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The use of matrix-specific calibrations for oxygen in analytical glow discharge spectrometry

2014, Gonzalez-Gago, C., Smid, P., Hofmann, T., Venzago, C., Hoffmann, V., Gruner, W.

The performance of glow discharge optical emission spectroscopy and mass spectrometry for oxygen determination is investigated using a set of new conductive samples containing oxygen in the percent range in three different matrices (Al, Mg, and Cu) prepared by a sintering process. The sputtering rate corrected calibrations obtained at standard conditions for the 4 mm anode (700 V, 20 mA) in GD-OES are matrix independent for Mg and Al but not for Cu. The importance of a "blue shifted" line of oxygen at 130.22 nm (first reported by Köster) for quantitative analyses by GD-OES is confirmed. Matrix-specific calibrations for oxygen in GD-MS are presented. Two source concepts - fast flow (ELEMENT GD) and low gas flow (VG9000) - are evaluated obtaining higher sensitivity with the static flow source. Additional experiments using Ar-He mixtures or μs pulsed GD are carried out in ELEMENT GD aiming to improve the oxygen sensitivity.

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Improvement of the optical properties after surface error correction of aluminium mirror surfaces

2021, Ulitschka, M., Bauer, J., Frost, F., Arnold, T.

Ion beam finishing techniques of aluminium mirrors have a high potential to meet the increasing demands on applications of high-performance mirror devices for visible and ultraviolet spectral range. Reactively driven ion beam machining using oxygen and nitrogen gases enables the direct figure error correction up to 1 μm machining depth while preserving the initial roughness. However, the periodic turning mark structures, which result from preliminary device shaping by single-point diamond turning, often limit the applicability of mirror surfaces in the short-periodic spectral range. Ion beam planarization with the aid of a sacrificial layer is a promising process route for surface smoothing, resulting in successfully reduction of the turning mark structures. A combination with direct surface smoothing to perform a subsequent improvement of the microroughness is presented with a special focus on roughness evolution, chemical composition, and optical surface properties. As a result, an ion beam based process route is suggested, which allows almost to recover the reflective properties and an increased long-term stability of smoothed aluminium surfaces.

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Atmospheric pressure plasma: A high-performance tool for the efficient removal of biofilms

2012, Fricke, K., Koban, I., Tresp, H., Jablonowski, L., Schröder, K., Kramer, A., Weltmann, K.-D., von Woedtke, T., Kocher, T.

Introduction: The medical use of non-thermal physical plasmas is intensively investigated for sterilization and surface modification of biomedical materials. A further promising application is the removal or etching of organic substances, e.g., biofilms, from surfaces, because remnants of biofilms after conventional cleaning procedures are capable to entertain inflammatory processes in the adjacent tissues. In general, contamination of surfaces by micro-organisms is a major source of problems in health care. Especially biofilms are the most common type of microbial growth in the human body and therefore, the complete removal of pathogens is mandatory for the prevention of inflammatory infiltrate. Physical plasmas offer a huge potential to inactivate micro-organisms and to remove organic materials through plasma-generated highly reactive agents. Method: In this study a Candida albicans biofilm, formed on polystyrene (PS) wafers, as a prototypic biofilm was used to verify the etching capability of the atmospheric pressure plasma jet operating with two different process gases (argon and argon/oxygen mixture). The capability of plasma-assisted biofilm removal was assessed by microscopic imaging. Results: The Candida albicans biofilm, with a thickness of 10 to 20 μm, was removed within 300 s plasma treatment when oxygen was added to the argon gas discharge, whereas argon plasma alone was practically not sufficient in biofilm removal. The impact of plasma etching on biofilms is localized due to the limited presence of reactive plasma species validated by optical emission spectroscopy.

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Epitaxial stannate pyrochlore thin films: Limitations of cation stoichiometry and electron doping

2021, Hensling, Felix V. E., Dahliah, Diana, Dulal, Prabin, Singleton, Patrick, Sun, Jiaxin, Schubert, Jürgen, Paik, Hanjong, Subedi, Indra, Subedi, Biwas, Rignanese, Gian-Marco, Podraza, Nikolas J., Hautier, Geoffroy, Schlom, Darrell G.

We have studied the growth of epitaxial films of stannate pyrochlores with a general formula A2Sn2O7 (A = La and Y) and find that it is possible to incorporate ∼25% excess of the A-site constituent; in contrast, any tin excess is expelled. We unravel the defect chemistry, allowing for the incorporation of excess A-site species and the mechanism behind the tin expulsion. An A-site surplus is manifested by a shift in the film diffraction peaks, and the expulsion of tin is apparent from the surface morphology of the film. In an attempt to increase La2Sn2O7 conductivity through n-type doping, substantial quantities of tin have been substituted by antimony while maintaining good film quality. The sample remained insulating as explained by first-principles computations, showing that both the oxygen vacancy and antimony-on-tin substitutional defects are deep. Similar conclusions are drawn on Y2Sn2O7. An alternative n-type dopant, fluorine on oxygen, is shallow according to computations and more likely to lead to electrical conductivity. The bandgaps of stoichiometric La2Sn2O7 and Y2Sn2O7 films were determined by spectroscopic ellipsometry to be 4.2 eV and 4.48 eV, respectively. © 2021 Author(s).

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Oxygen-deficient oxide growth by subliming the oxide source material: The cause of silicide formation in rare earth oxides on silicon

2013, Bierwagen, O., Proessdorf, A., Niehle, M., Grosse, F., Trampert, A., Klingsporn, M.

The fundamental issue of oxygen stoichiometry in oxide thin film growth by subliming the source oxide is investigated by varying the additionally supplied oxygen during molecular beam epitaxy of RE2O3 (RE = Gd, La, Lu) thin films on Si(111). Supplying additional oxygen throughout the entire growth was found to prevent the formation of rare earth silicides observed in films grown without an oxygen source. Postgrowth vacuum annealing of oxygen stoichiometric films did not lead to silicide formation thereby confirming that the silicides do not form as a result of an interface instability at growth temperature in vacuum but rather due to an oxygen deficiency in the source vapor. The average oxygen deficiency of the rare-earth containing species in the source vapor was quantified by the 18O tracer technique and correlated with that of the source material, which gradually decomposed during sublimation. Therefore, any oxide growth by sublimation of the oxide source material requires additional oxygen to realize oxygen stoichiometric films.

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Superconductivity in multi-phase Mg-B-O compounds

2012, Prikhna, T., Gawalek, W., Eisterer, M., Weber, H.W., Noudem, J., Sokolovsky, V., Chaud, X., Moshchil, V., Karpets, M., Kovylaev, V., Borimskiy, A., Tkach, V., Kozyrev, A., Kuznietsov, R., Dellith, J., Shmidt, C., Basyuk, T., Litzkendorf, D., Karau, F., Dittrich, U., Tomsic, M.

Structures of MgB2-based materials manufactured under pressure (up to 2 GPa) by different methods having high superconducting performance and connectivity are multiphase and contain different Mg-B-O compounds. Some oxygen can be incorporated into MgB2 and boron into MgO structures, MgBx (X=4-20) inclusions contain practically no oxygen. Regulating manufacturing temperature, pressure, introducing additions one can influence oxygen and boron distribution in the materials and thus, affect the formation, amount and sizes of Mg-B-O and MgBx inclusions and changing type of pinning, pinning force and so affect critical current density jc. The boron concentration increase in initial Mg and B mixture allows obtaining sample containing 88.5 wt% of MgB12 with Tc of 37.4 K (estimated magnetically).

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Pinning and trapped field in MgB2- and MT-YBaCuO bulk superconductors manufactured under pressure

2016, Prikhna, T., Eisterer, M., Chaud, X., Weber, H.W., Habisreuther, T., Moshchil, V., Kozyrev, A., Shapovalov, A., Gawalek, W., Wu, M., Litzkendorf, D., Goldacker, W., Sokolovsky, V., Shaternik, V., Rabier, J., Joulain, A., Grechnev, G., Boutko, V., Gusev, A., Shaternik, A., Barvitskiy, P.

The relevant pinning centers of Abrikosov vortices in MgB2-based materials are oxygen-enriched Mg-B-O inclusions or nanolayers and inclusions of MgBx (x>4) phases. The high critical current densities, jc, of 106 and 103A/cm2 at 1 and 8.5 T, respectively, at 20 K can be achieved in polycrystalline materials (prepared at 2 GPa) containing a large amount of admixed oxygen. Besides, oxygen can be incorporated into the MgB2 structure in small amounts (MgB1.5O0.5), which is supported by Auger studies and calculations of the DOS and the binding energy. The jc of melt textured YBa2Cu3O7-δ (or Y123)-based superconductors (MT-YBaCuO) depends not only on the perfectness of texture and the amount of oxygen in the Y123 structure, but also on the density of twins and micro-cracks formed during the oxygenation (due to shrinking of the c-lattice parameter). The density of twins and microcracks increases with the reduction of the distance between Y2BaCuO5 (Y211) inclusions in Y123. At 77 K jc=8·104 A/cm2 in self-field and jc=103 A/cm2 at 10 T were found in materials oxygenated at 16 MPa for 3 days with a density of twins of 22–35 per µm (thickness of the lamellae: 45-30 nm) and a density of micro-cracks of 200–280 per mm. Pinning can occur at the points of intersection between the Y123 twin planes and the Y211 inclusions. MTYBaCuO at 77 K can trap 1.4 T (38×38×17 mm, oxygenated at 0.1 MPa for 20 days) and 0.8 T (16 mm in diameter and 10 mm thick with 0.45 mm holes oxygenated at 10 MPa for 53 h). The sensitivity of MgB2 to magnetic field variations (flux jumps) complicates estimates of the trapped field. At 20 K 1.8 T was found for a block of 30 mm in diameter and a thickness of 7.5 mm and 1.5 T (if the magnetic field was increased at a rate of 0.1 T) for a ring with dimensions 24×18 mm and a thickness of 8 mm.

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Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol

2019, Bianchi, Federico, Kurtén, Theo, Riva, Matthieu, Mohr, Claudia, Rissanen, Matti P., Roldin, Pontus, Berndt, Torsten, Crounse, John D., Wennberg, Paul O., Mentel, Thomas F., Wildt, Jürgen, Junninen, Heikki, Jokinen, Tuija, Kulmala, Markku, Worsnop, Douglas R., Thornton, Joel A., Donahue, Neil, Kjaergaard, Henrik G., Ehn, Mikael

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research. © 2019 American Chemical Society.

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Reactive species driven oxidative modifications of peptides—Tracing physical plasma liquid chemistry

2021, Wenske, Sebastian, Lackmann, Jan-Wilm, Busch, Larissa Milena, Bekeschus, Sander, von Woedtke, Thomas, Wende, Kristian

The effluence of physical plasma consists of a significant share of reactive species, which may interact with biomolecules and yield chemical modifications comparable to those of physiological processes, e.g., post-translational protein modifications (oxPTMs). Consequentially, the aim of this work is to understand the role of physical plasma-derived reactive species in the introduction of oxPTM-like modifications in proteins. An artificial peptide library consisting of ten peptides was screened against the impact of two plasma sources, the argon-driven MHz-jet kINPen and the helium-driven RF-jet COST-Jet. Changes in the peptide molecular structure were analyzed by liquid chromatography–mass spectrometry. The amino acids cysteine, methionine, tyrosine, and tryptophan were identified as major targets. The introduction of one, two, or three oxygen atoms was the most common modification observed. Distinct modification patterns were observed for nitration (+N + 2O–H), which occurred in kINPen only (peroxynitrite), and chlorination (+Cl–H) that was exclusive for the COST-Jet in the presence of chloride ions (atomic oxygen/hypochlorite). Predominantly for the kINPen, singlet oxygen-related modifications, e.g., cleavage of tryptophan, were observed. Oxidation, carbonylation, and double oxidations were attributed to the impact of hydroxyl radicals and atomic oxygen. Leading to a significant change in the peptide side chain, most of these oxPTM-like modifications affect the secondary structure of amino acid chains, and amino acid polarity/functionality, ultimately modifying the performance and stability of cellular proteins.

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Remarkable performance recovery in highly defective perovskite solar cells by photo-oxidation

2023, Goetz, Katelyn P., Thome, Fabian T. F., An, Qingzhi, Hofstetter, Yvonne J., Schramm, Tim, Yangui, Aymen, Kiligaridis, Alexander, Loeffler, Markus, Taylor, Alexander D., Scheblykin, Ivan G., Vaynzof, Yana

Exposure to environmental factors is generally expected to cause degradation in perovskite films and solar cells. Herein, we show that films with certain defect profiles can display the opposite effect, healing upon exposure to oxygen under illumination. We tune the iodine content of methylammonium lead triiodide perovskite from understoichiometric to overstoichiometric and expose them to oxygen and light prior to the addition of the top layers of the device, thereby examining the defect dependence of their photooxidative response in the absence of storage-related chemical processes. The contrast between the photovoltaic properties of the cells with different defects is stark. Understoichiometric samples indeed degrade, demonstrating performance at 33% of their untreated counterparts, while stoichiometric samples maintain their performance levels. Surprisingly, overstoichiometric samples, which show low current density and strong reverse hysteresis when untreated, heal to maximum performance levels (the same as untreated, stoichiometric samples) upon the photooxidative treatment. A similar, albeit smaller-scale, effect is observed for triple cation and methylammonium-free compositions, demonstrating the general application of this treatment to state-of-the-art compositions. We examine the reasons behind this response by a suite of characterization techniques, finding that the performance changes coincide with microstructural decay at the crystal surface, reorientation of the bulk crystal structure for the understoichiometric cells, and a decrease in the iodine-to-lead ratio of all films. These results indicate that defect engineering is a powerful tool to manipulate the stability of perovskite solar cells.