Luminescence and non-radiative processes in lanthanide squarate hydrates

The luminescence properties of solid hydrated lanthanide squarates (Ln2(C4O4)3(H2O) x; x = 8 or 13;Ln3+ = Gd, La, Eu, Tb, Pr) are reported for temperatures down to 4.2K. The luminescence of the squarate group is observed for the Gd3+ and La3+ compounds at low temperatures (below 150K). The Pr3+ compound does not show any emission at all, not even at 4.2K. This is ascribed to the quenching of the Pr3+ emission by multiphonon relaxation and/or concentration quenching. The quantum efficiencies of the 5D0 emission of Eu3+ and of the 5D4 emission of Tb3+ in these squarate complexes are strikingly different. Whereas the Tb3+ emission shows a temperature independent quantum efficiency of 50% upon ligand excitation, the Eu3+ emission is strongly quenched, showing a temperature dependent quantum efficiency of 0.8% at 4.2K upon ligand excitation. This quenching is ascribed to the low energy position of the charge-transfer state of Eu3+ in these compounds.

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.

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.

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.

Transparent Er3+-activated lead fluorogermanate glass ceramics

Transparent glass ceramics containing β-PbF2:Er 3+ nanocrystals were obtained through appropriate thermal treatments of a glass of molar composition 60PbGeO3-10PbF2-30CdF 2 doped with 0.5 mol% Er3+. Their optical properties, as well as upconversion processes among erbium ions in the glass and glass ceramic matrix were studied. From absorption spectra, Judd-Ofelt parameters and radiative transition rates for several excited levels were calculated. Emission spectra in the visible and NIR regions were collected, and stimulated emission cross sections were obtained by McCumber theory for the 4F 13/2→4I15/2 transition at 1.5 μm. Red and green upconversion emissions were measured in glass and glass ceramics upon excitation at 980 nm; lifetimes were measured in order to assess the upconversion mechanisms.

Progress on holographic techniques to study photo-chemical reactions in solid state

In this paper it is presented recent developments in the heterodyne detection holographic techniques for studding photosensitive materials. The actual state of the technique allows simultaneous and independent measurement of the refractive index and of the absorption coefficient changes in photosensitive materials and their use to self-stabilize the fringe pattern. The modeling of the measured signal together with the fringe stabilization allow the long term-fitting of the optical properties and the study the photosensitive materials close to the saturation.

Electrical behavior of PU/POMA blends

The incorporation of conducting polymer into a conventional polymer matrix has received attention because of the possibility of combining the good processability and mechanical performance of the conventional polymer with the electrical and optical properties of conducting polymer. In this work, flexible films of polyurethane (PU) and Poli(o-metoxyaniline)(POMA) blends were obtained by casting and investigated using thermally stimulated depolarisation current (TSDC) measurements. Two relaxation peaks were found in the range of-20°C to 90°C. The first one at T=24°C was attributed as α relaxation associated to the glass transition of PU/POMA blend and the second one located at T=60°C can be attributed to space charge.

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Nanocrystalline GaN and GaN:H films grown by RF-magnetron sputtering

The structural and optical properties of nanocrystalline GaN and GaN:H films grown by RF-tnagnetron sputtering are focused here. The films were grown using a Ga target and a variety of deposition parameters (N 2/H 2/Arflow rates, RF power, and substrate temperatures). Si (100) and fused silica substrates were used at relatively low temperatures (T s ≤ 420K). The main effects resulting from the deposition parameters variations on the films properties were related to the presence of hydrogen in the plasma. The X-ray diffraction analysis indicates that the grain sizes (∼15nm) and the crystallized volume fraction significantly decrease when hydrogen is present in the plasma. The optical absorption experiments indicate that the hydrogenated films have absorption edges very similar to that of GaN single crystal films reported in the literature, while the non-hydrogenated samples present larger absorption tails encroaching into the gap energies.

Temporal evolution of sulfated zirconia sol-gel during dip coating: Analysis of mass drainage with time-varying refractive index

The formation of sulfated zirconia films from a sol-gel derived aqueous suspension is subjected to double-optical monitoring during batch dip coating. Interpretation of interferometric patterns, previously obscured by a variable refractive index, is now made possible by addition of its direct measurement by a polarimetric technique in real time. Significant sensitivity of the resulting physical thickness and refractive index curves (uncertainties of ±7 nm and ±0.005, respectively) to temporal film evolution is shown under different withdrawal speeds. As a first contribution to quantitative understanding of temporal film formation with varying nanostructure during dip coating, detailed analysis is directed to the stage of the process dominated by mass drainage, whose simple modeling with temporal t-1/2 dependence is verified experimentally. © 2006 Elsevier B.V. All rights reserved.

Antimony glasses with large nonlinear refractive indices, small two-photon absorption coefficients and ultrafast response at telecom wavelengths

Nonlinear (NL) optical properties of antimony oxide based glasses (AG) were characterized for excitation wavelengths from 800 to 1600 m. The NL refractive indices, n2, and the two-photon absorption (TPA) coefficient, β, have been evaluated using the Z-scan technique. Values of n2≈ 10-15 - 10-14 cm2/W of electronic origin were measured and negligible TPA coefficients (β < 0.003 cm/GW) were determined. The response time of the nonlinearity is faster than 100 fs as determined using the Kerr shutter technique. The figure-of-merit usually considered for all-optical switching, T = 2βλ/n2 , indicates that AG are very good materials for ultrafast switches at telecom wavelengths. © 2007 IEEE.

Waveguide features in self-patternable amine functionalized organic-inorganic hybrids

We report the use of organic-inorganic sol-gel derived poly(oxyehylene)/ siloxane hybrid doped with methacrylic acid modified zirconium (IV) n-propoxide for the fabrication of low cost waveguides trough direct UV laser writing. The organic-inorganic hybrids were processed as monoliths with size and shape control. The effective guiding region was identified and the number of modes was estimated via mode field analyses. A grating was successfully superimposed on the channel and the respective reflection spectrum was measured, enabling the determination of the guiding region dimension, the calculation of the effective refractive index of the guided mode. © 2007 IEEE.

Physiological maturity of Cnidosculus quercifolius Pax & K. Hoffm. seeds

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

Plasmonic structures fabricated by interference lithography for sensor applications

In this work we demonstrate the use of holographic lithography for generation of large area plasmonic periodic structures. Submicrometric array of holes, with different periods and thickness, were recorded in gold films, in areas of about 1 cm2, with homogeneity similar to that of samples recorded by Focused Ion Beam. In order to check the plasmonic properties, we measured the transmission spectra of the samples. The spectra exhibit the typical surface plasmon resonances (SPR) in the infrared whose position and width present the expected behavior with the period of the array and film thickness. The shift of the peak position with the permittivity of the surrounding medium demonstrates the feasebility of the sample as large area sensors. © 2009 SPIE.

Lidar observation campaign of sugar cane fires and industrial emissions in the State of São Paulo, Brazil

Brazil has an important role in the biomass burning, with the detection of approximately 100,000 burning spots in a single year (2007). Most of these spots occur in the southern part of the Amazon basin during the dry season (from August to november) and these emissions reach the southeast of the country, a highly populated region and with serious urban air pollution problems. With the growing demand on biofuels, sugarcane is considerably expanding in the state of São Paulo, being a strong contributor to the bad air quality in this region. In the state of São Paulo, the main land use are pasture and sugarcane crop, that covers around 50% and 10% of the total area, respectively. Despite the aerosol from sugarcane burning having reduced atmospheric residence time, from a few days to some weeks, they might get together with those aerosol which spread over long distances (hundreds to thousands of kilometers). In the period of June through February 2010 a LIDAR observation campaign was carried in the state of São Paulo, Brazil, in order to observe and characterize optically the aerosols from two distinct sources, namely, sugar cane biomass burning and industrial emissions. For this purpose 2 LIDAR systems were available, one mobile and the other placed in a laboratory, both working in the visible (532 nm) and additionally the mobile system had a Raman channel available (607 nm). Also this campaign counted with a SODAR, a meteorological RADAR specially set up to detect aerosol echoes and gas-particle analyzers. To guarantee a good regional coverage 4 distinct sites were available to deploy the instruments, 2 in the near field of biomass burning activities (Rio Claro and Bauru), one for industrial emissions (Cubatão) and others from urban sources (São Paulo). The whole campaign provide the equivalent of 30 days of measurements which allowed us to get aerosol optical properties such as backscattering/extinction coefficients, scatter and LIDAR ratios, those were used to correlate with air quality and meteorological indicators and quantities. In this paper we should focus on the preliminary results of the Raman LIDAR system and its derived aerosol optical quantities. © 2010 Copyright SPIE - The International Society for Optical Engineering.