In this work, we investigate structural and optical properties of metalorganic chemical vapor deposition grown wurtzite InxGa1−xN/GaN epitaxial layers with thicknesses that are close to the critical layer thickness (CLT) for strain relaxation. CLT for InxGa1−xN/GaN structures was calculated as a function of the InN content, x, using the energy balance model proposed by People and Bean [Appl. Phys. Lett. 47, 322 (1985)]. Experimentally determined CLT are in good agreement with these calculations. The occurrence of discontinuous strain relaxation (DSR), when the CLT is exceeded, is revealed in the case of a 120 nm thick In0.19Ga0.89N layer by x-ray reciprocal space mapping of an asymmetrical reflection. The effect of DSR on the luminescence of this layer is clear: The luminescence spectrum shows two peaks centered at ∼2.50 and ∼2.67 eV, respectively. These two components of the luminescence of the sample originate in regions of different strain, as discriminated by depth-resolving cathodoluminescence spectroscopy. DSR leads directly to the emergence of the second, lower-energy, peak. Based on this experimental evidence, it is argued that the appearance of luminescence doublets in InGaN is not evidence of “quantum dotlike In-rich” or “phase separated” regions, as commonly proposed
The behavior of the A1(LO) phonon mode of relaxed and pseudomorphic InxGa1−xN epilayers, at the surface, is investigated by Raman spectroscopy. This study involves relaxed and pseudomorphic samples, with a compositional range of 0.12⩽x<0.30 and 0.04<x⩽0.20, respectively. Raman measurements were performed under excitation at 3.71 eV. Due to the low depth penetration of the incident light (40 nm), the major contribution to Raman scattering comes from the surface, where strain and composition have been independently determined. For relaxed samples, a linear dependence of the A1(LO) phonon frequency is obtained, as theoretically expected for an one-mode behavior alloy: Ω0(x)=(736±1)-(149±2)x. In the case of pseudomorphic samples, the phonon frequency is almost composition independent up to x=0.11, probably due to the opposite effects of strain and alloying.
The concentrations of total and proportions of organic mercury were measured in tissues of 355 individuals of 8 species of Southern Ocean squid (Alluroteuthis antarcticus, Bathyteuthis abyssicola, Filippovia knipovitchi, Galiteuthis glacialis, Gonatus antarcticus, Kondakovia longimana, Psychroteuthis glacialis and Slosarczykovia circumantarctica). Squid were caught around South Georgia (Scotia Sea) during 5 cruises, between the austral summers of 2006/07 to 2016/17 to evaluate temporal changes in bioaccumulation and tissue partitioning. Total mercury concentrations varied between 4 ng g-1 and 804 ng g-1 among all tissues. Net accumulation of mercury in muscle with size was observed in A. antarcticus, B. abyssicola and P. glacialis, but no relationship was found for S. circumantarctica and lower concentrations were observed in larger individuals of G. glacialis. Muscle tissues had the highest mercury concentrations in the majority of species, except for F. knipovitchi for which the digestive gland contained highest concentrations. In terms of the percentage of organic mercury relative to total mercury in tissues, muscle always contained the highest values (67% to 97%), followed by the digestive gland (22% to 38%). Lowest organic mercury percentages were found consistently in the gills (9% to 19%), suggesting only low levels of incorporation through the dissolved pathway and/or a limited redistribution of dietary organic mercury towards this tissue. Overall, results are indicative of a decreasing trend of mercury concentrations in the majority of analysed species over the last decade. As cephalopods are an important Southern Ocean trophic link between primary consumers and top predators, these changes suggest decreasing mercury levels in lower trophic levels (i.e. squid prey) and an alleviation of the mercury burden on higher predators that consume squid.
Recently, anthropogenic enrichment of rare earth elements (REE) have been reported in natural environments, due to increasing use and discharges of hospital/industrial wastewaters. Gadolinium (Gd), which is mainly used as contrast agent for magnetic resonance imaging in medical exams, may reach concentrations in water up to two orders of magnitude larger than baseline levels. Nevertheless, in marine systems scarce information is available concerning the toxicity of REE towards inhabiting organisms. This study aimed to evaluate the biochemical impact of anthropogenic Gd in the Mediterranean mussel Mytilus galloprovincialis, which is a species of commercial interest and one of the most accepted pollution bioindicator. Organisms were exposed to different concentrations of Gd (0, 15, 30, 60, 120 µg/L) for 28 days. At the end of the experiments, biomarkers related to mussels' metabolic (electron transport system activity and energy reserves content), oxidative stress status (cellular damage and the activity of antioxidant and biotransformation enzymes) and neurotoxic effects (activity of the enzyme Acetylcholinesterase) were measured, as well as Gd bioconcentration in organisms. Results showed a high content of Gd (2.5±0.50 µg/g) in mussels exposed to the highest concentration, contrary to those at control condition and at 15 and 30 μg/L of Gd (levels below 0.38 µg/g). Although no mortality was observed during the experimental period, exposure to Gd strongly affected the biochemical performance of M. galloprovincialis, including the decrease on mussels' metabolism, induction of oxidative stress and neurotoxicity, particularly evidenced at intermediate concentrations. These results may indicate that up to certain stressful levels, although lowering their metabolism, organisms may be able to activate defense strategies to avoid cellular injuries which, on the other hand, may compromise mussels physiological performance such as growth and reproduction success. Nevertheless, our findings support that the widespread utilization of Gd may represent an environmental risk in the future.
Diamond-coated steel is considered an important issue in synthetic diamond technology due to the great economical importance of enhancing the wear resistance and surface hardness of commercial Fe-based alloys. However, direct diamond coating by chemical vapour deposition (CVD) is rather problematic-adhesion and growth are seriously affected. The use of interlayers is a common approach to minimise these problems. This work reports an investigation on the establishment of good nucleation and growth conditions of diamond films by microwave plasma CVD (MPCVD) on ferrous substrates coated with Ti and Cr interlayers. Commercial grade ferrous substrates were pre-coated with commercial interlayers by sputtering (Ti, Cr) and electroplating (Cr) techniques. Steel substrates led to better results than iron cast substrates. The best films were obtained on Ti pre-coated steel substrate. The results on Cr interlayers pointed to the advantage of electroplating over the physical vapour deposition (PVD) sputtering. From the two selected parameter sets for diamond deposition, the one using lower power level conducted to the best results. Initial roughness and growth parameters were found to counteract on the uniformity of the diamond films. The morphology was studied by scanning electron microscopy (SEM), the roughness was estimated by profilometry, while diamond quality and stress state were evaluated by m-Raman spectroscopy. ᮊ
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