National Institute Of Materials Physics - Romania

By performing comparative Raman studies on nanometric thin films (9.5, 39, 88 and 185 nm) of copper phthalocyanine (CuPc) deposited on glass, Au and Ag supports, we demonstrate that the mechanism of the surface-enhanced Raman scattering (SERS) generated on Au and Ag substrates differs in the Stokes and anti-Stokes Raman branches depending on whether non-resonant (515.5 nm) or resonant (647.1 nm) optical excitation is applied. The evaluation of the SERS effect via the I-aS/I-S ratio reveals that this ratio is smaller or larger than that predicted by the Boltzmann law for non-resonant or resonant optical excitation, respectively. In the former case, the enhancement of the Stokes Raman emission is similar to a stimulated Raman process resulting from the plasmon coupling associated with the incident excitation light and spontaneous Stokes Raman emission. For the latter case, the amplification of the anti-Stokes Raman emission results from a wave-mixing process reminiscent of a single-beam CARS effect.

We investigated the magnetic relaxation of weakly interacting, dispersive, single domain Fe nanoparticles in Fe/Al2O3 composites prepared by sequential pulsed laser deposition on (100) Si substrates. The external magnetic field was oriented parallel to the substrate and applied in zero-field cooling conditions. It was found that the relaxation of the irreversible magnetic moment m (irr) is similar to the well-known vortex-creep process in disordered superconductors with poor supercurrent redistribution across the sample, leading to a power-law dependence of m (irr)(t), with a well-defined time t exponent.

Hydroxyapatite (HA) is a widely used biomaterial for implant thin films, largely recognized for its excellent capability to chemically bond to hard tissue inducing the osteogenesis without immune response from human tissues. Nowadays, intense research efforts are focused on development of antimicrobial HA doped thin films. In particular, HA doped with Ag (Ag:HA) is expected to inhibit the attachment of microbes and contamination of metallic implant surface. We herewith report on nano-sized HA and Ag:HA thin films synthesized by pulsed laser deposition on pure Ti and Ti modified with 100 nm diameter TiO2 nanotubes (fabricated by anodization of Ti plates) substrates. The HA-based thin films were characterized by SEM, AFM, EDS, FUR, and XRD. The cytotoxic activity was tested with HEp2 cells against controls. The antifungal efficiency of the deposited layers was tested against the Candida albicans and Aspergillus niger strains. The Ti substrates modified with TiO2 nanotubes covered with Ag:HA thin films showed the highest antifungal activity. (C) 2013 Elsevier B.V. All rights reserved.

Bioactive glasses are osteoproductive-type inorganic materials possessing the highest indices of bioactivity in both bulk and thin film forms. The prerequisites for reliable implant-type coatings are both their biological and mechanical performances. Whilst the bioglass films' structural, chemical and biological properties have been studied extensively, information about their mechanical performance is scarce. Here, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, nanoindentation and pull-out measurements were employed to assess the morphological, chemical, structural and mechanical properties of the bioglass films deposited onto Ti substrates by radio-frequency magnetron sputtering (RF-MS). The biological safety of the thin bioglass films was evaluated preliminarily in vitro by investigating the adherence, proliferation and cytotoxicity of fibroblast cells cultivated on their surface. Our study emphasize the versatility of RF-MS, showing how bioglass films' features such as composition, structure, bonding strength, hardness, elastic modulus and biological response can be conveniently adapted by tuning the RF-MS working conditions, and therefore demonstrating the unexplored potential of this deposition technique for preparing quality biomimetic glass coatings. (C) 2013 Elsevier B. V. All rights reserved.

Electrode interface is a key element in controlling the macroscopic electrical properties of the ferroelectric capacitors based on thin films. In the case of epitaxial ferroelectrics, the electrode interface is essential in controlling the leakage current and the polarization switching, two important elements in the read/write processes of nonvolatile memories. However, the relation between the polarization bound charges and the electronic properties of the electrode interfaces is not yet well understood. Here we show that polarization charges are controlling the height of the potential barriers at the electrode interfaces in the case of Pb(Zr,Ti)O-3 and BaTiO3 epitaxial films. The results suggest that the height is set to a value allowing rapid compensation of the depolarization field during the polarization switching, being almost independent of the metals used for electrodes. This general behavior open a new perspective in engineering interface properties and designing new devices based on epitaxial ferroelectrics.

Perovskite complex ceramic oxides, BaTiO3 doped with 0.5 mol% Nb2O5 and then nanocoated with SiO2 (abbreviated as BT-Nb-0.005/SiO2) was successful prepared using conventional sol-gel processing. Phase composition, particle morphology, structure, and electric properties of BT-Nb-0.005 core and BT-Nb-0.005/SiO2 core-shell were examined and compared, using X-ray diffraction, transmission electron microscopy and, dielectric and ferroelectric measurements. Core-shell composite with well-defined perovskite tetragonal phase of BaTiO3 was achieved. Furthermore, single crystalline BT-Nb-0.005/SiO2 core-nanoshell heterostructure with similar to 34 nm shell thick was prepared, which is a novelty in ferroelectrics field. The ferroelectric quality of BT-Nb-0.005 has suffered an alteration when the (BT-Nb-0.005)/SiO2 core-shell heterostructure was realized. One-dimensional BT-Nb-0.005/SiO2 core-shell heterostructure exhibits an improvement of dielectric losses and a decrease of dielectric constant, compared to uncoated BT-Nb-0.005. The (BT-Nb-0.005)/SiO2 core-shell material could be interesting for application in the composite capacitors. (C) 2013 Elsevier B.V. All rights reserved.

Novel metal nanoporous transition metal oxides M (x) O (y) (Co3O4, CuO) have been synthesized by thermal decomposition of inorganic salts precursors (acetates, nitrates) impregnated into hexagonal mesoporous silica (OMS, ordered mesoporous silica) of SBA-15 type (prepared in-house) at different precursor loadings, the mesocomposites thus obtained being monitored after each impregnation-calcination step by small and wide angle powder XRD. The pore size for the ordered silica host range from 5.08 to 7.06 nm. Retention of the hexagonal silica framework has been observed in spite of the temperatures up to 500 A degrees C. Mesoporous Co3O4 has been obtained by leaching the silica through overnight HF dissolution, which partially preserved the small-range ordering found in the parent Co3O4@OMS composite prior to leaching. Both Co3O4 (meso) and Co3O4@SBA-15 have been tested in methane oxidation and were found to be superior to the bulk Co3O4 performance, with mesoporous Co3O4 being able to fully oxidize methane to CO2 and H2O at 350 A degrees C, while Co3O4@OMS exhibits a lower activity with 20 % conversion at 350 A degrees C. CuO@OMS shows the lowest activity, with only similar to 13 % conversion at 500 A degrees C.

A novel series of Pd(II) and Pt(II) complexes based on cyclometallated imine ligands and N-benzoylthiourea (BTU) derivatives as auxiliary ligands has been prepared and their liquid crystalline properties as well as photophysical properties have been investigated. The crystal structure of one cyclometallated Pt(II) complex with N-(p-F-phenyl)-N'-benzoylthiourea as a co-ligand has been solved. The liquid crystalline properties have been investigated by a combination of DSC, POM and variable temperature powder X-ray diffraction. These new metallomesogens display either a monotropic SmC phase or both SmA and SmC phases, depending on the number of alkoxy groups attached to the imine ligand, alkyl chain length or the use of branched alkoxy terminal groups. We found that the introduction of branched alkoxy terminal groups lead to lower transition temperatures and stabilization of the SmC phase in both the Pd(II) and Pt(II) complexes. While the Pd(II) complexes display no emission, the Pt(II) complexes show good emission properties in solution, in the solid state and as a PMMA film at room temperature, and their investigation is reported. (C) 2013 Elsevier Ltd. All rights reserved.

Magnetoresistive Fe-Co based thin film structures were produced using thermionic vacuum arc method. The purpose of this work was to obtain significant magnetic response on different granular combinatorial structures. The Giant Magnetoresistive (GMR) and combination between GMR and Tunneling Magnetoresistive (TMR) properties of the thin film structures were the aim of the work. The proposed method in order to obtain the desired granular structures is based on electron beam emitted by an externally heated cathode, accelerated by a high anodic potential. The work consisted in preparing two sets of samples, first being a combination between Fe-Co as magnetic materials embedded in a Cu matrix, with a total thickness of 200 nm. The second structure was a combination between Fe-Co (50%-50%) alloy, embedded in a matrix of Cu combined with MgO with a thickness of 200 nm. Both sets of samples were obtained by three simultaneous types of discharges. Because of the substrate positioning in respect with the three anode-cathode systems, different material concentrations were obtained, confirmed by Energy Dispersive Spectroscopy (EDS) measurement results. Structural and morphological properties were investigated using Scanning Electron Microscopy; Atomic Force Microscopy and EDS. Electrical properties of the obtained samples were studied using the 4 point measurement method. The magnetic properties were first studied using a non-destructive optical method called MOKE (Magneto-Optical Kerr Effect). Electrical resistance behavior of the granular type structures was studied for different values of the magnetic field, up to 03 T, at different values of the sample temperature. The magnetoresistive effect obtained for the two sets of samples varied from 1.5% to 81% in respect with the substrate positioning and sample temperature for a constant magnetic field. (C) 2014 The Authors. Published by Elsevier B.V. All rights reserved.