Espectroscopia óptica de vidros fluoroindatos dopados com íons Er3+ e Yb3+

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

The influence of cation segregation on the methanol decomposition on nanostructured SnO2

Here we describe a new route to synthesize ultrafine rare earth doped and undoped tin oxide particles for catalytic applications. The catalytic behavior observed in SnO2 samples suggests the control of the catalytic activity and the selectivity of the products by the segregation of a layer of a rare earth compound with the increase of the heat-treatment temperature. The ultrafine particles were characterized by means of BET, XPS, TEM, XRD and Rietveld refinement. It was demonstrated that the effects of the dopant on the methanol decomposition reaction and on the H-2 selectivity were correlated with the segregation of a rare earth layer on the tin oxide samples. (C) 2002 Published by Elsevier B.V. B.V.

Magnetic sol-gel derived poly(oxyethylene)-siloxane nanohybrids

The magnetic and structural properties of sol-gel derived organic/inorganic nanocomposites doped with Fe(II), Fe(III), Nd(III) and Eu (III) ions are discussed. These hybrids consist of poly(oxyethylene)-based chains grafted onto siloxane nanodomains by urea cross-linkages. Small angle X-ray scattering data show the presence of spatial correlations of siloxane domains embedded in the polymer matrix. The magnetic properties of rare-earth doped samples are determined by single ion crystal-field-splitted levels (Eu3+ J=0; Nd3+ J=9/2) and the small thermal irreversibility is mainly associated to structural effects. Fe2+ -doped samples behave as simple paramagnet with residual antiferromagnetic interactions. Fe3+-doped hybrids are much more complex, with magnetic hysterisis, exchange anisotropy and thermal irreversibility at low temperatures. Néel temperatures increase up to 14K for the highest (∼5.5%) Fe3+ mass concentration.

Interface formation of nanostructured heterojunction SnO 2:Eu/GaAs and electronic transport properties

Thin films of tin dioxide (SnO2) are deposited by the sol-gel-dip-coating technique, along with GaAs layers, deposited by the resistive evaporation technique. The as-built heterojunction has potential application in optoelectronic devices, combining the emission from the rare-earth doped transparent oxide (Eu3+-doped SnO2 presents very efficient red emission) with a high mobility semiconductor. The advantage of this structure is the possibility of separation of the rare-earth emission centers from the electron scattering, leading to a strongly indicated combination for electroluminescence. Electrical characterization of the heterojunction SnO2:Eu/GaAs shows a significant conductivity increase when compared to the conductivity of the individual films, and the monochromatic light irradiation (266 nm) at low temperature of the heterojunction GaAs/SnO2:Eu leads to intense conductivity increase. Scanning electron microscopy (SEM) of the heterojunction cross section shows high adherence and good morphological quality of the interfaces substrate/SnO2 and SnO2/GaAs, even though the atomic force microscopy (AFM) image of the GaAs surface shows disordered particles, which increases with sample thickness. On the other hand, the good morphology of the SnO2:Eu surface, shown by AFM, assures the good electrical performance of the heterojunction. The observed improvement on the electrical transport properties is probably related to the formation of short conduction channels at the semiconductors interface, which may exhibit two-dimensional electron gas (2DEG) behavior. © 2012 Elsevier B.V. All rights reserved.

Matrizes semicondutoras GaAs e Sn'X IND. 2' dopado com terras-raras Ce ou Eu: investigação do transporte elétrico

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

Estudo das propriedades ópticas e estruturais de espinélios do tipo 'ZNAL IND. 2 O IND. 4' contendo 'EU POT. 3+' ou 'TB POT. 3+'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Investigação de contatos elétricos e propriedades de filmes finos de SnO2 dopados com os íons terras raras Eu3+ e Ce3+

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Efficient 1535 nm light emission from an all-Si-based optical micro-cavity containing Er3+ and Yb3+ ions

This work reports on the construction and spectroscopic analyses of optical micro-cavities (OMCs) that efficiently emit at ~1535 nm. The emission wavelength matches the third transmission window of commercial optical fibers and the OMCs were entirely based on silicon. The sputtering deposition method was adopted in the preparation of the OMCs, which comprised two Bragg reflectors and one spacer layer made of either Er- or ErYb-doped amorphous silicon nitride. The luminescence signal extracted from the OMCs originated from the 4I13/2→4I15/2 transition (due to Er3+ ions) and its intensity showed to be highly dependent on the presence of Yb3+ ions.According to the results, the Er3+-related light emission was improved by a factor of 48 when combined with Yb3+ ions and inserted in the spacer layer of the OMC. The results also showed the effectiveness of the present experimental approach in producing Si-based light-emitting structures in which the main characteristics are: (a) compatibility with the actual microelectronics industry, (b) the deposition of optical quality layers with accurate composition control, and (c) no need of uncommon elements-compounds nor extensive thermal treatments. Along with the fundamental characteristics of the OMCs, this work also discusses the impact of the Er3+-Yb3+ ion interaction on the emission intensity as well as the potential of the present findings.

50th anniversary of the Judd–Ofelt theory: An experimentalist's view of the formalism and its application

The theory on the intensities of 4f-4f transitions introduced by B.R. Judd and G.S. Ofelt in 1962 has become a center piece in rare-earth optical spectroscopy over the past five decades. Many fundamental studies have since explored the physical origins of the Judd–Ofelt theory and have proposed numerous extensions to the original model. A great number of studies have applied the Judd–Ofelt theory to a wide range of rare-earth doped materials, many of them with important applications in solid-state lasers, optical amplifiers, phosphors for displays and solid state lighting, upconversion and quantum-cutting materials, and fluorescent markers. This paper takes the view of the experimentalist who is interested in appreciating the basic concepts, implications, assumptions, and limitations of the Judd–Ofelt theory in order to properly apply it to practical problems. We first present the formalism for calculating the wavefunctions of 4f electronic states in a concise form and then show their application to the calculation and fitting of 4f-4f transition intensities. The potential, limitations and pitfalls of the theory are discussed, and a detailed case study of LaCl3:Er3+ is presented.

Produção e caracterização de guias de onda dopados com terras-raras contendo nanopartículas semicondutoras.

O presente trabalho tem como objetivo estudar a produção e caracterização de filmes finos do tipo GeO2-Bi2O3 (BGO) produzidos por sputtering-RF com e sem nanopartículas (NPs) semicondutoras, dopados e codopados com íons de Er3+ ou Er3+/Yb3+ para a produção de amplificadores ópticos. A produção de guias de onda do tipo pedestal baseados nos filmes BGO foi realizada a partir de litografia óptica seguida por processo de corrosão por plasma e deposição física a vapor. A incorporação dos íons de terras-raras (TRs) foi verificada a partir dos espectros de emissão. Análises de espectroscopia e microscopia foram indispensáveis para otimizar os parâmetros dos processos para a construção dos guias de onda. Foi observado aumento significativo da luminescência do Er3+ (região do visível e do infravermelho), em filmes finos codopados com Er3+/Yb3+ na presença de nanopartículas de Si. As perdas por propagação mínimas observadas foram de ~1,75 dB/cm para os guias pedestal em 1068 nm. Para os guias dopados com Er3+ foi observado aumento significativo do ganho na presença de NPs de silício (1,8 dB/cm). O ganho óptico nos guias de onda amplificadores codopados com Er3+/Yb3+ e dopados com Er3+ com e sem NPs de silício também foi medido. Ganho de ~8dB/cm em 1542 nm, sob excitação em 980 nm, foi observado para os guias pedestal codopados com Er3+/Yb3+ (Er = 4,64.1019 átomos/cm3, Yb = 3,60.1020 átomos/cm3) com largura de 80 µm; para os guias codopados com concentração superior de Er3+/Yb3+ (Er = 1,34.1021 átomos/cm3, Yb = 3,90.1021 átomos/cm3) e com NPs de Si, foi observado aumento do ganho óptico de 50% para guia com largura de 100 µm. Os resultados apresentados demonstram que guias de onda baseados em germanatos, com ou sem NPs semicondutoras, são promissores para aplicações em dispositivos fotônicos.

Ginzburg-Landau turbulence in quasi-CW Raman fiber lasers

Fiber lasers operating via Raman gain or based on rare-earth-doped active fibers are widely used as sources of CW radiation. However, these lasers are only quasi-CW: their intensity fluctuates strongly on short time scales. Here the framework of the complex Ginzburg-Landau equations, which are well known as an efficient model of mode-locked fiber lasers, is applied for the description of quasi-CW fiber lasers. The vector Ginzburg-Landau model of a Raman fiber laser describes the experimentally observed turbulent-like intensity dynamics, as well as polarization rogue waves. Our results open debates about the common underlying physics of operation of very different laser types - quasi-CW lasers and passively mode-locked lasers. Fiber lasers operating via Raman gain or based on rare-earth-doped active fibers are widely used as sources of CW radiation. However, these lasers are only quasi-CW: their intensity fluctuates strongly on short time scales. Here the framework of the complex Ginzburg-Landau equations, which are well known as an efficient model of mode-locked fiber lasers, is applied for the description of quasi-CW fiber lasers. The vector Ginzburg-Landau model of a Raman fiber laser describes the experimentally observed turbulent-like intensity dynamics, as well as polarization rogue waves. Our results open debates about the common underlying physics of operation of very different laser types - quasi-CW lasers and passively mode-locked lasers.

Quantifying Aflatoxin B1 in peanut oil using fabricating fluorescence probes based on upconversion nanoparticles

Rare earth doped upconversion nanoparticles convert near-infrared excitation light into visible emission light. Compared to organic fluorophores and semiconducting nanoparticles, upconversion nanoparticles (UCNPs) offer high photochemical stability, sharp emission bandwidths, and large anti-Stokes shifts. Along with the significant light penetration depth and the absence of autofluorescence in biological samples under infrared excitation, these UCNPs have attracted more and more attention on toxin detection and biological labelling. Herein, the fluorescence probe based on UCNPs was developed for quantifying Aflatoxin B₁ (AFB₁) in peanut oil. Based on a specific immunity format, the detection limit for AFB₁ under optimal conditions was obtained as low as 0.2 ng·ml^{- 1}, and in the effective detection range 0.2 to 100 ng·ml^{- 1}, good relationship between fluorescence intensity and AFB₁ concentration was achieved under the linear ratios up to 0.90. Moreover, to check the feasibility of these probes on AFB₁ measurements in peanut oil, recovery tests have been carried out. A good accuracy rating (93.8%) was obtained in this study. Results showed that the nanoparticles can be successfully applied for sensing AFB₁ in peanut oil.

The influence of promoters (Zr, La, Tb, Pr) on the catalytic performance of CuO-CeO2 systems for the preferential oxidation of CO in the presence of CO2 and H2O

CuO supported on CeO2 and Ce0.9X0.1O2, where X is Zr, La, Tb or Pr, were synthesized using nitrate precursors, giving rise ceria based materials with a small particle size which interact with CuO species generating a high amount of interfacial sites. The incorporation of cations to the ceria framework modifies the CeO2 lattice parameter, improving the redox behavior of the catalytic system. The catalysts were characterized by X-ray fluorescence spectrometry (XRFS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, thermoprogrammed reduction with H2 (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalysts were tested in the preferential oxidation of CO under a H2-rich stream (CO-PROX), reaching conversion values higher than 95% between 115 and 140 °C and being the catalyst with 6 wt.% of Cu supported on Ce0.9Zr0.1O2 (sample 6CUZRCE) the most active catalyst. The influence of the presence of CO2 and H2O was also studied simulating a PROX unit, taking place a decrease of the catalytic activity due to the inhibitor effect both CO2 and H2O.

Spectroscopic properties and Judd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicate glass

Dy3+ doped oxyfluoride silicate glass was prepared and its optical absorption, 1.3 mu m emission, and upconversion luminescence properties were studied. Furthermore, the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] intensity parameters, oscillator strengths, spontaneous transition probability, fluorescence branching ratio and radiative lifetime were calculated by Judd-Ofelt theory, while stimulated emission cross section of H-6(9/2)+F-6(11/2)-> H-6(15/2) transition was calculated by McCumber theory [Phys. Rev. A. 134, 299 (1964)]. According to the obtained Judd-Ofelt intensity parameters Omega(2)=2.69x10(-20) cm(2), Omega(4)=1.64x10(-20) cm(2), and Omega(6)=1.64x10(-20) cm(2), the radiative lifetime was calculated to be 810 mu s for 1.3 mu m emission, whose full width at half maximum and sigma(e) were 115 nm and 2.21x10(-20)cm(2), respectively. In addition, near infrared to visible upconversion luminescence was observed and evaluated. The results suggest that Dy3+ doped oxyfluoride silicate glass can be used as potential host material for developing broadband optical amplifiers and laser applications.

Spectroscopic properties of neodymium doped high silica glass and aluminum codoping effects on the enhancement of fluorescence emission

Nd3+ -codoped and Al3+-Nd3+-codoped high silica glasses have been prepared by sintering nanoporous glasses impregnated with Nd3+ stop and Al3+ ions. The Judd-Ofelt intensity parameters Omega(2,4,6) of Nd3+-doped high silica glasses were obtained and used to analyze aluminum codoping effects. Fluorescence properties of Nd3+-doped high silica glasses strongly depend on the Al3+ concentration. While Nd3+ ion absorption and emission intensities of obviously increase when aluminum is added to Nd3+-doped high silica glasses, fluorescence lifetimes decrease and aluminum codoping has almost no influence on the radiative quantum efficiencies. This indicates that aluminum codoping is responsible for an anti-quenching effect through a local modification of rare-earth environments rather than through physical cluster dispersion.