National Institute Of Materials Physics - Romania

Laser pulse processing of surfaces and thin films is a useful tool for amorphous thin films crystallization, surface nanostructuring, phase transformation and modification of physical properties of thin films. Here we show the effects of nanostructuring produced at the surface and under the surface of amorphous GeTiO films through laser pulses using fluences of 10-30 mJ/cm(2). The GeTiO films were obtained by RF magnetron sputtering with 50:50 initial atomic ratio of Ge:TiO2. Laser irradiation was performed by using the fourth harmonic (266 nm) of a Nd:YAG laser. The laser-induced nanostructuring results in two effects, the first one is the appearance of a wave-like topography at the film surface, with a periodicity of 200 nm and the second one is the structure modification of a layer under the film surface, at a depth that is related to the absorption length of the laser radiation. The periodicity of the wave-like relief is smaller than the laser wavelength. In the modified layer, the Ge atoms are segregated in spherical amorphous nanoparticles as a result of the fast diffusion of Ge atoms in the amorphous GeTiO matrix. The temperature estimation of the film surface during the laser pulses shows a maximum of about 500 degrees C, which is much lower than the melting temperature of the GeTiO matrix. GeO gas is formed at laser fluences higher than 20 mJ/cm(2) and produces nanovoids in the laser-modified layer at the film surface. A glass transition at low temperatures could happen in the amorphous GeTiO film, which explains the formation of the wave-like topography. The very high Ge diffusivity during the laser pulse action, which is characteristic for liquids, cannot be reached in a viscous matrix. Our experiments show that the diffusivity of atomic and molecular species such as Ge and GeO is very much enhanced in the presence of the laser pulse field. Consequently, the fast diffusion drives the formation of amorphous Ge nanoparticles through the segregation of Ge atoms in the GeTiO matrix. The nanostructuring effects induced by the laser irradiation can be used in functionalizing the surface of the films.

The role of iron doping on magnetic properties of hydrothermal anatase TiO2:Fe-57 (0-1 at. %) nanoparticles is investigated by combining superconducting quantum interference device magnetometry with Mossbauer and electron paramagnetic resonance techniques. The results on both as-prepared and thermally treated samples in reduced air atmosphere reveal complexity of magnetic interactions, in connection to certain iron ion electron configurations and defects (oxygen vacancies, F-center, and Ti3+ ions). The distribution of iron ions is predominantly at nanoparticle surface layers. Formation of weak ferromagnetic domains up to 380 K is mainly related to defects, supporting the bound magnetic polaron model. (C) 2015 AIP Publishing LLC.

Fe-Ni graded films have been prepared by co-sputtering permalloy and Fe targets at different time-power sequences. Morpho-structural and magnetic investigations have been performed by transmission electron microscopy, Xray reflectometry, conversion electron Mossbauer spectroscopy and magneto-optic Kerr effect vector magnetometry, proving the thickness dependence of the properties. A magnetization reversal involving the displacement of Bloch-type walls is characteristic for a 115 nm thick Fe-Ni graded film whereas an in-plane coherent rotation of the spins, according to a Stoner-Wohlfarth mechanism was evidence for a 23 nm thick Fe-Ni graded film.

The content of defects in Bi4Ge3O12 (BGO) glass-ceramic materials together with their ordering during crystallization induces ferromagnetic behaviours in these materials. The observed ferromagnetism has to be associated strictly with the GeO4 related defects in the atypical amorphous phase. The photoluminescence of BGO glass-ceramic materials can give useful information about the nature of defects, especially the oxygen vacancies from the GeO4 tetrahedra and Bi4Ge3O12 cubic structures. The concentration of these defects depends on annealing between 600 degrees C and 700 degrees C where orthorhombic and cubic phases coexist. The magnetization at saturation is higher in the samples dominated by the amorphous phase and the strength of the exchange interaction is higher in the samples dominated by the cubic phase, obtained over 700 degrees C, when the GeO4 tetrahedra are rearranged during crystallization together with their oxygen vacancies. (C) 2014 Elsevier B.V. All rights reserved.

Two new coordination polymers have been assembled using the chromato ions as bridging ligands: (1)(infinity)[Ni(phen)(H2O)(2)(mu-O2CrO2)] 1, and (3)(infinity)[Mn(4,4'-bipy)(H2O)(mu-O3CrO)]center dot H2O 2. In crystal 1 the chromate ions act as bridges connecting two nickel ions through two oxygen atoms, resulting in infinite chains. 1,10-Phenanthroline acts as a blocking ligand. In compound 2, each chromato ion is connected to three manganese ions, resulting in layers which are parallel to the ab plane. The layers are constructed from {Mn3Cr3} meshes, each metal atom being shared between three other meshes. The structure is expanded into the third direction by connecting the inorganic layers through 4,4'-bipy spacers. The thermal decomposition of the two compounds has been investigated. (C) 2014 Elsevier B.V. All rights reserved.

Rare-earth free (RE-free) exchange coupling nanocomposite magnets are intensively studied nowadays due to their potential use in applications demanding stable high-temperature operation and corrosion resistance. In this respect, the FePt alloy system is one of the most actively addressed potential permanent magnet solutions. In FePt alloys, promising magnetic features arise from the co-existence of hard magnetic L1(0) FePt and soft magnetic L1(2) Fe3Pt phases emerged from the same metastable precursor. The present work deals with an in-situ temperature-resolved synchrotron radiation study of the thermal stability, thermal expansion and microstructure evolution in exchange-coupled FePtAgB alloys. The as-cast microstructural state as well as the optimized magnetic behavior are given as reference and correlated to the observed microstructural evolution with temperature. The melt-spun Fe48Pt28Ag6B18 alloy ribbons were examined in situ by synchrotron X-ray powder diffraction from ambient temperature up to 600 degrees C. The FePt-Fe3Pt exchange-coupled microstructure achieved by rapid solidification is not significantly altered during the high temperature exposure. The thermal expansion of the FePt L1(0) unit cell has been found to be strongly anisotropic, being essentially an in-plane expansion which may be seen as an anisotropic invar effect. For the FePt L1(0) phase, a significant deviation from linear thermal expansion is observed at the Curie temperature T-C = 477 degrees C. This non-linear behavior above T-C is tentatively linked to a diffusion/segregation mechanism of Ag. The promising hard magnetic properties as well as the direct formation of the L1(0) phase from the as-cast state are directly related to the presence of Ag in the intergranular regions. (C) 2014 Elsevier B.V. All rights reserved.

The charge storage properties of Ge nanocrystals-based MOS-like capacitors with tunnel and gate HfO2 are studied. HfO2/Ge/HfO2/Si trilayer structures were prepared by magnetron sputtering (in Ar) and subsequent rapid thermal annealing (650 degrees C). HfO2/Si structures were also prepared, some under similar conditions, while others were deposited in Ar:O-2. TEM investigations and C-V measurements were performed. TEM on annealed trilayers evidences the formation of ordered and precisely positioned array of Ge nanocrystals embedded in crystalline HfO2. The annealed Al/HfO2/Ge/HfO2/p-Si/Al capacitors present counterclockwise C-V hysteresis (0.8 V memory window) mainly given by Ge nanocrystals, with negligible contribution from crystallized-HfO2 traps.

One of the most fundamental aspects of the heterogeneous catalysis field is the manipulation of the catalysts' activity. In photocatalysis this is carried out by maximizing the right crystal plane of a semiconductor oxide. Until now, most of the papers have achieved this by a combination of different oxides, with noble metals and sometimes with carbon nanomaterials. In this work MWCNTs (multiwalled carbon nanotubes) were applied as "crystallization promoters" in a very simple, safe, one-step hydrothermal method. By this method TiO2 nano/micro crystals with exposed {001} facets were obtained in the first step. The next episode in the crystal manipulation "saga" was the modification of the (001) crystallographic plane's structure by creating ordered/own faceted "crystallographic holes". These elements are capable of further enhancing the obtained activity of titania microcrystals to a higher extent, as shown by the UV driven photocatalytic phenol degradation experiments. The appearance of the holes was "provoked" by simple calcination and their presence and influence were demonstrated by XPS and HRTEM.

Ge and Si nanocrystals (NCs), quantum dots (QDs), and amorphous nanoparticles (NPs) have a significant role in the developement of micro- and nanoelectronic devices due to capability to tune their electrical and photoconductive properties by tailoring the morphology and structure parameters. Ge and Si NCs/QDs/NPs are zero-dimensional (0D) systems and the SiO2 films containing them are percolative systems. In this review, the role of deposition and annealing conditions in the morphology and structure of Ge and Si NCs/QDs/NPs embedded in amorphous SiO2 matrix is discussed for a wide variety of films and multilayered structures. The electrical and photoconductive properties of nanostructures deposited by different techniques as magnetron sputtering, ion implantation, chemical vapour deposition, sol-gel and molecular beam epitaxy, and subsequently annealed in conventional furnace or by rapid thermal annealing under different conditions are analised. We demonstrate how the electrical and photoconductive properties of nanostructures can be tuned by varying the deposition and annealing parameters. The role of Si-rich oxide and defects in the formation of Ge and Si NCs is shown and the role of defects in improving electrical properties and enhancing the photoconductivity of films and multilayered structures is highlighted. We evidence the contribution of quantum confinement effect and show that the most probable transport mechanisms in these percolative systems are tunnelling and hopping.

The most widely occurring collagen in the extracellular matrix of the mammalian tissues - type I collagen has attracted huge interest from both theoretical and practical points of view. The results presented herein are mainly confined to a study of the thermal stability of type I collagen (CI) extracted from calfskin in acidic solutions (10(-2) M HCl). A two-step process associated with the heat-induced denaturation of CI was revealed by using ultra sensitive differential scanning calorimetry. The minor endothermic transition (peak temperatures of about 30.5-30.8 degrees C) has been assigned to the defibrillation of small supramolecular CI assemblies (occurring in solution) while the major endothermic transition (about 34.8-35.0 degrees C) has been ascribed to denaturation of CI, consisting of a complete unfolding of the native triple-helical conformation of the collagen molecule. The calorimetric data were supported by information obtained from capillary viscometry performed on the same solutions. The native state of CI (molecular integrity and triple-helical conformation) for all the systems studied in this paper was confirmed by transmission electron microscopy, ultraviolet circular dichroism and capillary viscometry. At the same time, based on the sodium dodecyl sulphate-polyacrylamide gel electrophoresis and an appropriate image processing of the corresponding electropherogram, a certain degree of intramolecular crosslinking of CI was detected, mainly between alpha 1 and alpha 2 chains of the collagen triple-helix. Such a feature seems to be caused by both the nature of the extraction procedure and the storage conditions.