CuxS thin films, 80 nm thick, are deposited by vacuum thermal evaporation of sulfur-rich powder mixture, Cu2S:S (50:50 wt.%) with no intentional heating of the substrate. The process of deposition occurs at very low deposition rates (0.1-0.3 nm/s) to avoid the formation of Cu or S-rich films. The evolution of CuxS films surface properties (morphology/roughness) under post deposition mild annealing in air at 270 degrees C and their integration in a thin film transistor (TFT) are the main objectives of this study. Accordingly, Scanning Electron Microscopy studies show CuxS films with different surface morphologies, depending on the post deposition annealing conditions. For the shortest annealing time, the CuxS films look to be constructed of grains with large dimension at the surface (approximately 100 nm) and consequently, irregular shape. For the longest annealing time, films with a fine-grained surface are found, with some randomly distributed large particles bound to this fine-grained surface. Atomic Force Microscopy results indicate an increase of the root-mean-square roughness of CuxS surface with annealing time, from 13.6 up to 37.4 nm, for 255 and 345 s, respectively. The preliminary integration of CuxS films in a TFT bottom-gate type structure allowed the study of the feasibility and compatibility of this material with the remaining stages of a TFT fabrication as well as the determination of the p-type characteristic of the CuxS material. (c) 2013 Elsevier B.V. All rights reserved.

In order to gain insights into the interplay between Cu(I) and Cu(II) in sulfur-rich protein environments, the first preparation and characterization of copper-substituted forms of the wild-type rubredoxin (Rd) from Desulfovibrio vulgaris Hildenborough are reported, as well as those of its variant C42A-Rd. The initial products appear to be tetrahedral Cu(I)(S-Cys)n species for the wild type (n=4) and the variant C42A (n=3, with an additional unidentified ligand). These species are unstable to aerial oxidation to products, whose properties are consistent with square planar Cu(II)(S-Cys)n species. These Cu(II) intermediates are susceptible to auto-reduction by ligand S-Cys to produce stable Cu(I) final products. The original Cu(I) center in the wild-type system can be regenerated by reduction, suggesting that the active site can accommodate Cu(I)(S-Cys)2 and Cys-S-S-Cys fragments in the final product. The absence of one S-Cys ligand prevents similar regeneration in the C42A-Rd system. These results emphasize the redox instability of Cu(II)-(S-Cys)n centers.

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Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the {[}1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

The non-avian saurischians that have associated eggshells and embryos are represented only by the sauropodomorph Massospondylus and Coelurosauria (derived theropods), thus missing the basal theropod representatives. We report a dinosaur clutch containing several crushed eggs and embryonic material ascribed to the megalosaurid theropod Torvosaurus. It represents the first associated eggshells and embryos of megalosauroids, thus filling an important phylogenetic gap between two distantly related groups of saurischians. These fossils represent the only unequivocal basal theropod embryos found to date. The assemblage was found in early Tithonian fluvial overbank deposits of the Lourinhã Formation in West Portugal. The morphological, microstructural and chemical characterization results of the eggshell fragments indicate very mild diagenesis. Furthermore, these fossils allow unambiguous association of basal theropod osteology with a specific and unique new eggshell morphology.