Waveguides and gratings fabrication in zirconium-based organic/inorganic hybrids

Sol-gel derived poly(oxyethylene)/siloxane organic/inorganic di-ureasil hybrids containing different amounts of methacrylic acid (McOH, CH(2)=C(CH(3))COOH)) modified zirconium oxo-clusters (Zr-OMc) were processed as thin films deposited in glassy substrates via spin coating and as transparent and shape controlled monoliths. Channel monomode waveguides and diffraction gratings were UV patterned using the Talbot interferometer and the Lloyd mirror interferometer experimental setups. The time dependence of the diffraction gratings efficiency was studied for hybrids containing different amounts of Zr-OMc. Finally, the number of propagating modes and the refractive index gradient within the waveguide region, determined as a Gaussian section located below the patterned channel, was evaluated and modeled, a maximum index contrast of 2.43 X 10(-5) being estimated.

NIR luminescent Er3+/Yb3+ co-doped SiO2-ZrO2 nanostructured planar and channel waveguides: Optical and structural properties

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

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optical Fiber Relative Humidity Sensor Based on a FBG with a Di-Ureasil Coating

In this work we proposed a relative humidity (RH) sensor based on a Bragg grating written in an optical fiber, associated with a coating of organo-silica hybrid material prepared by the sol-gel method. The organo-silica-based coating has a strong adhesion to the optical fiber and its expansion is reversibly affected by the change in the RH values (15.0-95.0%) of the surrounding environment, allowing an increased sensitivity (22.2 pm/%RH) and durability due to the presence of a siliceous-based inorganic component. The developed sensor was tested in a real structure health monitoring essay, in which the RH inside two concrete blocks with different porosity values was measured over 1 year. The results demonstrated the potential of the proposed optical sensor in the monitoring of civil engineering structures.

Filmes delgados luminescentes obtidos a partir de hidroxicarbonatos de ítrio ativados por európio ou térbio

These films were obtained by dip coating. Parameters like dislocation velocity; number of deposits, suspension concentration, and number of deposits followed or not by heat treatment between each deposit and calcination temperature were evaluated for establishing the best homogeneity. The obtained films were characterized in terms of their morphology, optical quality and photoluminescence by scanning electron microscopy (SEM), UV-vis absorption spectrophotometry and luminescence spectroscopy, respectively. The morphologic and luminescent characteristics showed dip coating as good laboratory technique for development of thin films for optical applications.

Hydrolysis rates of TMOS catalyzed by oxalic acid and stimulated by ultrasound

A simple calorimetric method was employed to study the kinetics of the hydrolysis of the solventless TMOS-water mixtures, under ultrasound stimulation, as a function of the concentration of oxalic acid. The reaction rates were obtained, in relative units, from the measured thermal peak of the reaction as a non-separated function of both the sonication time and the instantaneous temperature of the medium. For concentrations of oxalic acid below 0.01 M, polycondensation reaction starts before complete hydrolysis. For concentrations of oxalic acid above 0.01 M, hydrolysis is complete and, in addition, the inverse of the time, as measured from the starting of ultrasound action until the maximum hydrolysis heat release, was found to be a reasonable relative measure of the average hydrolysis rate constant. The average hydrolysis rate constant was found to be proportional to the square root of the molar concentration of the oxalic acid. This result is in agreement with the literature if we assume small dissociation degree for the catalyst in such a solventless alkoxyde-water medium.

Low optical loss planar waveguides prepared in an organic-inorganic hybrid system

HfO2-(3-glycidoxipropil)trimethoxisilane (GPTS) planar waveguides were prepared by a sol-gel route. A stable sol of Hafnia nanocrystals was prepared and characterized by photon correlation spectroscopy and high resolution transmission electron microscopy. The suspension was incorporated in GPTS host and the resulting sol was deposited on borosilicate substrates by the spin coating technique. Optical properties such as refractive index, thickness, number of propagating modes, and attenuation coefficient were measured at 632.8, 543.5, and 1550 nm by the prism coupling technique as a function of the HfO2 content. (C) 2000 American Institute of Physics. [S0003-6951(00)03348-9].

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

Structural characterization of undoped and Sb-doped SnO2 thin films fired at different temperatures

SnO2 thin films were obtained by the sol-gel method starting from inorganic precursor solutions. In this work, we compare the structure of undoped and Sb-doped SnO2 films prepared by dip-coating. The films were deposited on quartz substrates and then fired at different temperatures ranging from 383 up to 1173 K. The density and the thickness of the films were determined by X-ray reflectivity (XRR) and their porous nanostructure was characterized by grazing-incidence small angle X-ray scattering (GISAXS). XRR results corresponding to undoped and Sb-doped samples indicate a monotonous decrease in film thickness when they are fired at increasing temperatures. At same time, the apparent density of undoped samples exhibits a progressive increase while for Sb-doped films it remains invariant up to 973 K and then increases for T = 1173 K. Anisotropic GISAXS patterns of both films, Sb-doped and undoped, fired above 573 K indicate the presence of elongated pores with their major axis perpendicular to the film surface. For all firing temperatures the nanopores in doped samples are larger than in undoped ones. This suggests that Sb-doping favours the pore growth hindering the film densification. At the highest firing temperature (1173 K) this effect is reversed.

Structural modelling of Eu3+-based siloxane-poly( oxyethylene) nanohybrids

The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.

Er3+/Yb3+ co-activated silica-alumina monolithic xerogels

Monolithic silica xerogels doped with different concentrations of Er3+, Yb3+ and Al3+ were prepared by sol-gel route. Densification was achieved by thermal treatment in air at 950degreesC for 120 h with a heating rate of 0.1degreesC/min. We studied the luminescence properties of the I-4(13/2)-->I-4(15/2) emission band of Er3+ as a function of the Al/Er/Yb concentration and we paid particular attention to the alumina effects. Raman spectroscopy and Vis-NIR absorption were used to monitor the degree of densification of the glasses and the residual OH content.

Electrochemical oxidation of methanol on Pt nanoparticles dispersed on RuO2

Pt-modified RuO2 was prepared by a sol-gel procedure on titanium substrates in the form of thin films of similar to2-mum thickness. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that these films actually consist of Pt nanoparticles dispersed in RuO2 and that neither metallic Ru nor Pt-Ru alloy are present on the surface. Electrodes with different Pt:Ru nominal compositions were prepared and their electrocatalytic activity for the oxidation of methanol was investigated by potential sweeps and chronoamperometry. The results obtained show an enhancement effect for methanol oxidation that can be interpreted as associated to the formation of hydrous oxides on the RuO2 surface.

Electro-optical properties of Er-doped SnO2 thin films

Photoconductivity of SnO2 sol-gel films is excited, at low temperature, by using a 266 nm line-fourth harmonic-of a Nd:YAG laser. This line has above bandgap energy and promotes generation of electron-hole pairs, which recombines with oxygen adsorbed at grain boundary. The conductivity increases up to 40 times. After removing the illumination on an undoped SnO2 film, the conductivity remains unchanged, as long as the temperature is kept constant. Adsorbed oxygen ions recombine with photogenerated holes and are continuously evacuated from the system, leaving a net concentration of free electrons into the material, responsible for the increase in the conductivity. For Er doped SnO2, the excitation of conductivity by the laser line has similar behavior, however after removing illumination, the conductivity decreases with exponential-like decay. (C) 2003 Elsevier Ltd. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Layer-by-layer hybrid films of polyaniline and vanadium oxide

Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (LBL) technique. The films were characterized by vibrational analyses which indicated that the interactions between the two components lead to different properties in the films when compared to sol-gel films. of the neat compounds. In particular, using surface enhanced Raman scattering we were able to probe LBL film properties that depend on which material comprises the topmost layer.