National Institute Of Materials Physics - Romania

Porous reduced graphene oxide (rGO)/iron oxide nanohybrid thin films were grown through a laser-based technique onto flexible polymer, polydimethylsiloxane substrates. A frequency quadrupled pulsed Nd:YAG laser source (lambda = 266 nm, tau(FWHM) similar to 4 ns, upsilon = 10 Hz) was used for irradiation of dispersions containing the starting nano-materials, graphene oxide (GO) platelets and iron oxide nanoparticles (NPs), to be transferred to the substrates surface. The electrochemical response of the composite layers was investigated by cyclic voltammetry in dark and under UV/visible light illumination, as well as by electrochemical impedance spectroscopy. A comparative study was performed as a function of the nature of the GO base materials, monolayer or multilayer GO platelets, and relative concentration of GO/iron oxide NPs in the dispersions submitted to laser irradiation. The capacitance values of the nanohybrid materials which contain monolayer GO were found to be one order of magnitude higher as compared to their counterparts consisting of multilayer GO and iron oxide NPs. UV-visible light irradiation contributed to the significant enhancement of the electrochemical properties of the electrodes. These results indicate that the nanohybrid thin films are promising candidates as flexible electrodes in micro-supercapacitors and photoelectrochemical devices for simultaneous energy storage and solar energy conversion.

We report significant photoelectrochemical activity of Y-doped BiFeO3 (Y-BFO) epitaxial thin films deposited on Nb: SrTiO3 substrates. The Y-BFO photoanodes exhibit a strong dependence of the photocurrent values on the thickness of the films, and implicitly on the induced epitaxial strain. The peculiar crystalline structure of the Y-BFO thin films and the structural changes after the PEC experiments have been revealed by high resolution X-ray diffraction and transmission electron microscopy investigations. The crystalline coherence breaking due to the small ionic radius Y-addition was analyzed using Willliamson-Hall approach on the 2 theta-omega scans of the symmetric (00l) reflections and confirmed by high resolution TEM (HR-TEM) analysis. In the thinnest sample the lateral coherence length (L-parallel to) is preserved on larger nanoregions/ nanodomains. For higher thickness values L-parallel to is decreasing while domains tilt angles (alpha(tilt)) is increasing. The photocurrent value obtained for the thinnest sample was as high as J(ph) = 0.72 mA/cm(2), at 1.4 V(vs. RHE). The potentiostatic scans of the Y-BFO photoanodes show the stability of photoresponse, irrespective of the film's thickness. There is no clear cathodic photocurrent observation for the Y-BFO thin films confirming the n-type semiconductor behavior of the Y-BFO photoelectrodes.

We report on the successful laser transfer of biocompatible composite coatings based on polyaniline (PANI) embedded with magnetite (PANI-Fe3O4) and Lincomycin hydrochloride (PANI-Lincomycin) or Lincomycin-functionalized magnetite (PANI-Fe3O4@Lincomycin) by matrix assisted pulsed laser evaporation (MAPLE) technique. The physico-chemical investigations revealed relevant data regarding the stoichiometric deposition, morphology and topography of the as-deposited coatings. Regarding the MAPLE coatings, the FTIR studies evidenced the vibrational bands characteristic to pristine PANI material, while the SEM investigations unveiled a preferential particulate morphology (with aggregates shape and size depending on the deposited material). Additionally, the AFM measurements indicated variations of RMS value, following the Lincomycin and magnetite incorporation. The wettability measurements displayed a hydrophilic behavior of the synthesized coatings, while the electrochemical studies emphasized an enhanced resistance against corrosion in simulated body fluid when compared with bare Ti. Cellular viability, immunofluorescence and SEM results proved that the MAPLE coatings were suitable materials for beneficial adhesion, spreading and proliferation of osteoblast-like cells (MG-63). Moreover, an increased efficiency was evidenced against Staphylococcus aureus biofilm development. The multifunctional properties of the laser processed composite coatings - confirmed by cumulative biocompatible, antimicrobial and anticorrosive behaviors - recommend them as promising solutions for biomedical applications.

To avoid the deleterious effects of dopant segregation, synthesis methods that facilitate a homogenous dopant distribution in the ceria lattice were employed. Though doping ceria by wet impregnation was also credited to induce a homogeneous solid solution even in the heavy regime (concentration >= 20%, A. Corma, P. Atienzar, H. Garcia and J. Chane-Ching, Nat. Mater., 2004, 3, 394-397), no follow up investigation has been reported. Herein, we investigated ceria nanoparticles (1% Tm-CeO2 and 1% Eu-CeO2) wetimpregnated with trivalent rare-earth (Yb, 20%), bivalent (Ca, 20%) and isovalent (Zr, 30%) metals, followed by annealing in air. Homogeneity of the solid solutions of Yb-impregnated ceria was confirmed by a two-feature characterization toolbox that included X-ray diffraction, Raman spectroscopy, transmission electron microscopy, as well as up-conversion emission as a probe tool. Since the up-conversion emission of Tm was not detectable in the absence of Yb while its efficiency depends on the average distance between Yb and Tm ions, the Yb incorporation and its migration from the surface to the lattice bulk sites in wet-impregnated ceria can be "visualized" and compared with that of the Yb bulk-doped counterpart. The use of Eu luminescence as a local probe confirmed the homogeneity of solid solutions of Ca and Zr-impregnated ceria and also sustained the opposite roles of Ca and Zr as the repeller and the scavenger of oxygen vacancies, respectively. All these results suggested that heavy doping of ceria by wet impregnation with metals with +2, +3 and +4 valencies represent a facile alternative to conventional doping approaches. Therefore, the effects of the amount and the type of metal dopant on the structural properties of CeO2 could be investigated in a more systematic and probably a more reproducible manner, which would significantly increase the potential of ceria in catalysis and other applications.

Magnesium (Mg) alloys are very promising biocompatible materials for biodegradable biomedical implants, however, the main problem in using them is their fast degradation in the conditions of human body. In this work, we coated Mg-Ca (calcium) alloy substrate with hydroxyapatite (HA) to improve its resistance to corrosion and to control the in vitro degradation. Pulsed Laser Deposition technique was applied to deposit HA coatings. Their properties were investigated by X-ray diffraction, atomic force microscopy, scanning electron microscopy, high resolution transmission electron microscopy, Vickers microhardness, and Tafel plot electrochemical technique. The substrate temperature was ranged in the interval from room up to 400 degrees C. According to the obtained results, the recommended substrate temperatures are 200-300 degrees C, since higher ones lead to the HA decomposition. Furthermore, the HA films deposited at 200 and 300 degrees C show good corrosion resistance in Simulated Body Fluid. The obtained coatings are promising for a perspective use in biomedical implant applications.

We investigated the AC magnetic response of a YBa2Cu3O7 film with embedded BaZrO3 nanorods and Y2O3 nanoparticles at a static magnetic field H-dc lower than the matching field H-Phi. We proposed a practical formula for the determination of the induced current J during AC susceptibility measurements, which allows us to directly obtain the pinning potential U-c from the characteristics of electric field E versus J. We show that the dynamic critical current J(d) induced at the depinning frequency f(d) can be experimentally obtained by measuring m'(T) and m ''(T) at different frequencies and amplitudes. It was found that the value of f(d) obtained by extrapolation of J to J(d) in the PHz domain is much higher than the frequency reported for ordinary YBa2Cu3O7 thin films as determined by microwave impedance measurements. AC susceptibility, vortex dynamics, pinning energy, depinning frequency, dynamic critical current, microwave impedance measurements

The dynamic effects observed in the J-V measurements represent one important hallmark in the behavior of the perovskite solar cells. Proper measurement protocols (MPs) should be employed for the experimental data reproducibility, in particular for a reliable evaluation of the power conversion efficiency (PCE), as well as for a meaningful characterization of the type and magnitude of the hysteresis. We discuss here several MPs by comparing the experimental J-V characteristics with simulated ones using the dynamic electrical model (DEM). Pre-poling conditions and bias scan rate can have a dramatic influence not only on the apparent solar cell performance, but also on the hysteretic phenomena. Under certain measurement conditions, a hysteresis-free behavior with relatively high PCEs may be observed, although the J-V characteristics may be far away from the stationary case. Furthermore, forward-reverse and reverse-forward bias scans show qualitatively different behaviors regarding the type of the hysteresis, normal and inverted, depending on the bias pre-poling. We emphasize here that correlated double-scans, forward-reverse or reverse-forward, where the second scan is conducted in the opposite sweep direction and begins immediately after the first scan is complete, are essential for a correct assessment of the dynamic hysteresis. In this context, we define a hysteresis index which consistently assigns the hysteresis type and magnitude. Our DEM simulations, supported by experimental data, provide further guidance for an efficient and accurate determination of the stationary J-V characteristics, showing that the type and magnitude of the dynamic hysteresis may be affected by unintentional pre-conditioning in typical experiments.

In this study, we compared the structural, morphological, and optical properties of a series of Zn1-xFexO (x = 0.00, 0.01, and 0.03) powders synthesized via a hydrothermal route with and without cetyltrimethylammonium bromide as a cationic surfactant. Our results highlighted the critical effects of the surfactant and the iron concentration on the structure, morphology, and optical properties of ZnO. X-ray diffraction, Mossbauer spectroscopy, and X-ray photoelectron spectroscopy analyses indicated the presence of a single phase comprising ZnO with a hexagonal wurtzite structure in all samples and a single oxidation state (+3) for the iron (Fe3+) that replaced Zn2+ in the ZnO structure. Morphological investigations by scanning electron microscopy showed that the surfactant and Fe3+ dopant greatly affected the shape of the ZnO grains, which varied between sheets and rod-like flowers. We found that the morphological and photocatalytic properties of the two series of samples comprising iron-doped ZnO with and without the surfactant were in opposition. We propose a possible growth mechanism for the ZnO polycrystalline grains in the presence of the Fe dopant and/or surfactant. The photocatalytic properties increased for the samples prepared with surfactant as the iron content increased, which was confirmed by ultraviolet-visible reflection measurements. The photocatalytic activities of the samples prepared without surfactant decreased in both the ultraviolet and visible spectral regions as the iron content increased in the samples.

Four new Ni(II) complexes with acrylate and imidazole (Him) or imidazole derivatives [2-methylimidazole(2-MeIm)/5-methylimidazole(5-MeIm)/2-ethylimidazole(2-EtIm)] as ligands were prepared and characterized. All coordination compounds were characterized by elemental analysis, infrared (FTIR) and ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, mass spectroscopy, magnetic moments measurements and thermal analysis (TG). The resulted complexes were formulated as follows: [Ni(HIm)(2)(acr)(2)] (1), [Ni(2-MeIm)(2)(acr)(2)(H2O)] center dot H2O (2), [Ni(5-MeIm)(2)(acr)(2)]center dot H2O. (3), [Ni(2-EtIm)(2)(acr)(2)(H2O)] center dot H2O (4). On the basis of magnetic moments measurements and on UV-Vis-NIR spectra, for all Ni(II) complexes was proposed an octahedral stereochemistry. Acrylate ions act as bidentate in complexes (1) and (3); meanwhile, in (2) and (4) they behave as bidentate and unidentate. Antimicrobial activity of complexes was investigated on ATCC reference and clinical microbial strains. The MIC (minimum inhibitory concentration) values revealed moderate antimicrobial activity of complex (1) against Enterococcus faecium and of complex (2) against Pseudomonas aeruginosa and Bacillus subtilis.

Sm3+, Pr3+ and Dy3+-doped Ca3Nb1.6875Ga3.1875O12 - CNGG and Ca3Li0.275Nb1.775Ga2.95O12 - CLNGG crystals are of interest as solid-state laser materials emitting in the yellow-orange spectral range, especially for diode pumping due to their partially disordered nature. In this work, for the first time to our knowledge, single crystals of Sm, Pr and Dy-doped CNGG and CLNGG crystals were grown by the Czochralski method. For the doping of CNGG and CLNGG crystals, five new stoichiometric garnets were synthesised by solid-state reaction method: praseodymium-gallium-garnet (PrGG), dysprosium-gallium-garnet (DyGG) and praseodymium-lithium-niobium gallium-garnet (PrLNGG), samarium-lithium-niobium-gallium-garnet (SmLNGG), and dysprosium-lithium-niobium-gallium-garnet (DyLNGG). Samarium-gallium-garnet (SmGG) was also sintered and used for the doping of Sm:CNGG crystal. Structural properties of sintered materials and grown crystals were investigated by X-ray diffraction and the chemical compositions of the grown crystals were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) method. The spectroscopic investigations of the grown crystals have shown that they are promising laser materials in the yellow-orange spectral range.