Al3+ environments in nanostructured ZnAl2O4 and their effects on the luminescence properties

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

SnO2 nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The role of the Eu3+ ions in structure and photoluminescence properties of SrBi2Nb2O9 powders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis, characterization and photophysical properties of Eu3+ doped in BaMoO4

In this work Ba0.99Eu0.01MoO4 (BEMO) powders were prepared by the first time by the Complex Polymerization Method. The structural and optical properties of the BEMO powders were characterized by Fourier Transform Infra-Red (FTIR), X-ray Diffraction (XRD), Raman Spectra, High-Resolution Scanning Electron Microscopy (HR-SEM) and Photoluminescent Measurements. XRD show a crystalline scheelite-type phase after the heat treatment at temperatures greater than 400 degrees C. The ionic radius of Eu3+ (0.109 nm) is lower than the Ba2+ (0.149 nm) one. This difference is responsible for the decrease in the lattice parameters of the BEMO compared to the pure BaMoO4 matrix. This little difference in the lattice parameters show that Eu3+ is expected to occupy the Ba2+ site at different temperatures, stayed the tetragonal (S-4) symmetry characteristic of scheelite-type crystalline structures of BaMoO4. The emission spectra of the samples, when excited at 394 nm, presented the D-5(1)-> F-7(0, 1 and 2) and D-5(0)-> F-7(0, 1, 2, 3 and 4) Eu3+ transitions at 523, 533, 554, 578, 589, 614, 652 and 699 nm, respectively. The emission spectra of the powders heat-treated at 800 and 900 degrees C showed a marked increase in its intensities compared to the materials heat-treated from 400 to 700 C. The decay times for the sample were evaluated and all of them presented the average value of 0.61 ms. Eu3+ luminescence decay time follows one exponential curve indicating the presence of only one type of Eu3+ symmetry site.

Structural and optical properties of GdAlO3:RE3+ (RE = Eu or Tb) prepared by the Pechini method for application as X-ray phosphors

In this work, GdAlO3:RE3+ (RE = Eu or Tb) was successfully prepared by the Pechini method at lower temperatures when compared to others methods as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. The differential thermal analysis (DTA) shows a crystallization peak at 850 degrees C. The samples are composed by monocrystalline particles (50-120 nm) exhibiting the formation of aggregates among them, which indicates the beginning of the sinterization process. This feature indicates a strong tendency to the formation of aggregates, which is a suitable ability for the close-packing of particles, and hence a potential application in X-ray intensifying screens. Luminescence measurements indicate Gd3+ -> RE3+ energy transfer. The Eu3+ emission spectra exhibit all the characteristics D-5(0) -> F-7(j) transitions and the observed profile suggests that RE3+ ions occupy at least one site without center of symmetry. For terbium-doped samples, the D-5(3) -> F-7(j) (blue emission) and D-5(4) -> F-7(j) (green emission) transitions were observed and the ratio between them may depend on the Tb3+ content due to cross-relaxation processes. (C) 2009 Elsevier B.V. All rights reserved.

New phosphinate ligand synthesis and its effect on optical properties of the europium beta-diketonate complex

The synthesis and characterization of a new organic ligand monooctyldiphenylphosphinate (L) is described, as well as a new Eu(3+) diketonate complex [Eu(tta)(3)(L)(2)] (tta = thenoyltrifluoracetone). The ligand (L) was formed by substitution reaction (80% yield) and characterized by uni- and bidimensional (1)H, (13)C and (31)P NMR experiments, to confirm its molecular structure. The coordination of (L) to Eu(3+) in the complex [Eu(tta)(3)(L)(2)] was confirmed by FT-IR spectra. The emission spectra present the same profile when excited in Eu(3+) or in the ligands, suggesting an energy transfer from ligands to Eu(3+) ions. The emission spectra of the precursor [Eu(tta)(3)(H(2)O)(2)], and [Eu(tta)(3)(L(2))] present bands arising from f-f intra-configurational transitions. The only (5)D(0)-(7)F(0) transition shows the presence of at least one site without symmetry center. The FWHM of such transition is 7 cm(-1) and 57 cm(-1) for [Eu(tta)(3)(H(2)O)(2)] and [Eu(tta)(3)(L)(2)] complexes, respectively. This widening is provided by the presence of large groups around Eu(3+) ion. The calculated intensity parameters Omega(2) and Omega(4) show that the interaction features between center-ion and ligand are different; the small value of Omega(4) is related to long range effects of alkyl chain. The Langmuir isotherms of this ligand and complex have been investigated although their hydrolysis in water subphase does not allow stable monolayers. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Visible and near-infrared luminescent Eu3+ or Er3+ doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

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

Luminescent properties and lattice defects correlation on zinc oxide

The ZnO luminescent properties are strongly influenced by the preparation method and they are principally related to electronic and crystalline structures. This work reports about the correlation among luminescence properties of ZnO, obtained from zinc hydroxycarbonate, and crystalline lattice defects, microstrain, as function of thermal treatment. The crystallite size increase and the qualitative microstrain, obtained by Williamson-Hall plots, decrease as function of temperature. The evolution of electronic defects is analyzed by luminescence spectroscopy based on energy of the electronic transitions. From excitation spectrum, it is verified two bands around 377 nm and 405 nm attributed to the transitions between valence-conduction bands and valence band to interstitial zinc level, respectively. The emission spectra of sample treated at 600 degreesC shows large band at 670 nm. However, the green emission around 530 nm is observed for samples treated at 900 degreesC. The intensities of excitation and emission bands are associated with the increase of the electronic defects that depend on the strain lattice decrease. The lowest strain lattice results on the best green luminescent properties of zinc oxide. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Optical spectroscopy and frequency upconversion properties of Tm3+ doped tungstate fluorophosphate glasses

Tungstate fluorophosphate glasses of good optical quality were synthesized by fusion of the components and casting under air atmosphere. The absorption spectra from near-infrared to visible were obtained and the Judd-Ofelt parameters determined from the absorption bands. Transition probabilities, excited state lifetimes and transition branching ratios, were, determined from the measurements. Pumping with a 354.7 nm beam from a pulsed laser. resulted in emission at 450 nm. due to transition D-1(2)-->F-3(4) in Tm3+ ions and a broadband emission centered at approximate to 550 nm attributed to the glass matrix. When pumping at 650 nm, two emission bands at 450 nm (D-1(2)-->F-3(4)) and at 790 nm (H-3(4)-->H-3(6)) were observed. Excitation spectra were also obtained in order to understand the origin of both emissions. Theoretical and experimental lifetimes were determined and,the results were explained in terms of multiphonon relaxation. (C) 2003 American Institute of Physics.

Preparation, characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex

Langmuir-Blodgett (LB) films from a ruthenium complex, mer-[RuCl3(dppb)(py)] (dppb = PPh2(CH2)(4)PPh2; py = pyridine) (Rupy), and from mixtures with varied amounts of polyaniline (PANi) were fabricated. Molecular-level interactions between the two components are investigated by surface potential, dc conductivity and Raman spectroscopy measurements, particularly for the mixed film with 10% of Rupy. For the latter, the better miscibility led to an interaction with Rupy inducing a decrease in the conducting state of PANi, as observed in the Raman spectra and conductivity measurement. The interaction causes the final film properties to depend on the concentration of Rupy, and this was exploited to produce a sensor array made up of sensing units consisting of 11-layer LB films from pure PANi, pure Rupy and mixtures with 10 and 30% of Rupy. It is shown that the combination of only four non-specific sensing units allows one to distinguish the basic tastes detected by biological systems, viz. saltiness, sweetness, sourness and bitterness, at the muM level. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Changes of physical properties of glass surfaces exposed to KNO3 vapors

Modifications of glass surfaces were studied after exposure of samples to an atmosphere resulting from the decomposition of molten KNO3. The diffusion coefficient of K+ ions migrating into the surfaces of float glass and synthesized glasses doped with up to 5 wt% SnO2 was calculated by the Boltzmann-Matano technique. The Vickers hardness and the refractive index increase with exposure time. Infrared spectra show that the migration of K+ is responsible for an increase in the number of non-bridging oxygens in the exposed samples. The spectra of the synthesized glasses present evidences that their surfaces undergo crystallization during the exposure. All results lead to the conclusion that the presence of tin in the glasses hinders the diffusion of K+ ions, thus affecting the Vickers hardness, the refractive index and the infrared spectra. It is shown that the exposure method can be used as an alternative process to promote the K+ migration into glass surfaces. (c) 2006 Elsevier B.V. All rights reserved.

Optical properties and frequency upconversion fluorescence in a Tm3+-doped alkali niobium tellurite glass

Optical spectroscopic properties of Tm3+-doped 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) glass are reported. The absorption spectra were obtained and radiative parameters were determined using the Judd-Ofelt theory. Characteristics of excited states were studied in two sets of experiments. Excitation at 360 nm originates a relatively narrow band emission at 450 nm attributed to transition D-1(2)-->F-3(4) of the Tm3+ ion with photon energy larger than the band-gap energy of the glass matrix. Excitation at 655 nm originates a frequency upconverted emission at 450 nm (D-1(2)-->F-3(4)) and emission at 790 nm (H-3(4)-->H-3(6)). The radiative lifetimes of levels D-1(2) and H-3(4) were measured and the differences between their experimental values and the theoretical predictions are understood as due to the contribution of energy transfer among Tm3+ ions. (C) 2003 American Institute of Physics.

Synthesis of hybrid silicates containing porphyrins incorporated by a sol-gel process and their properties

Porphyrin was incorporated in a silicate network, via a covalent bond, by grafting a functional group with 3-aminopropyltriethoxysilane, using a sol-gel process. We have carried out the synthesis and measured the absorption spectra, nuclear magnetic resonance spectra, infrared (IR) spectra, luminescence spectra and lifetime of these hybrid silicates, porphyrinosilicas. These samples contained the following free-base porphyrins: meso-tetrakis-p-chlorobenzoylporphyrin, meso-tetrakis-2,6-dichloro-3-chlorosulfonylphenylporphyrin. The obtained porphyrinosilicas have similar absorption and luminescence spectra to the free base porphyrins in solution. IR spectra confirm the formation of monomeric species. Lifetime measurement for porphyrinosilica reveals that 32% +/- 2% of porphyrin is covalently bonded to the silica network. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Optical properties and energy transfer processes in (Tm3+, Nd3+) doped tungstate fluorophosphate glass

We investigate the linear optical properties and energy transfer processes in tungstate fluorophosphate glass doped with thulium (Tm3+) and neodymium (Nd3+) ions. The linear absorption spectra from 370 to 3000 nm were obtained. Transitions probabilities, radiative lifetimes, and transition branching ratios were determined using the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] theory. Frequency up-conversion to the blue region and fluorescence in the infrared were observed upon pulsed excitation in the range of 630-700 nm. The excitation spectra of the luminescence were obtained to understand the origin of the signals. The temporal decay of the fluorescence was measured for different concentrations of the doping ions. Energy transfer rates among the Tm3+ and Nd3+ ions were also determined.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.