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]

Structural refinement, growth process, photoluminescence and photocatalytic properties of (Ba1-xPr2x/3)WO4 crystals synthesized by the coprecipitation method

Barium praseodymium tungstate (Ba1-xPr2x/3)WO4 crystals with (x = 0, 0.01, and 0.02) were prepared by the coprecipitation method. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier-transform Raman (FT-Raman) and Fourier-transform infrared (FT-IR) spectroscopies. The shape and size of these crystals were observed by field emission scanning electron microcopy (FE-SEM). Their optical properties were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. Moreover, we have studied the photocatalytic (PC) activity of crystals for degradation of rhodamine B (RhB) dye. XRD patterns, Rietveld refinements data, FT-Raman and FT-IR spectroscopies indicate that all crystals exhibit a tetragonal structure without deleterious phases. FT-Raman spectra exhibited 13 Raman-active modes in a range from 50 to 1000 cm(-1), while FT-IR spectra have 8 infrared active modes in a range from 200 to 1050 cm(-1). FE-SEM images showed different shapes (bonbon-, spindle-, rice-and flake-like) as well as a reduction in the crystal size with an increase in Pr3+ ions. A possible growth process was proposed for these crystals. UV-vis absorption measurements revealed a decrease in optical band gap values with an increase of Pr3+ into the matrix. An intense green PL emission was noted for (Ba1-xPr2x/3)WO4 crystals (x = 0), while crystals with (x = 0.01 and 0.02) produced a reduction in the wide band PL emission and the narrow band PL emission which is related to f-f transitions from Pr3+ ions. High photocatalytic efficiency was verified for the bonbon-like BaWO4 crystals as a catalyst in the degradation of the RhB dye after 25 min under UV-light. Finally, we discuss possible mechanisms for PL and PC properties of these crystals.

K-41(n, gamma)K-42 thermal and resonance integral cross section measurements

We measured the K-41 thermal neutron absorption and resonance integral cross sections after the irradiation of KNO3 samples near the core of the IEA-R1 IPEN pool-type research reactor. Bare and cadmium-covered targets were irradiated in pairs with Au-Al alloy flux-monitors. The residual activities were measured by gamma-ray spectroscopy with a HPGe detector, with special care to avoid the K-42 decay beta(-) emission effects on the spectra. The gamma-ray self-absorption was corrected with the help of MCNP simulations. We applied the Westcott formalism in the average neutron flux determination and calculated the depression coefficients for thermal and epithermal neutrons due to the sample thickness with analytical approximations. We obtained 1.57(4) and 1.02(4) b, for thermal and resonance integral cross sections, respectively, with correlation coefficient equal to 0.39.

Aerosols in Amazonia: Natural Biogenic Particles and Large Scale Biomass Burning Impacts.

The Large Scale Biosphere Atmosphere Experiment in Amazonia (LBA) is a long term (20 years) research effort aimed at the understanding of the functioning of the Amazonian ecosystem. In particular, the strong biosphere-atmosphere interaction is a key component looking at the exchange processes between vegetation and the atmosphere, focusing on aerosol particles. Two aerosol components are the most visible: The natural biogenic emissions of aerosols and VOCs, and the biomass burning emissions. A large effort was done to characterize natural biogenic aerosols that showed detailed organic characterization and optical properties. The biomass burning component in Amazonia is important in term of aerosol and trace gases emissions, with deforestation rates decreasing, from 27,000 Km2 in 2004 to about 5,000 Km2 in 2011. Biomass burning emissions in Amazonia increases concentrations of aerosol particles, CO, ozone and other species, and also change the surface radiation balance in a significant way. Long term monitoring of aerosols and trace gases were performed in two sites: a background site in Central Amazonia, 55 Km North of Manaus (called ZF2 ecological reservation) and a monitoring station in Porto Velho, Rondonia state, a site heavily impacted by biomass burning smoke. Several instruments were operated to measured aerosol size distribution, optical properties (absorption and scattering at several wavelengths), composition of organic (OC/EC) and inorganic components among other measurements. AERONET and MODIS measurements from 5 long term sites show a large year-to year variability due to climatic and socio-economic issues. Aerosol optical depths of more than 4 at 550nm was observed frequently over biomass burning areas. In the pristine Amazonian atmosphere, aerosol scattering coefficients ranged between 1 and 200 Mm-1 at 450 nm, while absorption ranged between 1 and 20 Mm-1 at 637 nm. A strong seasonal behavior was observed, with greater aerosol loadings during the dry season (Jul-Nov) as compared to the wet season (Dec-Jun). During the wet season in Manaus, aerosol scattering (450 nm) and absorption (637 nm) coefficients averaged, respectively, 14 and 0.9 Mm-1. Angstrom exponents for scattering were lower during the wet season (1.6) in comparison to the dry season (1.9), which is consistent with the shift from biomass burning aerosols, predominant in the fine mode, to biogenic aerosols, predominant in the coarse mode. Single scattering albedo, calculated at 637 nm, did not show a significant seasonal variation, averaging 0.86. In Porto Velho, even in the wet season it was possible to observe an impact from anthropogenic aerosol. Black Carbon was measured at a high 20 ug/m³ in the dry season, showing strong aerosol absorption. This work presents a general description of the aerosol optical properties in Amazonia, both during the Amazonian wet and dry seasons.

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.

Effect of a polymeric protective coating on optical and electrical properties of poly (p-phenylene vinylene) derivatives

The resistance to photodegradation of poly [(2-methoxy-5-n-hexyloxy)-p-phenylene vinylene] (OC1OC6-PPV) films was significantly enhanced by the use of poly(vinyl alcohol) 99% hydrolyzed as protective coating. The deposition of poly(vinyl alcohol) onto OC1OC6-PPV films did not affect the absorption and the emission spectra of the luminescent polymer. The protected film showed 5% drop on the absorbance at 500nm after 270 hours of light exposure while the unprotected film completely degraded in the same conditions. The conductivity of the protected film remained stable (around 7 × 10-10 S/m) while the value for the unprotected one dropped around two orders of magnitude after 100 hours of light exposure.