Time-resolved Z-scan and thermal lens measurements in Er+3 and Nd+3 doped fluoroindate glasses

In rare earth ion doped solids, a resonant non-linear refractive index, n2, appears when the laser pumps one of the ion excited states and the refractive index change is proportional to the excited state population. In these solids there are usually thermal and non-thermal lensing effects, where the non-thermal one is due to the polarizability difference, Δα, between excited and ground states of the ions. We have used the time resolved Z-scan and a mode-mismatched thermal lens technique with an Ar+ ion laser in Er+3 (20ZnF2-20SrF2-2NaF-16BaF2-6GaF3-(36 - x)InF3-xErF3, with x= 1, 2, 3 and 4 mol%) and Nd+3 (20SrF2-16BaF2-20ZnF2-2GdF3-2NaF-(40 - x)InF3-xNdF3, with x = 0.1, 0.25, 0.5-1 mol%) doped fluoroindate glasses. In both samples we found that the non-linear refraction is due to the thermal effect, while the non-thermal effect is negligible. This result indicates that in fluoride glasses Δα is very small (less than 10-26 cm3). We also measured the imaginary part of the non-linear refractive index (n″2) due to absorption saturation.

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.

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

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.

Sol-Gel Erbium-Doped Silica-Hafnia Planar and Channel Waveguides

Erbium activated SiO2 -HfO2 planar waveguides, doped with Er3+ concentrations ranging from 0.01 to 4 mol%, were prepared by sol-gel method. The films were deposited on v-SiO2 and silica-on-silicon substrates using dip-coating technique. The waveguides show high densification degree, effective intermingling of the two film components, and uniform surface morphology. The waveguide deposited on silica-on-silicon substrates shows one single propagation mode at 1.5μm, with a confinement coefficient of 0.81 and an attenuation coefficient of 0.8 dB/cm at 632.8nm. Emission in the C-telecommunication band was observed at room temperature for all the samples upon continuouswave excitation at 980 nm or 514.5 nm. The shape of the emission band corresponding to the 4I13/2 → 4I15/2 transition is found to be almost independent both on erbium content and excitation wavelength, with a FWHM between 44 and 48 nm. The 4I13/2 level decay curves presented a single-exponential profile, with a lifetime ranging between 1.1 - 6.6 ms, depending on the erbium concentration. Infrared to visible upconversion luminescence upon continuous-wave excitation at 980 nm was observed for all the samples. Channel waveguide in rib configuration was obtained by etching the active film in order to have a well confined mode at 1.5 μm.

Tm3+ and Tm3+-Ho3+ doped fluorogermanate glasses for S-band amplifiers

Two series of glasses with composition (mol%) 70PbGeO3- 15PbF2-15CdF2, the first one with different Tm 3+ contents (0.2, 0.4, 0.6 and 0.8 mol%) and the second one with 0.2 mol% Tm3+ and different Ho3+ contents (0.1, 0.5, 1.0 and 1.5 mol%), have been prepared and some of their spectroscopic properties studied. Absorption in the visible-near infrared and emission in the near infrared region of the electromagnetic spectrum have been obtained. Concerning emission at the 1.4-1.5 μm region, optimization of rare earth ions content leads to 0.2 and 0.5 mol% for Tm3+ and Ho3+, respectively. We discuss potential application of these compositions. © 2005 Elsevier B.V. All rights reserved.

Compositional influence on spectroscopic properties of Yb3+ doped tellurite glasses

Spectroscopic properties of ytterbium-doped tellurile glasses with different compositions are reported. Results of linear refractive index, absorption and emission spectra, and fluorescence lifetimes are presented. The studied samples present high refractive index (∼2.0) and large transmission window (380-6000nm). Absorption and emission cross-sections are calculated as well as the minimum pump laser intensity. The results are compared with the values of other laser materials, in order to investigate applications as laser media in the infrared region.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Study of Er3+ fluorescence on tellurite glasses containing Ag nanoparticles

Optical characteristics of tellurite glasses containing silver nanoparticles (NPs) and the influence on the emission spectrum of Er 3+ ions were studied. The transitions 4f ↔ 4f from erbium ions, mainly the 4I13/2 → 4I15/2 transition that involve upconversion energy process, have a strongly dependence with the chemical structure of the rare earth ion. In the present work, silver nanparticles (NPs) embedded in the host vitreous material, show a significant enhance (or quenching) on the erbium fluorescence due the long-range electromagnetic interaction between the plasmon surface energy of the Ag NPs (Localized Surface Plasmon Resonance -LSPR) and the Er3+ ions.

Orange emission in Pr3+-doped fluoroindate glasses

We synthesize and study the properties of praseodymium doped fluoroindate glasses. Glass compositions with praseodymium molar concentrations up to 5% were obtained with good optical quality. Thermal, optical, and luminescence properties are investigated. Judd-Ofelt analysis is used to determine radiative lifetime and emission cross-section of the orange transition originating from the 3P0 level. We find that these glasses are good candidates for the realization of blue diode laser pumped orange lasers for quantum information processing applications. © 2012 Elsevier B.V. All rights reserved.

The role of Bi2O3 on the thermal, structural, and optical properties of tungsten-phosphate glasses

Glasses in the ternary system (70 - x)NaPO3-30WO 3-xBi2O3, with x = 0-30 mol %, were prepared by the conventional melt-quenching technique. X-ray diffraction (XRD) measurements were performed to confirm the noncrystalline nature of the samples. The influence of the Bi2O3 on the thermal, structural, and optical properties was investigated. Differential scanning calorimetry analysis showed that the glass transition temperature, Tg, increases from 405 to 440 C for 0 ≤ x ≤ 15 mol % and decreases to 417 C for x = 30 mol %. The thermal stability against devitrification decreases from 156 to 67 C with the increase of the Bi2O3 content. The structural modifications were studied by Raman scattering, showing a bismuth insertion into the phosphate chains by Bi-O-P linkage. Furthermore, up to 15 mol % of Bi 2O3 formation of BiO6 clusters is observed, associated with Bi-O-Bi linkage, resulting in a progressive break of the linear phosphate chains that leads to orthophosphate Q0 units. The linear refractive index, n0, was measured using the prism-coupler technique at 532, 633, and 1550 nm, whereas the nonlinear (NL) refractive index, n 2 was measured at 1064 nm using the Z-scan technique. Values of 1.58 ≤ n0 ≤ 1.88, n2 ≥ 10-15 cm 2/W and NL absorption coefficient, α2 ≤ 0.01 cm/GW, were determined. The linear and NL refractive indices increase with the increase of the Bi2O3 concentration. The large values of n0 and n2, as well as the very small α2, indicate that these materials have large potential for all-optical switching applications in the near-infrared. © 2012 American Chemical Society.

Nanoparticle characterization of Er-doped SnO2 pellets obtained with different pH of colloidal suspension

SnO2:2 at. %Er xerogel samples were obtained by sol-gel technique from colloidal suspensions with distinct pHs. The evaluation of critical regions inside the nanocrystallite is fundamental for the interpretation of the influence of pH on the emission data. In this way, the nanocrystal depletion layer thickness was obtained with the help of photoluminescence, Raman, X-ray diffraction, and field-emission gun scanning electron microscopy measurements. It was observed that acid suspensions (pH < 7) lead to high surface disorder in which a larger number of cross-linked bonds Sn-O-Sn among nanoparticles are present. For these samples, the nanoparticle depletion layer is larger as compared to samples obtained from other pH. Photoluminescence measurement in the near infrared region indicates that the emission intensity of the transition 4I13/2 → 4I15/2 is also influenced by the pH of the starting colloidal suspension, generating peaks more or less broadened, depending on location of Er3+ ions in the SnO2 lattice (high or low symmetry sites). © 2013 AIP Publishing LLC.

Resolução de sobreposição de picos de cristalização, pelo método de Kurajica, caso não isotérmico, em vidros teluretos e fosfatos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo estrutural e cristalização em vidros fluorogermanatos

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

Influência da adição de bioactive glass na liberação de íons do cimento de ionômero de vidro modificado por resina

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)