National Institute Of Materials Physics - Romania

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.

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.

We present the multifrequency measurements of the surface resistance of spark-plasma-sintered MgB2 performed through a dielectric loaded resonator operating at 16.5 and 26.7 GHz. By normally applying magnetic fields <= 1.2 T to the sample surface, we drove it in the mixed state. By means of data-rooted analysis, we found that the sample vortex dynamics could be fully described within a single-component approach. Pinning phenomena were present and characterized by a depinning frequency smaller than the measurement ones. The multiband nature of the superconductor emerged in the flux-flow resistivity, whose field dependence could be interpreted well within theoretical models. By exploiting them, the upper critical field was extracted in the low-temperature range, which exhibited a consistent temperature trend with the values obtained at the onset of the resistive transition near Tc, and was well in line with literature data on other polycrystalline samples.

In this work, Tungsten(W)-doped TiO2 nanoparticles were synthesized using the sol-gel method and were used as electrode materials in supercapacitor applications. The structural and morphological properties of the prepared samples were analyzed by means of XRD, STEM, TEM, and XPS. The analysis of the defect centers was carried out using EPR spectroscopy. The electrochemical analysis of the assembled supercapacitor was done using cyclic voltammetry, galvanostatic cycling with potential limitation technique, potentiostatic electrochemical impedance spectroscopy, and voltage-holding experiments. All the presented samples showed paramagnetic defects in the EPR analysis, while 0.5% W-doped TiO2 showed a maximum signal intensity. The supercapacitor performance from the synthesized electrode material showed highly encouraging results. The equivalent series resistance (R-s) value for all the designs showed values under "1 omega,' which reflects high conductivity. As the maximum EPR intensity comes from TiO2 doped with 0.5% W, the supercapacitor performance of this sample was tested with a newly designed five-electrode system. This design showed superior performance compared to any other used designs with a specific capacitance of 25.5 F g(-1), with an energy density of 14.16 Wh kg (-1 )at 302 kW kg (-1).

Multifunctional magnetic nanocomposites are among those heterogeneous nanosized systems where at least one phase component is magnetic and can act as an intermediate of either the actuation or the response of the overall system. The main advantage of heterogeneous nanosystems is the possibility of combining and inter-influencing the electronic properties of constituent interfaced nanophases. Consequently, unique physico-chemical properties of the hybrid materials of interest in various applications can be obtained. This Special Issue of Nanomaterials highlights the most advanced processing and characterization tools of some multifunctional magnetic nanocomposites and heterogeneous systems of interest in various applications, from biomedicine to sensoristics and energy-saving materials.

In our work, the kinetics of martensitic transformations and the influence of thermal treatments on martensitic transformations, as well as the related magnetic properties of the Ni49Mn32Ga19 ferromagnetic shape memory melt-spun ribbons, have been investigated. Thermal treatments at 673 K for 1, 4 and 8 h can be considered an instrument for fine-tuning the performance parameters of alloys. One-hour thermal treatments promote an improvement in the crystallinity of these otherwise highly textured ribbons, reducing internal defects and stress induced by the melt-spinning technique. Longer thermal treatments induce an important magnetization rise concomitantly with a slight and continuous increase in martensitic temperatures and transformation enthalpy. The activation energy, evaluated from differential scanning calorimeter experimental data with a Friedman model, significantly increases after thermal treatments as a result of the multi-phase coexistence and stabilization of the non-modulated martensitic phase, which increases the reverse martensitic transformation hindrance.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

In this study, we report the performance improvement of wound dressings by covering them with magnetite-based nanostructured coatings. The magnetite nanoparticles (Fe3O4 NPs) were functionalized with Nigella sativa (N. sativa) powder/essential oil and dicloxacillin and were synthesized as coatings by matrix assisted pulsed laser evaporation (MAPLE). The expected effects of this combination of materials are: (i) to reduce microbial contamination, and (ii) to promote rapid wound healing. The crystalline nature of core/shell Fe3O4 NPs and coatings was determined by X-ray diffraction (XRD). Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) have been coupled to investigate the stability and thermal degradation of core/shell nanoparticle components. The coatings' morphology was examined by scanning electron microscopy (SEM). The distribution of chemical elements and functional groups in the resulting coatings was evidenced by Fourier transform infrared (FTIR) spectrometry. In order to simulate the interaction between wound dressings and epithelial tissues and to evaluate the drug release in time, the samples were immersed in simulated body fluid (SBF) and investigated after different durations of time. The antimicrobial effect was evaluated in planktonic (free-floating) and attached (biofilms) bacteria models. The biocompatibility and regenerative properties of the nanostructured coatings were evaluated in vitro, at cellular, biochemical, and the molecular level. The obtained results show that magnetite-based nanostructured coatings functionalized with N. sativa and dicloxacillin are biocompatible and show an enhanced antimicrobial effect against Gram positive and Gram negative opportunistic bacteria.

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.

Due to the great significance of amino acids, a substantial number of research studies has been directed toward the development of effective and reliable platforms for their evaluation, detection, and identification. In order to support these studies, a new electrochemical platform based on PANI/ZnO nanowires' modified carbon inks screen-printed electrodes was developed for qualitative analysis of electroactive amino acids, with emphasis on tyrosine (Tyr) and tryptophan (Trp). A comparative investigation of the carbon ink before and after modification with the PANI/ZnO was performed by scanning electron microscopy and by Raman spectroscopy, confirming the presence of PANI and ZnO nanowires. Electrochemical investigations by cyclic voltammetry and electrochemical impedance spectroscopy have shown a higher charge-transfer rate constant, which is reflected into lower charge-transfer resistance and higher capacitance values for the PANI/ZnO modified ink when compared to the simple carbon screen-printed electrode. In order to demonstrate the electrochemical performances of the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes for amino acids analysis, differential pulse voltammograms were obtained in individual and mixed solutions of electroactive amino acids. It has been shown that the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes allowed for tyrosine and tryptophan a peak separation of more than 100 mV, enabling their screening and identification in mixed solutions, which is essential for the electrochemical analysis of proteins within the proteomics research field.