National Institute Of Materials Physics - Romania

In this work, new results concerning the potential of mixtures based on nitrogen doped titanium dioxide (TiO2:N) and carbon nanotubes (CNTs) as possible catalyst candidates for the rhodamine B (RhB) UV photodegradation are reported. The RhB photodegradation was evaluated by UV-VIS absorption spectroscopy using samples of TiO2:N and CNTs of the type of single-walled carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), and single-walled carbon nanotubes functionalized with carboxyl groups (SWNT-COOH) having various concentrations of CNTs. The best photocatalytic performance was obtained for sample containing TiO2:N and 2.5 wt.% SWNTs-COOH, when approx. 85% of dye removal was achieved after 300 min. of UV irradiation. The reaction kinetics of RhB aqueous solutions containing TiO2:N/CNT mixtures followed a complex first-order kinetic model. The TiO2:N/CNTs catalyst induced higher photodegradation efficiency of RhB than TiO2:N due to the presence of CNTs, which act as adsorbent and dispersing agent and capture the photogenerated electrons of TiO2:N hindering the electron-hole recombination.

The purpose of this study was to investigate the effectiveness in photodynamic therapy of iron oxide nanoparticles (gamma-Fe2O3 NPs), synthesized by laser pyrolysis technique, functionalized with 5,10,15,20-(Tetra-4-sulfonatophenyl) porphyrin tetraammonium (TPPS) on human cutaneous melanoma cells, after only 1 min blue light exposure. The efficiency of porphyrin loading on the iron oxide nanocarriers was estimated by using absorption and FTIR spectroscopy. The singlet oxygen yield was determined via transient characteristics of singlet oxygen phosphorescence at 1270 nm both for porphyrin functionalized nanoparticles and rose bengal used as standard. The irradiation was performed with a LED (405 nm, 1 mW/cm(2)) for 1 min after melanoma cells were treated with TPPS functionalized iron oxide nanoparticles (gamma-Fe2O3 NPs_TPPS) and incubated for 24 h. Biological tests revealed a high anticancer effect of gamma-Fe2O3 NPs_TPPS complexes indi-cated by the inhibition of tumor cell proliferation, reduction of cell adhesion, and induction of cell death through ROS generated by TPPS under light exposure. The biological assays were combined with the pharmacokinetic prediction of the porphyrin.

Plasmonic nanostructures based on AuAg nanoalloys were fabricated by thermal annealing of metallic films in an argon atmosphere. The nanoalloys were chosen because they can extend the wavelength range in which plasmon resonance occurs and thus allow the design of plasmonic platforms with the desired parameters. The influence of initial fabrication parameters and experimental conditions on the formation of nanostructures was investigated. For the surface morphology studies, chemical composition analysis and nanograin structure, Scanning Electron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), Energy Dispersive X-Ray Spectroscopy (EDS) and High-Resolution Transmission Electron Microscopy (HR TEM) measurements were performed. The position of the resonance band was successfully tuned in the 100 nm range. The EDS together with the XPS analysis confirmed the formation of an alloy with the aspect ratio of individual metals in a single nanoisland similar to the ratio of the thicknesses of the initially sputtered layers. The experimental research was complemented by the neural network model, which enables the calculation of the absorbance peak depending on the thickness of Au and Ag layers and the annealing time. The proposed model of machine learning makes it possible to fine-tune the desired position of the plasmon resonance.

The dependencies of the BiOi defect concentration on doping, irradiation fluence and particle type in p-type silicon diodes have been investigated. We evidenced that large data scattering occurs for fluences above 10(12) 1 MeV neutrons/cm(2), becoming significant larger for higher fluences. We show that the BiOi defect is metastable, with two configurations A and B, of which only A is detected by Deep Level Transient Spectroscopy and Thermally Stimulated Currents techniques. The defect' electrical activity is influenced by the inherent variations in ambient and procedural experimental conditions, resulting not only in a large scattering of the results coming from the same type of measurement but making correlation between different types of experiments difficult. It is evidenced that the variations in [BiOiA] are triggered by subjecting the samples to an excess of carriers, by either heating or an inherent short exposure to ambient light when manipulating the samples prior to experiments. For the samples investigated in this work both, the [BiOiA] as determined from electrical spectroscopic measurements and the full depletion voltage as measured from Current-Voltage characteristics reach a steady state in similar to 7h. Any electrical measurement performed before will give a different result. The bi-stable behavior of the BiOi defect fully accounts for these variations.

Zirconia- and hafnia-based thin films have attracted tremendous attention in the past decade because of their unexpected ferroelectric behavior at the nanoscale, which enables the downscaling of ferroelectric devices. The present work reports an unprecedented ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown directly on (111)-Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal (111)-oriented ZrO2 films under epitaxial compressive strain exhibiting switchable ferroelectric polarization of about 20.2 mu C/cm(2) with a coercive field of 1.5 MV/cm. Moreover, the time-dependent polarization reversal characteristics of Nb:SrTiO3/ZrO2/Au film capacitors exhibit typical bell-shaped curve features associated with the ferroelectric domain reversal and agree well with the nucleation limited switching (NLS) model. The polarization-electric field hysteresis loops point to an activation field comparable to the coercive field. Interestingly, the studied films show ferroelectric behavior per se, without the need to apply the wake-up cycle found in the orthorhombic phase of ZrO2. Overall, the rhombohedral ferroelectric ZrO2 films present technological advantages over the previously studied zirconia- and hafnia-based thin films and may be attractive for nanoscale ferroelectric devices.

Novel complexes of type [Cu(N-N)(dmtp)(2)(OH2)](ClO4)(2)& BULL;dmtp ((1) N-N: 2,2 & PRIME;-bipyridine; (2) L: 1,10-phenantroline and dmtp: 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine) were designed in order to obtain biologically active compounds. Complexes were characterized as mononuclear species that crystallized in the space group P-1 of the triclinic system with a square pyramidal geometry around the copper (II). In addition to the antiproliferative effect on murine melanoma B16 cells, complex (1) exhibited low toxicity on normal BJ cells and did not affect membrane integrity. Complex (2) proved to be a more potent antimicrobial in comparison with (1), but both compounds were more active in comparison with dmtp-both against planktonic cells and biofilms. A stronger antimicrobial and antibiofilm effect was noticed against the Gram-positive strains, including methicillin-resistant Staphylococcus aureus (MRSA). Both electron paramagnetic resonance (EPR) and Saccharomyces cerevisiae studies indicated that the complexes were scavengers rather than reactive oxygen species promoters. Their DNA intercalating capacity was evidenced by modifications in both absorption and fluorescence spectra. Furthermore, both complexes exhibited nuclease-like activity, which increased in the presence of hydrogen peroxide.

A research study was conducted to establish the effect of the presence of sodium bis-2-ethyl-hexyl-sulfosuccinate (DOSS) surfactant on the size, shape, and magnetic properties of cobalt ferrite nanoparticles, and also on their ability to remove anionic dyes from synthetic aqueous solutions. The effect of the molar ratio cobalt ferrite to surfactant (1:0.1; 1:0.25 and 1:0.5) on the physicochemical properties of the prepared cobalt ferrite particles was evaluated using different characterization techniques, such as FT-IR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 adsorption-desorption analysis, and magnetic measurements. The results revealed that the surfactant has a significant impact on the textural and magnetic properties of CoFe2O4. The capacity of the synthesized CoFe2O4 samples to remove two anionic dyes, Congo Red (CR) and Methyl Orange (MO), by adsorption from aqueous solutions and the factors affecting the adsorption process, such as contact time, concentration of dyes in the initial solution, pH of the media, and the presence of a competing agent were investigated in batch experiments. Desorption experiments were performed to demonstrate the reusability of the adsorbents.

Group IV nanocrystals (NCs), in particular from the Si-Ge system, are of high interest for Si photonics applications. Ge-rich SiGe NCs embedded in nanocrystallized HfO2 were obtained by magnetron sputtering deposition followed by rapid thermal annealing at 600 & DEG;C for nanostructuring. The complex characterization of morphology and crystalline structure by X-ray diffraction, mu-Raman spectroscopy, and cross-section transmission electron microscopy evidenced the formation of Ge-rich SiGe NCs (3-7 nm diameter) in a matrix of nanocrystallized HfO2. For avoiding the fast diffusion of Ge, the layer containing SiGe NCs was cladded by very thin top and bottom pure HfO2 layers. Nanocrystallized HfO2 with tetragonal/orthorhombic structure was revealed beside the monoclinic phase in both buffer HfO2 and SiGe NCs-HfO2 layers. In the top part, the film is mainly crystallized in the monoclinic phase. High efficiency of the photocurrent was obtained in a broad spectral range of curves of 600-2000 nm at low temperatures. The high-quality SiGe NC/HfO2 matrix interface together with the strain induced in SiGe NCs by nanocrystallization of both HfO2 matrix and SiGe nanoparticles explain the unexpectedly extended photoelectric sensitivity in short-wave infrared up to about 2000 nm that is more than the sensitivity limit for Ge, in spite of the increase of bandgap by well-known quantum confinement effect in SiGe NCs.

Nd-doped ZnO thin films were grown by pulsed-electron beam deposition (PED) on c-cut sapphire substrates under oblique angle incidence, at 10-2 mbar oxygen pressure and for a substrate temperature of 500 degrees C. The films were smooth, compact and constituted with columnar grains inclined at about 17 degrees +/- 4 degrees from the normal to the substrate surface. From X-ray diffraction and transmission electron microscopy experiments, it was found that the wurtzite phase of Nd-doped ZnO thin films is observed with the c-axis inclined around 35 degrees with respect to the normal axis of the substrate, with a three-fold azimuthal symmetry. Epitaxial relationships between Nd-doped ZnO films and sapphire substrate were determined from the asymmetric X-ray diffraction and are presented compared with those obtained for the films grown by non-oblique PED. The tilt of the ZnO c-axis has been explained by the epitaxy of the (2 2 9) ZnO plane on the (0 0 l) sapphire plane, such particular epitaxial growth having never been reported previously.