National Institute Of Materials Physics - Romania

Properties of surface species of the nematic mixture E7 in contact with inorganic oxides (especially those containing more or less aluminium ions) are in detail investigated by infrared spectroscopy and thermogravimetry. The absorption infrared peaks were decomposed into Gaussian components, the procedure allowing an easier comparison with the behaviour of related composites. We worked at enough small concentrations of the E7 relatively to support this ratio permitting the (partial) elimination of the species belonging to the bulk. Species put here in evidence are species that are hydrogen bonded to the surface of OH groups, molecules randomly oriented on the surface, some species bonded by involvement of pi electrons of the CN group to the aluminium ions, thus implying a strong interaction to the support. Supramolecular assemblies of E7 molecules are thus followed up.

Properties of surface species of the nematic mixture E7 in contact with inorganic oxides (especially those containing more or less aluminium ions) are in detail investigated by infrared spectroscopy and thermogravimetry. The absorption infrared peaks were decomposed into Gaussian components, the procedure allowing an easier comparison with the behaviour of related composites. We worked at enough small concentrations of the E7 relatively to support this ratio permitting the (partial) elimination of the species belonging to the bulk. Species put here in evidence are species that are hydrogen bonded to the surface of OH groups, molecules randomly oriented on the surface, some species bonded by involvement of pi electrons of the CN group to the aluminium ions, thus implying a strong interaction to the support. Supramolecular assemblies of E7 molecules are thus followed up.

This article's objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU-TiO2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 degrees C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO2 NW sample contains TiO2 tetragonal anatase (A), cubic Ti0.91O (C), and orthorhombic Ti2O3 (OR), as well as monoclinic H2Ti3O7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4 degrees and 48 degrees belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4 degrees is explained to be a consequence of the interaction of TiO2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765-771 cm(-1) and 3304-3315 cm(-1) from 4.68 to 4.21 and 3.83 for TPU and the TPU-TiO2 NW composites, respectively, with TiO2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm(-1) and 635 cm(-1), which were assigned to the vibrational modes E-g in TiO2 A and E-g in H2Ti3O7 (ITiO2-A/I-H2Ti3O7), respectively, from 3.45 in TiO2 NWs to 0.94-0.96 in the TPU-TiO2 NW composites, which indicates that the adsorption of TPU onto TiO2 NWs involves an exchange reaction of TPU in the presence of TiO2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of TixO2x-mn, Ti2O3, and Ti0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380-650 nm, in the presence of TiO2 NW. After increasing the TiO2 NW concentration in the TPU-TiO2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO2 NW surface from 12.6 degrees to 32 degrees and 45.9 degrees, respectively, took place.

This article's objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU-TiO2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 degrees C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO2 NW sample contains TiO2 tetragonal anatase (A), cubic Ti0.91O (C), and orthorhombic Ti2O3 (OR), as well as monoclinic H2Ti3O7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4 degrees and 48 degrees belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4 degrees is explained to be a consequence of the interaction of TiO2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765-771 cm(-1) and 3304-3315 cm(-1) from 4.68 to 4.21 and 3.83 for TPU and the TPU-TiO2 NW composites, respectively, with TiO2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm(-1) and 635 cm(-1), which were assigned to the vibrational modes E-g in TiO2 A and E-g in H2Ti3O7 (ITiO2-A/I-H2Ti3O7), respectively, from 3.45 in TiO2 NWs to 0.94-0.96 in the TPU-TiO2 NW composites, which indicates that the adsorption of TPU onto TiO2 NWs involves an exchange reaction of TPU in the presence of TiO2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of TixO2x-mn, Ti2O3, and Ti0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380-650 nm, in the presence of TiO2 NW. After increasing the TiO2 NW concentration in the TPU-TiO2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO2 NW surface from 12.6 degrees to 32 degrees and 45.9 degrees, respectively, took place.

As metasurfaces begin to find industrial applications there is a need to develop scalable and cost-effective fabrication techniques which offer sub-100 nm resolution while providing high throughput and large area patterning. Here we demonstrate the use of UV-Nanoimprint Lithography and Deep Reactive Ion Etching (Bosch and Cryogenic) towards this goal. Robust processes are described for the fabrication of silicon rectangular pillars of high pattern fidelity. To demonstrate the quality of the structures, metasurface lenses, which demonstrate diffraction limited focusing and close to theoretical efficiency for NIR wavelengths lambda is an element of (1.3 mu m, 1.6 mu m), are fabricated. We demonstrate a process which removes the characteristic sidewall surface roughness of the Bosch process, allowing for smooth 90-degree vertical sidewalls. We also demonstrate that the optical performance of the metasurface lenses is not affected adversely in the case of Bosch sidewall surface roughness with 45 nm indentations (or scallops). Next steps of development are defined for achieving full wafer coverage.

Green nanotechnology is a rapidly growing field linked to using the principles of green chemistry to design novel nanomaterials with great potential in environmental and health protection. In this work, metal and semiconducting particles (AuNPs, AgClNPs, ZnO, AuZnO, AgClZnO, and AuAgClZnO) were phytosynthesized through a "green" bottom-up approach, using burdock (Arctium lappa L.) aqueous extract. The morphological (SEM/TEM), structural (XRD, SAED), compositional (EDS), optical (UV-Vis absorption and FTIR spectroscopy), photocatalytic, and bio-properties of the prepared composites were analyzed. The particle size was determined by SEM/TEM and by DLS measurements. The phytoparticles presented high and moderate physical stability, evaluated by zeta potential measurements. The investigation of photocatalytic activity of these composites, using Rhodamine B solutions' degradation under solar light irradiation in the presence of prepared powders, showed different degradation efficiencies. Bioevaluation of the obtained composites revealed the antioxidant and antibacterial properties. The tricomponent system AuAgClZnO showed the best antioxidant activity for capturing ROS and ABTS center dot(+) radicals, and the best biocidal action against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa. The "green" developed composites can be considered potential adjuvants in biomedical (antioxidant or biocidal agents) or environmental (as antimicrobial agents and catalysts for degradation of water pollutants) applications.

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.

In this article, we review recent progress concerning the development of sensorial platforms based on graphene derivatives and conducting polymers (CPs), alternatively deposited or co-deposited on the working electrode (usually a glassy carbon electrode; GCE) using a simple potentiostatic method (often cyclic voltammetry; CV), possibly followed by the deposition of metallic nanoparticles (NPs) on the electrode surface (ES). These materials have been successfully used to detect an extended range of biomolecules of clinical interest, such as uric acid (UA), dopamine (DA), ascorbic acid (AA), adenine, guanine, and others. The most common method is electrochemical synthesis. In the composites, which are often combined with metallic NPs, the interaction between the graphene derivatives-including graphene oxide (GO), reduced graphene oxide (RGO), or graphene quantum dots (GQDs)-and the CPs is usually governed by non-covalent functionalization through pi-pi interactions, hydrogen bonds, and van der Waals (VW) forces. The functionalization of GO, RGO, or GQDs with CPs has been shown to speed up electron transfer during the oxidation process, thus improving the electrochemical response of the resulting sensor. The oxidation mechanism behind the electrochemical response of the sensor seems to involve a partial charge transfer (CT) from the analytes to graphene derivatives, due to the overlapping of pi orbitals.

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.

Cu2SnSe3 (CTSe) is a polyvalent material that can be used as an absorber layer for thin film solar cells or as a starting layer for the synthesis of CZTSe or CZTSSe compounds. Obtaining CTSe single phase films with opti-mized properties for thin film solar cells is a difficult task. A systematic study using both metallic and binary chalcogenides precursors for the formation of the CTSe phase was not performed. The films consisting of four different stacks (Sn\Cu, SnSe2\Cu, Sn\Cu2Se, and SnSe2\Cu2Se) were prepared by magnetron sputtering on soda lime glass (SLG) and molybdenum (Mo) coated SLG substrates, followed by annealing at 550 degrees C under Sn + Se atmosphere. X-ray diffraction and Raman spectroscopy results indicated the formation of a single CTSe phase in most of the stacks deposited on both substrates. Scanning electron microscopy images showed compact surfaces with large grains in the films deposited on Mo substrate, while the films on SLG have more voids on their sur-faces. The elemental analysis measured by energy dispersive spectroscopy revealed stoichiometric films on Mo, and copper and tin rich compositions on SLG substrates. The band gap values inferred by conventional spec-troscopy are between 0.81 and 1.95 eV. It was found that the SnSe2\Cu and Sn\Cu2Se stacks are preferred for the formation of a single CTSe phase, with dense surface morphology, a stoichiometric composition, and an optimal absorber layer band gap. This study opens the way to comprehend the formation reactions during the seleni-zation of metallic and binary chalcogenides precursors towards the optimization of kesterite absorber for photovoltaic device fabrication.