National Institute Of Materials Physics - Romania

The formation of separate phases in crystalline materials is promoted by doping with elements with different valences and ionic radii. Control of the formation of separate phases in multiferroics is extremely important for their magnetic, ferroelectric and elastic properties, which are relevant for multifunctional applications. The ordering of dopants and incipient phase separation were studied in lead titanate-based multiferroics with the formula (Pb0.88Nd0.08)(Ti0.98-xFexMn0.02)O-3 (x = 0.00, 0.03, 0.04, 0.05) by means of a combination of Mossbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy. We found that Fe ions are substituted as Fe3+ at Ti sites and preferentially exhibit pentahedral coordination, whereas Ti ions have coexisting valences of Ti4+/Ti3+. Fe3+ ions are preferentially ordered in clusters, and there exists a transition temperature T-C1, below which phase separation occurs between a tetragonal phase T1 free of magnetic clusters and a cubic phase, and a lower transition temperature T-C2, below which the cubic phase rich in magnetic clusters is transformed into a tetragonal phase T2. The phase separation persists at the nanoscale level down to room temperature and is visible in HRTEM images as a mixing of nanodomains with different tetragonality ratios. This phase separation was observed over the whole studied concentration range of x(Fe) values. It occurs progressively with the value of x(Fe), and the transition temperature T-C2 decreases with the concentration from about 620 K (x(Fe) = 0.03) to about 600 K (x(Fe) = 0.05), while T-C1 remains nearly constant.

H2 plasma has been used to generate carbon vacancies on reduced graphene oxide to increase its catalytic activity as a hydrogenation catalyst. A relationship between the power of the plasma treatment and the exposure time with the activity of the material was observed for CvC double bond hydrogenation. The activity data in the case of 1-octene, showing skeletal isomerization besides hydrogenation, indicate that H2 plasma treatment can introduce hydrogenating and acid sites rendering a bifunctional catalyst that is reminiscent of the activity of noble metals supported on acid supports.

We report on Matrix-Assisted Pulsed Laser Evaporation (MAPLE) deposition of Carbon thin films, simple or reinforced with intended concentrations of Ag and Si. A KrF* (lambda = 248 nm, tau(FWHM) < 25 ns, v = 10 Hz) excimer laser was used for irradiation. The effect of a post-deposition thermal treatment in vacuum was studied. Besides detailed morphological, compositional, structural and pull-out adherence characterizations, the potential of the carbonaceous films for medical applications was investigated in vitro by anti-biofilm and cytocompatibility assays. The microscopic images evidenced no delaminations. Micro-Raman spectroscopy revealed a graphitization tendency depending on preparation conditions, thermal treatment and reinforcing agents' presence. Adherence values improved considerably after thermal treatment. In vitro biological evaluation showed that the films containing similar to 1.85 at.% Ag were non-cytotoxic for MG63 cells, while eliciting a limited antimicrobial activity. The increase of Ag content to 3.6 at.% results in a significant enhancement of antimicrobial activity, whilst maintaining the cytotoxic action and adherence characteristics at acceptable levels. We propose a new class of metamaterials based on C reinforced with Ag and Si obtained by MAPLE for medical applications, i.e. the prevention and treatment of various infections associated with biofilms developed on implants and other medical equipments. (C) 2018 Elsevier B.V. All rights reserved.

The development of novel nano-oxide spintronic devices would benefit greatly from interfacing with emergent phenomena at oxide interfaces. In this paper, we integrate highly spin-split ferromagnetic semiconductor EuO onto perovskite SrTiO3 (001). A careful deposition of Eu metal by molecular beam epitaxy results in EuO growth via oxygen out-diffusion from SrTiO3. This in turn leaves behind a highly conductive interfacial layer through generation of oxygen vacancies. Below the Curie temperature of 70 K of EuO, this spin-polarized two- dimensional t(2g) electron gas at the EuO/SrTiO3 interface displays very large positive linear magnetoresistance (MR). Soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) reveals the t(2g) nature of the carriers. First principles calculations strongly suggest that Zeeman splitting, caused by proximity magnetism and oxygen vacancies in SrTiO3, is responsible for the MR. This system offers an as-yet-unexplored route to pursue proximity-induced effects in the oxide two- dimensional t(2g) electron gas.

Cu-(Mn)-Zn-Mg-Al mixed oxides with Cu/Zn atomic ratio of 1 and different Mn contents were synthesized by thermal decomposition of layered double hydroxides (LDHs) precursors. They were characterized using X-ray diffraction, textural measurements, EDX, TEM, H-2-TPR and XPS techniques, and their catalytic properties in the total oxidation of methane were evaluated. The precursors consisted in nitrate-interlayered multicationic LDH phase with additional Mn3O4 side phase for Mn-containing systems. Their thermal decomposition resulted in complex mixed oxides containing periclase-like, CuO and different spinel (Cu1.5Mn1.5O4, CuMn2O4, and MnAl2O4) phases. XPS analysis confirmed the existence of copper and manganese with different valence states in the Cu,Mn-containing mixed oxides. The catalytic activity expressed as the intrinsic rate of CH4 conversion increased by adding Mn to the CuZnMgAl mixed oxide calcined at 650 degrees C and by increasing its content. The intrinsic activity also strongly increased when the calcination temperature increased from 650 to 800 degrees C. The increased activity was correlated to enhanced catalyst reducibility due to the favorable Cu-Mn interaction. Among the different catalytic active phases, i.e. CuO, Cu1.5Mn1.5O4 and CuMn2O4, the Cu1.5Mn1.5O4 spinel seems to be the most active one. (C) 2017 Elsevier B.V. All rights reserved.

Different amounts of TiO2 and ZnO particles were deposited upon wool fabrics, which are among the less studied textiles. The materials were get from industry or were home made. Model samples for these oxide deposition and properties were also considered. Either sputtering or chemical sol-gel/electro less technique was respectively applied. The coated samples were then characterized structurally and morphologically, by XRD, SEM and XPS and were checked for photocatalytic properties. Both UV and vis light beams were used for irradiation. The photocatalytic experiments were performed by photodegradation of methylene blue in the PCC2 checker apparatus. The fabrics were firstly impregnated with the dye solution and then dried: self cleaning of the wool fabric samples took in fact place. Reflectance data in the visible spectral range of highest absorption band served for direct analysis of MB degradation. The photocatalytic properties of the coated fabrics increased much in comparison with the raw materials. The photocatalytic decolorization of methylene blue follows up a simple apparently first order kinetic equation in many studied cases. Thus it was demonstrated that MB decolorization can serve as a test reaction at least for self cleaning of fabrics. (C) 2017 Elsevier B.V. All rights reserved.

We report a direct photoelectrochemical response from low cost carbon dots (CDs) prepared from chitosan via a solvothermal method. The carbon dots were covalently linked to an indium tin oxide (ITO) surface through a self-assembled silane monolayer. We attribute the photocurrent of the ITO-silane-CD surface to a photogenerated electron-transfer process by CDs under illumination with a wavelength of 420 nm to 450 nm. The self-assembled monolayer of CDs was used for ac-photocurrent imaging of the surface with micron scale lateral resolution. This discovery opens up new applications for CDs as biocompatible, light-addressable electrochemical sensors in bioanalytical and bioimaging applications.

The catalytic performances of two different classes of catalysts containing nickel or/and ruthenium as the active sites were studied in the depolymerisation of lignin isolated from Miscanthus x giganteus. The catalysts were prepared either by coprecipitation (ie, (RuNiMgAlO)x, (RuNiAlO)x, (NiAlO)x, (NiMgAlO)x) or by wet impregnation (ie, Ru/Al2O3) and characterized by nitrogen physisorption (BET), XRD, XPS, NH3-TPD, Raman and H-2-TPR techniques. The experimental results indicate that the presence of ruthenium led to dimers as dominant products.

The growth of graphene by molecular beam epitaxy from an elemental carbon precursor is a very promising technique to overcome some of the main limitations of the chemical vapour deposition approach, such as the possibility to synthesize graphene directly on a wide variety of surfaces including semiconductors and insulators. However, while the individual steps of the chemical vapour deposition growth process have been extensively studied for several surfaces, such knowledge is still missing for the case of molecular beam epitaxy, even though it is a key ingredient to optimise its performance and effectiveness. In this work, we have performed a combined experimental and theoretical study comparing the growth rate of the molecular beam epitaxy and chemical vapour deposition processes on the prototypical Ir (111) surface. In particular, by employing high-resolution fast X-ray photoelectron spectroscopy, we were able to follow the growth of both single- and multi-layer graphene in real time, and to identify the spectroscopic fingerprints of the different C layers. Our experiments, supported by density functional theory calculations, highlight the role of the interaction between different C precursor species and the growing graphene flakes on the growth rate of graphene. These results provide an overview of the main differences between chemical vapour deposition and molecular beam epitaxy growth and thus on the main parameters which can be tuned to optimise growth conditions.

This work focuses on the kinetic mechanisms responsible for the annealing behavior of radiation cluster-related defects with impact on the electrical performance of silicon sensors. Such sensors were manufactured on high resistivity n-type standard float-zone (STFZ) and oxygen enriched float-zone (DOFZ) material and had been irradiated with mono-energetic electrons of 3.5 MeV energy and fluences of 3 x 10(14) cm(-2) and 6 x 10(14) cm (-2). After irradiation, the samples were subjected either to isochronal or isothermal heat treatments in the temperature range from 80 degrees C to 300 degrees C. The specific investigated defects are a group of three deep acceptors [H(116 K), H(140 K), and H(152 K)] with energy levels in the lower half of the band gap and a shallow donor E(30 K) with a level at 0.1 eV below the conduction band. The stability and kinetics of these defects at high temperatures are discussed on the basis of the extracted activation energies and frequency factors. The annealing of the H defects takes place similarly in both types of materials, suggesting a migration rather than a dissociation mechanism. On the contrary, the E(30 K) defect shows a very different annealing behavior, being stable in STFZ even at 300 degrees C, but annealing-out quickly in DOFZ material at temperatures higher than 200 degrees C, with a high frequency factor of the order of 10(13) s(-1). Such a behavior rules out a dissociation process, and the different annealing behavior is suggested to be related to a bistable behavior of the defect. Published by AIP Publishing.