National Institute Of Materials Physics - Romania

We present photo-electrical properties of thin films formed of Ge nanoparticles in TiO2 correlated with structure and morphology. The films co-deposited on Si using magnetron sputtering were annealed in conventional oven at 550 degrees C. We performed structure investigations by X-ray diffraction, transmission electron microscopy and measured current-voltage characteristics in dark and under illumination at different temperatures. We show that the films are formed of cubic Ge nanoparticles in nanostructured anatase TiO2 matrix. Also, (TiGe)O-2 with rutile structure was observed. The films have high photosensitivity under white light as the ratio between photo- and dark currents (-1 V) is of similar to 10(2).

Films of amorphous Ge nanoparticles in Si3N4 on heated Si and quartz substrates at 300 degrees C were obtained by co-sputtering Ge, and Si3N4. The films structure and photo-electrical behaviour were studied through transmission electron microscopy and, current voltage and spectral photo-current investigations, respectively. The spectral photo-current were correlated with results obtained from transmission electron microscopy. Under illumination the current present a high increase with about one order of magnitude compared with the dark one. The photo-current spectra show a widening in near infrared to 0.97eV. Internal quantum efficiency values for -1V and 0V were determined.

The VIS-SWIR photosensing properties of Ge and GeSi NCs embedded in TiO2 films are investigated. For this, we deposit GeTiO2 and GeSiTiO2 films, respectively by magnetron sputtering and then we perform rapid thermal annealing (RTA) for Ge NCs and GeSi NCs formation, respectively. Raman studies and spectral photocurrent measurements were carried out. Ge NCs formation is evidenced in the Raman spectrum of GeTiO2 film annealed at 550 degrees C. The photocurrent spectra measured on the Ge NCs-TiO2 film present four peaks separated by deconvolution. The broad peaks at similar to 700, 890, 1010 nm are due to photo-effects in the Ge NCs-TiO2 film. More than that, the photocurrent increases exponentially with the increase of bias voltage. The cut-off wavelength is similar to 1240 nm. We achieve the extension of the photosensitivity limit to similar to 1310 nm in GeSi NCs-TiO2 films (800 degrees C RTA).

Radiometric methods aimed the use of liquid scintillation counting for tritium evaluation in different environmental compartments, alpha-beta and high resolution gamma spectrometry in determining radionuclides in soils, sediments and building materials. The non radiometric methods were focused on radiocarbon dating by accelerator mass spectrometry of bones, on FTIR and TGA analyzes of raw bone material vs. extracted collagen, and on the PIXE compositional analysis of archaeological materials.

Five new copper(II) acrylate complexes (acr is the acrylate anion: C3H3O2) with imidazole derivatives (2-methylimidazole/2-MeIm, 5-methylimidazole/5-MeIm, 2-ethylimidazole/2-EtIm) of type: cis-[Cu(2-RIm)(2)(acr)(2)]xH(2)O ((1): R = -CH3, x = 2; (4): R = -CH2-CH3, x = 0), trans-[Cu(2-RIm)(2)(acr)(2)] ((2): R = -CH3; (5): R = -CH2-CH3) and trans-[Cu(5-RIm)(2)(acr)(2)] ((3): R = -CH3) have been prepared and characterized by elemental analysis, Fourier Transform Infrared spectrometry (FTIR), Electron Paramagnetic Resonance (EPR), electronic reflectance spectroscopy, scanning electron microscopy, and mass spectrometry. The single crystal X-ray diffraction study of complexes (2) and (5) reveals that the copper(II) ion is located on an inversion center and show elongated octahedral geometry completed by two coplanar bidentate acrylates and two unidentate imidazole derivatives displayed in trans positions. For complex (4) the single crystal X-ray diffraction shows that the copper(II) ion is in a distorted octahedral environment which can be easily confused with a trigonal prism completed by two bidentate acrylates and two unidentate imidazole derivatives displayed in cis positions. These results indicate the fact that complexes (4) and (5) are the geometric isomers of the same compound bis(acrylate)-bis(2-ethylimidazole)-copper(II). Complexes (1) and (2), as well as (4) and (5), were produced simultaneously in the reaction of the corresponding copper(II) acrylate with imidazole derivatives in methanol solution. Furthermore, in order to be able to formulate potential applications of the obtained compounds, our next goal was to investigate the in vitro antimicrobial activity of the synthesized complexes against Gram-positive and Gram-negative bacteria, as well as fungal strains, of both clinical and ecological importance (biodeterioration of historical buildings). The trans isomers (2) and (5), followed by (4) have shown the broadest range of antimicrobial activity. In case of (1) and (2) isomers, the trans isomer (2) was significantly more active than cis (1), while the cis isomer (4) proved to be more active than trans (5). Taken together, the biological evaluation results indicate that the trans (2) was the most active complex, demonstrating its potential for the development of novel antimicrobial agents, with potential applications in the biomedical and restoration of architectural monuments fields.

Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0-80mg/kg of Zn, 5.4-60mg/kg of Fe and 0.5-4.5mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

Here, we show that wet impregnation of ZrO2 nanoparticles with 10% and 20% Eu oxide followed by thermal anneal in air above 500 degrees C produces full stabilization of the tetragonal phase of ZrO2 without evidencing any phase separation. The bare ZrO2 nanoparticles were obtained using three synthetic methods: oil in water microemulsion, rapid hydrothermal, and citrate complexation methods. The homogeneity of the solid solutions was assessed using X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy, and advanced luminescence spectroscopy. Our findings show that wet impregnation, which is a recognized method for obtaining surface doped oxides, can be successfully used for obtaining doped oxides in the bulk with good homogeneity at the atomic scale. The limits of characterization technique in detecting minor phases and the roles of dopant concentration and host structure in formation of phase stabilized solid solutions are also analyzed and discussed.

Photo-induced effects on charging and discharging of nanocrystals (NCs) in capacitor memories with Ge NCs in an HfO2 matrix as a floating gate layer are studied. The sequence of layers HfO2/Ge-HfO2/ HfO2 was deposited on a p-Si substrate using magnetron sputtering. Well separated Ge NCs are obtained after rapid thermal annealing at 600 degrees C. The optoelectric capacitor memories were fabricated with a semi-transparent electrode on top of the structure and an Al electrode on the back side of the Si substrate. Light illumination effects on hysteresis curves were investigated using different operation modes. The hysteresis window increases by increasing the light exposure time. The spectral dependence of the hysteresis window shows the maximum contribution of the light in the wavelength range of 950-1000 nm, corresponding to both contributions from the Si substrate and from Ge NCs. The stored information about the electrical and optical pulses is also investigated in the regime of the flat band potential measurements (retention measurements). It is shown that in our memory structure, the photo-effect on the memory retention corresponds to a tunnelling transfer of negative charges from the Si substrate to Ge NCs, up to a mean value of 1.6 electrons per NC. Published by AIP Publishing.

Two ZnO materials of spherical hierarchical morphologies, with hollow (ZnOHS) and solid cores (ZnOSS), were obtained through the hydrolysis of zinc acetylacetonate in 1,4-butanediol. The nature of the defects and surface reactivity for the two ZnO materials were investigated through photoluminescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy proving the coexistence of shallow and deep defects and, also, the presence of polyol byproducts adsorbed on the outer layers of the ZnO samples. The EPR spectroscopy coupled with the spin-trapping technique showed that the surface of the ZnO samples generates reactive oxygen species (ROS) like hydroxyl (OH) and singlet oxygen (O-1(2)) as well as carbon-centered radicals. The ZnO materials exhibited a wide spectrum of antimicrobial activity, being active against Gram-positive, Gram-negative, and fungi strains, both in planktonic and, more importantly, adherent groywth states. The decrease of antimicrobial efficiency in the presence of a ROS scavenger (mannitol) and the decrease of the cell viability with the ROS level suggest that one of the mechanisms that governs both the antimicrobial and cytotoxic activities on human liver cells is ROS-mediated. However, at active antimicrobial concentrations, the biocompatibility of the tested materials is very good.

Sensors based networked mesoporous SnO2 nanostructures templated by non-ionic surfactant - Brij (R) 35 were prepared via hydrothermal chemistry route. Specific patterns of the structure, morphology, surface chemistry and sensing properties were obtained by pH and autogenous pressure tuning. Consequently, the as-obtained SnO2 powders were subjected to extensive BET, Raman, TEM, HRTEM and XPS complementary investigations. The sensitive films were obtained by screen printing deposition of the powders onto commercial Al2O3 substrates. The gas sensing properties were assessed towards different hazardous gas species: CO, CH4, NH3, NO2, SO2 and H2S over a wide range of operating temperatures. Our particular SnO2 HP sensor synthesized at high autogenous pressure showed the highest selective-sensitivity to H2S (< 5 ppm) under 50% relative humidity (RH). The enhancement in the H2S sensitivity at low operating temperature under infield conditions was found to be closely connected to the morphological aspects and surface chemistry, peculiarities that can be assessed as consequences of the chemical tuning.