Nanoestruturas de GaN crescidas pelas técnicas de epitaxia por magnetron sputtering e epitaxia por feixe molecular

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

Síntese e caracterização de materiais semicondutores nanoestruturados luminescentes à base de ZnS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica

Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).

Raman and XRD study on brookite-anatase coexistence in cathodic electrosynthesized titania

Among the many methods developed for the synthesis of titanium dioxide, cathodic electrosynthesis has not received much attention because the resulting amorphous oxy-hydroxide matrix demands a further thermal annealing step to be transformed into crystalline titania. However, the possibility of filling deep recessed templates by the control of the solidliquid interface makes it a potentially suitable technique for the fabrication of porous scaffolds for photovoltaics and photocatalysis. Furthermore, a careful control of the crystallization process enables the growth of larger grains with lower density of grain boundaries, which act as electron traps that slow down electronic transport and promote charge recombination. In this report, well crystallized titania deposits were obtained by thermal annealing of amorphous deposits fabricated by cathodically assisted electrosynthesis on indium-tin oxide (ITO)substrates. The combined use of Raman spectroscopy and X-ray diffraction showed that the crystallization process is more intricate than previously assumed. It is shown that the amorphous matrix evolves into a rutile-free mixture of brookite and anatase at temperatures as low as 200 degrees C that persists up to 800 degrees C, when pure anatase dominates. The amount of brookite in the brookiteanatase mixture reaches a maximum at 400 degrees C. This very simple method for obtaining a brookiteanatase mixture and the ability to tune their proportions by thermal annealing is a promising alternative whose potential for solar cells and photocatalysis deserves a careful evaluation. Copyright (C) 2011 John Wiley & Sons, Ltd.

Tailoring the structure, composition, optical properties and catalytic activity of Ag-Au nanoparticles by the galvanic replacement reaction

This Letter reports on the synthesis of Ag-Au nanoparticles (NPs) with controlled structures and compositions via a galvanic replacement reaction between Ag NPs and AuCl4(aq)- followed by the investigation of their optical and catalytic properties. Our results showed the formation of porous walls, hollow interiors and increased Au content in the Ag-Au NPs as the volume of AuCl4(aq)- employed in the reaction was increased. These variations led to a red shift and broadening of the SPR peaks and an increase of up to 10.9-folds in the catalytic activity towards the reduction of 4-nitrophenol relative to Ag NPs. (C) 2012 Elsevier B.V. All rights reserved.

Temperature-dependent Raman study of thermal parameters in CdS quantum dots

We report on the strong temperature-dependent thermal expansion, alpha(D), in CdS quantum dots (QDs) embedded in a glass template. We have performed a systematic study by using the temperature-dependent first-order Raman spectra, in CdS bulk and in dot samples, in order to assess the size dependence of alpha(D), and where the role of the compressive strain provoked by the glass host matrix on the dot response is discussed. We report the Gruneisen mode parameters and the anharmonic coupling constants for small CdS dots with mean radius R similar to 2.0 nm. We found that gamma parameters change, with respect to the bulk CdS, in a range between 20 and 50%, while the anharmonicity contribution from two-phonon decay channel becomes the most important process to the temperature-shift properties.

Urea-Based Synthesis of Zinc Oxide Nanostructures at Low Temperature

The preparation of nanometer-sized structures of zinc oxide (ZnO) from zinc acetate and urea as raw materials was performed using conventional water bath heating and a microwave hydrothermal (MH) method in an aqueous solution. The oxide formation is controlled by decomposition of the added urea in the sealed autoclave. The influence of urea and the synthesis method on the final product formation are discussed. Broadband photoluminescence (PL) behavior in visible-range spectra was observed with a maximum peak centered in the green region which was attributed to different defects and the structural changes involved with ZnO crystals which were produced during the nucleation process.

Gold-platinum alloys and Vegard's law on the nanoscale

The structure of gold-platinum nanoparticles is heavily debated as theoretical calculations predict core-shell particles, whereas x-ray diffraction experiments frequently detect randomly mixed alloys. By calculating the structure of gold-platinum nanoparticles with diameters of up to approximate to 3.5 nm and simulating their x-ray diffraction patterns, we show that these seemingly opposing findings need not be in contradiction: Shells of gold are hardly visible in usual x-ray scattering, and the interpretation of Vegard's law is ambiguous on the nanoscale. DOI: 10.1103/PhysRevB.86.241403

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

Optical and structural properties of planar and channel waveguides based on sol gel Er3+ and Yb3+ co-doped SiO2-ZrO2 are reported. Microstructured channels with high homogeneous surface profile were written onto the surface of multilayered densified films deposited on SiO2/Si substrates by a femtosecond laser etching technique. The densification of the planar waveguides was evaluated from changes in the refractive index and thickness, with full densification being achieved at 900 degrees C after annealing from 23 up to 500 min, depending on the ZrO2 content Crystal nucleation and growth took place together with densification, thereby producing transparent glass ceramic planar waveguides containing rare earth-doped ZrO2 nanocrystals dispersed in a silica-based glassy host Low roughness and crack-free surface as well as high confinement coefficient were achieved for all the compositions. Enhanced NIR luminescence of the Er3+ ions was observed for the Yb3+- codoped planar waveguides, denoting an efficient energy transfer from the Yb3+ to the Er3+ ion. (C) 2012 Elsevier B.V. All rights reserved.

APTES-Modified RE2O3:Eu3+ Luminescent Beads: Structure and Properties

Europium-doped lanthanide oxide RE2O3:Eu3+ (RE = Y or Gd) luminescent beads, with a spherical shape and a diameter of 150 +/- 15 nm, have been modified by reaction with 3-aminopropyltriethoxysilane (APTES), in order to introduce reactive amine groups at their surfaces. The direct silanation has resulted in the formation of a nanometric layer at the surface of the beads, with an optimum grafting rate of 0.055 +/- 0.005 mol APTES/mol RE2O3. Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies confirmed the condensation of an organosilane layer, made of cross-linked -O-Si-O-Si- and of groups -O-Si-R (with R = (CH2)(3)NH2 or O-Et). Titration of the accessible amine groups has been performed by simultaneously measuring the luminescence of grafted fluorescein isothiocyanate and that of core particles: there are about 2.3 X 10(4) (2.8 X 10(4)) -NH2 per Y2O3:Eu3+ (Gd2O3:Eu3+) bead. The isoelectronic point was shifted by one pH unit after APTES modification. The surface modification by APTES at least preserved (for Gd2O3:Eu3+) or improved (for Y2O3:Eu3+) the red emission of the beads.

IMPROVEMENT TO THE MARGINAL COPING FIT OF COMMERCIALLY PURE TITANIUM CAST IN PHOSPHATE-BONDED INVESTMENT BY USING A SIMPLE PATTERN COATING TECHNIQUE

Statement of problem. Coatings of zirconite, Y2O3 or ZrO2 on wax patterns before investing in phosphate-bonded investments have been recommended to reduce the reaction layer in titanium castings, but they are not easily obtainable. Spinel-based investments are relatively stable with molten titanium and could be used as coatings to improve the quality of castings made with those investments. Purpose. The purpose of this study was to evaluate the effect of pattern coating with a commercial spinel-based investment before investing in 1 of 3 phosphate-bonded investments on the marginal coping fit and surface roughness of commercially pure titanium castings. Material and methods. Ten square acrylic resin patterns (12 x 12 x 2 mm) per group were invested in the phosphate-bonded investments Rematitan Plus (RP), Rema Exakt (RE), and Castorit Super C (CA) with or without a coating of the spinel-based investment, Rematitan Ultra (RU). After casting, the specimens were cleaned and the surface roughness was measured with a profilometer. Copings for dental implants with conical abutment were invested, eliminated, and cast as previously described. The copings were cleaned and misfit was measured with a profile projector (n=10). For both tests, the difference between the mean value of RU only and each value of the phosphate-bonded investment was calculated, and the data were analyzed by 2-way ANOVA and Tukey's HSD test (alpha=.05). In addition, the investment roughness was measured in bar specimens (30 x 10 x 10 mm), and the data (n=10) were analyzed by 1-way ANOVA and Tukey's HSD post hoc test (alpha=.05). Results. Two-way ANOVA for casting surface roughness was significant because of the investment, the coating technique, and the interaction between variables. One-way ANOVA was performed to prove the interaction term, and Tukey's post hoc test showed that RP with coating had the lowest mean, while RP had the highest. CA with coating was not different from RP with coating or CA without coating. RE with coating was similar to CA, while RE was different from all groups. For coping marginal fit, the 2-way ANOVA was significant for the investment, the coating technique, and the interaction between variables. The interaction was analyzed by1-way ANOVA and Tukey's HSD test that showed no significant difference among the coated groups, which had better marginal fit than the groups without coating. Among the groups without coating, CA had significant lower marginal misfit than RP, while RE was not different from CA and RP. For the investment surface roughness, the 1-way ANOVA was significant. CA and RU were smoother than RE and RP (P<.001). Conclusions. The coating technique improved the quality of castings fabricated with phosphate-bonded investments. (J Prosthet Dent 2012;108:51-57)

Structural and magnetic characterization of colloidal CdMnS

This paper reports on the synthesis (chemical co-precipitation reaction) and characterization (X-ray diffraction, magnetization, and electron paramagnetic resonance) of nanosized Cd1-xMnxS particles with manganese concentration up to x = 0.73. Though the literature reports that nanosized (bulk) CdS can incorporate as much as 30% (50%) of manganese ion within its crystal structure we found manganese segregation at the nanoparticle surface at doping levels as low as 14%. We found that both XRD and magnetization data support the presence of the Mn3O4 phase (observed spin-glass transition around 43 K) at the high manganese doping levels whereas the EPR data strongly suggest preferential incorporation of manganese at the nanoparticle's surface, even at low manganese doping levels. Analyses of the experimental data strongly suggest the preparation of well-defined core/shell (Cd1-xMnxS/Mn3O4) structures at higher levels of manganese doping.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

We report herein for the first time a facile synthesis method to obtain SrTi1-xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 degrees C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (E-gap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.

Cellulose micro/nanofibres from Eucalyptus kraft pulp: Preparation and properties

There is growing interest in cellulose nanofibres from renewable sources for several industrial applications. However, there is a lack of information about one of the most abundant cellulose pulps: bleached Eucalyptus kraft pulp. The objective of the present work was to obtain Eucalyptus cellulose micro/nanofibres by three different processes, namely: refining, sonication and acid hydrolysis of the cellulose pulp. The refining was limited by the low efficiency of isolated nanofibrils, while sonication was more effective for this purpose. However, the latter process occurred at the expense of considerable damage to the cellulose structure. The whiskers obtained by acid hydrolysis resulted in nanostructures with lower diameter and length, and high crystallinity. Increasing hydrolysis reaction time led to narrower and shorter whiskers, but increased the crystallinity index. The present work contributes to the different widespread methods used for the production of micro/nanofibres for different applications. (C) 2012 Elsevier Ltd. All rights reserved.

Effect of different surfactants on the shape, growth and photoluminescence behavior of MnWO4 crystals synthesized by the microwave-hydrothermal method

In this communication, we report the effect of different surfactants [cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and sodium bis(2-ethylhexyl)sulfosuccinate (AOT)] on the shape, growth and photoluminescence (PL) behavior of manganese tungstate (MnWO4) crystals synthesized by the microwave-hydrothermal (MH) method at 413 K for 45 min. These crystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and PL measurements. XRD patterns proved that these crystals have a monoclinic structure. FE-SEM images showed that MnWO4 crystals exhibit different shapes and growth mechanisms depending on the surfactant employed. The CTAB cationic surfactant promotes the hindrance of small nuclei that leads to the formation of flake-like nanocrystals, while SDS and AOT anionic surfactants promote a growth of crystals to plate-like and leaf-like crystals due to considerable size effect of counter-ions (RSO4- and RSO2O-) and an increase in Na+ ion remnants. UV-vis absorption spectroscopy revealed different optical band gap values due to modifications in the shape, surface and crystal size. Finally, the effect of surfactants on the crystal shapes and average crystal size distribution causing changes in the PL behavior of MnWO4 crystals was explained. (C) 2011 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.