TL, EPR and optical absorption in natural grossular crystal

Grossular is one of six members of silicate Garnet group. Two samples GI and GII have been investigated concerning their luminescence thermally stimulated (TL). EPR and optical absorption and the measurements were carried out to find out whether or not same point defects are responsible for all three properties. Although X-rays diffraction analysis has shown that both GI and GII have practically the same crystal structure of a standard grossular crystal, they presented different behavior in many aspects. The TL glow curve shape, TL response to radiation dose, the effect of annealing at high temperatures before irradiation, the dependence of UV bleaching parameters on peak temperature, all of them differ going from GI to GII. The EPR signals around g = 2.0 as well as at g = 4.3 and 6.0 have much larger intensity in GI than in GII. Very high temperature (> 800 degrees C annealing causes large increase in the bulk background absorption in GI, however, only very little in GII. In the cases of EPR and optical absorption, the difference in their behavior can be attributed to Fe3+ ions; however, in the TL case one cannot and the cause was not found as yet. (C) 2008 Elsevier B.V. All rights reserved.

Elaboration and optimization of (Y,Er)Al(3)(BO(3))(4) glassy planar waveguides through the sol-gel process

In this work, a sol-gel route was used to prepare Y(0.9)Er(0.1)Al(3)(BO(3))(4) glassy thin films by spin-coating technique looking for the preparation and optimization of planar waveguides for integrated optics. The films were deposited on silica and silicon substrates using stable sols synthesized by the sol-gel process. Deposits with thicknesses ranging between 520 and 720 nm were prepared by a multi-layer process involving heat treatments at different temperatures from glass transition to the film crystallization and using heating rates of 2 degrees C/min. The structural characterization of the layers was performed by using grazing incidence X-ray diffraction and Raman spectroscopy as a function of the heat treatment. Microstructural evolution in terms of annealing temperatures was followed by high resolution scanning electron microscopy and atomic force microscopy. Optical transmission spectra were used to determine the refractive index and the film thicknesses through the envelope method. The optical and guiding properties of the films were studied by m-line spectroscopy. The best films were monomode with 620 nm thickness and a refractive index around 1.664 at 980 nm wavelength. They showed good waveguiding properties with high light-coupling efficiency and low propagation loss at 632.8 and 1550 nm of about 0.88 dB/cm. (C) 2009 Elsevier B.V. All rights reserved.

Influence from the sulfonate group (RSO(3)(-)) on the conversion process and emission efficiency of poly(p-phenylene vinylene)

The discovery of an alternative route to convert poly(xylyliden tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylene vinylene) (PPV) using dodecylbenzenesulfonate (DBS) has allowed the formation of ultrathin films with unprecedented control of architecture and emission properties. In this work, we show that this route may be performed with several sufonated compounds where RSO(3)(-) replaces the counter-ion (Cl(-)) of PTHT, some of which are even more efficient than DBS. Spin-coating films were produced from PTHT and azo-dye molecules, an azo-polymer and organic salts as counter-ions of PTHT. The effects of the thermal annealing step of PTHT/RSO(3)(-) films at 110 and 230 degrees C were monitored by measuring the absorption and emission spectra. The results indicate that the exchange of the counterion Cl(-) of PTHT by a linear long chain with RSO(3)(-) group is a general procedure to obtain PPV polymer at lower conversion temperature (ca. 110 degrees C) with significant increase in the emission efficiency, regardless of the chemical position and the number of sulfonate groups. With the enhanced emission caused by Congo Red and Tinopal as counter-ions, it is demonstrated that the new synthetic route is entirely generic, which may allow accurate control of conversion and emission properties. (C) 2010 Elsevier B.V. All rights reserved.

Influence of chromium concentration on the optical-electronic properties of ruby microstructures

Films of amorphous aluminium nitride (AlN) were prepared by conventional radio frequency sputtering of an Al + Cr target in a plasma of pure nitrogen. The Cr-to-Al relative area determines the Cr content, which remained in the similar to 0-3.5 at% concentration range in this study. Film deposition was followed by thermal annealing of the samples up to 1050 degrees C in an atmosphere of oxygen and by spectroscopic characterization through energy dispersive x-ray spectrometry, photoluminescence and optical transmission measurements. According to the experimental results, the optical-electronic properties of the Cr-containing AlN films are highly influenced by both the Cr concentration and the temperature of the thermal treatments. In fact, thermal annealing at 1050 degrees C induces the development of structures that, because of their typical size and distinctive spectral characteristics, were designated by ruby microstructures (RbMSs). These RbMSs are surrounded by a N-rich environment in which Cr(3+) ions exhibit luminescent features not present in other Cr(3+)-containing systems such as ruby, emerald or alexandrite. The light emissions shown by the RbMSs and surroundings were investigated according to the Cr concentration and temperature of measurement, allowing the identification of several Cr(3+)-related luminescent lines. The main characteristics of these luminescent lines and corresponding excitation-recombination processes are presented and discussed in view of a detailed spectroscopic analysis.

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

A novel MAP-MRF approach for multispectral image contextual classification using combination of suboptimal iterative algorithms

In this paper we present a novel approach for multispectral image contextual classification by combining iterative combinatorial optimization algorithms. The pixel-wise decision rule is defined using a Bayesian approach to combine two MRF models: a Gaussian Markov Random Field (GMRF) for the observations (likelihood) and a Potts model for the a priori knowledge, to regularize the solution in the presence of noisy data. Hence, the classification problem is stated according to a Maximum a Posteriori (MAP) framework. In order to approximate the MAP solution we apply several combinatorial optimization methods using multiple simultaneous initializations, making the solution less sensitive to the initial conditions and reducing both computational cost and time in comparison to Simulated Annealing, often unfeasible in many real image processing applications. Markov Random Field model parameters are estimated by Maximum Pseudo-Likelihood (MPL) approach, avoiding manual adjustments in the choice of the regularization parameters. Asymptotic evaluations assess the accuracy of the proposed parameter estimation procedure. To test and evaluate the proposed classification method, we adopt metrics for quantitative performance assessment (Cohen`s Kappa coefficient), allowing a robust and accurate statistical analysis. The obtained results clearly show that combining sub-optimal contextual algorithms significantly improves the classification performance, indicating the effectiveness of the proposed methodology. (C) 2010 Elsevier B.V. All rights reserved.

The effects of temperature on the molecular orientation of zinc phthalocyanine films

Phthalocyanine compounds have been widely investigated as candidate materials for technological applications, which is mainly due to their thermal stability and possibility of processing in the form of thin films. In most applications, the controlled growth of thin films with high crystalline quality is essential. In this study, zinc phthalocyanine (ZnPc) thin films were prepared by evaporation on glass and Au-coated glass substrates with subsequent annealing at different temperatures in ambient atmosphere. The morphological and structural features of 80 nm thick zinc phthalocyanine films were investigated, evidencing an alpha -> beta phase transformation after annealing the films at 200 A degrees C, as indicated by UV-Vis spectroscopy and FTIR analyses. A better uniformity of the annealed films was also evidenced via AFM analysis, which may be of importance for applications where film homogeneity and excellent optical quality are required.

Characteristics of thin cellulose ester films spin-coated from acetone and ethyl acetate solutions

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated.

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

Silver Nanoparticles Obtained in PAH/PAA-Based Multilayers by Photochemical Reaction

Carboxylic acid groups in PAH/PAA-based multilayers bind silver cations by ion exchange with the acid protons. The aggregation and spatial distribution of the nanoparticles proved to be dependent oil the process used to reduce the silver acetate aqueous solution. The reducing method with ambient light formed larger nanoparticles with diameters ranging from 4-50 nm in comparison with the reduction method using UV light, which gave particles with diameters of 2-4 nm The high toughness of samples reduced by ambient light is a result of two population distributions of particle sizes caused by different mechanisms when compared with the UV light process. According to these phenomena, a judicious choice of the spectral source call be used as a way to control the type and size of silver nanoparticles formed on PEMs. Depending on the energy of the light source, the Ag nanoparticles present cubic and/or hexagonal crystallographic structures, as confirmed by XRD. Beyond the kinetically controlled process of UV photoinduced cluster formation, the annealing produced by UV light allowed a second mechanism to modify the growth rates, spatial distribution, and phases.