Optical energy storage properties of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr(2)MgSi(2)O(7):Eu(2+),R(3+) material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 A degrees C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R(3+) co-dopants.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.

Optical and dielectric relaxor behaviour of Ba(Zr(0.25)Ti(0.75))O(3) ceramic explained by means of distorted clusters

In this work, Ba(Zr(0.25)Ti(0.75))O(3) ceramic was prepared by solid-state reaction. This material was characterized by x-ray diffraction and Fourier transform Raman spectroscopy. The temperature dependent dielectric properties were investigated in the frequency range from 1 kHz to 1 MHz. The dielectric measurements indicated a diffuse phase transition. The broadening of the dielectric permittivity in the frequency range as well as its shifting at higher temperatures indicated a relaxor-like behaviour for this material. The diffusivity and the relaxation strength were estimated using the modified Curie-Weiss law. The optical properties were analysed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements at room temperature. The UV-vis spectrum indicated that the Ba(Zr(0.25)Ti(0.75))O(3) ceramic has an optical band gap of 2.98 eV. A blue PL emission was observed for this compound when excited with 350 nm wavelength. The polarity as well as the PL property of this material was attributed to the presence of polar [TiO(6)] distorted clusters into a globally cubic matrix.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Effects of torsional disorder on poly-para-phenylene

We study the effect of thermal disorder on the electronic structure of one-dimensional poly-para-phenylene (PPP). In a real chain the torsion angles between rings are bound to be distributed over a range of values, which depend on temperature, and thus the chain is intrinsically disordered. In this study we simulated this kind of thermally induced off-diagonal disorder through the simple Huckel method. We base our Hamiltonian on ab initio results for the effect of temperature on torsion angles, and the effect of torsion angles on the energy gap. We analyze the electronic structure of 200-monomer-long chains focusing on the density of states, and the associated localization character (measured by the inverse participation ratio). Our results contrast with the usually assumed Gaussian-shaped density of localized states for disordered systems. (C) 2009 Elsevier B.V. All rights reserved.

A new processing method of CaZn(2)(OH)(6)center dot 2H(2)O powders: Photoluminescence and growth mechanism

In this communication, we report on the formation of calcium hexahydroxodizincate dehydrate, CaZn(2)(OH)(6)center dot 2H(2)O (CZO) powders under microwave-hydrothermal (MH) conditions. These powders were analyzed by X-ray diffraction (XRD), Field-emission gum scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns confirmed that the pure CZO phase was obtained after MH processing performed at 130 degrees C for 2 h. FEG-SEM micrographs indicated that the morphological modifications as well as the growth of CZO microparticles are governed by Ostwald-ripening and coalescence mechanisms. UV-vis spectra showed that this material have an indirect optical band gap. The pure CZO powders exhibited an yellow PL emission when excited by 350 nm wavelength at room temperature. (C) 2009 Elsevier Masson SAS. All rights reserved.

Photoswitches and Luminescent Rigidity Sensors Based on fac-[Re(CO)(3)(Me(4)phen)(L)](+)

The fac-[Re(CO)(3)(Me(4)phen)(trans-L)](+) complexes, Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline and L = 4-styrylpyridine, stpy, or 1,2-bis(4-pyridyl)ethylene, bpe, were synthesized and characterized by their spectroscopic, photochemical, and photophysical properties. The complexes exhibit trans-to-cis isomerization upon 313, 334, 365, and 404 nm irradiation, and the true quantum yields can be efficiently determined by absorption changes combined with (1)H NMR data. For fac-[Re(CO)(3)(Me(4)phen)(trans-bpe)](+) similar quantum yields were determined at all wavelengths investigated. However, a lower value (phi(true) = 0.35) was determined for fac-[Re(CO)(3)(Me(4)phen)(trans-stpy)](+) at 404 nm irradiation, which indicates different pathways for the photoisomerization process. The photoproducts, fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+), exhibit luminescence at room temperature with two maxima ascribed to the (3)IL(Me4phen) and (3)MLCT(Re -> Me4phen) excited states. The luminescence properties were investigated in different media, and the behavior in glassy EPA at 77 K showed that the contribution of each emissive state is dependent on the excitation wavelength. The photochemical and photophysical behavior of the complexes were rationalized in terms of the energy gap of excited states and can be exploited in photoswitchable luminescent rigidity sensors.

Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Electrodeposition and characterization of thin selenium films modified with lead ad-atoms

The deposition and characterization of Se films doped with Pb underpotentially deposited (UPD) ad-atoms was studied in this work. The employed experimental techniques were cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, UV-vis spectroscopy and atomic force microscopy. The initial deposition of Se film by chronoamperometry yielded a thin film composed of approximately 700 layers. The Pb UPD on Se was achieved by chronoamperometry in a potential value previously determined in voltammetric experiments. This deposition yielded a deposition charge of approximately 7.5% of the total one. The film resistance altered from 320 Omega cm(2) for Se to 65 Omega cm(2) for the Se/Pb one. Flat band potential values and number of acceptors and donors were also calculated for both films and the values obtained were + 0.95 and -0.51 V for Se and Se/Pb, respectively. The Se coating presented 1.2 x 10(17) cm(3) acceptors while the Se/Pb one presented 3.2 x 10(17) cm(3) donors. The band gap values for both films were 2.4 eV and 1.9 eV, correspondingly. (C) 2008 Elsevier B.V. All rights reserved.

MAGNETIC FIELD INDUCED NEAR-BAND-GAP OPTICAL PROPERTIES IN EuTe LAYERS

The magnetic response of the near-band-edge optical properties is studied in EuTe layers. In several magneto-optical experiments, the absorption and emission are described as well as the related Stokes shift. Specifically, we present the first experimental report of the photoluminescence excitation (PLE) spectrum in Faraday configuration. The PLE spectra shows to be related with the absorption spectra through the observation of resonance between the excitation light and the zero-field band-gap. A new emission line appears at 1.6 eV at a moderate magnetic field in the photoluminescence (PL) spectra. Furthermore, we examine the absorption and PL red-shift induced by the magnetic field in the light of the d-f exchange interaction energy involved in these processes. Whereas the absorption red-shift shows a quadratic dependence on the field, the PL red-shift shows a linear dependence which is explained by spin relaxation of the excited state.

Electrical, optical, and structural studies of shallow-buried Au-polymethylmethacrylate composite films formed by very low energy ion implantation

The authors present here a summary of their investigations of ultrathin films formed by gold nanoclusters embedded in polymethylmethacrylate polymer. The clusters are formed from the self-organization of subplantated gold ions in the polymer. The source of the low energy ion stream used for the subplantation is a unidirectionally drifting gold plasma created by a magnetically filtered vacuum arc plasma gun. The material properties change according to subplantation dose, including nanocluster sizes and agglomeration state and, consequently also the material electrical behavior and optical activity. They have investigated the composite experimentally and by computer simulation in order to better understand the self-organization and the properties of the material. They present here the results of conductivity measurements and percolation behavior, dynamic TRIM simulations, surface plasmon resonance activity, transmission electron microscopy, small angle x-ray scattering, atomic force microscopy, and scanning tunneling microscopy. (C) 2010 American Vacuum Society [DOI: 10.1116/1.3357287]

Ab initio study of the electronic and optical properties of sillimanite (Al(2)SiO(5)) crystal

Ab initio calculations based on the density functional theory (DFT) are used to investigate the electronic and optical properties of sillimanite. The geometrical parameters of the unit cell, which contain 32 atoms, have been fully optimized and are in good agreement with the experimental data. The electronic structure shows that sillimanite has an indirect band gap of 5.18 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of sillimanite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s, Si-3s states play the major role in optical transitions as initial and final states, respectively. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical investigation of electronic and optical properties of andalusite within density functional theory

The electronic and optical properties of andalusite were studied by using quantum-mechanical calculations based on the density functional theory (DFT). The electronic structure shows that andalusite has a direct band gap of 5.01 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of andalusite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s states play a major role in optical transitions as initial and final states, respectively. (C) 2010 Elsevier Ltd. All rights reserved.