Raman investigation of structural photoinduced irreversible changes of Ga10Ge25S65 chalcogenide glasses

The influence of time exposure, when exposed to above band gap light (3,52 eV) and annealing, on Ga10Ge25S65 glasses has been studied through their effects on the structure and optical properties. To evaluate the photostructural change infrared and Raman spectra for bulk Ga10Ge25S65 glasses have been measured before and after exposure. The Raman spectra are interpreted in terms of models in which the Ge atoms are fourfold coordinated and the S atoms are two fold coordinated. The observed changes in the spectral region of (S-S) stretching vibration (470-490 cm (-1)) is a direct evidence for the occurrence of important structural changes in local bonding configuration caused by optical irradiation. It is shown that the dominant photostrucural changes are chain formation tendency of the chalcogenide atoms under the laser irradiation rather than rings.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.

Characterization of the reversible photoinduced optical changes in Sb-based glasses

Changes occurring in absorption coefficients when glasses in the SbPO4-WO3 binary system were irradiated by light, at the edge of the absorption band, were measured in real time. These glasses present good thermal and optical properties and photoinduced changes in the absorption coefficients are reversible by heat treatment around 150 degrees C. Subsequent recording/erasing cycles could be made without sample degradation. The sensitivity of the induced optical changes was studied for different wavelengths, light powers and energy of light dose exposures, and for different compositions of the glasses. The changes in the absorption coefficients of the glass samples were accompanied by a color change from yellow to blue, and were also characterized by visible spectroscopy. The color changes occurred through the entire volume of the glass (similar to 2 mm thickness) for the Ar-ion laser lines at the edge of the absorption band. (c) 2006 Elsevier B.V. All rights reserved.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Preparation, structural and optical characterization of BaWO4 and PbWO4 thin films prepared by a chemical route

Polycrystalline BaWO4 and PbWO4 thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO4 and PbWO4 phase crystallize at 500 degreesC from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 degreesC and the appearance of two sharp and intense bands between 1000 and 600 cm(-1) assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO4 and PbWO4 thin films have Eg = 5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO4 and PbWO4 thin films. (C) 2003 Elsevier Ltd. All rights reserved.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Microstructural and optical characterization of CaWO4 and SrWO4 thin films prepared by a chemical solution method

Stoichiometric CaWO4 and SrWO4 thin films were synthesized using a chemical solution processing, the so-called polymeric precursor method. In this soft chemical method, soluble precursors such as strontium carbonate, calcium carbonate and tungstic acid, as starting materials, were mixed in an aqueous solution. The thin films were deposited on glass substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Nucleation stages and surface morphology evolution of the thin films on glass substrates were studied by atomic force microscopy. The films nucleate at 300 degreesC, after the coalescence of small nuclei into larger grains yielding a homogeneous dense surface. XRD characterization of these films showed that the CaWO4 and SrWO4 phases crystallize at 400 degreesC from an inorganic amorphous phase. No intermediate crystalline phase was identified. The optical properties were also studied. It was found that CaWO4 and SrWO4 thin films have an optical band gap, E-gap=5.27 and 5.78 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity confirmed that this soft solution processing provides an inexpensive and environmentally friendly route for the preparation of CaWO4 and SrWO4 thin films. (C) 2003 Elsevier B.V. All rights reserved.

Thermo-optical characterization of tellurite glasses by thermal lens, thermal relaxation calorimetry and interferometric methods

In this work the thermal lens, thermal relaxation calorimetry and interferometric methods are applied to investigate the thermo-optical properties of tellurite glasses (in mol%: 80TeO(2)-20 Li2O(TeLi), 80TeO(2)-15Li(2)O-5TiO(2) (TeLiTi-5) and 80TeO(2)-10Li(2)O-10TiO(2) (TeLiTi-10)). Thermal diffusivity, thermal conductivity, specific heat and the temperature coefficients of refractive index, optical path length, thermal expansion and electronic polarizability were determined. The use of three independent methods was useful for a complete characterization of the studied tellurite glasses. In addition, our results showed that the thermal expansion coefficient and the temperature coefficient of the optical path length (dS/dT) were significantly modified with the introduction of titanium, which may be relevant for the application of these glasses in the photonic area. (c) 2006 Elsevier B.V. All rights reserved.

Influence of the network former on the properties of magnesium spinels

Undoped and/or doped with 1 mol% of Co2+ Mg2TiO4 and Mg2SnO4 powders were synthesized by the polymeric precursor method. The influence of the network former (Sn4+ or Ti4+) on the thermal, structural and optical properties was investigated. The recorded mass losses are due to the escape of water and adsorbed gases and to the elimination of the organic matter. Mg2TiO4 crystallizes at lower temperatures and also presents more ordered structure with a smaller unit call and having more intense green color than Mg2SnO4 has.

Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

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

Effects of self-assembly process of latex spheres on the final topology of macroporous silica

This paper surveys the topology of macroporous silica prepared using latex templates covering the submicrometric range (0.1-0.7 mu m). The behavior of latex spheres in aqueous dispersion has been analyzed by dynamic light scattering (DLS) measurement indicating the most appropriate conditions to form well-defined cubic arrays. The optical behavior of latex spheres has been analyzed by transmittance and reflectance measurements in order to determine their diameter and filling factor when they were assembled in bidimensional arrays. Macroscopic templates have been obtained by a centrifugation process and their crystalline ordering has been confirmed by porosimetry and scanning electron microscopy. These self-assembled structures have been used to produce macroporous silica, whose final topology depends on the pore size distribution of the original template. It has been seen that latex spheres are ordered in a predominant fcc arrangement with slipping of tetragonal pores due to the action of attractive electrostatic interactions. The main effect is to change the spherical shape of voids in macroporous silica into a hexagonal configuration with possible applications to fabricate photonic devices with novel optical properties. (c) 2005 Elsevier B.V. All rights reserved.

Effects of dispersion by Gd3+ upon europium diphenylphosphinate luminescence

A series of binary diphenylphosphinates with Eu3+ and Gd3+ were prepared. The compounds have the general formula Gd1-xEux(DPP)(3), where x ranges from 0 to 1. The spectroscopic measurements show interesting behavior. The intensity of the D-5(0) --> F-7(2) transitions decreases relative to D-5(0) --> F-7(1) With an increase in europium dispersion. Inside the temporal domain, the same decrease is observed with increasing delay after excitation. The lifetimes are also affected, which can be seen in the x = 1 compound, where the decay is a first-order process and lifetime values are 4.81 ms. In the binary compound, as an effect of dispersion, the lifetime of the D-5(0) level measured at the D-5(0) --> F-7(1) transition increases with europium dispersion, and the average along the series is 6.25 ms. The decay measured at the D-5(0) --> F-7(2) transitions reveals a second-order process with lifetimes ranging from 1.90 to 6.00 ms. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Effect of the order and disorder of BaMoO4 powders in photoluminescent properties

The study of the photoluminescent properties affected by order and disorder of the BaMoO4 powders is the principal objective in this work. BaMoO4 compounds were prepared using soft chemical process called Complex Polymerization Method. In this work, different deagglomeration types and different heating rates were used to promote different disorder degrees. Scheelite type phase (BaMoO4) was determined by X-ray Diffraction (XRD), Fourier Transformed Infra-Red (FTIR) and Raman spectroscopy after heat treating the sample at 400 degrees C. The room temperature luminescence spectra revealed an intense single-emission band in the visible region. Based on XRD and Raman data it was observed that the transition between the completely disordered structure to completely ordered structure is a good condition for photoluminescence (PL) emission. The best PL emission is obtained when the material possesses short range disorder, i.e., is periodically ordered (XRD), but some disorder as measured by Raman spectroscopy. The excellent optical properties observed for disordered BaMoO4 suggested that this material is a highly promising candidate for optical applications.

Structural refinement and photoluminescence properties of irregular cube-like (Ca-1_Cu-x(x))TiO3 microcrystals synthesized by the microwave-hydrothermal method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+-codoped fluorogermanate glass and glass ceramic

Energy-transfer excited upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+ -codoped PbGeO3-PbF2-CdF2 glass and glass-ceramic under infrared excitation is investigated. In Ho3+/Yb3+-codoped samples, green (545 nm), red (652 nm), and near-infrared (754 nm) upconversion emission corresponding to the S-5(2) (F-5(4)) -> I-5(8), F-5(5) -> I-5(8), and S-5(2)(F-5(4)) -> I-5(7) transitions, respectively, was observed. Blue (490 nm) emission assigned to the F-5(2,3) -> I-5(8) transition was also detected. In the Tb3+/Yb3+-codoped system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the D-5(3)((5)G(6)) -> F-7(J)(J = 6, 5, 4) and D-5(4) -> F-7(J)(J = 6, 5, 4, 3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicated that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed. (c) 2007 Elsevier B.V. All rights reserved.