National Institute Of Materials Physics - Romania

EIS and XPS investigations on the interaction of hemin with p- and n-doped GaAs(100) electrodes in PBS solution revealed significant differences concerning both the adsorbed species and the mechanism of the redox process caused by dopant nature. XPS data show that hemin is adsorbed on p-GaAs(100) by its carboxyl groups and adopts a vertical position favorable to a polymeric film formation whereas on n-GaAs(100), the adsorbed hemin is monomeric and has a rather planar configuration involving mainly the OH groups of the organic molecule. Hemin gives rise to a reversible redox process at the p-GaAs(100) electrode whereas at n-GaAs(100), there is only one reduction wave of a considerably lower current density appearing at a more negative potential. The effects of the applied potential on the phase angle measured at p-GaAs(100) point out major changes not only in the insulating properties of the adsorbed layer, as found at n-GaAs(100), but also in the electronic properties of the semiconductor triggered by the hemin redox process. Analysis of the experimental data points to a mechanism of charge transfer through surface states, the observed differences being related to the location of the surface states with respect to the formal potential of the hemin redox couple.

Bovine hydroxyapatite (BHA) and BHA blended with clinoptilolite (CLIN) and alumina (Al2O3) coatings were synthesized using pulsed laser deposition (PLD) with a KrF* excimer laser source (lambda = 248 nm, tau(FWHM) <= 25 ns). Physical-chemical characteristics and the potential use of coatings for preventing bacteria adhesion and biofilm formation were investigated. Optimized PLD conditions were selected for coatings with rough morphologies, suitable for good cell adhesion and implant anchorage and good replication of the source target composition. The crystallinity of composite coatings was progressively decreasing with the augment of the Al2O3 and CLIN contents, which in turn can facilitate an efficacious release of active components. Al2O3- and CLIN-containing coatings exhibited high cytocompatibility and specific antibiofilm profiles, preventing the initiation and maturation of bacterial biofilms. Optimum biological activity profiles associated with the use of sustainable and/or inexpensive materials are, in our opinion, of key importance for the future development of performant implant coatings, which should he perfectly compatible with the surrounding tissue while preventing postsurgical endogenous or nosocomial infections.

Ba0.6Sr0.4TiO3 (BST) ferroelectric thick films were grown on MgO(001) and Al2O3 (0 0 0 1) single-crystal substrates by using a pulsed laser deposition method. Structural, morphological, optical, and terahertz characterization of the BST films were performed by X-ray Diffraction, Atomic Force Microscopy, Spectroscopic Ellipsometry (SE), and Terahertz Time-Domain Spectroscopy (THz-TDS). Single-phase samples with strong preferred (1 1 1) orientation and surface roughness lower than 1.5% of their thicknesses have been obtained for both types of substrates. SE was employed to extract the thickness and optical properties by using a 3-layer optical model (substrate/thin film/roughness). The inferred refractive index @630 nm is around 2.05, while the optical interference is visible until 3.3 eV. The THz-TDS measurements in transmission set-up were carried out one after the other on substrates before and after the BST film deposition. The standard THz-TDS analysis of double-layer samples proved difficult to complete in the cases in which a thin or thick film is deposited on a much thicker substrate of known dielectric properties. However, we have been able to extract the complex dielectric permittivity in the THz domain for BST samples with thicknesses of few microns, by developing a specific procedure of data analysis.

A complex investigation of the morpho-structural, magnetic, magneto-optical and magneto-transport properties of amorphous Fe-Gd thin films crossing the magnetization compensation point is reported and the unexpected observed magneto-functionalities are discussed. A tendency of magnetic domain formation with increasing the Fe content over the compensation concentration is observed. The switch from a reversed Magneto-optical Kerr Effect loop to a direct loop when increasing the Fe content over the compensation point is explained via the specific contribution to the rotation of the polarization vector from each magnetic sublattice, belonging to Fe and Gd, respectively. Local atomic configurations and magnetic interactions ascertained the amorphous character and revealed an out-ofplane orientation of the magnetic moment of Fe above the compensation point. The thermomagnetic curves prove a concentration dependent behavior, explained by weakly coupled magnetization relaxation processes of the two magnetic sub-lattices. On the other hand, the magnetic hysteresis loops gave evidence of two exchange coupled magnetic phases with different coercive fields. According to structural and Fe-57 Mossbauer Spectroscopy results, the two phases correspond to definite nanosized volumes of two different average concentrations (one of them closer to the compensation point) which are randomly distributed in the film. The unexpected single step-like behavior of the magneto-resistivity curves was explained by dissimilar switching of the spins in these two magnetic phases distributed in nano-sized volumes.

We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.

In the present work, a magnetodielectric flexible thick film composite with a quaternary Ba12Fe28Ti15O84 ferrite filler (<= 9 vol%) embedded into PVDF polymer matrix was investigated. The role of filler volume on the macroscopic dielectric, magnetic and ferroelectric properties as well as on the nanoscale magnetic and piezoelectric response was analyzed. The formation of small amounts of polar phases besides the majority alpha-phase of PVDF was shown by XRD and FTIR combined analysis. The electrical properties are dominated by the polymer response, while magnetic order is derived as sum property from the ferrite ones, having a predominant soft magnetic character with small coercivity of H-c similar to 60 Oe and high saturation magnetization of M-s = 2.6 emu/g for the highest concentration of 9 vol%. Permittivity and losses slightly increase with ferrite filler addition, and the composite maintains a dielectric character for all the compositions. Local PFM and MFM investigations have shown a combined ferro/piezoelectric character and magnetic order, with magnetoelectric coupling demonstrated by the reorientation of filler particles and modifications of local piezoresponse when applying a static magnetic field.

A versatile, modular in situ high-intensity monochromatic illumination set-up installed on a standard Q-band ESR spectrometer equipped with a cryostat and probe head for measurements at cryogenic temperatures, which can be easily assembled from commercially available optical components is presented. Using as monochromatic light sources pig-tailed laser diodes (LDs) or fiber-coupled light-emitting diodes (LEDs), a high efficiency of the light transfer (more than 95%) through an optical guide inserted in the sample holder is achieved in the sample area of the microwave cavity. With various LEDs and LDs, one can perform ESR in situ illumination experiments from UV to far-IR, in both cw and pulse mode. Its operation is illustrated with an experiment revealing the presence of certain ESR silent defects in oxygen-doped floating-zone ultrapure Si samples irradiated at room temperature with high-energy-high-fluence electron beams and pulse annealed up to 300 degrees C. New information is obtained by comparing the ESR spectra recorded at T = 120 K, without and with 1.06 mu m across-the-gap in situ illumination.

A complete characterization from optical, morphological, electrical, photo-electrical and thermo-electrical point of view was done for PEDOT:PSS thin films and DMSO and EG sensitized PEDOT:PSS films. The studies on the electrical conductivity and electrical photoconductivity allowed the calculation of different relaxation times. The relaxation time of the electrical conductivity is of order of femtosecond and is multiplied by a factor 10 when PEDOT: PSS thin films were deposited on surfaces sensitized with DMSO and EG. Besides, the photoconduction excitation and relaxation times are of order of seconds. An increase in the relaxation photoconduction time by 2 was observed for films deposited on surfaces sensitized with DMSO and by 1.2 for films deposited on surfaces sensitized with EG. The time response of electrical conductivity after exposure to light adds supplementary knowledge for the understanding of the inertial processes, or hysteresis behavior of organic or perovskite solar cells involving PEDOT:PSS films. The electrical conductivity increases with the temperature and the use of DMSO and EG as surfactants lead to higher values of electrical conductivity and Seebeck coefficient. A better stability of the electrical conductivity with the temperature increase, was noticed for films deposited on surfaces sensitized with DMSO.

Tellurium metallic colloids were evidence in the phosphate tellurite glasses obtained by the melt quenching method over 1000 degrees C. The concentration and subsequent color of these glasses strongly depend on the preparation conditions due to the significant differences among the melting point of the component oxides. The presence of Te metallic colloids was evidenced by the magneto-optical measurements at different temperatures, by the shift of the emissions spectra with the excitation wavelength and the thermoluminescence spectra as a result of recombination between the hole centers, created during x-ray irradiation, with the quasi coupled electrons from the surface of the metallic colloids. The peak position in the absorption spectra of these metallic colloids was modeled based on generalized Mie light scattering theory on these metallic structures, taking into account the size and shape of colloids but also the dielectric constant of the phosphate tellurite glasses in which these colloids are embedded.

A facile and cheap surfactant-assisted hydrothermal method was used to prepare mesoporous cobalt ferrite nanosystems with BET surface area up to 151 m(2)/g. These mesostructures with high BET surface areas and pore sizes are made from assemblies of nanoparticles (NPs) with average sizes between 7.8 and 9.6 nm depending on the initial pH conditions. The pH proved to be the key factor for controlling not only NP size, but also the phase purity and the porosity properties of the mesostructures. At pH values lower than 7, a parasite hematite phase begins to form. The sample obtained at pH = 7.3 has magnetization at saturation M-s = 38 emu/g at 300 K (54.3 emu/g at 10 K) and BET surface area S-BET = 151 m(2)/g, whereas the one obtained at pH = 8.3 has M-s = 68 emu/g at 300 K (83.6 emu/g at 10 K) and S-BET = 101 m(2)/g. The magnetic coercive field values at 10 K are high at up to 12,780 Oe, with a maximum coercive field reached for the sample obtained at pH = 8.3. Decreased magnetic performances are obtained at pH values higher than 9. The iron occupancies of the tetrahedral and octahedral sites belonging to the cobalt ferrite spinel structure were extracted through decomposition of the Mossbauer patterns in spectral components. The magnetic anisotropy constants of the investigated NPs were estimated from the temperature dependence of the hyperfine magnetic field. Taking into consideration the high values of BET surface area and the magnetic anisotropy constants as well as the significant magnetizations for saturation at ambient temperature, and the fact that all parameters can be adjusted through the initial pH conditions, these materials are very promising as recyclable anti-polluting agents, magnetically separable catalysts, and targeted drug delivery vehicles.