avoid overbonding of the NBO’s. A glass series with varying Ca²⁺/Na⁺ concentration ratio shows that Nd³⁺ cations are able to maintain this average coordination site even at high alkaline-earth content.     

FTIR and UV–VIS optical absorption spectra of gamma-irradiated MoO3-doped lead borate glasses

Structure and optical properties of MoO₃-doped lead borate glasses which contain high PbO content (60, 70 and 80%) have been studied using Fourier transform infrared (FTIR) and ultraviolet–visible (UV–VIS) spectroscopic tools. FTIR spectra reveal absorption bands which are characteristic for various structural units of borate network, mainly BO₃ triangles and BO₄ tetrahedra, in addition to the PbO_n (where n = 3 and/or 4) structural units. UV–VIS optical absorption spectra reveal broad intense charge transfer UV bands due to Pb^2 + ions in the range 320–385 nm. Within this range, molybdenum ions, preferably Mo^3 + and Mo^5 +, can interfere at about 360–385 nm. Additionally, molybdenum ions give a weak visible band at about 850–860 nm. The optical absorption spectra of the studied glasses show marked resistance to successive gamma irradiation up to 5 Mrad. This shielding behavior can be related to the present high content of the high atomic mass Pb^2 + ions. Changes in the atomic structure before and after gamma irradiation are described and explained.     

Laser transition characteristics of Nd3+-doped fluorophosphate laser glasses

Fluorophosphate glasses of composition P₂O₅–K₂O–MgO–Al₂O₃–AlF₃ and P₂O₅–K₂O–MgO–Al₂O₃–BaF₂ were prepared with different Nd³⁺ ion concentrations. The absorption and emission spectra in the UV–VIS–NIR region were measured for these glasses. Judd–Ofelt analysis has been carried out using the absorption spectra of 1.0 mol% Nd³⁺-doped glasses to evaluate the radiative properties for some luminescent levels of the Nd³⁺ ion. The stimulated emission cross-sections of the ⁴F_3/2 → ⁴I_11/2 laser transition for the present glasses are found to be higher than for other Nd³⁺-doped glasses. Branching ratio calculations also revealed the potentiality of the ⁴F_3/2 → ⁴I_11/2 transition for laser action in these glasses. The observed concentration quenching of the lifetime of the ⁴F_3/2 level is explained as a result of cross-relaxation process between the Nd³⁺ ions.     

Compositional dependences on the mechanism of upconversion in Nd3+/Tm3+ co-doped chalcohalide glasses

Mechanisms of the compositional dependence of blue emission from Nd³⁺/Tm³⁺ co-doped Ge–Ga–S–CsBr chalcohalide glasses were investigated. The blue upconversion emissions (centered at 475 nm) due to the Tm³⁺: ¹G₄ → ³H₆ transition decreased as the CsBr/Ga ratio in glasses while the other upconversion emissions from the Nd³⁺ ions increased. Changes in the local environment of rare-earth ions incurred by the CsBr addition significantly increased the excited state absorption within Nd³⁺ ions. This resulted in the decrease in the Nd³⁺ → Tm³⁺ energy transfer rates that led to the large decrease in blue upconversion emission.     

Optical and FTIR studies of CuO-doped lead borate glasses and effect of gamma irradiation

CuO doped lead borate glasses of the composition PbO 70%–B₂O₃ 30% with varying CuO contents were prepared. UV–visible and infrared spectroscopic studies were measured before and after successive gamma irradiation with two different doses namely 2 and 8 Mrad. The experimental results indicate that the undoped sample reveals strong UV–near visible absorption while copper doped samples show additional broad visible band due to (Cu^2 +) ions.FT infrared absorption spectrum reveals vibrational bands due to triangular and tetrahedral borate groups together with the sharing of Pb–O vibrations.CuO-doped glasses have been found to show a shielding behavior towards the effects of progressive gamma irradiation causing the maintenance of the spectral curves. The changes in the UV–visible and infrared spectral data are discussed in relation to the states of copper ions and structural evolution caused by the change in glass composition including the CuO.     

Quantitative UV–VIS spectroscopic studies of photo-thermo-refractive glasses. I. Intrinsic,bromine-related,and impurity-related UV absorption in photo-thermo-refractive glass matrices

The paper opens up a series of papers on the origin and parameters of spectral features forming the absorption of photo-thermo-refractive (PTR) glasses in the UV. Problems to be cleared for gaining further insight into the spectroscopic manifestations of species responsible for the photo-induced processes in PTR glasses are discussed. The samples of bromine-containing and bromine-free PTR glass matrices are synthesized and their absorption spectra in the 28,500 to 50,000 cm^–1 region are recorded. The dispersion analysis of the spectra is conducted based on the convolution model for the complex dielectric function of glasses. The matrix electronic transitions that set the real part of the complex dielectric function and form the intrinsic absorption tail of the matrix are simulated with a series of effective oscillators. Spectral features forming the total absorption spectrum of PTR glass matrices in the 28,500 to 50,000 cm^–1 region are deconvoluted. These features are (i) the intrinsic absorption tail, (ii) for the bromine-containing matrix, the low-wavenumber wing of an envelope around ~ 51,400 cm^–1 covering the bromine-related spectral feature(s), (iii) Fe²⁺- and Fe³⁺-related impurity bands, and also (iv) a structureless absorption mostly due to the high-wavenumber wings of other impurity bands below 28,500 cm^–1.     

Fluorescence properties and laser demonstrations of Nd-doped high silica glasses prepared by sintering nanoporous glass

Porous glass with high-SiO₂ content was impregnated with Nd ions, and subsequently sintered at 1100 °C into a compact non-porous glass in air or reducing atmosphere. Sintering in a reducing atmosphere produced an intense violet–blue fluorescence at 394 nm. However, the sintering atmospheres almost did not affect the fluorescence properties in the infrared range. A good performance Nd³⁺-doped silica microchip laser operating at 1064 nm was demonstrated. The Nd-doped sintering glasses with high-SiO₂ content are potential host materials for high power solid-state lasers and new transparent fluorescence materials.     

2 μm spectroscopic investigation of Tm3+-doped tellurite glass fiber

TmF₃ doped TeO₂–ZnO–La₂O₃ (TZL) glasses and fibers have been prepared by the conventional melt-quenching and suction casting methods, respectively. 2 μm emission properties and energy transfer mechanisms of the TZL glasses and fibers have been analyzed and discussed. The oscillator strength, Judd–Ofelt parameters, radiative transition probability and radiative lifetime of Tm³⁺ have been calculated based on the absorption spectra and Judd–Ofelt theory. The maximum emission cross-section of Tm³⁺ is 6.9 × 10^?21 cm² near 2 μm. Emission spectra have been obtained from both TZL fibers and bulk glass when excited with a 794 nm pump. The results of 2 μm emission spectra indicate that the line width of Tm³⁺ measured in fibers is narrower than that in the bulk glass sample. The peak position of the emission spectra shifts to longer wavelength with increment of the fiber length.     

Spectroscopic studies of tungsten ions in PbO–PbF2–SiO2 glasses

40PbO–(10 ? x)PbF₂–50 SiO₂:xWO₃ (where x = 1 to 7 mol%) glasses are prepared in the glass forming region. Spectroscopic studies (UV–Vis absorption, ESR, IR) are carried out for these glasses. Interesting changes are observed in the spectroscopic parameters of these glasses when the concentration of WO₃ is changing in the glass matrix. Two absorption bands are observed around at 830 and 620 nm. ESR signal are measured at room temperature for these glasses, the strength of the signal is increased and hyperfine splitting is resolved with increasing the concentration of WO₃ in the glass matrix. IR transmission gives valuable information about the nature of bonds in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

Spectral investigations on VO2+ ion doped in CaO–SrO–Na2O–B2O3 glass systems

Glasses of the (20 ? x)CaO–xSrO–(20 ? y)Na₂O–60B₂O₃ ? y (CSNB) system with (5 ≤ x ≤ 15) mol% and y = 0.1 mol% of V₂O₅ were characterized by X-ray diffraction (XRD), EPR (Electron Paramagnetic Resonance), Optical absorption Spectra and FT-IR (Fourier transform Infrared Spectroscopy) studies. EPR spectra of all the glass samples exhibit resonance signals characterstic of VO²⁺ ions. The values of spin-Hamiltonian parameters indicate that the VO²⁺ ions in CSNB glasses were present in octahedral sites with tetragonal compression and belong to C_4v symmetry. Spin-Hamiltonian parameters ‘g’ and ‘A’ were evaluated. The Optical band energy (E_opt) and Urbach energy (ΔE) were calculated from their ultra violet edges. By correlating EPR and Optical data the molecular orbital coefficients have been evaluated. IR spectra of these glasses were analyzed in order to identify the contribution of each component to the local structure that determines the physical properties of these glasses.     

Photoinduced redox-reactions and transmission changes in glasses doped with 4d- and 5d-ions

(Fluoride)phosphate and borosilicate glasses of high intrinsic transparency in the deep ultraviolet (UV), were doped with 50–5000 ppm of the 4d- and 5d-ions Zr, Nb, Ta, Mo, or W. All of these ions absorb strongly in the UV. Samples plates were irradiated by UV lasers and the as a consequence generated various extrinsic and intrinsic defects were characterized by optical and EPR spectroscopy. The laser induced transmission changes depend not only on the glass matrix, but also on the valence of the dopants. Only fully oxidized d⁰-ions are observed in fluoroaluminate glasses. Laser irradiation photoreduces the d⁰-ions to extrinsic electron-centers (EC). Laser induced transmission changes extend from the UV up to 600 nm in the visible. The dopants are easily reduced to lower valences in metaphosphate glasses. Extrinsic hole centers (HC) replace intrinsic HC in samples containing the reduced transition metal ions. The strong transmission changes seen below 300 nm arise from intrinsic EC and extrinsic HC. The few remaining intrinsic HC (300–600 nm) recombine rapidly with EC or transform into more stable extrinsic HC. Borosilicate glasses show the formation of intrinsic boron oxygen hole center in the EPR spectra and of intrinsic HC and EC in the optical spectra. The d¹-ion Mo⁵⁺ is the only identified reduced dopant species in the borosilicate glasses. The band intensity of intrinsic EC in relation to intrinsic HC is correspondingly highest for the Mo-doped samples, in which extrinsic HC are generated.     

Optical properties and valence state of Sm ions in aluminoborosilicate glass under β-irradiation

Sm-doped borosilicate glasses exposed to β-irradiation with doses from 8 × 10⁵ up to 4 × 10⁹ Gy have been studied by luminescence, Raman and electron paramagnetic resonance (EPR) spectroscopies. The luminescence spectra for pristine and irradiated glasses reveal that the β-irradiation process affects valence state of samarium ions. Intense emission at 684 and 727 nm excited by Ar+ laser (514.5 nm) due to the transition of Sm²⁺ ion was observed after irradiation. Relative proportion of Sm²⁺ ions estimated as a function of both Sm₂O₃ content and irradiation dose has the tendency to increase with increasing irradiation dose. In contrast, the EPR spectra of the studied samples reveal a decrease of the defect content, which are mostly hole defects, produced during irradiation, as a function of Sm₂O₃ content. Finally, the addition of Sm₂O₃ leads to a decrease of the Si–O–Si bending vibration modes shift and polymerisation changes under irradiation.     

Glass formation in and structural investigation of Li2S + GeS2 + GeO2 composition using Raman and IR spectroscopy

Li₂S + GeS₂ + GeO₂ ternary glasses have been prepared and a wide glass-forming range was obtained. The glass transition temperatures increase with the GeO₂ concentration in the glasses. The vibrational modes of both bridging (Ge–S–Ge) and non-bridging (Ge–S⁻) sulfurs are observed in Raman and IR spectra of binary Li₂S + GeS₂ glasses. Additions of GeO₂ to this binary glass increase the bridging oxygen band (Ge–O–Ge) at the expense of decreasing the bridging sulfur band (Ge–S–Ge), whereas the bands associated with the non-bridging sulfurs (Ge–S⁻) remain constant in intensity up to high GeO₂ concentrations. At higher concentrations of GeO₂ (⩾60%), the non-bridging oxygen band, which is not observed at low and intermediate GeO₂ concentrations, appears and grows stronger. From these observations, it is suggested that the added lithium ions favor the non-bridging sulfur sites over the oxygen sites to form non-bridging sulfurs, whereas the added oxygen prefers the higher field strength Ge⁴⁺ cation to form bridging Ge–O–Ge bonds. The structural groups in the Li₂S + GeS₂ + GeO₂ glasses that are consistent with results of Raman and IR spectra are described and are used to develop a structural model of these glasses.     

Alkaline earth zinc borate glasses doped with Cu2+ ions studied by EPR,optical and IR techniques

Copper ions incorporated into alkaline earth zinc borate glasses 10RO + 30ZnO + 60B₂O₃ (R = Mg, Ca and Sr) and 10SrO + (30 ? x)ZnO + 60B₂O₃ + xCuO (x = 0, 0.1, 0.3, 0.5, and 0.7 wt.%) were characterized by electron paramagnetic resonance (EPR), optical absorption and FTIR techniques. The EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in alkaline earth zinc borate glasses were present in octahedral sites with tetragonal distortion. The spin concentration (N) participating in resonance was calculated as a function of temperature for strontium zinc borate (SrZB) glass sample containing 0.7 wt.% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility (χ) was calculated at different temperatures and the Curie constant was evaluated from the 1/χ-T graph. The optical absorption spectra of these samples show only one absorption band. The optical band gap energies (E_g) and Urbach energy (ΔE) are calculated from their ultraviolet edges. The FTIR studies show different stretching and bending vibrations of alkaline earth zinc borate glasses.     

Optical and thermoluminescence properties of R2O–RF–B2O3 glass systems doped with MnO

Alkali fluoroborate glass systems containing manganese cations have been thoroughly investigated in order to obtain information about the structural role of manganese in such glass hosts. The amorphous phase of the prepared glass samples R₂O–RF–B₂O₃:MnO (with R = Li and Na) was confirmed from their X-ray diffraction. From the infrared spectra of these glass systems it was concluded that the glass structure contains two group of bands; one due to trigonal BO₃ units and the second due to the tetrahedral BO₄ units. As manganese was introduced, replacing lithium or sodium, it acts as a network modifier and the intensity of the second group of bands increases at the expense of the first group of bands. The optical absorption spectra of R₂O–RF–B₂O₃:MnO exhibited two conventional absorption bands; one due to Mn²⁺ ions and the other due to Mn³⁺ ions. The ESR spectra of these glasses showed a six-line hyper-fine structure centered at g = 2.01 (due to Mn²⁺ ions) and another signal at g = 4.3 (due to Mn³⁺ ions). The intensity of optical absorption bands and the ESR signal due to Mn²⁺ ions decreases with increasing MnO concentration indicating the conversion of Mn²⁺ ions into Mn³⁺ ions in the glass network. The thermoluminescence studies on these glass systems showed a quenching of TL output with increase in the concentration of MnO. All the obtained results were discussed on the basis of the glass structure and the conversion of Mn²⁺ into Mn³⁺ ions with increasing concentration of MnO in the glass systems.     

UV assisted local crystallization in Er3+ doped oxy-fluoride glass

We report on fabrication of Er³⁺-activated LaF₃ nanocrystals in transparent glasses using an original technique, which combines both heat treatment, below glass crystallization temperature, and ultraviolet laser irradiation at 244 nm. The main advantage of this method is to control the spatial localization of the nanoparticles in the glass sample, whereas annealing solely at the crystallization temperature leads to a fully crystallized glass sample. Thermal differential analysis was used to determine the crystallization temperature of the sample. The photoluminescence spectra behaviour of Er³⁺ ions, collected from the UV-irradiated and unirradiated regions, allowed us to follow and to distinguish the structural changes in the glass network under heat treatment and ultraviolet exposure.     

Redox reactions during temperature change in soda-lime–silicate melts doped with copper and iron or copper and manganese

Glasses with the base composition 16Na₂O · 10CaO · 74SiO₂ doped with copper and iron or copper and manganese were studied by high temperature UV–vis–NIR spectroscopy. The spectra exhibited distinct absorption bands attributed to the respective transition metal ions present (Cu²⁺, Fe²⁺, Fe³⁺, Mn³⁺). In glasses doped with only one polyvalent element, the absorption decreases linearly with increasing temperature, the absorption bands are shifted to smaller wave numbers and get broader. In glasses doped with two types of transition metals, the situation is the same up to a temperature of around 550 °C. At larger temperature, the Cu²⁺-absorption in glasses also co-doped with iron increases again, while in glasses doped with both copper and manganese the absorption is approximately the same as in glasses solely doped with copper. It is shown that this is due to redox reactions between polyvalent species. These reactions are frozen in at temperatures <550 °C.     

Glasses in the SbPO4–WO3 system

Glasses in the binary system (100 − x)SbPO₄–xWO₃ (20 ⩽ x ⩽ 60, x in mol%) have been prepared and characterized. Differential thermal analysis (DTA) shows that the glass transition temperature, T_g, increases from 412 °C, for samples containing 20 mol% of WO₃, to 481 °C observed for glass containing 60 mol%. Sample containing 40 mol% in WO₃ were observed to be the most stable against devitrification. The structural organization of the glasses has been studied by using Fourier transform infra-red (FTIR), Raman, ³¹P Magic angle spinning (MAS) and spin echo nuclear magnetic resonance (NMR) spectroscopies. Results suggest two distinct networks comprising the glass structure, one with high SbPO₄ content and the other characteristic of the highest WO₃ content samples. The glasses present photochromic properties. Colour changes are observed for samples after exposure to ultraviolet or visible laser light. XANES, at L₁ absorption edge of tungsten, suggests partial reduction from W⁶⁺ to W⁵⁺ species during the laser irradiation. The photochromic effects and the colour changes, promoted by laser excitation, are reversible and easily removed by heat for during 1 h at 150 °C. Subsequent ‘write/erase’ cycles can be done without degradation of the glasses.