National Institute Of Materials Physics - Romania

The hysteretic behavior of the epitaxial Pb(Zr,Ti)O-3 thin films with different top metal electrodes is studied, with emphasis on the influence of the leakage current and trap generation current on the shape of the loop as well as on the magnitude of the measured polarization. Cu, Pt, and SrRuO3 were used as top contacts and important differences were observed for measurements performed in both dynamic and static modes, although the contacts were deposited on the same epitaxial Pb(Zr,Ti)O-3 film grown on SrRuO3/SrTiO3 substrate. A peculiar behavior was observed especially for the static hysteresis loops where, depending of the top contact, the loop is influenced mainly by the leakage current (Pt) or by the trap generation current (Cu and SrRuO3). The last one can contribute with an additive charge, having a linear dependence on the applied voltage, as suggested by the simple model developed to explain the abnormally high values of the dielectric constant extracted from the linear part of the static hysteresis loop. It is concluded that the properties of the top electrode interface can significantly impact the hysteretic behavior of the ferroelectric films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754318]

Acid-base interactions between amino-silica and carboxyl-gold protected nanoparticles, functionalized or not with free stable radicals or fluorescent moieties, were studied by ESR, fluorescence, and TEM. While those nanoparticles are stable in solution, mixing them induces aggregation, due to acid-base interactions; addition of a base or an acid redissolves them. By ESR, strong spin-spin interactions were noticed; by fluorescence, only small differences may be observed, while by TEM, it was noticed that gold nanoparticles are distributed evenly on the surface of the silica nanoparticles. (C) 2012 Elsevier B.V. All rights reserved.

The effects of the self-assembled 4,4'-thio-bis-benzenethiolate protected gold nanoclusters onto a p-GaAs (1 0 0) electrode were examined by AFM, XPS, SHG and EIS investigations. The AFM and XPS results revealed a well-ordered overlayer exhibiting a bi-modal highly correlated fractal behavior which, however, cannot fully protect the semiconducting surface against the oxidation in air. The EIS data pointed out the influence exerted by the gold-monolayer protected clusters (Au-MPCs) over the charging/discharging processes observed at p-GaAs (1 0 0) electrode. Although the applied potential is varied linearly, the potential drop within the semiconductor space charge region as well as that across the Au-MPCs layer undergoes stepped changes supposed to result in the discrete charging of the Au-MPCs. These effects point to an electronic equilibrium between the Au-MPCs and the semiconducting substrate. Fermi level pinning and enhancement of the SHG response in the potential range where the surface/interface states in the semiconductor band gap become electrically active bring further proof in this respect. (c) 2012 Elsevier Ltd. All rights reserved.

The films containing Ge nanoparticles embedded in SiO2 matrix were prepared by RF magnetron sputtering and subsequently by thermal annealing. Their structure was investigated by conventional transmission electron microscopy and high resolution transmission electron microscopy together with energy-dispersive X-ray spectroscopy. The electrical behavior of films was studied by measuring current-temperature and current-voltage characteristics. The structure investigation reveals two kinds of features: a low density of big Ge nanoparticles with sizes from 20 to 50 nm and a network of small amorphous Ge nanoregions/nanoparticles (5 nm size or less) with high density, both being embedded in amorphous SiO2 matrix. The electrical transport was shown to take place through the network of amorphous Ge nanoregions. At low temperature, the T-1/4 dependence of the current was evidenced, while at high temperature, the T-1 Arrhenius dependence was found. At both low and high temperatures, the conductivity is nearly constant. The behavior at low temperature was explained by the hopping mechanism on localized states located in a band near the Fermi energy, while at high temperature by the charge excitation to the extended states.

The purpose of this work was to obtain precipitated calcium carbonate (PCC) particles in polymorphic form of vaterite via gas-liquid route in controlled pH conditions. The effect of CO2 concentration (12.5-100%), feed gas (CO2-air) flow rate, pH, and conductivity of solution upon the PCC particles properties was studied. On the basis of the experimental data, the main factors leading to vaterite formation as major product were established. It was found that the buffer solution has a decisive role in determining polymorphic phase of PCC while CO2 concentration and feed gas flow rate have no significant influence. It was demonstrated that spherical vaterite particles of high purity can be produced under controlled reaction conditions. Also, some considerations on the mechanism of carbonation process were formulated.

We present the preparation, structural and magnetic properties of nanosized magnetite obtained by the crystallization of a series of Fe-containing borosilicate glasses. Several compositions with the ratio Fe2O3/SiO2 spanning from 0.37 to 0.67 were investigated as a function of two nucleators Cr2O3 and P2O5, respectively, and modifiers and intermediates (Al2O3 and MgO). Mossbauer spectroscopy revealed the degree, the type and the location of disorder induced by a specific composition and nucleators. In addition to magnetite, it was also revealed the presence of large amounts of Fe-rich paramagnetic phases. The magnetic response is analysed in relation with the amount of Fe ions which remain dispersed in the glassy matrix as noninteracting (paramagnetic) ions. We discuss the role of the nucleators on the disorder in both tetrahedral and octahedral sites of the magnetite.

The complementary investigation techniques, Mossbauer spectroscopy, transmission electron microscopy with selected area electron diffraction (TEM/SAED), X-ray diffraction (XRD) have been used to investigate the fate of the Valea lui Stan, Romania, gold-ore nanoscale-minerals during the long time of residence in the waste dumps. The preliminary investigations showed such waste dumps to contain significant amount of metals which cannot be identified by conventional methods. An intense research activity started up in order to evaluate the possibilities to recycle Valea lui Stan waste dumps and to recover metals by chemical or phytoextraction procedures. The waste dumps naturally show different mineral constituents with clay minerals as major phases, observed by XRD-technique. Although the waste dumps materials have whitish-yellowish colours, MOSSBAUER technique evidences the presence of the finely dispersed iron bearing minerals. The authors are focusing to inspect and analyze Fe-compounds in the samples collected from Valea lui Stan's waste dumps in order to identify the magnetic phases by Mossbauer technique.

Iron doped (0.25-7.5% molar) hydrothermal nano-SnO2 was characterized by electron magnetic resonance (EMR) and Mossbauer spectroscopies. Only a small fraction of transition metal ions are in magnetic ordered state, contrary to the similar crystallographic compound TiO2. Temperature dependences of spectra suggest that by increasing iron concentration, or annealing temperature, iron ions migrate to nanoparticles surfaces forming disordered iron oxides.

The influence of Au nanoparticles dimension on the photocatalytic performances of the TiO2 aerogels-Au composites was evaluated. Structural and morphological peculiarities of the TiO2 aerogel, unloaded and loaded with 5 and 22 nm Au nanoparticles, were studied by transmission electron microscopy technique, X-ray diffraction and N-2-sorption measurements. UV-Vis diffuse reflectance measurements were performed to determine the band gap energies. The photocatalytic activity was evaluated by monitoring the salicylic acid photodegradation. It was found that the Au nanoparticles promote the anatase phase crystallization and produce the decrease of the specific surface area and band gap energy values. The porous composite with the smallest Au nanoparticles dimension exhibits the best photocatalytic performances.

The synthesis of a new garnet, Er3Li0.275Nb0.275Ga4.45O12 (ErLNGG), by solid-state reaction, is reported. A comparison of the fluorescence spectra of Er3+ in ErLNGG, Er-doped (0.1 at.%) calcium lithium niobium gallium garnet (CLNGG), and Er(50 at.%):CLNGG is presented. The narrowing of luminescence lines suggests an ordering of the partially disordered CLNGG with the increase of erbium concentration.