Upconversion in Nd(3+)-doped glasses: Microscopic theory and spectroscopic measurements

In this work, we report a systematic investigation of upconversion losses and their effects on fluorescence quantum efficiency and fractional thermal loading in Nd(3+)-doped fluoride glasses. The energy transfer upconversion (gamma(up)) parameter, which describes upconversion losses, was experimentally determined using different methods: thermal lens (TL) technique and steady state luminescence (SSL) measurements. Additionally, the upconversion parameter was also obtained from energy transfer models and excited state absorption measurements. The results reveal that the microscopic treatment provided by the energy transfer models is similar to the macroscopic ones achieved from the TL and SSL measurements because similar gamma(up) parameters were obtained. Besides, the achieved results also point out the migration-assisted energy transfer according to diffusion-limited regime rather than hopping regime as responsible for the upconversion losses in Nd-doped glasses. (c) 2008 American Institute of Physics.

Durango apatite fission-track dating using length-based age corrections and neutron fluence measurements by natural thorium thin films and natural U-doped glasses calibrated through natural uranium thin films

In this work, we present an approach for neutron fluence measurements based on natural thorium thin films and natural uranium-doped glasses calibrated through natural uranium thin films to be used for dating with the Fission-Track Method (FTM). This neutron dosimetry approach allows the employment of FTM even when dating is carried out using low neutron themalization facilities. Besides, it makes possible the determination of the Th/U ratio of the mineral to be dated. Durango apatite which is often employed in FTM as an age standard was analyzed. This apatite presented a fairly high Th/U ratio, 29.9 +/- 1.7. Th fissions were 18%, 12% and 10% of the total for irradiations where thermal to fast neutron flux ratios were 2.4, 4.4 and 5,2, respectively. These results show that Th fission must be considered for this apatite, when not well-thermalized irradiation facilities are used. The ratio between spontaneous and induced track length, L(S)/L(1), close to 0.89, indicates a certain amount of rejuvenation of the age of Durango apatite. Therefore, its apparent age should be corrected, the application of a technique based on track-length measurements produced a corrected age of 29.7 +/- 1.1 Ma, consistent with the independent reference age of this apatite (31.4 +/- 0.5 Ma). This result represents a support for viability of the neutron dosimetry approach studied in this work for FTM.(C) 2002 Elsevier B.V. B.V. All rights reserved.

Evaluation of laser level populations of erbium-doped glasses

A simulation of erbium-doped glass systems, which provides population density for the excited states involved in the 1.5 mu m and also for 2.7 mu m emissions when pumped around 980 nm, is presented. To describe the diode pump laser processes, a theoretical model based in a coupled system of differential rate equations was developed. The approach used and the obtained spectroscopic parameters are discussed. The materials under study are two oxide glasses, lead fluoroborate (PbO-PbF2-B2O3), and heavy metal oxide (Bi2O3 PbO-Ga2O3) and a fluoride glass (ZrF4-BaF2-LaF3-AlF3-NaF), all of them doped with Er3+. (c) 2006 Elsevier B.V. All rights reserved.

PbO-GeO2 rare earth doped glasses with silver nanoparticles as materials for IR laser triggers

We have shown the possibility of operation by the piezooptical response of PbO-GeO2 glasses doped with rare earth ions and silver nanoparticles by illumination of double frequency CO2 nanosecond laser. Substantial influence of thermoannealing on the output photoinduced elastooptical susceptibilities was established. The effect is very sensitive to temperature and to the corresponding tensor components. The effect of thermoannealing leads to enhanced long-range ordering with the occurrence of corresponding trapping levels within the forbidden gaps. The discovered effects may be used for creation of low-temperature IR laser triggers.

Physical properties of silicate glasses doped with SnO2

The presence of tin in the network of silicate glasses produces changes in several of their physico-chemical properties. Glasses with the composition (mol%) 22Na(2)O (.) 8CaO (.) 70SiO(2) containing up to 5 wt% of SnO2 were analyzed under several experimental techniques. Dilatometric measurements showed an increase of the glass transition temperature with increasing tin content, while the average thermal expansion coefficient is reduced. Vickers microhardness, density, and refractive index also increase with the tin content. Diffuse reflectance spectra in the infrared (DRIFT) showed that the presence of tin, even at low concentrations, is responsible for some structural changes since there is an increase of the bridging oxygen concentration. The doped glasses present a brown color and optical absorption spectra measurements are interpreted as being due to precipitation of tin in the form of colloidal particles during cooling of the melted glass. In the Na+ <-> K+ ion exchange process the presence of tin in the glass network hinders the diffusion of these ions. The diffusion coefficients of those ions were calculated by the Boltzmann-Matano technique, after concentration profiles obtained by EDS measurements. All results obtained present evidences that Sn4+ cation acts as a glass network former. (c) 2005 Elsevier B.V. All rights reserved.

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.

Recalibration of U-doped standard glasses through uranium thin film for neutron-fluence measurements

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y(2)O(3))(0.2)-(Al(2)O(3))(x)-(B(2)O(3))(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 <= x <= 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three-and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly ""aluminate-like'' with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.

Sol-gel preparation of near-infrared broadband emitting Er(3+)-doped SiO(2)-Ta(2)O(5) nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO(2)-Ta(2)O(5) nanocomposite films obtained by the sol-gel process. The films were doped with Er(3+) and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 degrees C. The onset of crystallization and devitrification, with the growth of Ta(2)O(5) nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er(3+)-doped nanocomposite annealed at 900 degrees C consists of Ta(2)O(5) nanoparticles, with sizes around 2 nm, dispersed in the SiO(2) amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the (4)I(13/2)->(4)I(15/2) transition of the Er(3+) ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the (4)I(13/2) levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide. (C) 2010 Elsevier B.V. All rights reserved.

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

Fission-track dating of Macusanite glasses with plateau and size correction methods

Two Macusanite pebbles (MB1 and MB2) were dated with the fission-track method. Six irradiations were carried out in different nuclear reactors: Pavia (Italy), IPEN-CNEN (Brazil) and IPEN-Lima (Peru). Measurements of the thorium and uranium induced-fission per target nucleus using natural thorium thin films and natural U-doped glasses calibrated against natural uranium thin films, together with lambda(F) of 8.46 x 10(-17) a(-1) were used to determine the ages. The apparent ages were corrected using the plateau and size correction methods. Track measurements were performed by different analysts, using different counting criteria. In addition, tracks were measured on samples which had been submitted to thermal treatment as well as on samples which had not been heated. Thermal treatments were carried out to erase the fossil tracks before neutron irradiation. No significant differences have been found in individual results, using the two Macusanite pebbles and the different nuclear reactors, age correction techniques, analysts, track-counting criteria, and thermal treatments before neutron irradiation. The great majority of the results (14/17) is compatible with the Ar-Ar ages of 5.12 +/- 0.11 and 5.10 +/- 0.11 Ma, Macusanite MB1 and MB2, respectively. However, the fission-track ages are systematically less (similar to8%) than the Ar-Ar ages of the two Macusanite samples studied. (C) 2003 Published by Elsevier Ltd.

Effect of PbS impurity on crystallization mechanism of phosphate glasses studied by differential scanning calorimetry

In this work, differential scanning calorimetry (DSC) was used to study effect of PbS impurity on crystallization mechanism of phosphate glasses. Bulk glasses presented one crystallization peak while powdered glasses presented two distinct crystallization peaks. For both undoped and doped glasses were determined the activation energies for the crystallization and the Avrami n parameters. The activation energies for undoped phosphate glass were 336 +/- 6 and 213 +/- 3 kJ mol(-1), respectively, associated with first and second crystallization peaks. For doped glass, the obtained energies were 373 +/- 9 and 286 +/- 7 kJ mol(-1). The calculated Avrami parameters, based on first crystallization peaks, for undoped and doped glasses were 2.25 +/- 0.01 and 1.75 +/- 0.02, respectively. These values suggest that the first DSC peak, in both glasses, may be associated with surface crystallization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.