Influence of hydrogen on the structural stability of annealed ultrathin Si/Ge amorphous layers

Semiconductor structures based on Si and Ge are generally submitted to hydrogenation because H passivates the dangling bonds of Si and Ge. By this way the devices prepared from those semiconductors, e.g., solar cells, have much better electrical properties. However, H stability is still a critical issue. In fact, there is wide evidence that H is very unstable against illumination as well as heat treatment. It has been seen that H out effuses from the samples under such treatments. As this causes unsaturation of the dangling bonds the electrical properties worsen significantly. In this work we will show that in the case of ultrathin Si/Ge amorphous layers the H thermal instability also affects the structural stability even up to the micrometric scale depending on the H content. Such type of structure can also be used to prepare SiGe alloys by mixing the layers with heat treatments. The samples were amorphous multilayers (MLs) of alternating ultrathin (3 nm) layers of Si and Ge deposited by sputtering on (100) oriented Si substrate. The total thickness of the MLs was 300 nm. The samples were hydrogenated by introducing H in the sputter chamber with flow rates varying from 0.8 to 6 ml/min. The MLs underwent different heat treatments, from the one at 350 ?C for 1 h up to the one at 250 ?C for 0.5 h + 450 ?C for 5 h. The samples were analysed by AFM, TEM, energy filtering TEM and Small-Angle X-Ray Diffraction (SAXRD). AFM showed that upon annealing the structure of the samples degrades with formation of surface bumps whose size increases by increasing the annealing temperature and/or time, for the same H content, or by increasing the H content for the same annealing conditions. For high H content and/or annealing conditions AFM showed that the bumps have blown up giving rise to craters. This suggests that H was released from its dangling bonds to Si and Ge and formed H bubbles in the MLs because of the energy supplied by the annealing. Additional energy for the break of the Si-H and Ge-H bonds could be the one supplied by the recombination of thermally generated carriers associated with the band gap fluctuations caused by the not uniform distribution of H in the MLs. The first sites of H accumulation are very likely nanocavities certainly present in the amorphous MLs. By TEM it has been seen that layer intermixing occurred which could be the first step of H bubbles formation. SAXRD measurements as well as TEM energy filtering maps for Si and Ge showed that Si and Ge interdiffusion took place in an asymmetric way as Si was seen to diffuse to the Ge layers whereas Ge did not diffuse to the Si layers. This might be due to the higher density of free dangling bonds in the Ge layers created by annealing because the binding energy of the Ge-H bond is smaller than the one of the Si-H bond

Evolution of nano-pores during annealing of technically pure molybdenum sheet produced from different sintered formats

Molybdenum is a refractory metal with no phase transformation in the solid state and a high melting point. It is therefore an excellent structural material for various high temperature applications. Especially in this field of operation, significant creep resistance is essential. To achieve this, a microstructure with grains in the range of millimeters is desired. However, as demonstrated in the present study, the onset temperature for secondary recrystallization, which would lead to a beneficial grain size, is among other things dependent on the initial dimensions of the sintered part. One possible reason for the different microstructural evolutions is the influence of residual pores in sub-micrometer size. Sheets were thus fabricated via three different production routes employing the same initial Mo powder to exclude chemical variation as an influencing factor. The samples were investigated by in-situ small-angle X-ray scattering at a synchrotron radiation source with two different heating rates. Additionally, selected annealed samples were studied ex-situ with high energy X-rays. The apparent volume fraction of pores is compared to a volatilization model for the vaporization of typical accompanying elements and the induced thermal expansion

Structural Instability of Annealed a-Si/a-Ge Nanostructures

It is shown that heat treatments cause remarkable structural instability in nanostructures made of alternating 3 nm thick hydrogenated layers of a-Si and a-Ge deposited by sputtering. Upon annealing surface bumps form whose size and density increase with increasing H content. They are due to the presence of H bubbles inside the samples, which even blow up for the highest H content. The H bubbles form by accumulation of H2 molecules made possible by the break of the Si-H and Ge-H bonds driven by the energy supplied by the heat treatment and by the recombination of thermally generated carriers

Carbon nanotube dosimetry: from workplace exposure assessment to inhalation toxicology

BACKGROUND: Dosimetry for toxicology studies involving carbon nanotubes (CNT) is challenging because of a lack of detailed occupational exposure assessments. Therefore, exposure assessment findings, measuring the mass concentration of elemental carbon from personal breathing zone (PBZ) samples, from 8 U.S.-based multi-walled CNT (MWCNT) manufacturers and users were extrapolated to results of an inhalation study in mice. RESULTS: Upon analysis, an inhalable elemental carbon mass concentration arithmetic mean of 10.6 μg/m(3) (geometric mean 4.21 μg/m(3)) was found among workers exposed to MWCNT. The concentration equates to a deposited dose of approximately 4.07 μg/d in a human, equivalent to 2 ng/d in the mouse. For MWCNT inhalation, mice were exposed for 19 d with daily depositions of 1970 ng (equivalent to 1000 d of a human exposure; cumulative 76 yr), 197 ng (100 d; 7.6 yr), and 19.7 ng (10 d; 0.76 yr) and harvested at 0, 3, 28, and 84 d post-exposure to assess pulmonary toxicity. The high dose showed cytotoxicity and inflammation that persisted through 84 d after exposure. The middle dose had no polymorphonuclear cell influx with transient cytotoxicity. The low dose was associated with a low grade inflammatory response measured by changes in mRNA expression. Increased inflammatory proteins were present in the lavage fluid at the high and middle dose through 28 d post-exposure. Pathology, including epithelial hyperplasia and peribronchiolar inflammation, was only noted at the high dose. CONCLUSION: These findings showed a limited pulmonary inflammatory potential of MWCNT at levels corresponding to the average inhalable elemental carbon concentrations observed in U.S.-based CNT facilities and estimates suggest considerable years of exposure are necessary for significant pathology to occur at that level

Joint stochastic simulation of petrophysical properties with elastic attributes based on parametric copula models

The spatial stochastic co-simulation method based on copulas is a general method that allows simulating variables with any type of dependency and probability distribution functions. This flexibility comes from the use of a copula model for the representation of the joint probability distribution function. The method has been mainly implemented through a non-parametric approach using Bernstein copulas and has been successfully applied for the simulation of petrophysical properties using elastic seismic attributes as secondary variables. In the present work this method is implemented through two other approaches: parametric and semi-parametric. Specifically, for the parametric approach the family of Archimedean copulas is used. First, the parametric approach is validated against a published case, and then a comparison of the three approaches in terms of accuracy and performance is made. The results showed that the parametric approach is the one that reproduces the data statistics worse and presents greater uncertainty with a lower computational cost, while the non-parametric approach was the one that best reproduces the dependence of the data at a high computational cost. The semi-parametric approach reduces the computational cost by 10% compared to the non-parametric approach, but its accuracy is significantly degraded

Cytotoxic Effect of Poly-Dispersed Single Walled Carbon Nanotubes on Erythrocytes In Vitro and In Vivo

Single wall Carbon Nanotubes (SWCNTs) are hydrophobic and do not disperse in aqueous solvents. Acid functionalization of SWCNTs results in attachment of carboxy and sulfonate groups to carbon atoms and the resulting acid functionalized product (AF-SWCNTs) is negatively charged and disperses easily in water and buffers. In the present study, effect of AF-SWCNTs on blood erythrocytes was examined. Incubation of mouse erythrocytes with AF-SWCNTs and not with control SWCNTs, resulted in a dose and time dependent lysis of erythrocyte. Using fluorescence tagged AF-SWCNTs, binding of AF-SWCNTs with erythrocytes could be demonstrated. Confocal microscopy results indicated that AF-SWCNTs could enter the erythrocytes. Treatment with AF-SWCNTs resulted in exposure of hydrophobic patches on erythrocyte membrane that is indicative of membrane damage. A time and dose dependent increase in externalization of phosphatidylserine on erythrocyte membrane bilayer was also found. Administration of AF-SWCNTs through intravenous route resulted in a transient anemia as seen by a sharp decline in blood erythrocyte count accompanied with a significant drop in blood haemoglobin level. Administration of AF-SWCNTs through intratracheal administration also showed significant decline in RBC count while administration through other routes (gavage and intra-peritoneal) was not effective. By using a recently developed technique of a two step in vivo biotinylation of erythrocytes that enables simultaneous enumeration of young (age <10 days) and old (age>40 days) erythrocytes in mouse blood, it was found that the in vivo toxic effect of AF-SWCNTs was more pronounced on older subpopulation of erythrocytes. Subpopulation of old erythrocytes fell after treatment with AF-SWCNTs but recovered by third day after the intravenous administration of AF-SWCNTs. Taken together our results indicate that treatment with AF-SWCNTs results in acute membrane damage and eventual lysis of erythrocytes. Intravenous administration of AF-SWCNTs resulted in a transient anemia in which older erythrocytes are preferably lysed

Evaluation of pulmonary and systemic toxicity following lung exposure to graphite nanoplates: a member of the graphene-based nanomaterial family

Background: Graphene, a monolayer of carbon, is an engineered nanomaterial (ENM) with physical and chemical properties that may offer application advantages over other carbonaceous ENMs, such as carbon nanotubes (CNT). The goal of this study was to comparatively assess pulmonary and systemic toxicity of graphite nanoplates, a member of the graphene-based nanomaterial family, with respect to nanoplate size. Methods: Three sizes of graphite nanoplates [20 μm lateral (Gr20), 5 μm lateral (Gr5), and \u3c2 \u3eμm lateral (Gr1)] ranging from 8–25 nm in thickness were characterized for difference in surface area, structure,, zeta potential, and agglomeration in dispersion medium, the vehicle for in vivo studies. Mice were exposed by pharyngeal aspiration to these 3 sizes of graphite nanoplates at doses of 4 or 40 μg/mouse, or to carbon black (CB) as a carbonaceous control material. At 4 h, 1 day, 7 days, 1 month, and 2 months post-exposure, bronchoalveolar lavage was performed to collect fluid and cells for analysis of lung injury and inflammation. Particle clearance, histopathology and gene expression in lung tissue were evaluated. In addition, protein levels and gene expression were measured in blood, heart, aorta and liver to assess systemic responses. Results: All Gr samples were found to be similarly composed of two graphite structures and agglomerated to varying degrees in DM in proportion to the lateral dimension. Surface area for Gr1 was approximately 7-fold greater than Gr5 and Gr20, but was less reactive reactive per m2 . At the low dose, none of the Gr materials induced toxicity. At the high dose, Gr20 and Gr5 exposure increased indices of lung inflammation and injury in lavage fluid and tissue gene expression to a greater degree and duration than Gr1 and CB. Gr5 and Gr20 showed no or minimal lung epithelial hypertrophy and hyperplasia, and no development of fibrosis by 2 months post-exposure. In addition, the aorta and liver inflammatory and acute phase genes were transiently elevated in Gr5 and Gr20, relative to Gr1. Conclusions: Pulmonary and systemic toxicity of graphite nanoplates may be dependent on lateral size and/or surface reactivity, with the graphite nanoplates \u3e 5 μm laterally inducing greater toxicity which peaked at the early time points post-exposure relative to the 1–2 μm graphite nanoplate

Physicochemical characterization and genotoxicity of the broad class of carbon nanotubes and nanofibers used or produced in US facilities

Background Carbon nanotubes and nanofibers (CNT/F) have known toxicity but simultaneous comparative studies of the broad material class, especially those with a larger diameter, with computational analyses linking toxicity to their fundamental material characteristics was lacking. It was unclear if all CNT/F confer similar toxicity, in particular, genotoxicity. Nine CNT/F (MW #1-7 and CNF #1-2), commonly found in exposure assessment studies of U.S. facilities, were evaluated with reported diameters ranging from 6 to 150 nm. All materials were extensively characterized to include distributions of physical dimensions and prevalence of bundled agglomerates. Human bronchial epithelial cells were exposed to the nine CNT/F (0-24 mu g/ml) to determine cell viability, inflammation, cellular oxidative stress, micronuclei formation, and DNA double-strand breakage. Computational modeling was used to understand various permutations of physicochemical characteristics and toxicity outcomes. Results Analyses of the CNT/F physicochemical characteristics illustrate that using detailed distributions of physical dimensions provided a more consistent grouping of CNT/F compared to using particle dimension means alone. In fact, analysis of binning of nominal tube physical dimensions alone produced a similar grouping as all characterization parameters together. All materials induced epithelial cell toxicity and micronuclei formation within the dose range tested. Cellular oxidative stress, DNA double strand breaks, and micronuclei formation consistently clustered together and with larger physical CNT/F dimensions and agglomerate characteristics but were distinct from inflammatory protein changes. Larger nominal tube diameters, greater lengths, and bundled agglomerate characteristics were associated with greater severity of effect. The portion of tubes with greater nominal length and larger diameters within a sample was not the majority in number, meaning a smaller percentage of tubes with these characteristics was sufficient to increase toxicity. Many of the traditional physicochemical characteristics including surface area, density, impurities, and dustiness did not cluster with the toxicity outcomes. Conclusion Distributions of physical dimensions provided more consistent grouping of CNT/F with respect to toxicity outcomes compared to means only. All CNT/F induced some level of genotoxicity in human epithelial cells. The severity of toxicity was dependent on the sample containing a proportion of tubes with greater nominal lengths and diameters

Arginase activities and global arginine bioavailability in wild-type and ApoE-deficient mice: Responses to high fat and high cholesterol diets

Increased catabolism of arginine by arginase is increasingly viewed as an important pathophysiological factor in cardiovascular disease, including atherosclerosis induced by high cholesterol diets. Whereas previous studies have focused primarily on effects of high cholesterol diets on arginase expression and arginine metabolism in specific blood vessels, there is no information regarding the impact of lipid diets on arginase activity or arginine bioavailability at a systemic level. We, therefore, evaluated the effects of high fat (HF) and high fat-high cholesterol (HC) diets on arginase activity in plasma and tissues and on global arginine bioavailability (defined as the ratio of plasma arginine to ornithine + citrulline) in apoE-/- and wild-type C57BL/6J mice. HC and HF diets led to reduced global arginine bioavailability in both strains. The HC diet resulted in significantly elevated plasma arginase in both strains, but the HF diet increased plasma arginase only in apoE-/- mice. Elevated plasma arginase activity correlated closely with increased alanine aminotransferase levels, indicating that liver damage was primarily responsible for elevated plasma arginase. The HC diet, which promotes atherogenesis, also resulted in increased arginase activity and expression of the type II isozyme of arginase in multiple tissues of apoE-/- mice only. These results raise the possibility that systemic changes in arginase activity and global arginine bioavailability may be contributing factors in the initiation and/or progression of cardiovascular disease