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- ItemStrong out-of-plane magnetic anisotropy in ion irradiated anatase TiO2 thin films(New York, NY : American Inst. of Physics, 2016) Stiller, M.; Barzola-Quiquia, J.; Esquinazi, P.; Spemann, D.; Meijer, J.; Lorenz, M.; Grundmann, M.The temperature and field dependence of the magnetization of epitaxial, undoped anatase TiO2 thin films on SrTiO3 substrates was investigated. Low-energy ion irradiation was used to modify the surface of the films within a few nanometers, yet with high enough energy to produce oxygen and titanium vacancies. The as-prepared thin film shows ferromagnetism which increases after irradiation with low-energy ions. An optimal and clear magnetic anisotropy was observed after the first irradiation, opposite to the expected form anisotropy. Taking into account the experimental parameters, titanium vacancies as di-Frenkel pairs appear to be responsible for the enhanced ferromagnetism and the strong anisotropy observed in our films. The magnetic impurities concentrations was measured by particle-induced X-ray emission with ppm resolution. They are ruled out as a source of the observed ferromagnetism before and after irradiation.
- ItemNanometer-resolved mechanical properties around GaN crystal surface steps(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2014) Buchwald, J.; Sarmanova, M.; Rauschenbach, B.; Mayr, S.G.The mechanical properties of surfaces and nanostructures deviate from their bulk counterparts due to surface stress and reduced dimensionality. Experimental indentation-based techniques present the challenge of measuring these effects, while avoiding artifacts caused by the measurement technique itself. We performed a molecular dynamics study to investigate the mechanical properties of a GaN step of only a few lattice constants step height and scrutinized its applicability to indentation experiments using a finite element approach (FEM). We show that the breakdown of half-space symmetry leads to an "artificial" reduction of the elastic properties of comparable lateral dimensions which overlays the effect of surface stress. Contact resonance atomic force microscopy (CR-AFM) was used to compare the simulation results with experiments.
- ItemDeposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2017) Börner, Martin; Blömer, Laura; Kischel, Marcus; Richter, Peter; Salvan, Georgeta; Zahn, Dietrich R. T.; Siles, Pablo F.; Fuentes, Maria E. N.; Bufon, Carlos C. B.; Grimm, Daniel; Schmidt, Oliver G.; Breite, Daniel; Abel, Bernd; Kersting, BertholdThe chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.
- ItemPlasma-assisted synthesis and high-resolution characterization of anisotropic elemental and bimetallic core-shell magnetic nanoparticles(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2014) Hennes, M.; Lotnyk, A.; Mayr, S.G.Magnetically anisotropic as well as magnetic core-shell nanoparticles (CS-NPs) with controllable properties are highly desirable in a broad range of applications. With this background, a setup for the synthesis of heterostructured magnetic core-shell nanoparticles, which relies on (optionally pulsed) DC plasma gas condensation has been developed. We demonstrate the synthesis of elemental nickel nanoparticles with highly tunable sizes and shapes and Ni@Cu CS-NPs with an average shell thickness of 10 nm as determined with scanning electron microscopy, high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements. An analytical model that relies on classical kinetic gas theory is used to describe the deposition of Cu shell atoms on top of existing Ni cores. Its predictive power and possible implications for the growth of heterostructured NP in gas condensation processes are discussed.
- ItemTopography evolution of germanium thin films synthesized by pulsed laser deposition(New York, NY : American Inst. of Physics, 2017) Schumacher, P.; Mayr, S.G.; Rauschenbach, B.Germanium thin films were deposited by Pulsed Laser Deposition (PLD) onto single crystal Ge (100) and Si (100) substrates with a native oxide film on the surface. The topography of the surface was investigated by Atomic Force Microscopy (AFM) to evaluate the scaling behavior of the surface roughness of amorphous and polycrystalline Ge films grown on substrates with different roughnesses. Roughness evolution was interpreted within the framework of stochastic rate equations for thin film growth. Here the Kardar-Parisi-Zhang equation was used to describe the smoothening process. Additionally, a roughening regime was observed in which 3-dimensional growth occurred. Diffusion of the deposited Ge adatoms controlled the growth of the amorphous Ge thin films. The growth of polycrystalline thin Ge films was dominated by diffusion processes only in the initial stage of the growth.
- ItemHuman health risk evaluation of a microwave-driven atmospheric plasma jet as medical device(Amsterdam [u.a.] : Elsevier, 2017) Lehmann, A.; Pietag, F.; Arnold, T.Purpose: The aim of this study was the characterisation of a microwave-driven atmospheric plasma jet (APJ) dedicated for medical applications. The scientific focus includes harmless sterilization of surfaces and therapeutic treatments in dentistry. Methodes: The plasma was investigated with respect to potential health risks for human beings, which could occur especially by the gas temperature, heat flow, patient leakage current, UV emission and ozone emission from the plasma jet, according to DIN SPEC 91315:2014-06 (General requirements for plasma sources in medicine) [1]. Results: The results of the experiments indicate a high potential of the plasma jet to be used as a medical device exhibiting low gas temperatures up to 34 °C. The calculated leakage currents are mostly below the 10 μA threshold. The limiting UV exposure duration for the APJ with a calculated maximum effective irradiance of 2.6 μW/cm2 is around 19 min, based on the exposure limits of the international commission on non-ionizing radiation protection guidelines (ICNIRP) [2]. A significant ozone concentration was observed mainly in the axial effluent gas flow. Ozone concentration strongly decreases with increasing distance from the plasma source exit nozzle. Conclusion: The investigated APJ exhibits physical properties that might not constitute health risks to humans, e.g. during treatment in dentistry. Thus, the APJ shows a high potential for application as a device in dental therapy.
- ItemKLaF4 nanocrystallisation in oxyfluoride glass-ceramics(Cambridge : RSC, 2013) De Pablos-MartÃn, A.; Muñoz, F.; Mather, G.C.; Patzig, C.; Bhattacharyya, S.; Jinschek, J.R.; Höche, T.; Durán, A.; Pascual, M.J.Nanocrystallisation of the cubic and hexagonal polymorphs of KLaF 4 in a 70SiO2-7Al2O3-16K 2O-7LaF3 (mol%) glass has been achieved by heat treatment above the glass transition temperature. For treatment at 580°C, only the cubic structure crystallises, with a maximum crystallite size of ~9 nm. At higher temperatures, crystallisation of the hexagonal structure also takes place. The crystallisation process has been analysed using several thermal and structural techniques and is revealed to occur from a constant number of nuclei. The formation of a viscous barrier which inhibits further crystal growth and limits the crystal size to the nanometric range is observed. The title materials doped with lanthanide ions may be good candidates for optical applications.
- ItemThin film deposition using energetic ions(Basel : MDPI, 2010) Manova, D.; Gerlach, J.W.; Mändl, S.One important recent trend in deposition technology is the continuous expansion of available processes towards higher ion assistance with the subsequent beneficial effects to film properties. Nowadays, a multitude of processes, including laser ablation and deposition, vacuum arc deposition, ion assisted deposition, high power impulse magnetron sputtering and plasma immersion ion implantation, are available. However, there are obstacles to overcome in all technologies, including line-of-sight processes, particle contaminations and low growth rates, which lead to ongoing process refinements and development of new methods. Concerning the deposited thin films, control of energetic ion bombardment leads to improved adhesion, reduced substrate temperatures, control of intrinsic stress within the films as well as adjustment of surface texture, phase formation and nanotopography. This review illustrates recent trends for both areas; plasma process and solid state surface processes. © 2010 by the authors.
- ItemIncreased biocompatibility and bioactivity after energetic PVD surface treatments(Basel : MDPI, 2009) Mändl, S.Ion implantation, a common technology in semiconductor processing, has been applied to biomaterials since the 1960s. Using energetic ion bombardment, a general term which includes conventional ion implantation plasma immersion ion implantation (PIII) and ion beam assisted thin film deposition, functionalization of surfaces is possible. By varying and adjusting the process parameters, several surface properties can be attuned simultaneously. Extensive research details improvements in the biocompatibility, mainly by reducing corrosion rates and increasing wear resistance after surface modification. Recently, enhanced bioactivity strongly correlated with the surface topography and less with the surface chemistry has been reported, with an increased roughness on the nanometer scale induced by self-organisation processes during ion bombardment leading to faster cellular adhesion processes. © 2009 by the authors;.
- ItemElectron beam-induced immobilization of laccase on porous supports for waste water treatment applications(Basel : MDPI AG, 2014) Jahangiri, E.; Reichelt, S.; Thomas, I.; Hausmann, K.; Schlosser, D.; Schulze, A.The versatile oxidase enzyme laccase was immobilized on porous supports such as polymer membranes and cryogels with a view of using such biocatalysts in bioreactors aiming at the degradation of environmental pollutants in wastewater. Besides a large surface area for supporting the biocatalyst, the aforementioned porous systems also offer the possibility for simultaneous filtration applications in wastewater treatment. Herein a "green" water-based, initiator-free, and straightforward route to highly reactive membrane and cryogel-based bioreactors is presented, where laccase was immobilized onto the porous polymer supports using a water-based electron beam-initiated grafting reaction. In a second approach, the laccase redox mediators 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and syringaldehyde were cross-linked instead of the enzyme via electron irradiation in a frozen aqueous poly(acrylate) mixture in a one pot set-up, yielding a mechanical stable macroporous cryogel with interconnected pores ranging from 10 to 50 μm in size. The membranes as well as the cryogels were characterized regarding their morphology, chemical composition, and catalytic activity. The reactivity towards waste-water pollutants was demonstrated by the degradation of the model compound bisphenol A (BPA). Both membrane- and cryogel-immobilized laccase remained highly active after electron beam irradiation. Apparent specific BPA removal rates were higher for cryogel-than for membrane-immobilized and free laccase, whereas membrane-immobilized laccase was more stable with respect to maintenance of enzymatic activity and prevention of enzyme leakage from the carrier than cryogel-immobilized laccase. Cryogel-immobilized redox mediators remained functional in accelerating the laccase-catalyzed BPA degradation, and especially ABTS was found to act more efficiently in immobilized than in freely dissolved state.