Energy transfer and frequency upconversion in Yb3+-Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er3+-Yb3+-codoped PbO-GeO2 glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the F-2(5/2)-> F-2(7/2) transition of Yb3+ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er3+ transitions. The simultaneous influence of the Yb3+-> Er3+ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.

Infrared-to-visible upconversion in Yb3+/Er3+ co-doped PbO-GeO2 glass with silver nanoparticles

Enhanced frequency upconversion (UC) emission was studied in Yb3+/Er3+ co-doped PbO-GeO2 glass containing silver nanoparticles (NPs). Optical excitation was achieved with a laser operating at 980 nm in resonance with the Yb3+ transition F-4(5/2)-> F-4(7/2). The intensity of the whole UC spectrum from 400 to 700 nm was intensified due to the influence of silver NPs. The green and red emissions were enhanced by more than 300%. Emission bands centered at 408 nm and 480 nm were also detected corresponding to the H-2(9/2)-> I-4(15/2) and F-4(7/2)-> I-4(15/2) transitions of Er3+ ion. An intensity enhancement of approximate to 150% due to the NPs was measured. For the first time the influence of silver NPs on the blue emission of Yb3+/Er3+ co-doped PbO-GeO2 glass is reported. The large enhancement in the whole UC spectrum is due to the increased local field in the Er3+ ions locations and the proximity between the luminescence wavelengths and the NPs surface plasmon resonance. (C) 2010 Elsevier B.V. All rights reserved.

Influence of the heat treatment on the nucleation of silver nanoparticles in Tm3+ doped PbO-GeO2 glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

NDACC/SAOZ UV-visible total ozone measurements: improved retrieval and comparison with correlative ground-based and satellite observations

Accurate long-term monitoring of total ozone is one of the most important requirements for identifying possible natural or anthropogenic changes in the composition of the stratosphere. For this purpose, the NDACC (Network for the Detection of Atmospheric Composition Change) UV-visible Working Group has made recommendations for improving and homogenizing the retrieval of total ozone columns from twilight zenith-sky visible spectrometers. These instruments, deployed all over the world in about 35 stations, allow measuring total ozone twice daily with limited sensitivity to stratospheric temperature and cloud cover. The NDACC recommendations address both the DOAS spectral parameters and the calculation of air mass factors (AMF) needed for the conversion of O-3 slant column densities into vertical column amounts. The most important improvement is the use of O-3 AMF look-up tables calculated using the TOMS V8 (TV8) O-3 profile climatology, that allows accounting for the dependence of the O-3 AMF on the seasonal and latitudinal variations of the O-3 vertical distribution. To investigate their impact on the retrieved ozone columns, the recommendations have been applied to measurements from the NDACC/SAOZ (Systeme d'Analyse par Observation Zenithale) network. The revised SAOZ ozone data from eight stations deployed at all latitudes have been compared to TOMS, GOMEGDP4, SCIAMACHY-TOSOMI, SCIAMACHY-OL3, OMI-TOMS, and OMI-DOAS satellite overpass observations, as well as to those of collocated Dobson and Brewer instruments at Observatoire de Haute Provence (44 degrees N, 5.5 degrees E) and Sodankyla (67 degrees N, 27 degrees E), respectively. A significantly better agreement is obtained between SAOZ and correlative reference ground-based measurements after applying the new O-3 AMFs. However, systematic seasonal differences between SAOZ and satellite instruments remain. These are shown to mainly originate from (i) a possible problem in the satellite retrieval algorithms in dealing with the temperature dependence of the ozone cross-sections in the UV and the solar zenith angle (SZA) dependence, (ii) zonal modulations and seasonal variations of tropospheric ozone columns not accounted for in the TV8 profile climatology, and (iii) uncertainty on the stratospheric ozone profiles at high latitude in the winter in the TV8 climatology. For those measurements mostly sensitive to stratospheric temperature like TOMS, OMI-TOMS, Dobson and Brewer, or to SZA like SCIAMACHY-TOSOMI, the application of temperature and SZA corrections results in the almost complete removal of the seasonal difference with SAOZ, improving significantly the consistency between all ground-based and satellite total ozone observations.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

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.

GDP 4.0 transfer to SGP 3.0 for SCIAMACHY no2 column processing: Verification with SDOAS / GDOAS prototype algorithms and delta-validation with NDACC / UV-visible network data

Until mid 2006, SCIAMACHY data processors for the operational retrieval of nitrogen dioxide (NO2) column data were based on the historical version 2 of the GOME Data Processor (GDP). On top of known problems inherent to GDP 2, ground-based validations of SCIAMACHY NO2 data revealed issues specific to SCIAMACHY, like a large cloud-dependent offset occurring at Northern latitudes. In 2006, the GDOAS prototype algorithm of the improved GDP version 4 was transferred to the off-line SCIAMACHY Ground Processor (SGP) version 3.0. In parallel, the calibration of SCIAMACHY radiometric data was upgraded. Before operational switch-on of SGP 3.0 and public release of upgraded SCIAMACHY NO2 data, we have investigated the accuracy of the algorithm transfer: (a) by checking the consistency of SGP 3.0 with prototype algorithms; and (b) by comparing SGP 3.0 NO2 data with ground-based observations reported by the WMO/GAW NDACC network of UV-visible DOAS/SAOZ spectrometers. This delta-validation study concludes that SGP 3.0 is a significant improvement with respect to the previous processor IPF 5.04. For three particular SCIAMACHY states, the study reveals unexplained features in the slant columns and air mass factors, although the quantitative impact on SGP 3.0 vertical columns is not significant.

Efficient UV-visible upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate vitroceramic

Cooperative energy-transfer upconversion luminescence in Tb 3+/Yb 3+-codoped PbGeO 3-PbF 2-CdF 2 vitroceramic and its precursor glass under resonant and off-resonance infrared excitation, is investigated. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm, identified as due to the 5D 3( 5G 6 → 7F J(J=6,5,4) and 5D 4 → 7F J(J=6,5,4,3) transitions, respectively, were readily observed. The results indicate that cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The comparison of the upconversion process in a vitroceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.

On the application of nanostructured electrodes prepared by Ti/TiO2/WO3 template : A case study of removing toxicity of indigo using visible irradiation

New assays with HepG2 cells indicate that Indigo Carmine (IC), a dye that is widely used as additive in many food and pharmaceutical industries exhibited cytotoxic effects. This work describes the development of a bicomponent nanostructured Ti/TiO2/WO3 electrode prepared by template method and investigates its efficiency in a photoelectrocatalytic method by using visible light irradiation and applied potential of 1V. After 2h of treatment there are reduction of 97% discoloration, 62% of mineralization and formation of three byproducts assigned as: 2-amine-5-sulfo-benzoic acid, 2,3-dioxo-14-indole-5-sulfonic acid, and 2-amino-α-oxo-5-sulfo-benzeneacetic acid were identified by HPLC-MS/MS. But, cytotoxicity was completely removed after 120min of treatment. © 2013 Elsevier Ltd.

Upconversion luminescence in Er3+ doped Ga10Ge 25S65 glass and glass-ceramic excited in the near-infrared

The infrared-to-visible frequency upconversion was investigated in Er 3+-doped Ga10Ge25S65 glass and in the transparent glass-ceramic obtained by heat-treatment of the glass above its glass-transition temperature. Continuous-wave and pulsed lasers operating at 980 nm and 1480 nm were used as excitation sources. The green (2H 11/2 → 4I15/2; 4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) photoluminescence (PL) signals due to the Er3+ ions were characterized. The PL decay times were influenced by energy transfer among Er3+ ions, by cross-relaxation processes and by energy transfer from the Er3+ ions to the host material. The PL from the Er3+ ions hosted in the crystalline phase was distinguished only when the glass-ceramic was excited by the 1480 nm pulsed laser. The excitation pathways responsible for the green and red PL bands are discussed to explain the differences between the spectra observed under continuous-wave and pulsed excitation. © 2013 American Institute of Physics.

Infrared to visible up-conversion emission in Er3+/Yb 3+ codoped fluoro-phosphate glass-ceramics

Erbium Er3+ and ytterbium Yb3+ codoped fluoro-phosphate glasses belonging to the system NaPO3-YF 3-BaF2-CaF2 have been prepared by the classical melt-quenching technique. Glasses containing up to 10 wt% of erbium and ytterbium fluorides have been obtained and characterized using differential scanning calorimetry (DSC) and UV-visible and near-infrared spectroscopy. Transparent and homogeneous glass-ceramics have been then reproducibly synthetized by appropriate heat treatment above glass transition temperature of a selected parent glass. Structural investigations of the crystallization performed through X-ray diffractometry (XRD) and scanning electron microscopy (SEM) have evidenced the formation of fluorite-type cubic crystals based during the devitrification process. Finally, infrared to visible up-conversion emission upon excitation at 975 nm has been studied on the Er3+ and Yb 3+ codoped glass-ceramics as a function of thermal treatment time. A large enhancement of intensity of the up-conversion emissions-about 150 times- has been observed in the glass-ceramics if compared to the parent glass one, suggesting an incorporation of the rare-earth ions (REI) into the crystalline phase. © 2012 The American Ceramic Society.

Photoelectrochemical properties of FTO/m-BiVO4 electrode in different electrolytes solutions under visible light irradiation

Photoelectrochemical properties of FTO/BiVO4 electrode were investigated in different electrolytic solutions, potassium chloride (KCl) and sodium sulphate (Na2SO4), and under visible light irradiation condition. In order to accomplish that, an FTO/BiVO4 electrode was built by combining the solution combustion synthesis technique with the dip-coating deposition process. The morphology and structure of the BiVO4 electrode were investigated through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photoelectrochemical properties were analyzed through chronoamperometry measurements. Results have shown that the FTO/BiVO4 electrode presents higher electroactivity in the electrolyte Na2SO4, leading to better current stabilization, response time, and photoinduced current density, when compared to KCl electrolyte. Besides, this electrode shows excellent performance for methylene blue degradation under visible light irradiation condition. In Na2SO4, the electrode has shown higher degradation rate, 51 %, in contrast to 44 % in KCl, plus higher rate constant, 174 × 10-4 min-1 compared to 150 × 10-4 min-1 in KCl. Results presented in this communication leads to the indication of BiVO4 thin films as alternate materials to use in heterogeneous photoelectrocatalysis, more specifically in decontamination of surface water. © 2013 Springer-Verlag Berlin Heidelberg.

Photoelectrocatalytic oxidation of hair dye basic red 51 at W/WO 3/TiO2 bicomposite photoanode activated by ultraviolet and visible radiation

We prepared a W/WO3/TiO2 bicomposite photoanode by simple electrochemical anodization of W foil, followed by cathodic electrodeposition of TiO2 and annealing at 450 C for 30 min. This photoanode shows good photoactivity under irradiation with UV and visible light. In optimized conditions, it promotes complete photoelectrocatalytic oxidation of 3.33 × 10-5 mol L-1 basic red 51 solution (which is used in hair dye) at 0.1 mol L-1 Na2SO4, pH 2.0, under a current density of 1.25 mA cm-2 and ultraviolet and visible radiation-total organic carbon removal is 94 and 88%, respectively. This effect paves the way for the sustainable solar-assisted remediation of water bodies contaminated with organic components of hair dyes. © 2013 Elsevier Ltd. All rights reserved.

Visible to infrared energy conversion in Pr3+-Yb3+ co-doped fluoroindate glasses

Processes involving visible to infrared energy conversion are presented for Pr3+-Yb3+ co-doped fluoroindate glasses. The emission in the visible and infrared regions, the luminescence decay time of the Pr 3+:3P0 → 3H4 (482 nm), Pr3+:1D2 → 3H6 (800 nm), Yb3+:2F5/2 → 2F 7/2 (1044 nm) transitions and the photoluminescence excitation spectra were measured in Pr3+ samples and in Pr3+-Yb 3+ samples as a function of the Yb3+ concentration. In addition, energy transfer efficiencies were estimated from Pr3+: 3P0 and Pr3+:1D2 levels to Yb3+:2F7/2 level. Down-Conversion (DC) emission is observed due to a combination of two different processes: 1-a one-step cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) resulting in one photon emitted by Pr3+ (1G4 → 3H5) and one photon emitted by Yb3+ (2F7/2 → 2F5/2); 2-a resonant two-step first order energy transfer, where the first part of energy is transferred to Yb3+ neighbor through cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) followed by a second energy transfer step (Pr 3+:1G4 → 3H4; Yb3+:2F7/2 → 2F5/2). A third process leading to one IR photon emission to each visible photon absorbed involves cross relaxation energy transfer (Pr3+: 1D2 → 3F4; Yb 3+:2F7/2 → 2F5/2). © 2013 Elsevier B.V. All rights reserved.

Resistência à cárie de esmalte dental irradiado por lasers de Er:YAG e Nd:YAG, avaliada através da morfologia e proporção Ca/P

Pós-graduação em Ciências Odontológicas - FOAR