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.

2014, Asenova, I., Manova, D., Mändl, S.

In this paper we investigate the possibility of incorporating nitrogen into amorphous, photocatalytic TiO2 thin films, prepared at room temperature, during the growth process. The aim is to reduce the bandgap of the UV active thin films. Physical vapor deposition experiments employing a titanium vacuum arc with gas backfill ranging from pure oxygen to pure nitrogen, are carried out. The resulting films are characterized for chemical composition, phase composition, optical properties and hydrophilicity in order to determine a correlation between gas composition and thin film properties. The experimental results point that a visible change in the band structure of the deposited layers is achieved.

2014, Ehrhardt, M., Lorenz, P., Lotnyk, A., Romanus, H., Thelander, E., Zimmer, K.

Laser embossing allows the micron and submicron patterning of metal substrates that is of great interest in a wide range of applications. This replication process enables low-cost patterning of metallic materials by non-thermal, high-speed forming which is driven by laser-induced shock waves. In this study the surface topography characteristics as well as the material structure at laser embossing of sub-micrometre gratings into solid copper is presented. The topography of the laser-embossed copper pattern is analysed with atomic force microscopy (AFM) in comparison to the master surface. The height of the embossed structures and the replicated pattern fidelity increases up to a laser fluence of F ∼ 10 J/cm2. For higher laser fluences the height of the embossed structures saturates at 75% of the master pattern height and the shape is adequate to the master. Structural modifications in the copper mono crystals after the laser embossing process were investigated with transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). Almost no modifications were detected. The residual stress after laser embossing of 32 MPa (F = 30 J/cm2) has only a limited influence on the surface pattern formation.

2014, Naumov, S.S., Knolle, W., Naumov, S.P., Pöppl, A., Janovský, I.

The radical cation of s-trioxane, radiolytically generated in a freon (CF3CCl3) matrix, was studied in the 10-140 K temperature region. Reversible changes of the EPR spectra were observed, arising from both ring puckering and ring inversion through the molecular plane. The ESREXN program based on the Liouville density matrix equation, allowing the treatment of dynamical exchange, has been used to analyze the experimental results. Two limiting conformer structures of the s-trioxane radical cation were taken into account, namely "rigid" half-boat and averaged planar ones, differing strongly in their electron distribution. The spectrum due to the "rigid" half-boat conformer can be observed only at very low (<60 K) temperatures, when the exchange of conformers is very slow. Two transition states for interconversion by puckering and ring-inversion were identified, close in activation energy (2.3 and 3.0 kJ/mol calculated). Since the energy difference is very small, both processes set on at a comparable temperature. In the case of nearly complete equilibration (fast exchange) between six energetically equivalent structures at T > 120 K in CF3CCl3, a septet due to six equivalent protons (hfs splitting constant 5.9 mT) is observed, characteristic of the dynamically averaged planar geometry of the radical cation. DFT quantum chemical calculations and spectral simulation including intramolecular dynamical exchange support the interpretation.

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.

2014, Raz, Y., Adler, J., Vogel, A., Scheidt, H.A., Häupl, T., Abel, B., Huster, D., Miller, Y.

Tau is a microtubule-associated protein and is involved in microtubule assembly and stabilization. It consists of four repeats that bind to the microtubule. The ΔK280 deletion mutation in the tau R2 repeat region is directly associated with the development of the frontotemporal dementia parkinsonism linked to chromosome 17 (FTDP-17). This deletion mutation is known to accelerate tau R2 repeat aggregation. However, the secondary and the tertiary structures of the self-assembled ΔK280 tau R2 repeat mutant aggregates are still controversial. Moreover, it is unclear whether extensions by one residue in the N- or the C-terminus of this mutant can influence the secondary or the tertiary structure. Herein, we combine solid-state NMR, atomic force microscopy, electron microscopy and all-atom explicit molecular dynamics simulations to investigate the effects of the deletion mutation and the N- and the C-terminal extension of this mutant on the structure. Our main findings show that the deletion mutation induces the formation of small aggregates, such as oligomers, and reduces the formation of fibrils. However, the extensions in the N- or the C-terminus revealed more fibril formation than small aggregates. Further, in the deletion mutation only one structure is preferred, while the N- and the C-terminal extensions strongly lead to polymorphic states. Finally, our broad and combined experimental and computational techniques provide direct structural information regarding ΔK280 tau R2 repeat mutant aggregates and their extensions in the N- and C-terminii by one residue.

2014, Zimmer, K., Wang, X., Lorenz, P., Bayer, L., Ehrhardt, M., Scheit, C., Braun, A.

The optimization of laser scribing for the interconnection of CIGS solar cells is a current focus of laser process development. In addition to the geometry of the laser scribes the impact of the laser patterning to the electrical properties of the solar cells has to be optimized with regards to the scribing process and the laser sources. In-process measurements provide an approach for reliable evaluation of the electrical characteristics. In particular, the parallel resistance Rp that was calculated from the measured I-V curves was measured in dependence on the scribing parameters of a short-pulsed ns laser in comparison to a standard ps laser at a wavelength of 1.06 μm. With low pulse overlap of ∼ 20% a reduction of Rp to 2/3 of the initial value has been achieved for ns laser pulses. In comparison to ps laser slightly more defects were observed at the investigated parameter range.

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.

2014, Lorenz, P., Ehrhardt, M., Zimmer, K.

The defect-free laser-assisted structuring of thin films on flexible substrates is a challenge for laser methods. However, solving this problem exhibits an outstanding potential for a pioneering development of flexible electronics. Thereby, the laser-assisted delamination method has a great application potential. At the delamination process: the localized removal of the layer is induced by a shock wave which is produced by a laser ablation process on the rear side of the substrate. In this study, the thin-film patterning process is investigated for different polymer substrates dependent on the material and laser parameters using a KrF excimer laser. The resultant structures were studied by optical microscopy and white light interferometry (WLI). The delamination process was tested at different samples (indium tin oxide (ITO) on polyethylene terephthalate (PET), epoxy-based negative photoresist (SU8) on polyimide (PI) and indium tin oxide/copper indium gallium selenide/molybdenum (ITO/CIGS/Mo) on PI.

2014, Teichmann, M., Lorbeer, J., Frost, F., Rauschenbach, B.

Abstract: The temporal evolution of ripple pattern on Ge, Si, Al2O3, and SiO2 by low-energy ion beam erosion with Xe + ions is studied. The experiments focus on the ripple dynamics in a fluence range from 1.1 × 1017 cm-2 to 1.3 × 1019 cm-2 at ion incidence angles of 65° and 75° and ion energies of 600 and 1,200 eV. At low fluences a short-wavelength ripple structure emerges on the surface that is superimposed and later on dominated by long wavelength structures for increasing fluences. The coarsening of short wavelength ripples depends on the material system and angle of incidence. These observations are associated with the influence of reflected primary ions and gradient-dependent sputtering. The investigations reveal that coarsening of the pattern is a universal behavior for all investigated materials, just at the earliest accessible stage of surface evolution.