National Institute Of Materials Physics - Romania

Electrodes constituted by nitrogen-doped reduced graphene oxide (NrGO) in combination with NiO nanostructures were fabricated by means of reactive inverse matrix assisted pulsed laser evaporation technique. The structure-composition of the electrode composites was tailored by laser-inducing chemical reactions of graphene oxide (GO) flakes with different precursor molecules (citric acid, ascorbic acid and imidazole) during GO deposition. Structural characterizations reveal the formation of wrinkles and nanoholes in the NrGO sheets, besides their coating with NiO nanostructures. Compositional studies disclose that imidazole precursor promotes the synthesis of NrGO with the largest degree of reduction and nitrogen doping (mainly with graphitic and pyridinic N). Electrochemical analyses of the obtained electrodes reveal that NiO nanostructures increase surface charge storage processes (double layer - pseudocapacitive) over diffusive ones, being the imidazole-based electrodes the ones exhibiting the best performance (up to 114 F cm(-3) at 10 mV s(-1)). Symmetric and asymmetric electro-chemical capacitors were also fabricated showing excellent robustness over 10,000 charge-discharge cycles at high specific currents.

We recall theoretical studies on transient transport through interacting mesoscopic systems. It is shown that a generalized master equation (GME) written and solved in terms of many-body states provides the suitable formal framework to capture both the effects of the Coulomb interaction and electron-photon coupling due to a surrounding single-mode cavity. We outline the derivation of this equation within the Nakajima-Zwanzig formalism and point out technical problems related to its numerical implementation for more realistic systems which can neither be described by non-interacting two-level models nor by a steady-state Markov-Lindblad equation. We first solve the GME for a lattice model and discuss the dynamics of many-body states in a two-dimensional nanowire, the dynamical onset of the current-current correlations in electrostatically coupled parallel quantum dots and transient thermoelectric properties. Secondly, we rely on a continuous model to get the Rabi oscillations of the photocurrent through a double-dot etched in a nanowire and embedded in a quantum cavity. A many-body Markovian version of the GME for cavity-coupled systems is also presented.

We have investigated the structural and electronic properties of the alpha-GeSe surface using atomic force microscopy, scanning tunneling microscopy and density functional theory calculations. GeSe belongs to the group-VI transition metal monochalcogenides and occurs in two polymorphs, alpha-GeSe and beta-GeSe. The most redundant polymorph, alpha-GeSe, has a structure that is very similar to black phosphorene. The alpha-GeSe surface has a centered rectangular unit cell with dimensions a = 3.8 angstrom and b = 4.4 angstrom, respectively. In scanning tunneling microscopy images only the Se atoms are resolved owing to the substantial transfer of electrons from the Ge to the Se surface atoms. This experimental finding is fully in line with density functional theory calculations. Scanning tunneling spectroscopy reveals that the alpha-GeSe surface is a p-type semiconductor with a band gap of 1.0 eV. The GeSe surface is stable at ambient conditions, which makes this material very appealing for technological applications.

The crystallization of ferroelectric (Hf,Zr)O-2 thin films is achieved by playing on the deposition pressure during reactive magnetron sputtering from a Hf/Zr metallic target. Postdeposition annealing was tried at different temperatures in order to optimize the quality of the samples. Structural characterizations are performed by transmission electron microscopy (TEM) and electrical characterizations are carried out. TEM analyses reveal that the samples deposited at a low working pressure show no orthorhombic phase, and thus are not ferroelectric, whereas the samples deposited at higher working pressure show the orthorhombic ferroelectric phase. The maximum remnant polarization is 6 mu C/cm(2) and is obtained for the sample annealed at 600 degrees C. The maximum cycles to breakdown is higher than 2 x 10(10) cycles and is reached for the sample annealed at 400 degrees C. These results are discussed in the matter of phase transition and oxygen vacancies redistribution. (c) 2019 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

N-doped defective graphene [(N)G] obtained by pyrolysis at 900 degrees C of chitosan contains about 3.7% of residual N atoms, distributed as pyridinic, pyrrolic and graphitic N atoms. It has been found that (N)G acts as basic catalyst promoting two classical C-C bond forming nucleophilic additions in organic chemistry, such as the Michael and the Henry additions. Computational calculations at DFT level of models corresponding to the various N atoms leads to the conclusion that N atoms are more stable at the periphery of the graphene sheets and that H adsorption on these sites is a suitable descriptor to correlate with the catalytic activity of the various sites. According to these calculations the most active sites are pyridinic N atoms at zig-zag edges of the sheets. In addition, N as dopant changes the reactivity of the neigh. bour C atoms. Water was found a suitable solvent to achieve high conversions in both reactions. In this solvent the initial distribution of N atoms is affected due to the easy protonation of the N-py to N-pyH sites. As an effect, C edge sites adjacent at N-PyH with an appropriate reactivity towards the alpha-C-H bond breaking are formed. The present results show the general activity of N-doped graphene as base catalysts and illustrate the potential of carbocatalysis to promote reactions of general interest in organic synthesis. (C) 2019 Elsevier Inc. All rights reserved.

The paper describes an innovative bio-design of some hybrid nanoarchitectures containing bioartificial membranes and silver nanoparticles phytogenerated by using a natural extract Caryophyllus aromaticus (cloves) that contains many bioactive compounds. Two kinds of liposomes with and without chlorophyll a (Chla) obtained through thin film hydration method were used to achieve bio-green-generated hybrids by a simple, cost effective bottom-up approach. The characteristic peaks of CE-nAg monitored by UV-Vis absorption have firstly demonstrated the biohybrids formation. The slightly blue shift and fluorescence quenching observed by fluorescence emission spectra highlighted the formation of hybrid systems by biointeraction between lipid vesicles and silver nanoparticles. The incorporation of silver nanoparticles in lipid vesicles resulted in significant changes of FT-IR spectra of liposomes, indicating a reorganization of biomimetic membranes. All the microscopic methods (SEM, AFM and TEM) confirmed the biosynthesis of "green" AgNPs together with associated biohybrids, their spherical and quasi-spherical shapes with nano-scaled size. By TEM assay it was shown that CE-nAg are surrounded by petal like cloud structures that consist of biopolymers like proteins or polysaccharides and other phytochemicals arising from clove extract. EDS spectra confirmed the formation of phyto-nanoAg and also the presence of silver in the biohybrids. In addition, Selected Area Electron Diffraction showed characteristic polycrystalline ring patterns for a cubic structure of the clove-generated AgNPs. The hybrid materials showed efficient physical stability, ie. xi value of - 28.0 mV (for biohybrids without Chla, BH) and of - 31.7 mV (for biohybrids labelled with Chla, Chla-BH), assured by strong electrostatic repulsive forces between particles. The "green" nano-silver particles (CE-nAg) showed remarkable antioxidant activity (AA = 90.2%). The biohybrids loaded with clove-AgNPs proved to be more effective, scavenging about 98.8% of free radicals (in case of ChlaBH), and of 92.6% (in case of BH). The antibacterial effectiveness showed that green AgNPs combine in a synergistic manner the antibacterial properties of clove extract with those of silver, resulting in an enhancement of inhibition diameter, by 20%. Chla-BH proved to be more potent against Escherichia coli, than BH, exhibiting an inhibition diameter of 42 mm. Regarding the in vitro cytotoxicity against tumour cells, the CE-nAg concentration significantly influenced the cell viability, ie. IC50 was 3.6% (v/v) for HT-29 cells. Chla-BH was more effective against HT-29 cancer cells at the concentrations ranging from 0 to 18% (v/v), when the normal cells were not affected. Clove-generated AgNPs exhibited haemolytic activity against hRBCs, while the biohybrids were haemocompatible. The action mechanism on the two cell lines (mouse fibroblast L929 cells and human colorectal adenocarcinoma HT-29 cells) investigated by fluorescence microscopy demonstrated that CE-nAg killed almost all the cells (94%) through necrosis at a concentration of 33.4% (v/v). The treatment of HT-29 cells with BH resulted in: 71.5% viable cells, 19.5% apoptotic and only 9% necrotic cells, while in the case of Chla-BH treatment, only 77.5% cells were viable, 16% cells were apoptotic and 6.5% were necrotic. In this way, the developed silver-based nanoparticles can represent viable promoters to develop new biohybrids with improved features, e.g. antioxidant and antibacterial effectiveness, haemolytic activity and greater specificity towards tumour cells.

Ferroelectric capacitors based on aluminium (Al) doped hafnium oxide (HfO2) thin films grown on silicon substrates were fabricated by Atomic Layer Deposition (ALD), taking into account two methods. The first one involved the growth of a binary oxide, in a laminar way, by alternating the ALD cycles of HfO2 and Al2O3, and the second, the two precursors were sequentially mixed on the surface. The composition and structure of deposited aluminium doped hafnium oxide (Al: HfO2) thin films have been studied using X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXRD). XPS measurements show the formation of opposite ferroelectric polarization areas. Via GIXRD, it was found that the Al: HfO2 films deposited on Si have a structure with polycrystalline domains. Recording and investigation of ferroelectric domains were performed by Piezoresponse Force Microscopy (PFM), while the electrical performances of obtained devices were analysed by capacitance-voltage (C-V) and current-voltage (I-V) characteristics. The PFM measurements show there is a mechanical non-zero response even outside the written area and for an appropriate value of the electrical stress the difference in phase between successive areas is saturated to a value close to 180 degrees. The atomic force microscopy (AFM) analyses indicate a very low value of roughness average, for all grown thin films, similar to 0.2 nm, for a thickness of similar to 7 nm. From C-V characteristics, the memory window was extracted and the calculated values were found to be 0.8 V for the device obtained by the first ALD method, and 0.44 V for the second one, respectively. Moreover, in the case of the device based on the ferroelectric layer grown by the second ALD method, the memory window extends over a much wider applied voltage domain, in the range (+/- 4 V; +/- 8 V), at a signal of 100 kHz.

In this work, rapid thermal annealing (RTA) was applied to indium tin oxide (ITO) films in ambient atmosphere, resulting in significant improvements of the quality of the ITO films that are commonly used as conductive transparent electrodes for photovoltaic structures. Starting from a single sintered target (purity 99.95%), ITO thin films of predefined thickness (230 nm, 300 nm and 370 nm) were deposited at room temperature by radio-frequency magnetron sputtering (rfMS). After deposition, the films were subjected to a RTA process at 575 degrees C (heating rate 20 degrees C/s), maintained at this temperature for 10 minutes, then cooled down to room temperature at a rate of 20 degrees C/s. The film structure was modified by changing the deposition thickness or the RTA process. X-ray diffraction investigations revealed a cubic nanocrystalline structure for the as-deposited ITO films. After RTA, polycrystalline compounds with a textured (222) plane were observed. X-ray photon spectroscopy was used to confirm the beneficial effect of the RTA treatment on the ITO chemical composition. Using a Tauc plot, values of the optical band gap ranging from 3.17 to 3.67 eV were estimated. These values depend on the heat treatment and the thickness of the sample. Highly conductive indium tin oxide thin films (rho = 7.4 x 10(-5) Omega cm) were obtained after RTA treatment in an open atmosphere. Such films could be used to manufacture transparent contact electrodes for solar cells.

In this work we prepared films of amorphous germanium nanoparticles embedded in SiO2 deposited by magnetron sputtering on Si and quartz heated substrates at 300, 400 and 500 degrees C. Structure, morphology, optical, electrical and photoconduction properties of all films were investigated. The Ge concentration in the depth of the films is strongly dependent on the deposition temperature. In the films deposited at 300 degrees C, the Ge content is constant in the depth, while films deposited at 500 degrees C show a significant decrease of Ge content from interface of the film with substrate towards the film free surface. From the absorption curves we obtained the Ge band gap of 1.39 eV for 300 degrees C deposited films and 1.44 eV for the films deposited at 500 degrees C. The photocurrents are higher with more than one order of magnitude than the dark ones. The photocurrent spectra present different cutoff wavelengths depending on the deposition temperature, i.e. 1325 nm for 300 degrees C and 1267 nm for 500 degrees C. These films present good responsivities of 2.42 AW(-1) (52 mu W incident power) at 300 degrees C and 0.69 AW(-1) (57 mW) at 500 degrees C and high internal quantum efficiency of similar to 445% for 300 degrees C and similar to 118% for 500 degrees C.

ZnxCo1-xFe2O4/SiO2 (x = 0, 0.25, 0.50, 0.75, 1.00) nanocomposites (NCs) have been investigated through structural, morphological and magnetic measurements. X-ray diffraction and Mossbauer data indicated the presence of nanocrystalline mixed cubic spinel. The lattice parameters gradually decreased with increasing Zn content and follow Vegard's law. The crystallite size, X-ray density and porosity of ZnxCo1-xFe2O4 decreased with increasing Zn content. The ferrite nanoparticles spherical shape and size (32.0-6.5, 17.5-8.1 and 36.2-18.6 nm for the NCs annealed at 500, 800 and 1100 degrees C, respectively) was established by transmission electron microscopy. The Mossbauer spectra showed the characteristic magnetic patterns of Co and Zn spinels. The shape of hysteresis loops revealed the dependence of superparamagnetic behavior on the structural properties. The saturation magnetization (M-s) and coercive field (H-c) were also influenced by Co substitution with Zn, showing the decrease of M-s and H-c. The replacement of magnetic Co2+ with the zero magnetic moment Zn2+ induces a gradual reduction of magnetocrystalline anisotropy and decrease of H-c. (C) 2019 Elsevier B.V. All rights reserved.