Publications

Nanocomposite thin films, sensitive to methane at the room temperature (25-30 degrees C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (H-1-NMR and C-13-NMR), Atomic Force Microscopy (AFM), SEM and Electron Paramagnetic Resonance (EPR) techniques. Film deposition was made by drop casting from a suitable solvent for the two starting materials, after mixing them in an ultrasonic bath. The thickness of these films were estimated from SEM images, and found to be around 1.3 mu m. These thin films proved to be sensitive to a threshold methane (CH4) concentration as low as 1000 ppm, at a room temperature of about 25 degrees C, without the need for heating the sensing element. The nanocomposite material has a prompt and reproducible response to methane in the case of air, with 50% relative humidity (RH) as well. A comparison of the methane sensing performances of our new nanocomposite film with that of other recently reported methane sensitive materials is provided. It is suitable for signaling gas presence before reaching the critical lower explosion limit concentration of methane at 50,000 ppm.

We report the facile and low-cost preparation as well as detailed characterization of dense arrays of passivated ferromagnetic nickel (Ni) nanotubes (NTs) vertically-supported onto solid Au-coated Si substrates. The proposed fabrication method relies on electrochemical synthesis within the nanopores of a supported anodic aluminum oxide (AAO) template and allows for fine tuning of the NTs ferromagnetic walls just by changing the cathodic reduction potential during the nanostructures' electrochemical growth. Subsequently, the experimental platform allowed further passivation of the Ni NTs with the formation of ultra-thin antiferromagnetic layers of nickel oxide (NiO). Using adequately adapted magnetic measurements, we afterwards demonstrated that the thickness of the NT walls and of the thin antiferromagneticNiO layer, strongly influences the magnetic behavior of the dense array of exchange-coupled Ni/NiO NTs. The specific magnetic properties of these hybrid ferromagnetic/antiferromagnetic nanosystems were then correlated with the morpho-structural and geometrical parameters of the NTs, as well as ultimately strengthened by additionally-implemented micromagnetic simulations. The effect of the unidirectional anisotropy strongly amplified by the cylindrical geometry of the ferromagnetic/antiferromagnetic interfaces has been investigated with the magnetic field applied both parallel and perpendicular to the NTs axis.

The matrix-assisted pulsed laser evaporation (MAPLE) technique was used for depositing thin films based on a recently developed conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT) and fullerene C60 blends. The targets used in the MAPLE process were obtained by freezing chloroform solutions with different DPP-DTT:C60 weight ratios, with the MAPLE deposition being carried at a low laser fluence, varying the number of laser pulses. The structural, morphological, optical, and electrical properties of the DPP-DTT:C60 blend layers deposited by MAPLE were investigated in order to emphasize the influence of the DPP-DTT:C60 weight ratio and the number of laser pulses on these features. The preservation of the chemical structure of both DPP-DTT and C60 during the MAPLE deposition process is confirmed by the presence of their vibrational fingerprints in the FTIR spectra of the organic thin films. The UV-VIS and photoluminescence spectra of the obtained organic layers reveal the absorption bands attributed to DPP-DTT and the emission bands associated with C60, respectively. The morphology of the DPP-DTT:C60 blend films consists of aggregates and fibril-like structures. Regardless the DPP-DTT:C60 weight ratio and the number of laser pulses used during the MAPLE process, the current-voltage characteristics recorded, under illumination, of all structures developed on the MAPLE deposited layers evidenced a photovoltaic cell behavior. The results proved that the MAPLE emerges as a viable technique for depositing thin films based on conjugated polymers featured by a complex structure that can be further used to develop devices for applications in the solar cell area.

We fabricated Sn-doped TiO2 nanotubular film via annealing of anodized TiO2 nanotubes grown on F-SnO2 (FTO) glass. Annealing was carried out at 500 degrees C in ambient air. Anatase crystal structure was achieved with no change in nanotubular morphology in respect to as-anodized amorphous TiO(2 )nanotubes. The X-ray photoelectron spectroscopy analysis revealed Sn on the surface of TiO2 film, following the thermal treatment, probably caused by the diffusion from FTO glass. Depth profile examination of the film chemical composition was conducted by elastic recoil detection analysis, which showed that in addition to the diffusion of Sn from FTO, diffusion of Ti to FTO concurrently occurred. Thus, a higher concentration of Sn was found at the bottom of the tubes, while a lower concentration was present on the tubes' surface top. This explains the improved optical response revealed by a diffuse reflectance spectroscopy. The absorption enhancement demonstrated that Sn-doped TiO2 film was efficient in the degradation of methyl orange dye under visible light.

An europium doped BaO-B2O3-BaCl2 chloroborate glass-ceramic containing a BaCl2 nanocrystalline phase was produced by melt-quenching followed by glass crystallization during annealing. Structural and morphological investigations using x-ray diffraction and scanning electron microscopy have shown fvBaCl(2) nanocrystals of about tens of nm size accompanied by a smaller amount of the BaB2O4 crystalline phase. Photoluminescence spectra have indicated the reduction of Eu3+ to Eu2+ during processing in air or a reducing atmosphere. The spectra analysis showed the presence of Eu3+ ions in the borate glass matrix, while the Eu2+ were incorporated in both the BaCl2 nanocrystals and glass matrix. Thermoluminescence properties were due to the recombination of F(Cl) centers and Eu2+ related hole centers produced by irradiation within the BaCl2 nanocrystals. The color impression of the samples and the photoluminescence quantum efficiency were influenced by the glass processing.

ZnO nanostructures with intrinsic and extended defects were prepared by rapid decomposition of zinc-propio-nate and annealing at 400 degrees C-970 degrees C. The correlation between the structure/morphology, type of native defects (photoluminescence (PL), EPR) and ferromagnetism was investigated, together with ammonia adsorption capacity. All the samples show room temperature ferromagnetism (RTFM). Crystallite size increases while the unit cell volume, c-axis constant, microstrain and saturation magnetization relax with increasing temperature; morphology varies from aggregated nanoparticles to frameworks of well-welded crystals. 400 degrees C-800 degrees C annealed samples show a broad visible and/or a prominent violet-blue PL emission and, two narrow g = 2.0065 and g = 1.9632 EPR signals. 800 degrees C-970 degrees C annealed samples exhibit very intense green-yellow photoluminescence. The intrinsic defects in conjunction with a deformed lattice and/or pinned by grain-boundaries appear responsible for RTFM and Curie temperature exceeding 700 degrees C. Tuning the morphology, PL intensity and ferromagnetic signal by choice of annealing temperature can find applications in (gas) sensing, photonic/optoelectronic and spintronic devices.

We report on new biomaterials with promising bone and cartilage regeneration potential, from sustainable, cheap resources of fish origin. Thin films were fabricated from fish bone-derived bi-phasic calcium phosphate targets via pulsed laser deposition with a KrF * excimer laser source (lambda = 248 nm, tau(FWHM) <= 25 ns). Targets and deposited nanostructures were characterized by SEM and XRD, as well as by Energy Dispersive X-ray (EDX) and FTIR spectroscopy. Films were next assessed in vitro by dedicated cytocompatibility and antimicrobial assays. Films were Ca-deficient and contained a significant fraction of beta-tricalcium phosphate apart from hydroxyapatite, which could contribute to an increased solubility and an improved biocompatibility for bone regeneration applications. The deposited structures were biocompatible as confirmed by the lack of cytotoxicity on human gingival fibroblast cells, making them promising for fast osseointegration implants. Pulsed laser deposition (PLD) coatings inhibited the microbial adhesion and/or the subsequent biofilm development. A persistent protection against bacterial colonization (Escherichia coli) was demonstrated for at least 72 h, probably due to the release of the native trace elements (i.e., Na, Mg, Si, and/or S) from fish bones. Progress is therefore expected in the realm of multifunctional thin film biomaterials, combining antimicrobial, anti-inflammatory, and regenerative properties for advanced implant coatings and nosocomial infections prevention applications.

Due to the extraordinary versatility of the perovskite structure in accommodating different dopant ions in its structure, in recent years a huge number of multifunctional perovskite materials have been developed. In this work we aim to obtain high temperature-stable and huge dielectric constant materials for supercapacitors by doping divalent Mg2+ and trivalent Sb3+ ions into the octahedral sites, and divalent Sr2+ ions into the dodecahedral sites of lead zirconate-titanate perovskite. The resulting (Pb0.95Sr0.05)(Zr0.425Ti0.45Mg0.042Sb0.083)O3-delta is examined by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), dielectric spectroscopy (DS) and resonance dielectric spectroscopy (RDS) in order to correlate composition, local structure, ion valence and chemical environment of the doped material with the dielectric properties. HRTEM evidences that a composite structure, with co-existent ferroelectric domains and relaxor nanodomains, is formed by doping. XPS shows that Sb3+ and Mg2+ substitute for the Ti4+/Zr4+ ions, pointing to these strong defects as the main cause for the appearance of the relaxor phase. DS and RDS found that the ferroelectric lead zirconate-titanate transforms into a re-entrant relaxorferroelectric composite with a huge dielectric constant of about 10(4) which remains stable (within +/- 10%) in the high temperature range up to 250 degrees C, pointing to this mechanism of relaxor phase re-entrance below the normal ferroelectric phase transition, as being responsible for the enhancement. (C) 2020 Elsevier Ltd. All rights reserved.

Chitosan-hydroxyapatite composite layers were deposited on Si substrates in radio frequency magnetron sputtering discharges. The plasma parameters calculated from the current-voltage radio frequency-compensated Langmuir probe characteristics indicate a huge difference between the electron temperature in the plasma and at the sample holder. These findings aid in the understanding of the coagulation pattern of hydroxyapatite-chitosan macromolecules on the substrate surface. An increase in the sizes of the spherical-shape grain-like structures formed on the coating surface with the plasma electron number density was observed. The link between the chemical composition of the chitosan-hydroxyapatite composite film and the species sputtered from the target or produced by excitation/ionization mechanisms in the plasma was determined on the basis of X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and residual gas mass spectrometry analysis.