Publications

The negative-capacitance effect in devices based on combined ferroelectric-dielectric gate oxides is thought to be a potential solution to break free from the so-called Boltzmann tyranny. To lower the power consumption in field-effect transistors, the subthreshold swing factor S should be reduced below the ther-modynamic limit of 60 mV per decade. Yet, despite numerous studies dedicated to this effect in the past decade, its origin in ferroelectric capacitors or ferroelectric-based superlattices remains unclear, being considered either a transitory product of polarization switching or an intrinsic phenomenon related to the presence of ferroelectric polarization. In this study it is shown, starting from simple electrostatic con-siderations, that negative capacitance is present during polarization switching and is accompanied by a significant increase of the current flowing through the ferroelectric capacitor. Coupled with piezo-force microscopy results, it is shown that the polarization orientation suddenly changes at the coercive voltage, accompanied by a complete reconfiguration of the potential barriers at the Schottky-like contacts present at the electrode-ferroelectric interfaces. A method to estimate the polarization-switching time, as the time associated with the presence of the negative-capacitance effect, is proposed. Values in the range from 100 to 1000 ns are obtained for epitaxial PbZr0.2Ti0.8O3 films. These findings suggest that negative capacitance may be an intrinsic effect in ferroelectrics but that it is a transitory effect, present only when ferroelectric polarization passes through zero (switching).

We have grown, by Pulsed Laser Deposition (PLD), a large number of YBa2Cu3O7 films with artificial pinning centers, with various impurities, various architectures and thickness, and various techniques of nano-scale pinning engineering: substrate decoration, BaZrO3 (BZO) nano-inclusions, and (quasi) multilayer architecture. Here we will present the results regarding vortex matter, dynamics, and pinning, in some of our best samples. Magnetic relaxation studies with magnetic field perpendicular to the film show that in both cases the splayed defects and/or nanoscale inclusions help reduce the dissipation in certain field-temperature range, by inhibiting the detrimental double vortex-kink formation. The response of the vortex system to AC excitation is rather complex but extremely useful for the characterization of the vortex dynamics. We have measured AC susceptibility in various DC fields, with various AC fields and frequencies and found that the effective vortex activation energy U-eff has a logarithmic dependence on the AC-field-induced current density J. Synergetic pinning centers assured a low anisotropy of the critical current for various field orientations, a property desired in coil/solenoid applications.

Hematite (alpha-Fe2O3) is a promising and Earth-abundant material for solar fuel production, and Si-doping has been employed as a general strategy to improve its performance. However, an atomistic description that reconciles the modifications that Si-doping induces on the morphology, crystalline lattice, and electronic and magnetic properties of alpha-Fe2O3 has remained elusive. Here we report on the role of electron small polarons in driving the morphological transition from nearly rounded-shaped to nanowire nanocrystals in Si-doped hematite alpha-Fe2O3. Electron small polaron formation is evidenced by the formation of Fe2+ and the increase of FeO6 distortion at increasing Si content. Local analysis via pair distribution function highlights an unreported crossover from small to large polarons, which affects the correlation length of the polaronic distortion from short to average scales. Ferromagnetic double exchange interactions between Fe2+/Fe3+ species are found to be the driving force of the crossover, constraining the chaining of chemical bonds along the [110] crystallographic direction. This promotes the increase in the reticular density of Fe atoms along the hematite basal plane only, which boosts the anisotropic growth of nanocrystals with more extended [110] facets. Our results show that magnetic and electronic interactions drive preferential crystallographic growth in Si-doped alpha-Fe2O3, thus providing new insights for the nanoscale structural design of efficient solar fuel devices.

We have measured the two-dimensional image potential states (IPS) of a germanene layer synthesized on a Ge2Pt crystal using scanning tunnelling microscopy and spectroscopy. The IPS spectrum of germanene exhibits several differences as compared to the IPS spectrum of pristine Ge(001). First, then = 1peak of the Rydberg series of the IPS spectrum of germanene has two contributions, labelledn = 1(-)andn = 1(+), respectively. The peak at the lower energy side is weaker and is associated to the mirror-symmetric state with opposite parity. The appearance of this peak indicates that the interaction between the germanene layer and the substrate is very weak. Second, the work function of germanene is about 0.75 eV lower in energy than the work function of Ge(001). This large difference in work function of germanene and pristine Ge(001) is in agreement with first-principles calculations.

Melanin is a natural pigment present in almost all biological groups, and is composed of indolic polymers and characterized by black-brown colorization. Furthermore, it is one of the pigments produced by extremophiles including those living in the Antarctic desert, and is mainly involved in their protection from high UV radiation, desiccation, salinity and oxidation. Previous studies have shown that melanized species have an increased capability to survive high level of radiation compared with the non-melanized counterpart. Understanding the molecular composition of fungal melanin could help to understand this peculiar capability. Here, we aimed to characterize the melanin pigment extracted from the Antarctic black fungus Cryomyces antarcticus, which is a good test model for radioprotection researches, by studying its chemical properties and spectral data. Our results demonstrated that, in spite of having a specific type of melanin as the majority of fungi, the fungus possesses the ability to produce both 1,8-dihydroxynaphthalene (DHN) and l 3-4 dihydroxyphenylalanine (L-DOPA) melanins, opening interesting scenarios for the protection role against radiation. Researches on fungal melanin have a huge application in different fields, including radioprotection, bioremediation, and biomedical applications.

The effects of 4-(2-hydroxyphenyl)-2-(morpholin-4-yl)-1,3-thiazole (Pr02), 1-(3,5-dibromo-2-hydroxyphenyl)-1-oxoethan-2-yl-N,N-diethyldithiocarbamate (Pr04) and 1-(5-bromo-2-hydroxy-3-methylphenyl)-1-oxoethan-2-yl-O- ethyl xanthate (Pr06) on the aqueous oxidation of chalcopyrite (CuFeS2) in air-equilibrated solution at a temperature of 25 degrees C and a pH of 2.5 were studied. The effects were investigated by using potentiodynamic polarization, electro-chemical impedance spectroscopy (EIS), scanning electron microscopy coupled with energy dispersive X-ray (SEM/EDX) analysis, aqueous batch experiments, Fourier transform infrared (FTIR) spectroscopy, Raman scattering and quantum chemical calculations. It is found that the anodic current densities decrease in the order of EtOH Pr02 > Pr04 > Pr06. These results, along with those of the EIS measurements, show that Pr02, Pr04 and Pr06 are effective anodic inhibitors of chalcopyrite aqueous oxidation. Both Raman scattering and FTIR spectroscopy indicate that the elemental sulfur, polysulfide and ferric oxyhydroxides that form on the surface of the mineral are not responsible when it comes to the aqueous oxidation inhibition of chalcopyrite. Quantum chemical calculations show that the adsorption of the tested compounds on the chalcopyrite surface is energetically favorable and so, it can explain the inhibiting effects that were observed.

This work is focused on investigation of thermal, structural, optical, magnetic, and magneto-optical properties of novel titanium phosphate-tellurite glass applied as Faraday rotators. The glass belonging to the system 35Li(2)O-10Al(2)O(3)-5TiO(2)-45P(2)O(5)-5TeO(2) was prepared by a nonconventional wet route of raw materials processing, followed by melting-quenching-annealing steps. Some important physical properties of the investigated glass have been measured and calculated, providing knowledge related to glass compactness, electronic structure, glass forming capability, etc. XRD analysis evidenced an amorphous network structure of the investigated glass. The optical absorption in the Vis domain is mainly due to Ti3+ ions and Te-2 clusters formed during the glass melting process. A relatively low optical absorption is noticed over 600 nm that activates a significant Faraday magneto-optical effect. Photoluminescence bands in the blue, red, and infrared domains are observed, caused by Te-2 clusters formed during the glass melting process. The magnetization in dependency on applied magnetic field reveals a complex behavior of the glass, depending on temperature. Thus, it is found a ferromagnetic behavior up to 2000 Oe, a paramagnetic component up to 40 000 Oe, followed by a diamagnetic one over 40 000 Oe. Faraday rotation angle and Verdet constant values in the visible domain are correlated with the reduced TeO2 content of the glass.

In recent years, luminescence nanothermometers with near infrared light (NIR) emission excited in the NIR range have attracted much attention due to their potential in bio applications. Here, we propose a new nanothermometer based on triple doped 1%Ho, 1%Er, 1%Yb - Y(2)O(3)that operates in the second and third biological windows around 1200 and 1530 nm under pulsed excitation at 905 nm. The NIR emissions were analysed in the temperature range of 298-473 K in terms of intensity, shape and dynamics. The nanothermometer performances were described using the luminescent intensity ratio (LIR) corresponding to the(5)I(6)-(5)I(8)and(4)I(13/2)-(4)I(15/2)emissions transitions of Ho and Er, respectively. A maximum relative sensitivity of 1.5% K(-1)was achieved at 309 K, which is among the highest five values reported so far for the NIR to NIR downconversion nanothermometers. The thermometer performance for biological application was assessed in terms of nanothermometer reliability and stability as well as emission shape changes induced by water and custom designed optical phantoms. Combination between use of pulsed excitation and identification of Ln doping configuration offering both excitation and emission in the biological windows represent a solid approach that can be easily translated to other hosts to develop a new class of near infrared nanothermometers.

Magnetic nanoscale materials exhibiting the L1(0)tetragonal phase such as FePt or ternary alloys derived from FePt show most promising magnetic properties as a novel class of rare earth free permanent magnets with high operating temperature. A granular alloy derived from binary FePt with low Pt content and the addition of Mn with the nominal composition Fe(57)Mn(8)Pt(35)has been synthesized in the shape of melt-spun ribbons and subsequently annealed at 600 degrees C and 700 degrees C for promoting the formation of single phase, L1(0)tetragonal, hard magnetic phase. Proton-induced X-ray emission spectroscopy PIXE has been utilized for checking the compositional effect of Mn addition. Structural properties were analyzed using X-ray diffraction and diffractograms were analyzed using full profile Rietveld-type analysis with MAUD (Materials Analysis Using Diffraction) software. By using temperature-dependent synchrotron X-ray diffraction, the disorder-order phase transformation and the stability of the hard magnetic L1(0)phase were monitored over a large temperature range (50-800 degrees C). A large interval of structural stability of the L1(0)phase was observed and this stability was interpreted in terms of higher ordering of the L1(0)phase promoted by the Mn addition. It was moreover found that both crystal growth and unit cell expansion are inhibited, up to the highest temperature investigated (800 degrees C), proving thus that the Mn addition stabilizes the formed L1(0)structure further. Magnetic hysteresis loops confirmed structural data, revealing a strong coercive field for a sample wherein single phase, hard, magnetic tetragonal L1(0)exists. These findings open good perspectives for use as nanocomposite, rare earth free magnets, working in extreme operation conditions.

The catalytic activity of a series of vanadium aluminophosphates catalysts prepared by sol-gel method followed by combustion of the obtained gel was evaluated in glycerol conversion towards methanol. The materials were characterized by several techniques such as X-ray diffraction (XRD), UV-vis, Fourier-transform infrared (FTIR), Raman and X-ray photoelectron (XPS) spectroscopies. The amount of vanadium incorporated in aluminophosphates framework played an important role in the catalytic activity, while in the products distribution the key role is played by the vanadium oxidation state on the surface. The sample that contains a large amount of V(4+)has the highest selectivity towards methanol. On the sample with the lowest vanadium loading the oxidation path to dihydroxyacetone is predominant. The catalyst with higher content of tetrahedral isolated vanadium species, such V5APO, is less active in breaking the C-C bonds in the glycerol molecule than the one containing polymeric species.