National Institute Of Materials Physics - Romania

An inciting and much debated subject in the surface enhanced Raman (SERS) studies is an unusual anti-Stokes Raman spectrum distinguished by an abnormal intensity, increasing with the vibrational wavenumber and some discrepancies with regard to the Stokes spectrum. We demonstrate that the abnormal anti-Stokes Raman emission on single walled carbon nanotubes and poly(3,4-ethylenedioxy thiophene) synthtetized electrochemically appears as a consequence of two corroborating effects: resonance, which occurs when the energy of the excitation light is near or coincident with the energy of an electronically allowed transition, and the SERS effect achieved by the excitation of surface plasmons. An abnormal intense Raman emission in the Stokes branch, reminiscent to a stimulated Raman effect, which increases exponentially with the intensity of exciting light is reported for the first time in the case of SWNTs.

The wettability of 18 dental impression materials, commercially available, during their working time was investigated using the contact angle method, as a good wettability is desired to obtain a high fidelity impression. Polyetheric materials, A-silicones with added surfactants and C-silicones were found to have a good wettability. Alginate was found to be the most hydrophilic material, but this quality decreases in time. In the paper an explanation for the time dependence of the contact angle is advanced.

Carbon nanotubes are attractive materials with numerous possibilities of applications in various domains. Nevertheless, pertinent characterization studies are required in order to insure reproducibility in preparation, handling and incorporation in devices. Several spectroscopic tools have been developed so far, such as transmission electron microscopy and near-field electrical microscopy. Optical techniques have also been improved with the use of Raman Scattering, Surface Enhanced Raman Scattering (SERS) and near-field optical spectroscopy (SNOM). These non-destructive techniques have been used for nanotubes after synthesis and exploited to follow the modifications of their spectroscopic features when they are functionalized or embedded in host matrices. In this paper, we show that, by using SERS conditions, a new effect is observed: a "single-beam pumped'' Coherent anti-Stokes Raman Scattering (CARS). We demonstrate that under a tight-focusing of the excitation light, this emission, resulting from a wave mixing process between the incident laser light (omega(l)) and Stokes Raman light (omega(s)), is generated by a Surface Enhanced Raman Scattering (SERS) mechanism. Since abnormal anti-Stokes/Stokes intensity ratios are also observed for carbon nanotubes in powders, we have investigated in details their behaviour as a function of several parameters which include the excitation wavelengths, the laser power, the sample support, as well as the presence of nanotubes in isolated or in bundled form. It appears that resonance phenomena explain the anti-Stokes/Stokes intensity ratios in the case of powders and that CARS is only observed when SERS conditions are used. In addition, we have investigated other materials in which anomalies are also observed. This is the case of poly(bithiophene) (PBTh) electrochemically polymerized on carbon nanotubes for which its main Raman line at 1450 cm(-1) is enhanced, this enhancement being presumably generated by the plasmon excitation of metallic tubes. In the case of PEDOT, the analysis of the anti-Stokes branch provides additional information on the functionalization of carbon nanotubes with this polymer.

Different phases of boron nitride (BN) nano-structures are synthesized from an hBN ceramic target immersed in acetone, by ablation with a high power pulsed Nd: YAG laser. Transmission electron microscopy (TEM) and electron diffraction (ED) are used to identify the morphology and structure of the prepared colloidal suspensions. It is revealed that by varying solely a single experimental parameter, i.e. the laser pulse fluency, a large variety of BN nanostructures can be produced: nanotubes, very thin graphene-like foils, nano-curls and nanoparticles, all with the hexagonal graphite-like hBN structure, as well as high pressure BN phases: orthorhombic explosion E-BN nano-rods, or cubic diamond-like cBN nano-particles.

Tin chalcogenides SnX2 and SnX, where X = S, Se and Te present a particularly interest for their electronic properties and applications in gas sensors. The state of tin in these materials is important for understanding of the sensing effect and improvement of the sensor performances. Mossbauer spectroscopy is a widely used technique for the analysis of the local electronic structure or chemical bonding in solids. In this paper we applied Mossbauer technique for the investigation of bulk and thin films of SnSe2 chalcogenide. The films of SnSe2 chalcogenide were obtained by the methods: PLD ("Pulsed laser deposition") and PED ("Pulsed electron deposition"). Mossbauer measurements were performed by transmission (TMS), respectively conversion electron spectroscopy (CEMS). By CEMS spectroscopy surfaces, coatings and thin films containing Sn can be studied on substrates and to various depths up to 1000 nanometers.

The most promising media for rewritable applications are the phase change materials [ 1]. For the modelling of the phase transition processes in phase change materials it has been considered the switching unit called "commuton" [2]. A commuton is a minimum cluster of atoms that supports the reversible change from OFF to ON state under the influence of an external applied energy pulse. It was developed a bidimensional model based on the cellular automata approach [3] to predict switching behavior in a Ge2Sb2Te5 phase change chalcogenide film. We suppose that the formation of the percolation paths as a function of phase change induced in commutons can explain the switching phenomenon. The percolation thresholds of the switching were calculated for different sizes of the simulated system and the percolation kinetics was investigated.

LiF:Pb doped crystals were successfully grown by Kyropoulos method, starting with drying powders. The presence of Pb2+ ions in the LiF crystals were evidenced by the absorption band at 278 nm and by 375 nm photoluminescence. The presence of some other Pb structures with oxygen compounds in the as made samples was evidenced, decreasing after some annealing procedures. The local environment and valence state of Pb in LiF were studied by X-ray Absorption Spectroscopy at the Pb L-III and L-I edges. XANES data reveal that Pb is present as Pb2+ whereas EXAFS data show that it is incorporated in the crystal and not forming PbF2 precipitates. Identical spectra are obtained for samples as prepared and after thermal annealing up to 650 degrees C demonstrating the stability of the incorporation site. Also the concentration of Pb in the crystal has no effect on the location site of the metal as the same spectrum is obtained for specimens with different dopant concentrations.

Electrodeposition of manganese doped ZnO wires into polycarbonate membranes from an aqueous solution containing Zn(NO3)(2), Mn(NO3)(2) and lactic acid was investigated using linear sweep voltammetry and electrochemical impedance spectroscopy (EIS). The equivalent electrical circuits used for fitting experimental results were similar to those for characterization of metal/polymer coating systems. The precipitation of metal oxides in the pores of membrane used as template was observed at potentials between -0.9 and -1.15V/SCE. Morphology of the ZnO: Mn submicron wires arrays was observed by scanning electron microscopy and the Mn content of the obtained samples was measured by X-ray analysis. The submicron wires prepared at a potential of -1.1V/SCE have a composition expressed by the formula Zn0.97Mn0.03.

The quantitative structure - activity relationship in antidiabetic oral drugs has been analyzed on the basis of topological indices that allow to discriminate the structure of different molecules either small or large. The overall correlation structure - activity allows to find the best antidiabetic drugs and to predict the activity of new compound proposed as oral antidiabetic. The screened procedure based on topological indices prevents the expensive and long testing of a high number of compounds.

This paper presents a study of two copolymers, maleic anhydride and methylmethacrilate/maleic anhydride and vinyl benzyl chloride, functionalised with polar chromophoric groups such as 2,4 dinitroaniline. Thin films have been prepared by vacuum evaporation and spin coating methods on silicon and glass substrates. UV-VIS, FTIR, XRD and Photoluminescence Spectroscopy have been used to comparatively investigate the effect of the preparation method on the properties of the thin films obtained with functionalized copolymer. SEM has evidenced differences in the morphologies of the layers suggesting a degradation of the polymeric chain during the evaporation process to fragments that conserve unchanged the chromophoric group. This explains the presence of two types of non-linear phenomena, the second harmonic emission and two-photon luminescence emissions for both vacuum evaporated and spin coated films.