Production of defects in ZBLAN, ZBLAN : Tm3+ and ZBLAN : Cr3+ glasses by ultra-short pulses laser interaction

In this work we have studied pure and thulium- and chromium-doped ZBLAN glasses irradiated by ultra-short laser pulses. A Ti:sapphire CPA system was used, producing a 500 Hz train of pulses, centered at 830 nm, with 375 mu J of energy and 50 fs of duration (FWHM). The beam was focused by a 20 Him lens, producing a converging beam with a waist of 12 pin. The absorption spectra before and after laser irradiation were obtained showing production of color centers in pure, thulium-doped and chromium-doped ZBLAN glasses. A damage threshold of 9.56 TW/cm(2) was determined for ZBLAN. (C) 2007 Elsevier Ltd. All rights reserved.

Redox Behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO(3) with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.

Thermal, structural and optical properties of new tungsten lead-pyrophosphate glasses

Crystalline lead-pyrophosphate precursor was prepared in aqueous solution from lead nitrate and phosphoric acid and characterized by X-ray diffraction, thermogravimetry and Raman scattering. This crystalline lead-phosphate was then used to prepare glass samples in the binary system Pb(2)P(2)O(7)-WO(3). Dependence of WO(3) content on thermal, structural and optical properties were investigated by thermal analysis (DSC), Raman spectroscopy, UV-visible and near-infrared absorption and M-Line technique to access refractive index values. Incorporation of WO(3) in the lead-pyrophosphate matrix enhances the glass transition temperature and thermal stability against devitrification, favors formation of P-O-W bonds and WO(6) clusters. In addition, optical properties are strongly modified with a redshift of the optical bandgap with WO(3) incorporation as well as an increase of the refractive index from 1.89 to 2.05 in the visible. (C) 2011 Elsevier B.V. All rights reserved.

Crystallization study of molybdate phosphate glasses by thermal analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

1.5 mu m and visible up-conversion emissions in Er3+/Yb3+ co-doped tellurite glasses and optical fibers for photonic applications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Local order around rare earth ions during the devitrification of oxyfluoride glasses

Erbium L-3-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er3+ emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er3+ ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er3+ ions were performed, and results indicate that Er3+ ions lower the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er3+ ions in the devitrification process of PbF2 has been investigated. Although Er3+ ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance. (c) 2008 American Institute of Physics.

Stabilization of fluoroindate glasses by magnesium fluoride and other heavy metal fluorides

Their extended transparency in the IR makes them attractive for use as optical fibers for CO laser power delivery and optical amplification. This paper firstly describes the spectacular stabilizing effect of MgF2 on the binary system InF3-BaF2. The investigation of the InF3-BaF2-MgF2 system led to samples up to 5mm in thickness. Further optimization of this system was achieved by incorporation of limited amounts of other fluorides and resulted in increased resistence to devitrification. The second approach of this work was concerned to the investigation of the pseudo-ternary system InF3-GdF3-GaF3 at constant concentrations of ZnF2-SrF2-BaF2-NaF. Several compositions were studied in this system. The samples presented a better thermal stability when compared to other families of fluoride glasses. Therefore, these glasses seem to be very promising for the fabrication of special optical fibers. Thermal data are reported.

New compositions of fluoroindate glasses with higher chemical resistance

In this paper, glasses in the systems In-Ba-Mg and In-Ba-Zn-Sr-Mg were water leachead at 80ºC showing surface degradation after 72 hours of leaching. The extent of such degradation is determined by the solubility and the concentration of the elemental fluorides that constitute the glasses. The formation of a layer of crystallized phases on the surface of the samples was observed. Small weight losses were registered and the absence of water on the glass matrix after the attack suggested that the use of MgF2 in the systems studied can lead to better results against moisture corrosion when compared to other fluoride glasses such as the fluorozirconates.

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sintering of tin oxide and its applications in electronics and processing of high purity optical glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Time dependence and energy-transfer mechanisms in Tm3+Ho3+ and Tm3+-Ho3+ co-doped alkali niobium tellurite glasses sensitized by Yb3+

Glass samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb3+-5% Tm3+ and 5% Yb3+-5% Tm3+-0.5% Ho3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb3+ F-2(5/2) excited state. A good fit for the luminescence time evolution was obtained with the Yokota-Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb-5% Tm. 5% Yb-0.5% Ho and 5% Yb-5% Tm-0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from (1)G(4) and F-3(2) Tm3+ energy levels in all samples. The S-5(2) Ho3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Blue cooperative luminescence in Yb3+-doped tellurite glasses excited at 1.064 mu m

Blue luminescence emission around 480 nm through cooperative upconversion from pairs of Yb3+ ions implanted into 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) tellurite glasses and excited by a cw laser at 1.064 mum is demonstrated. Cooperative luminescence emission enhancement owing to the temperature dependent multiphonon-assisted anti-Stokes excitation process of the ytterbium ions is also observed. The experimental results revealed a fourfold enhancement in the cooperative luminescence emission when the sample was heated in the temperature range of 20 degreesC-260 degreesC. The thermally induced enhancement is assigned to the effective absorption cross-section for the ytterbium ions which is an increasing function of the medium temperature. (C) 2002 American Institute of Physics.

Test of the adiabatic nucleation model in SeTe and GeSnSe glasses

Se1-yTey and Ge1-ySnySe2.5 glasses, with compositions Y less than or equal to 0.5 and Y less than or equal to 0.6 respectively, are investigated. These glasses show a glass transition temperature (T-g) above the stability limit, indicated by the Adiabatic Nucleation Model (ANM). This effect has to be so because, other-wise, when cooled, these undercooled liquids would crystallize by generalized nucleation near the stability limit and no T-g could be observed. This shows that Se1-yTey glasses for Y < 0.5 are structurally stable. Limiting cases are pure Te and Se50Te50, which have T'(g)'s on the stability limit. Pure amorphous Te has to be obtained by fast quenching techniques, where the effective (fast quenching) T-g(*) is higher and Se50Te50 tends to crystallize easily. (C) 2004 Elsevier B.V. All rights reserved.

Luminescence quenching by iron in barium aluminoborate glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structure and crystallization of lanthanum fluorozirconate glasses

Glasses with compositions (1-x)ZrF4-xLnF(3), 0.2 less than or equal to x less than or equal to 0.4 and Ln = La or La, Eu have been synthesized and investigated using differential scanning calorimetry, X-ray diffraction, Raman scattering and Eu3+ optical spectroscopy. Single-phase polycrystalline lanthanum fluorozirconates with Zr/Ln ratio equal to 1, 2 and 3 have been investigated using the same techniques for comparison. The crystalline phases LnZrF(7), LnZr(2)F(11), LT-LnZr(3)F(15) (orthorhombic) and HT-LnZr(3)F(15) (trigonal) have been characterized in the recrystallized glasses and in samples spontaneously crystallized from the melt. Another phase has also been observed but remains undefined, the Raman scattering spectra of the vitreous samples are related to the vibration modes of [ZrF6] isolated octahedra, and of [ZrF7] and [ZrF8] structural units with bridging fluorine ions. The Eu3+ fluorescence data are related to a predominant local environment of the lanthanide ions in the glasses similar to that of the lanthanide in LnZrF(7).