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In pulsed laser deposition, along the traditionally exploited deposition on the front-side of the plasma-plume, a coating forms on the surface of the target as well. For reproducibility, this residue is usually cleaned and discarded. Here we instead investigate the target-side coated materials and employ them as a binder-free supercapacitor electrode. The ballistic-aggregated, target-side nanofoam is compact and features a larger fraction of sp2-carbon, higher nitrogen content with higher graphitic-N and lower oxygen content with fewer COOH groups than that of diffusive-aggregated conventional nanofoams. They are highly hydrogenated graphite-like amorphous carbon and superhydrophilic. The resulting symmetric micro-supercapacitor delivers higher volumetric capacitance of 522 mF/cm3 at 100 mV/s and 104% retention after 10000 charge-discharge cycles over conventional nanofoam (215 mF/cm3 and 85% retention) with an areal capacitance of 134 {\mu}F/cm2 at 120 Hz and ultrafast frequency response. Utilizing the normally discarded target-side material can therefore enable high performing devices while reducing waste, cost and energy input per usable product. leading towards a greater sustainability on nanomaterials synthesis and deposition techniques., Comment: 22 pages, 8 figures in text, 8 figures in supplementary, 1 table

Titanium (Ti), due to its excellent properties, is widely exploited in thin film technology that usually leads to the production of {\alpha}-phase (hcp) Ti films. In this work, we investigate the phase evolution of Ti films deposited by varying type and energy of the film-forming species. To investigate different plasma species environments, films with different thicknesses are grown by using conventional Direct Current Magnetron Sputtering (DCMS) and High Power Impulse Magnetron Sputtering (HiPIMS). Furthermore, HiPIMS depositions with different substrate bias voltage US (0 V, -300 V and -500 V) are performed to investigate different ion energy ranges. Microstructure, morphology and residual stress of the deposited films, as well as the DCMS and HiPIMS plasma composition, are analysed with different characterization techniques. The DCMS samples exhibit the Ti {\alpha}-phase only and show a tensile residual stress decreasing with thickness. As far as HiPIMS samples are concerned, a compressive-tensile-compressive (CTC) behavior is observed for residual stresses as thickness increases. Specifically, films deposited in low energy ion conditions (US =0 V) show the presence of the Ti fcc phase up to a maximum thickness of about 370 nm. Differently, films deposited under high energy conditions (US = -300 V and -500 V) show the nucleation of the Ti {\omega}-phase for thicknesses greater than 260 and 330 nm, respectively. The formation of these unusual Ti phases is discussed considering the different deposition conditions., Comment: This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ENSURE grant agreement No. 647554)

Raman microscopy is one of the methods that could be used for future post-mortem analyses of samples extracted from ITER plasma facing. This study shows that this technique is useful for studying tungsten-based materials containing impurities including oxides and nitrides. Here, we apply pulsed laser deposition and DC argon glow discharges to produce tungsten-containing synthetic films (compact, porous) and nanoparticles and investigate the influence of their morphology on the measured Raman spectra. The amounts of oxygen and/or nitrogen in the films are also investigated. Comparative data are obtained by X-ray Photoelectrons Spectroscopy, Atomic Force Microscopy, Electron Microscopies (Scanning and Transmission), Energy Dispersive X-ray spectroscopy, Time-of-Flight Elastic Recoil Detection Analysis. The power density of the laser beam used to perform Raman microscopy is varied by up to 4 orders of magnitude (0.01-20 mW/$\mu$m 2) to investigate thermal stability of films and nanoparticles. As a first result, we give evidence that Raman microscopy is sensitive enough to detect surface native oxides. Secondly, more tungsten oxides are detected in porous materials and nanoparticles than in compact films, and the intensities of the Raman band correlate to their oxygen content. Thirdly, thermal stability of these films (i.e. structural and chemical modification under laser heating) is poor when compact films contain a sufficiently large amount of nitrogen. This finding suggests that nitrogen can be substituted by oxygen during Raman laser induced heating occurring in ambient air. Finally, our methodology can be used to rapidly characterize morphology and chemistry of the samples analyzed, and also to create oxides at the micrometer scale. keywords: PLD, Raman spectroscopy, tungsten oxide, tungsten nitride, plasma wall interaction, laser heating, post-mortem analysis 2, Comment: Nuclear Fusion, IOP Publishing, 2020

In this paper we report the development of a new method for the evaluation of thin films mass thickness and composition based on the Energy Dispersive X-Ray Spectroscopy (EDS). The method exploits the theoretical calculation of the in-depth characteristic X-ray generation distribution function, $\phi$/($\rho$ z), in multilayer samples, obtained by the numerical solution of the electron transport equation, to achieve reliable measurements without the need of a reference sample and multiple voltages acquisitions. The electron transport model is derived from the Boltzmann transport equation and it exploits the most updated and reliable physical parameters in order to obtain an accurate description of the phenomenon. The method for the calculation of film mass thickness and composition is validated with benchmarks from standard techniques. In addition, a model uncertainty and sensitivity analysis is carried out and it indicates that the mass thickness accuracy is in the order of 10 $\mu$g/cm$^2$, which is comparable to the nuclear standard techniques resolution. We show the technique peculiarities in one example measurement: two-dimensional mass thickness and composition profiles are obtained for a ultra-low density, high roughness, nanostructured film., Comment: This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ENSURE grant agreement No. 647554)

In this work, we investigate the correlation between morphology, composition, and the mechanical properties of metallic amorphous tungsten-oxygen and amorphous tungsten-oxide films deposited by Pulsed Laser Deposition. This correlation is investigated by the combined use of Brillouin Spectroscopy and the substrate curvature method. The stiffness of the films is strongly affected by both the oxygen content and the mass density. The elastic moduli show a decreasing trend as the mass density decreases and the oxygen-tungsten ratio increases. A plateaux region is detected in correspondence of the transition between metallic and oxide films. The compressive residual stresses, moderate stiffness and high local ductility that characterize compact amorphous tungsten-oxide films make them promising for applications involving thermal or mechanical loads. The coefficient of thermal expansion is quite high (i.e. 8.9 $\cdot$ 10$^{-6}$ K$^{-1}$), being strictly correlated to the amorphous structure and stoichiometry of the films. Under thermal treatments they show a quite low relaxation temperature (i.e. 450 K). They crystallize into the $\gamma$ monoclinic phase of WO$_3$ starting from 670 K, inducing an increase by about 70\% of material stiffness., Comment: The research leading to these results has also received funding from the European Research Council Consolidator Grant ENSURE (ERC-2014-CoG No. 647554). The views and opinions expressed herein do not necessarily reflect those of the European Commission

Micron-thick boron films have been deposited by Pulsed Laser Deposition in vacuum on several substrates at room temperature. The use of high energy pulses (>700 mJ) results in the deposition of smooth coatings with low oxygen uptake even at base pressures of 10$^{-4}$ - 10$^{-3}$ Pa. A detailed structural analysis, by X-Ray Diffraction and Raman, allowed to assess the amorphous nature of the deposited films as well as to determine the base pressure that prevents boron oxide formation. In addition the crystallization dynamics has been characterized showing that film crystallinity already improves at relatively low temperatures (800 {\deg}C). Elastic properties of the boron films have been determined by Brillouin spectroscopy. Finally, micro-hardness tests have been used to explore cohesion and hardness of B films deposited on aluminum, silicon and alumina. The reported deposition strategy allows the growth of reliable boron coatings paving the way for their use in many technology fields., Comment: The research leading to these results has also received funding from the European Research Council Consolidator Grant ENSURE (ERC-2014-CoG No. 647554)