Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

Qualidade da Dieta Selecionada por Bovinos na Sub-Região da Nhecolândia, Pantanal

Objetivou-se com o estudo determinar o valor nutritivo da dieta selecionada por vacas de cria, numa área característica da sub-região da Nhecolândia, Pantanal, durante dois anos hidrológicos (outubro de 1997 a setembro de 1999). Mensalmente foram colhidas manualmente amostras das partes das principais forrageiras selecionadas por bovinos, identificadas por meio de observação direta, para análise de proteína bruta (PB), fibra em detergente neutro (FDN), fibra em detergente ácido (FDA) e lignina (LIG). A digestibilidade da matéria orgânica (DMO) da dieta foi avaliada em amostras fecais com o uso da espectrofotometria de reflectância no infravermelho proximal (NIRS). Houve efeito interativo de ano e época para todos os constituintes químicos analisados na dieta. O valor nutritivo da dieta selecionada por bovinos diminuiu no período de abril a junho, em ambos os anos estudados. As vacas apresentaram uma melhor condição corporal de setembro a março do ano hidrológico 1998/99, no qual a dieta apresentou valores médios de 60,4% de digestibilidade, 10% de PB; 40,20% de FDA; 71% de FDN e 6,0% de lignina, considerada adequada para obtenção de um desempenho reprodutivo satisfatório. Portanto, o valor nutritivo da dieta selecionada por bovinos na sub-região da Nhecolândia depende especialmente da intensidade e distribuição das chuvas, responsáveis pela maior ou menor presença de água nas unidades mais baixas, que possuem forrageiras de melhor qualidade.

Increased Viability of Odontoblast-Like Cells Subjected to Low-Level Laser Irradiation

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

Effect of low-level laser irradiation on odontoblast-like cells

Low-level laser therapy (LLLT), also referred to as therapeutic laser, has been recommended for a wide array of clinical procedures, among which the treatment of dentinal hypersensitivity. However, the mechanism that guides this process remains unknown. Therefore, the objective of this study was to evaluate in vitro the effects of LLL irradiation on cell metabolism (MTT assay), alkaline phosphatase (ALP) expression and total protein synthesis. The expression of genes that encode for collagen type-1 (Col-1) and fibronectin (FN) was analyzed by RT-PCR. For such purposes, oclontoblast-like cell line (MDPC-23) was previously cultured in Petri dishes (15000 cells/cm(2)) and submitted to stress conditions during 12 h. Thereafter, 6 applications with a monochromatic near infrared radiation (GaAlAs) set at predetermined parameters were performed at 12-h intervals. Non-irradiated cells served as a control group. Neither the MTT values nor the total protein levels of the irradiated group differed significantly from those of the control group (Mann-Whitney test; p > 0.05). on the other hand, the irradiated cells showed a decrease in ALP activity (Mann-Whitney test; p < 0.05). RT-PCR results demonstrated a trend to a specific reduction in gene expression after cell irradiation, though not significant statistically (Mann-Whitney test; p > 0.05). It may be concluded that, under the tested conditions, the LLLT parameters used in the present study did not influence cell metabolism, but reduced slightly the expression of some specific proteins.

In vitro effect of low-level laser on odontoblast-like cells

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

Effects of Different Swimming Exercise Intensities on Bone Tissue Composition in Mice: A Raman Spectroscopy Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Color tunability of intense upconversion emission from Er3+-Yb3+ co-doped SiO2-Ta2O5 glass ceramic planar waveguides

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

Redox Behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO(3) with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.

Thermal, structural and optical properties of new tungsten lead-pyrophosphate glasses

Crystalline lead-pyrophosphate precursor was prepared in aqueous solution from lead nitrate and phosphoric acid and characterized by X-ray diffraction, thermogravimetry and Raman scattering. This crystalline lead-phosphate was then used to prepare glass samples in the binary system Pb(2)P(2)O(7)-WO(3). Dependence of WO(3) content on thermal, structural and optical properties were investigated by thermal analysis (DSC), Raman spectroscopy, UV-visible and near-infrared absorption and M-Line technique to access refractive index values. Incorporation of WO(3) in the lead-pyrophosphate matrix enhances the glass transition temperature and thermal stability against devitrification, favors formation of P-O-W bonds and WO(6) clusters. In addition, optical properties are strongly modified with a redshift of the optical bandgap with WO(3) incorporation as well as an increase of the refractive index from 1.89 to 2.05 in the visible. (C) 2011 Elsevier B.V. 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.

Electrosynthesis of binuclear ruthenium complexes from [RuCl3(dppb)(L)] precursors [L = pyridine, 4-methylpyridine or dimethyl sulfoxide; dppb=1,4-bis(diphenylphosphino)butane]

Electrolysis has been examined as a method of synthesis for [(L)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] complexes, where dppb = 1,4-bis(diphenylphosphino)butane and L = pyridine (py), 4-methylpyridine (4-pic) or dimethyl sulfoxide (DMSO), by using [RuCl3(dppb)(L)] as precursors. The products of the electrolysis were characterized by P-31-{H-1} NMR, cyclic voltammetry and near infrared spectroscopy. The presence of the [Ru2Cl5(dppb)(2)] complex in the electrochemical cell suggests a mechanism by which the starting original species from the bulk solution reacts with the reduced form [RuCl2(dppb)(L)] generated at the surface of the electrode. The crystal structure of the precursor mer-[RuCl3(dppb)(4-pic)] was determined by X-ray diffraction.

Spectral redistribution of waveguided emission in BEH-PPV films

We report on spectral redistribution of the photoluminescence (PL) emission from the edge of thin-film planar waveguides of the conjugated polymer BEH-PPV [Poly(2,5-bis(2'-ethyl-hexyl)-1,4-phenylenevinylene] induced by self-absorption in the polymer film. The PL spectra present drastic changes and displace to longer wavelengths with increasing self-absorption. We observe an enhancement of the absolute PL intensity at longer wavelengths, which was interpreted as due to re-emission of self-absorbed photons. The significant efficiency for the PL re-emission suggests the use of self-absorption as a mechanism for tuning the emission into the near infrared.

Influence of the common varistor dopants (CoO, Cr2O3 and Nb2O5) on the structural properties of SnO2 ceramics

The influence of dopants commonly used in SnO2 varistor ceramics, such as CoO, Cr2O3 or Nb2O5, on the structural properties of SnO2 was investigated. Several SnO2-based ceramics containing only one of the dopants were prepared and characterized. Spectroscopic investigations [visible, near infrared (IR) and IR region] were performed to obtain information about dopants valence states inside the ceramics, as well as about their influence on electronic structure of the material. Structural properties were investigated by X-ray diffraction analysis and mechanisms of dopant incorporation were proposed. Obtained results were confirmed with results of the electrical measurements. Microstructural changes in doped ceramics were investigated by scanning electron microscopy (SEM) analysis that showed great differences in densities, grain size, and morphology of the SnO2 ceramics depending on type of dopants and their distribution. (C) 2004 Published by Elsevier B.V.

Drude's model calculation rule on electrical transport in Sb-doped SnO2 thin films, deposited via sol-gel

The evaluation of free carrier concentration based on Drude's theory can be performed by the use of optical transmittance in the range 800-2000 nm (near infrared) for Sb-doped SnO2 thin films. In this article, we estimate the free carrier concentration for these films, which are deposited via sol-gel dip-coating. At approximately 900 mn, there is a separation among transmittance curves of doped and undoped samples. The plasma resonance phenomena approach leads to free carrier concentration of about 5 x 1020 cm(-3). The increase in the Sb concentration increases the film conductivity; however, the magnitude of measured resistivity is still very high. The only way to combine such a high free carrier concentration with a rather low conductivity is to have a very low mobility. It becomes possible when the crystallite dimensions are taken into account. We obtain grains with 5 nm of average size by estimating the grain size from X-ray diffraction data, and by using line broadening in the diffraction pattern. The low conductivity is due to very intense scattering at the grain boundary, which is created by the presence of a large amount of nanoscopic crystallites. Such a result is in accordance with X-ray photoemission spectroscopy data that pointed to Sb incorporation proportional to the free electron concentration, evaluated according to Drude's model. (c) 2006 Elsevier Ltd. All rights reserved.

MAGNETOOPTICAL PROPERTIES OF F-2(+) CENTER IN KCL-SH-

The magnetic circular dichroism (MCD) of F2+ centers in KCl:SH- has been measured in absorption in the 1ssigma(g) --> 2p(y)pi(u) transitions at 493 and 509 nm, with fields up to 5 T and in the temperature range 1.5 K < T < 77 K. Within the limit of detection, no MCD is observed in the near infrared transition 1ssigma(g) --> 2psigma(u) as well as in both emissions 2ppi(u) --> 1ssigma(g) and 2psigma(u) --> 1ssigma(g). The optical detection of EPR in the F2+ ground state presents an isotropic single band with g = 1.965 +/- 0.007. The spin-lattice relaxation measured at H = 0.32 T is typical of a direct process T-1 = 4.3 x 10(-2_ coth (gmu(B)H/2k(B)T). The spectral variation of the MCD is calculated using perturbation theory to first order. The Hamiltonian includes the spin-orbit interaction in the 2ppi(u) excited state and the orbital molecular wave functions are obtained by a linear combination of 1s and 2p atomic orbitals. The calculated MCD is in good agreement with the observed one, for the spin-orbit interaction strength Pound(z) = 3.6 meV.