Spectroscopy of InF3 based glasses containing a large amount of GdF3

Glass formation in the pseudo ternary system ZnF2-GdF3-BaF2-InF3 and other complex systems stabilized by NaF, CaF2, AlF3 and YF3 have been investigated. Samples with greater stability have been prepared and their properties measured. Optical absorption and emission spectra of Gd3+ ions doped glasses with 2, 4, 10 and 20% concentrations have been measured. Using the Judd-Ofelt theory and the experimental oscillator strengths, the Judd-Ofelt parameters have been calculated. The emission of Gd3+ ions from 6I and 6P has been detected and the lifetime has been measured.

Violet-blue emissions due to frequency up-conversion in Nd3+-doped fluoroindate glasses

We report the observation of intense frequency up-conversion in Nd3+-doped fluoroindate glasses pumped by the second harmonic of a cw mode-locked Nd: YAG laser. Mechanisms for generating the observed emissions are discussed.

Optical properties of chromium-doped fluoroindate glasses

This work reports on the optical properties of Cr3+ ions in the pseudoternary system InF3-GdF3-GaF3. Linear properties, investigated through absorption and emission spectra, provide information on the crystal field, the frequency, and number of phonons emitted during the absorption to the 4T2 band and the emission to the 4A2 ground state, and the Fano antiresonance line shape in the vicinity of the 4A2→2E transition. A study of the nonlinear refractive index as a function of the wavelength, carried out with the Z-scan technique, provides spectroscopic data about electronic transitions starting from the excited state.

Crystallization of ZrF4-LaF3-AlF3 glasses

0.7125ZrF4-0.2375(1 - xLaF3 • xLnF3)-0.05AIF3 with x = 0.01, 0.02 and 0.03 for Ln = Er and x = 0.03 for Ln = Pr, Nd glasses were studied by differential thermal analysis (DTA), X-ray diffraction and optical spectroscopy. Avrami parameters (Ec and n) were obtained from DTA curves. With La3+ substitution a decrease in the stability against crystallization was observed. This decrease follows the order Er3+ > Nd3+ ≈ Pr3+ for 3% molar substitution. n values suggest an interface controlled growth mechanism with grain edge nucleation abler saturation. Two crystalline polymorphs of the LaZr3F15 phase were identified. With the substitution of 3 mol% of Pr3+, Nd3+ or Er3+ for La3+ only the crystallization of the rhombohedral α-LnZr3F15 phase was observed. An increase in Ω6 Judd's intensity parameter occurs with crystallization and also an increase in the 1.04 μm peak emission cross-section for Nd3+ 4I3/2 state suggesting the potential application of these glass ceramics in optical amplification devices. © 1997 Elsevier Science B.V.

Crystallization of fluorindate and fluorogallate glasses

Crystallization of binary InF3-MF2 and GaF3-MF2 (where M = Ba, Sr and Ca) glasses was studied. Characteristic temperatures and kinetic parameters E (activation energy) and n (Avrami exponent) were obtained. Stability against devitrification is discussed in terms of the above cited parameters and also of some others parameters proposed in literature. Optical properties (IR and upconversion emissions) are reported in different crystallized samples containing Nd3+. The main observation is that up conversion emission presents an enhanced sensibility to crystallization when compared to conventional emission. © 1997 Published by Elsevier Science B.V.

Optical spectroscopy of Er3+ and Yb3+ co-doped fluoroindate glasses

Optical absorption, Stokes, and anti-Stokes photoluminescence were performed on Er3+-Yb3+ co-doped fluoroindate glasses. For compounds prepared with a fixed 2 mol % ErF3 concentration and YbF3 contents ranging from 0 to 8 mol %, important upconversion processes were observed as a function of temperature and photon excitation energy. Based on the experimental data, two mechanisms for the upconversion (or anti-Stokes photoluminescence) processes were identified and analyzed in detail. At high Yb contents, the upconversion mechanisms are mostly determined by the population of the 2F5/2 levels of Yb3+ ions (or 4I11/2 levels of Er3+ ions, by energy transfer) regardless of the photon excitation energy and temperature of measurement. Moreover, green and red light emission have similar intensities when a large Yb3+ content is present. © 1998 American Institute of Physics.

Magneto-optical rotation of heavy-metal oxide glasses

Magneto-optical rotation was measured at room temperature for glasses containing Bi2O3-CdO-GeO2 (BCG), and Bi2O3-PbO-GeO2-B2O3 (BPGP). A pulsed magnetic field between 50 and 80 KG was used to measure Faraday rotation at 632.8 nm as a function of the concentration of Bi and Cd for BCG and Bi and Pb for BPGB. Verdet constant as high as 0.162 min G-1 cm-1 at 632.8 nm for the BPGB sample with the highest concentrations of Bi and Cd was found. Verdet constant increases linearly with the heavy-metal concentration for the BPGB whereas it reaches some saturation for the BCG system. Measurements of the magneto-optical rotation at other wavelengths in the visible and the refractive index at 632.8 nm are also reported. © 1998 Elsevier Science B.V. All rights reserved.

In(PO3)3 stabilised fluoroindate glasses

Results on thermal and optical characterization of new lanthanide containing fluoroindate glasses in the system InF3-BaF2-In(PO3)3 are presented. Good optical quality and very stable glasses presenting up to 5 mm in thickness could be prepared in this system. Thermal analysis, Raman scattering and Eu3+ luminescence were the techniques utilized. A novel method for In(PO3)3 synthesis is proposed and the dependence of physical properties and structural features on the polyphosphate content is stressed. © 1998 Elsevier Science S.A.

Viscosity of fluoroindate glasses

The viscosity of two fluoroindate glasses was measured as a function of temperature in the range of 310 °C - 362 °C. In such interval, the viscosity values were found to be similar to those reported for fluorozirconate glasses. The log η - 1/T plots had an unexpected behavior: two viscosity regions that seem to obey Arrhenius equation were identified and the activation energy for viscous flow (EA) for the region near Tg is smaller than the value found above the transition range. This behavior is probably due to structural changes occurred around Tg. The low values of the activation energy for viscous flow obtained for the indium fluoride-based glasses studied, suggest a good resistance against the devitrification process, what can make them suitable for fiber preparation.

Violet and blue light amplification in Nd3+-doped fluoroindate glasses

We report optical gain at 382 and 414 nm from Nd3+-doped fluroindate glasses after excitation with lasers operating either at 583 or 532 nm. Stimulated emission due to a frequency upconversion process results in increase of the emitted violet and blue light intensity and emission line narrowing. Large optical gain is measured by pump-probe spectroscopy using samples with various Nd3+ concentrations. © 1999 American Institute of Physics.

Non-isothermal study of the devitrification kinetics of fluoroindate glasses

The understanding of the kinetics of devitrification of a glass is important for anticipating its stability in a particular purpose, such as fiber-drawing processes. The crystallization kinetics of (BaF2)16(ZnF2)20(SrF 2)20(NaF)2 (GaF3)5(InF3)36(GdF 3)1 glass prepared by quenching were studied by differential scanning calorimetry (DSC). Avrami's exponent (n) obtained by a non-isothermal method was 4.3 for a solid and 2.4 for a powdered sample. According to the classical interpretation of n, these magnitudes correspond to an interface-controlled crystal growth and a diffusion-controlled crystal growth, respectively. The activation energies for crystallization (E) was 62 ± 1 kJ/mol for solid glass and 245 ± 2 kJ/mol for powdered glass. These results are discussed in terms of glass particle size. © 2000 Elsevier Science B.V. All rights reserved.

Non isothermal study of the devitrification kinetics of fluoroindate glasses

The kinetics of crystallization in an indium fluoride-based glass was studied by a non-isothermal method using differential scanning calorimetry. The experiments led to an Avrami's exponent of 4.6 for solid glass and 2.2 for a powdered sample. The apparent activation energy for crystallization was found to be 130 kJ/mol for solid glass and 354 kJ/mol for the powder. These results express the profound effect of glass particle size on those kinetic parameters, as different crystallization mechanisms take place during sample heating.

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho3+, Tm3+ and Nd3+ ions and codoped with Pr3+/Nd3+ and Yb3+/Tb3+ ions. The results for the Ho3+-doped samples show strong evidence of energy transfer (ET) between Ho3+ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm3+-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr3+/Nd3+ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd 3+ and the Pr3+ ions. It was observed that the presence of Nd3+ ions enhanced the Pr3+ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd3+-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd3+ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb3+/ Tb3+-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb3+ emission in the blue is due to ET from a pair of excited Yb3+ ions followed by ESA in the Tb 3+ ions. © 2002 Académie des sciences/Éditions scientifiques et médicales Elsevier SAS.

Ceramic Crucible Corrosion by Heavy Metal Oxide Glasses, Part I: Phenomenological Study

Heavy metal oxide (HMO) glasses have received special attention due to their optical, electrical and magnetic properties. The problem with these glasses is their corrosive nature. In this work, three ceramic crucibles (Al 2O 3, SnO 2 and ZrO 2) were tested in the melting of the system 40 PbO-35 BiO 1.5-25 GaO 1.5 (cation-%). After glass melting, crucibles were transversally cut and analyzed by scanning electronic microscopy (SEM), coupled to microanalysis by energy dispersive spectroscopy (EDS). Results indicated that zirconia crucibles presented the highest corrosion, probably due to its smallest grain size. Tin oxide crucibles presented a low corrosion with small penetration of the glass into the crucible. This way, these crucibles are an interesting alternative to melt corrosive glasses in instead of gold or platinum crucibles. It is important to emphasize the lower cost of tin oxide crucibles, compared to gold or platinum ones.

Ceramic Crucible Corrosion by Heavy Metal Oxide Glasses, Part II: Diffusion Study

Due to their low cost and high resistance to corrosion, ceramic crucibles can be used for the melting of PBG glasses (PbO-BiO 1.5GaO 1.5). These glasses present good window transmission from ultra-violet to infrared, making their use as optical fibres promising. However, their disadvantage is the high reactivity, leading to the corrosion of different crucibles, including gold and platinum ones. In this work, the corrosion of Al 2O 3, SnO 2 and ZrO 2 crucibles after melting at temperatures varying from 850 to 1000°C, was evaluated by Scanning Electronic Microscopy (SEM) in conjunction with microanalysis by EDS. The lead diffusion profile in the crucible material was obtained. Diffusion coefficients were calculated according to the Fick and Fisher theories. Results indicated that the different crucibles presented similar behaviour: in the region near the interface, diffusion occurs in the volumetric way and in regions away from the interface, diffusion occurs through grain boundary.