National Institute Of Materials Physics - Romania

Using surface-enhanced Raman scattering (SERS) and photoluminescence (PL) studies, new data concerning the electrochemical oxidation both of poly[(2,5-bisoctyloxy)-1,4-phenylene-vinylene] (BO-PPV) and the BO-PPV/HIPCO single-walled carbon nanotubes (SWNTs) composite are presented in this paper. The SERS studies performed at the excitation wavelengths of 752 nm and 532 nm of the BO-PPV/SWNTs composite that ensure the resonant excitation of the semiconductor and metallic nanotubes, respectively, reveal that the mixing of the two constituents results, on the one hand, in an isolation of semiconducting nanotubes from the bundles containing both metallic and semiconducting tubes and, on the other hand, in a functionalization of metallic SWNTs with BO-PPV. The isolation of semiconducting SWNTs is demonstrated by the narrowing of the G band and the change of the ratio between the intensities of the Raman lines situated in the low-frequency range that are assigned to the radial breathing vibrational modes. An additional isolation of the semiconducting nanotubes from the SWNTs bundles is reported when an electro-oxidation of the BO-PPV/SWNTs composite was performed in the potential range of (0; +2) V vs. Ag/AgCl. According to the Fourier transformed infra-red (FTIR) spectra and the SERS studies performed at an excitation wavelength of 1064 nm, the chemical interaction of BO-PPV with HIPCO SWNTs reveals a charge transfer between the two constituents that leads to the formation of BO-PPV covalently functionalized SWNTs. The BO-PPV luminescence quenching effect induced by the presence of SWNTs that consists of a change in the relative intensities of the three PL bands of the polymer peaked at 1.73 eV, 1.9 eV and 2.07 eV is due to the metallic tubes. The appearance of a new emission band at 2.32 eV was regularly observed when electrochemical oxidation of the BO-PPV/SWNTs composite was performed in the potential range of (0; +2) V. The PL band at 2.32 eV corresponds to ClO4- ions, which compensates the positive charges of BO-PPV generated during the electrochemical doping process. (C) 2014 Elsevier B.V. All rights reserved.

Nanosized TiO2 layers containing polyethylene glycol (PEG) with 20,000 molecular weight were prepared by sol gel method and deposited on three different substrates: microscope standard slides, Fluorine doped Tin Oxide (FTO) glass and Silicon, followed by thermal treatment at 450 degrees C. The effects of the substrate on the microstructural, morphological, chemical and optical properties of the films have been studied by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), Atomic Force Microscopy (AFM), X-ray Photo-electron Spectroscopy (XPS) and Spectroscopic Ellipsometry (SE). The XRD showed that the film crystallization depends very much on the substrate used, thus the films deposited on glass are amorphous even after 1 h thermal treatment at 450 degrees C, while the films deposited on Silicon and FTO substrates are crystallized in anatase phase, in good agreement with the TEM analysis. The XPS analysis showed that a rather high carbon relative concentration in the TiO2 film (without PEG) exists; this suggests that an unavoidable carbon contamination occurs and is not related on the presence or absence of PEG. The thickness and surface roughness of the films are clearly dependent on the substrate type. The flat surfaces of glass and Si lead to the formation of thinner TiO2 films (around 30 nm thicknesses), while the FTO substrate surface leads to thicker film (thickness similar to 100 nm). The porosity of TiO2 films as found by SEM and TEM analyzes is dependent of substrate type; small pore sizes up to 20 nm are characteristic for the films deposited on glass, while larger pore sizes up to 200 nm are found for the films deposited on FTO substrate. Not least, the film transmissions in the visible region are also substrate dependent and the highest values (80%) were obtained for the films deposited on glass. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory.

Magnetic and electrical properties of the nanostructured ZnO films are affected by the nonrandom distribution of impurities in the film due to segregation at grain boundaries (GBs) or extended defects. However, mapping the nature and distribution of the impurities in the film is not trivial. Here we demonstrate a simple, statistically relevant, and nondestructive procedure of quantitative determination of the paramagnetic impurities segregated at the GBs in nanostructured semiconducting and insulating films. From correlated electron paramagnetic resonance and transmission electron microscopy investigations, we determined the localization of trace amounts of Mn2+ ions, present as native impurities in a ZnO film deposited by magnetron sputtering at room temperature. In the as-deposited ZnO film, the Mn2+ ions were all localized in nanosized pockets of highly disordered ZnO dispersed between nanocrystalline columns. After the samples had been annealed in air at >400 degrees C, the size of the intercrystalline region decreased and the diffusion in GBs was activated, resulting in the localization of a portion of the Mn2+ ions in the peripheral atomic layers of the ZnO columns neighboring the GBs. The proportion of Mn2+ ions still localized at the GBs after annealing at 600 degrees C was 37%. The proposed method for the assessment of the presence and nature of impurities and the quantitative evaluation of their distribution in semiconducting and insulating nanostructures is expected to find direct applications in nanotechnology, in the synthesis and quality assurance of thin films for spintronics and opto- and nanoelectronics.

Relaxor ferroelectrics have neither long range ferroelectric order nor structural transformation down to the lowest temperatures, and display isotropic optical properties like quadratic electro-optic effect. However, if an anisotropy is forced through an external agent, like electric field or uniaxial strain, a ferroelectric and structural long range order can be induced in these materials. Here, we show that epitaxial strain in relaxor ferroelectric thin films can be employed to induce a linear electro-optic effect, opening the path to new strain-controlled electro-optic materials. Epitaxial thin films with Pb1-3x/2LaxZr0.2Ti0.8O3 (x = 0.22) composition grown by pulsed laser deposition on (001) SrRuO3/SrTiO3 single crystal heterostructures become tetragonal below the susceptibility peak, which occurs at a temperature 140K higher as compared to bulk. These films show piezoelectric properties and almost linear electro-optic behaviour. (C) 2014 AIP Publishing LLC.

The emergence of magnetic properties and quadratic magnetoelectric coupling in a material with outstanding ferroelectric properties has been pursued. Thus, the multiferroicity driven by the substitution of rare earth R3+ ions (R = Sm, Nd) on the A-site of PbTiO3 perovskite ceramics has been investigated. In some samples, a transition element with large ionic radius, like Fe2+, has been also added on the A site. Polycrystalline ceramic samples with composition (Pb1-3x/2-yRxFey) (Ti0.98Mn0.02)O-3 (R = Sm; x = 0.08, y = 0.035) and (Pb1-3x/2Rx)(Ti0.98Mn0.02)O-3 (R = Nd, x = 0.08) have been prepared by conventional solid state ceramic processing, starting from reagent grade oxide powders. X-ray diffraction analysis confirmed the obtaining of a crystalline phase with tetragonal P4mm symmetry. Transmission electron microscopy and high resolution transmission electron microscopy investigations have been carried out in order to analyze the local structure. Temperature dependence of dielectric permittivity revealed a strong anomaly at the temperature T-c of the paraelectric-ferroelectric phase transition. Transition temperature values depend on the R ion type and are lower than in pure lead titanate by 80-100K. A broad anomaly of dielectric permittivity is found below 140-180K, where magnetization also increases due to the quadratic magnetoelectric coupling between ferroelectric and magnetic states. For the (Pb0.845Sm0.08Fe0.035)(Ti0.98Mn0.02)O-3 composition, the piezoelectric charge coefficient at room temperature was d(31) similar to-6.5 pC/N and the remanent magnetization Mr at room temperature was about 0.1 emu/g. (C) 2014 AIP Publishing LLC.

For practical applications of superconducting materials in applied magnetic fields, artificial pinning centres in addition to natural ones are required to oppose the Lorentz force. These pinning centres are actually various types of defects in the superconductor matrix. The pinning centres can be categorised on their dimension (volume, surface, or point) and on their character (normal cores or Delta kappa cores). We have used the Dew Hughes approach to determine the types of pinning centres present in various samples, with various thicknesses, temperatures and nanostructured additions to the superconducting matrix. Results show that normal surface pinning centres are present throughout almost all the samples, as dominant pinning mechanism. Such 2D extended pinning centres are mainly due to dislocations, grain boundaries, nanorods. Strong normal point pinning centres were found to be common in BZO doped YBCO samples. Other types of pinning centres, in various (minor) concentrations were also found in some of the samples. (C) 2014 Elsevier B.V. All rights reserved.