Abstract: The characterization of Ni-silicides using electron energy loss spectroscopy (EELS) based methods is discussed. A series of Ni-silicide phases is examined: Ni3Si, Ni31Si12, Ni2Si, NiSi and NiSi2. The composition of these phases is determined by quantitative core-loss EELS. A study of the low loss part of the EELS spectrum shows that both the energy and the shape of the plasmon peak are characteristic for each phase. Examination of the Ni-L edge energy loss near edge structure (ELNES) shows that the ratio and the sum of the L2 and L3 white line intensities are also characteristic for each phase. The sum of the white line intensities is used to determine the trend in electron occupation of the 3d states of the phases. The dependence of the plasmon energy on the electron occupation of the 3d states is demonstrated.

Abstract: Molecular dynamics (MD) simulations were performed to provide atomic scale insight in the initial interaction between hydroxyl radicals (OH) and peptide systems in solution. These OH radicals are representative reactive oxygen species produced by cold atmospheric plasmas. The use of plasma for biomedical applications is gaining increasing interest, but the fundamental mechanisms behind the plasma modifications still remain largely elusive. This study helps to gain more insight in the underlying mechanisms of plasma medicine but is also more generally applicable to peptide oxidation, of interest for other applications. Combining both reactive and nonreactive MD simulations, we are able to elucidate the reactivity of the amino acids inside the peptide systems and their effect on their structure up to 1 μs. Additionally, experiments were performed, treating the simulated peptides with a plasma jet. The computational results presented here correlate well with the obtained experimental data and highlight the importance of the chemical environment for the reactivity of the individual amino acids, so that specific amino acids are attacked in higher numbers than expected. Furthermore, the long time scale simulations suggest that a single oxidation has an effect on the 3D conformation due to an increase in hydrophilicity and intra- and intermolecular interactions.

Abstract: Cold atmospheric pressure plasmas have proven to provide an alternative treatment of cancer by targeting tumorous cells while leaving their healthy counterparts unharmed. However, the underlying mechanisms of the plasma–cell interactions are not yet fully understood. Reactive oxygen species, and in particular hydroxyl radicals (OH), are known to play a crucial role in plasma driven apoptosis of
malignant cells. In this paper we investigate the interaction of OH radicals, as well as H2O2 molecules and HO2 radicals, with DNA by means of reactive molecular dynamics simulations using the ReaxFF force field. Our results provide atomic-scale insight into the dynamics of oxidative stress on DNA caused by the OH radicals, while H2O2 molecules appear not reactive within the considered timescale. Among the observed processes are the formation of 8-OH-adduct radicals, forming the first stages towards the formation of 8-oxoGua and 8-oxoAde, H-abstraction reactions of the amines, and the partial opening of loose DNA ends in aqueous solution.

Abstract: Tunnel field-effect transistors (TFETs) are potential successors of metal-oxide-semiconductor FETs because scaling the supply voltage below 1 V is possible due to the absence of a subthreshold-swing limit of 60 mV/decade. The modeling of the TFET performance, however, is still preliminary. We have developed models allowing a direct comparison between the single-gate, double-gate, and gate-all-around configuration at high drain voltage, when the drain-voltage dependence is negligible, and we provide improved insight in the TFET physics. The dependence of the tunnel current on device parameters is analyzed, in particular, the scaling with gate-dielectric thickness, channel thickness, and dielectric constants of gate dielectric and channel material. We show that scaling the gate-dielectric thickness improves the TFET performance more than scaling the channel thickness and that improvements are often overestimated. There is qualitative agreement between our model and our experimental data.

Abstract: Plasma has been studied for several years to convert CO2 into value-added products. If CO2 could be converted in the presence of H2O as a cheap H-source for making syngas and oxygenates, it would mimic natural photosynthesis. However, CO2/H2O plasmas have not yet been extensively studied, not by experiments, and certainly not computationally. Therefore, we present here a kinetic modelling study to obtain a greater understanding of the vibrational kinetics of a CO2/H2O microwave plasma. For this purpose, we first created an electron impact cross section set for H2O, using a swarm-derived method. We added the new cross section set and CO2/H2O-related chemistry to a pure CO2 model. While it was expected that H2O addition mainly causes quenching of the CO2 asymmetric mode vibrational levels due to the additional CO2/H2O vibrational-translational relaxation, our model shows that the modifications in the vibrational kinetics are mainly induced by the strong electron dissociative attachment to H2O molecules, causing a reduction in electron density, and the corresponding changes in the input of energy into the CO2 vibrational levels by electron impact processes.

Abstract: In the manufacturing of multi-Vt FinFET transistors, the gate material deposited in the nano-spaces left by the removed dummy gate must be etched back in mask-defined wafer areas. Etch conformality is a necessary condition for the control of under-etch at the boundary between areas defined by masking. We studied the feasibility of TiN etching by APM (ammonia peroxide mixture, also known as SC1) in nano-confined volumes representative of FinFET transistors of the 7 nm node and below, namely nanotrenches with 1-D confinement and nanoholes with 2-D confinement. TiN etching was characterized for rate and conformality using different electron microscopy techniques. Etching in closed nanotrenches was conformal, starting and progressing all along the 2-D seam, with a rate that was 38% higher compared to a planar film. Etching in closed nanoholes proved also to be conformal and faster than planar films, but with a delay to open the 1-D seam that seemed to depend strongly on small variations in the hole diameter. However, holes between the fins at the bottom of the removed dummy gate, are not circular and do present 2-D seams that should lend themselves for an easier start of conformal etching as compared to the circular nanoholes used in this study. Finally, to explain the higher etch rate observed in nano-confined features, concentrations of ions in nanoholes were calculated taking the overlap of electrostatic double layers (EDL) into account. With negatively charged TiN walls, as measured by streaming potential on planar films, ammonium was the dominant ion in nanoholes. As no chemical reaction proposed in the literature for TiN etching matched with this finding, we proposed that the formation of ammine complexes, dissolving the formed Ti oxide, was the rate-determining step.

Abstract: Amino acids have huge potential as platform chemicals in the biobased industry. Pd-catalyzed decarboxylation is a very promising route for the valorization of these natural compounds derived from protein waste or fermentation. We report that the highly abundant and nonessential amino acid L-proline is very reactive in the Pd-catalyzed decarboxylation. Full conversions are obtained with Pd/C and different Pd/MeOx catalysts; this allowed the identification of the different side reactions and the mapping of the reaction network. Due to the high reactivity of pyrrolidine, the selectivity for pyrrolidine was initially low. By carefully modifying Pd/ZrO2 with Pb in a controlled manner-via two incipient wetness impregnation steps-the selectivity increased remarkably. Finally, a thorough investigation of the reaction parameters resulted in an increased activity of this modified catalyst and an even further enhanced selectivity under a low H-2 pressure of 4 bar at 235 degrees C in water. This results in a very selective and sustainable production route for the highly interesting pyrrolidine.

Abstract: <script type='text/javascript'>document.write(unpmarked('A new synthetic approach based on chemical transport reactions has been introduced to obtain the Nowotny chimney ladder phase Fe2Ge3 in the form of single crystals and polycrystalline powders. The single crystals possess the stoichiometric composition and the commensurate chimney ladder structure of the Ru2Sn3 type in contrast to the polycrystalline samples that are characterized by a complex microstructure. In compliance with the 18-n electron counting rule formulated for T-E intermetallics, electronic structure calculations reveal a narrow-gap semiconducting behavior of Fe2Ge3 favorable for high thermoelectric performance. Measurements of transport and thermoelectric properties performed on the polycrystalline samples confirm the formation of a narrow band gap of similar to 30 meV and reveal high absolute values of the Seebeck coefficient at elevated temperatures. Low glass-like thermal conductivity is observed in a wide temperature range that might be caused by the underlying complex microstructure.'));