National Institute Of Materials Physics - Romania

The aim of our research was to synthesize and investigate the physico-chemical and biological features of composite coatings based on poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and commercial calcium phosphates (CaPs), hydroxyapatite and beta-tricalcium phosphate, obtained by means of matrix assisted pulsed laser evaporation (MAPLE) technique. In this respect, laser fluence and dropcast studies were performed for pristine polymer and PHBV-CaPs composites. The microstructure of the synthesized coatings was investigated by scanning electron microscopy, while for the chemical structure and functional integrity we performed Fourier transform infrared spectroscopy comparative analysis. By using the X-ray diffraction measurements we experimentally evaluated the crystalline nature of the obtained composite materials, while relevant data regarding the hydrophilic/hydrophobic behavior of the synthesized coatings were obtained by performing static CA measurements. The biocompatibility of PHBV/CaPs coatings was evaluated by performing cellular adhesion and differentiation in vitro assays on mesenchymal stem cells. (C) 2017 Elsevier B.V. All rights reserved.

In this study, coatings based on lysozyme embedded into a matrix of polyethylene glycol (PEG) and polycaprolactone (PCL) were fabricated by two different methods (Matrix Assisted Pulsed Laser Evaporation -MAPLE and Dip Coating) for obtaining antimicrobial coatings envisaged for long term medical applications. Coatings with different PEG: PCL compositions (3: 1; 1: 1; 1: 3) were synthesized in order to evaluate the antimicrobial activity of lysozyme embedded into the polymeric matrix. The main surface features, such as roughness and wettability, with impact on the microbial adhesion as well as on the eukaryote cell function were measured. The obtained composite coatings exhibited a significant antibacterial activity against Escherichia coli, Bacillus subtilis, Enterococcus faecalis and Staphylococcus aureus strains. As well, specific blended coatings showed appropriate viability, good spreading and normal cell morphology of SaOs2 human osteoblasts and mesenchymal stem cells (MSCs). These investigations highlight the suitability of biodegradable composites as implant coatings for decreasing the risk of bacterial contamination associated with prosthetic procedures. (C) 2016 Elsevier B.V. All rights reserved.

Mixed layers of azomethine oligomers containing 2,5-diamino-3,4-dicyanothiophene as central unit and triphenylamine (LV5) or carbazol (LV4) at both ends as donor and fullerene derivative, [6,6]-phenylC61 butyric acid butyl ester ([C60] PCB-C4) as acceptor, have been prepared by Matrix Assisted Pulsed Laser Evaporation (MAPLE) on glass/ITO and Si substrates. The effect of weight ratio between donor and acceptor (1: 1; 1: 2) and solvent type (chloroform, dimethylsulphoxide) on the optical (UV-vis transmission/absorption, photoluminescence) and morphological properties of LV4 (LV5): [C60] PCB-C4 mixed layers has been evidenced. Dark and under illumination I-V characteristics of the heterostructures realized with these mixed layers sandwiched between ITO and Al electrodes have revealed a solar cell behavior for the heterostructures prepared with both LV4 and LV5 using chloroform as matrix solvent. The solar cell structure realized with oligomer LV5, glass/ITO/LV5: [C60] PCB-C4 (1: 1) has shown the best parameters. (C) 2017 Elsevier B.V. All rights reserved.

Organic heterostructures based on poly(3-hexylthiophene) (P3HT) and fullerene (C60) as blends or multilayer were deposited on Al:ZnO (AZO) by Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. The AZO layers were obtained by Pulsed Laser Deposition (PLD) on glass substrate, the high quality of the films being reflected by the calculated figure of merit. The organic heterostructures were investigated from morphological, optical and electrical point of view by atomic force microscopy (AFM), UV-vis spectroscopy, photoluminescence (PL) and current-voltage (I-V) measurements, respectively. The increase of the C60 content in the blend heterostructure has as result a high roughness. Compared with the multilayer heterostructure, those based on blends present an improvement in the electrical properties. Under illumination, the highest current value was recorded for the heterostructure based on the blend with the higher C60 amount. The obtained results showed that MAPLE is a useful technique for the deposition of the organic heterostructures on AZO as transparent conductor electrode. (C) 2017 Elsevier B.V. All rights reserved.

The crystallization mechanism of sol-gel-derived NaYF4:(Yb, Er) up-converting phosphors has been studied by differential scanning calorimetry analysis using both model-free and model fitting approaches. Structural and optical data have shown that the hexagonal NaYF4:(Yb, Er) phase crystallization process occurs at around 315 degrees C as a result of the thermal decomposition of the metal trifluoroacetates. As the annealing temperature increases, sphere-like microcrystals of about 1-2 mu m size (at 300 degrees C) break up into smaller ones (400-500 nm size) and finally collapse at higher temperatures (600 degrees C); the up-conversion luminescence signal intensity increases due to the crystallinity improvement and dehydration process. The crystallization process can be described as an autocatalytic-type reaction where the accompanying cubic NaYF4 phase played a catalytic role by reducing the energy barrier against the crystallization of the hexagonal NaYF4 phase, causing its fast self-accelerated crystallization. The energy resulting from the disintegration process of the initial NaYF4 microcrystals contributed to the growth and agglomeration processes and finally the collapse of the crystalline fragments with increasing temperature.

The exciton-phonon interaction, considered as a stimulated Raman scattering process, is studied in different semiconductor mixtures: PbI2/TiO2, PbI2/Si and CdS/Si. Raman spectra recorded at excitation wavelengths of 514.5 and 488 nm for PbI2 and CdS, respectively, reveal a strong enhancement of the Raman lines peaked at 97 and 305 cm(-1), evaluated by the ratio I-TK/I-300 (K) between the relative intensities of the spectra recorded in the temperature range of 88-300 K. It is found that PbI2 and CdS exhibit a decrease in the Raman intensity modes with decreasing temperature, while in TiO2 and Si an increase in the Raman lines intensities peaked at 138 and 520 cm(-1) is observed. This behavior can be explained by an energy transfer process from PbI2 or CdS towards TiO2 and Si. This explanation is supported by the schematic potential energy levels diagram obtained from the density of states, which is calculated using the density functional theory. According to this energy levels diagram, the electrons are expected to migrate directly from the conduction band (CB) energetic levels of the PbI2 and CdS towards the CB levels of TiO2 and Si.

Graphene is widely used in nanotechnologies to amplify the photocatalytic activity of TiO2, but the development of TiO2/graphene composites imposes the assessment of their risk to human and environmental health. Therefore, reduced graphene oxide was decorated with two types of TiO2 particles co-doped with 1% iron and nitrogen, one of them being obtained by a simultaneous precipitation of Ti3+ and Fe3+ ions to achieve their uniform distribution, and the other one after a sequential precipitation of these two cations for a higher concentration of iron on the surface. Physico-chemical characterization, photocatalytic efficiency evaluation, antimicrobial analysis and biocompatibility assessment were performed for these TiO2-based composites. The best photocatalytic efficiency was found for the sample with iron atoms localized at the sample surface. A very good anti-inhibitory activity was obtained for both samples against biofilms of Gram-positive and Gram-negative strains. Exposure of human skin and lung fibroblasts to photocatalysts did not significantly affect cell viability, but analysis of oxidative stress showed increased levels of carbonyl groups and advanced oxidation protein products for both cell lines after 48 h of incubation. Our findings are of major importance by providing useful knowledge for future photocatalytic self-cleaning and biomedical applications of graphene-based materials.

The implementation of dense, one-selector one-resistor (1S1R), resistive switching memory arrays, can be achieved with an appropriate selector for correct information storage and retrieval. Ovonic threshold switches (OTS) based on chalcogenide materials are a strong candidate, but their low thermal stability is one of the key factors that prevents rapid adoption by emerging resistive switching memory technologies. A previously developed map for phase change materials is expanded and improved for OTS materials. Selected materials from different areas of the map, belonging to binary Ge-Te and Si-Te systems, are explored. Several routes, including Si doping and reduction of Te amount, are used to increase the crystallization temperature. Selector devices, with areas as small as 55 x 55 nm(2), were electrically assessed. Sub-threshold conduction models, based on Poole-Frenkel conduction mechanism, are applied to fresh samples in order to extract as-processed material parameters, such as trap height and density of defects, tailoring of which could be an important element for designing a suitable OTS material. Finally, a glass transition temperature estimation model is applied to Te-based materials in order to predict materials that might have the required thermal stability. A lower average number of p-electrons is correlated with a good thermal stability.

Thick slices mechanically polished cut from a pure benzil ingot grown from melt in a modified Bridgman-Stockbarger configuration were irradiated with Ni ions having a specific energy of 11.4 MeV/u at different fluences. The effect of radiation on the properties of bulk benzil has been investigated. The chemical structure was not substantially affected as shown by infrared spectrum. The changes induced on the disorder degree have been evaluated from the Urbach law and X Ray Diffraction measurements. The morphology and surface topography have been analyzed emphasising a decrease in the size of granules and an increase in the surface roughness by irradiation. No effect of irradiation on the photoluminescence emission and optical nonlinear properties has been evidenced. These results recommend benzil as candidate for applications in space technology.

BaFBr:Er3+ @SiO2 core-shell composites were synthesized starting from BaFBr:Er3+ phosphor core grains (BaFBr doped with 1 at% Er3+) prepared by coprecipitation method. A sol-gel process was used to obtain the outer Si02 layer shell from silica sol precursor. The polycrystalline BaFBr:Er3+ @SiO2 heterostructures were formed following calcination at 700 degrees C, in air. The resulting material was characterized in terms of microstructure, photoluminescence and up-conversion luminescence properties. The results indicate that the as-obtained composite has a core-shell structure and shows good luminescence properties. The BaFBr:Er3+ @SiO2 heterostructure is made of BaFBr:Er3+ square sheets encased in a SiO2 shell layer with thickness values between 100 and 400 nm. Under 810 nm laser light pumping, the core-shell heterostructure exhibits Er3+ green up conversion luminescence bands ((H-2(11/2),S-4(3/2)) -> I-4(15/2)) at 525 and 545 nm, ascribed to a two-photon process.