National Institute Of Materials Physics - Romania

Europium doped (0.1% and 1%) chlomborate BaO-B2O3-BaCl2 glass and glass-ceramic with embedded BaCl2 nanocrystals have been synthesised, investigated, and compared with the corresponding nanocrystalline powder. The structural analysis of the glass evidenced ionic bonds characteristic to the glass host structure and compositional changes during the melting. X-ray diffraction and transmission electron microscopy revealed the formation of orthorhombic BaCl2 nanocrystals of about tens on nm in size and a smaller amount of BaB2O4 nanocrystals. Structural analysis of the Eu2+-doped BaCl2 nanocrystals has shown a distortion of the crystalline cell assigned to the growth process, affected by defects and ionic impurities. Photoluminescence spectra of the glass-ceramic revealed Eu3+ and Eu2+ luminescent ion species, but only Eu2+ is incorporated within the BaCl2 nanocrystalline phase. Electron paramagnetic resonance measurements in X-band sustain the presence of Eu2+ ions. The EPR parameters (g values and hyperfine constants) resulting from the Q-band EPR spectra simulations recorded on glass-ceramic are similar to those in Eu2+-doped BaCl2 and confirmed the partial incorporation of Eu2+ ions within the BaCl2:Eu2+ nanocrystals in the glass-ceramics.

Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb0.98Sr0.02 ((Ti0.49Zr0.51)(1-0.015-x)Mn0.015Sbx)O-3 with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn2+ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb3+ ions substituting Pb2+ at the A-sites and the Mn2+ ions, localized at the B-sites. The incorporation of Sb3+ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn2+ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.

Many magnetotactic bacteria (MTB) biomineralize magnetite crystals that nucleate and grow inside intracellular membranous vesicles originating from invaginations of the cytoplasmic membrane. The crystals together with their surrounding membranes are referred to as magnetosomes. Magnetosome magnetite crystals nucleate and grow using iron transported inside the vesicle by specific proteins. Here, we tackle the question of the organization of magnetosomes, which are always described as constituted by linear chains of nanocrystals. In addition, it is commonly accepted that the iron oxide nanocrystals are in the magnetite-based phase. We show, in the case of a wild species of coccus-type bacterium, that there is a double organization of the magnetosomes, relatively perpendicular to each other, and that the nanocrystals are in fact maghemite. These findings were obtained, respectively, by using electron tomography of whole mounts of cells directly from the environment and high-resolution transmission electron microscopy and diffraction. Structure simulations were performed with the MacTempas software. This study opens new perspectives on the diversity of phenotypes within MTBs and allows to envisage other mechanisms of nucleation and formation of biogenic iron oxide crystals.

Epitaxial La0.7Sr0.3MnO3 films with different thicknesses (9-90 nm) were deposited on SrTiO3 (0 0 1) substrates by pulsed laser deposition. The films have been investigated with respect to morpho-structural, magnetic, and magneto-transport properties, which have been proven to be thickness dependent. Magnetic contributions with different switching mechanisms were evidenced, depending on the perovskite film thickness. The Curie temperature increases with the film thickness. In addition, colossal magnetoresistance effects of up to 29% above room temperature were evidenced and discussed in respect to the magnetic behavior and film thickness.

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.

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.