National Institute Of Materials Physics - Romania

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.

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.

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.

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.

The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.

TiO2-C (carbon) hybrid materials are promising electrocatalyst supports because the presence of TiO2 results in enhanced stability. Use of new types of carbonaceous materials such as reduced graphene oxide instead of traditional active carbon provides certain benefits. Although the rutile polymorph of TiO2 seems to have the most beneficial properties in these hybrid materials, the anatase type is more frequent in TiO2-rGO composites, especially in graphite oxide (GO) derived ones, as GO has several properties which may interfere with rutile formation. To explore and evaluate these peculiarities and their influence on the composite formation, we compared TiO2-C systems formulated with GO and Black Pearls (BP) carbon. Various physicochemical methods, such as attenuated total reflection infrared (ATR-IR)-, solid state NMR-, Raman- and X-ray photoelectron spectroscopy, X-ray powder diffraction (XRD), electron microscopy, etc. were used to characterize the samples from the different stages of our multistep sol-gel synthesis. Our experiments demonstrated that utilization of GO is indeed feasible for composite preparation, although its sodium contamination has to be removed during the synthesis. On the other hand, high temperature treatment and/or solvothermal treatment during composite synthesis resulted in decomposition of the functional groups of the GO and the functional properties of the final product were similar in case of both composites. However, Pt/TiO2-GO derived sample showed higher oxygen reduction reaction activity than Pt/TiO2-BP derived one. Based on the decrease of electrochemical surface area, the stability order was the following: Pt/C (commercial) < Pt/TiO2-BP derived C < Pt/TiO2-GO derived C.

Pristine high-density bulk disks of MgB2 with added hexagonal BN (10 wt.%) were prepared using spark plasma sintering. The BN-added samples are machinable by chipping them into desired geometries. Complex shapes of different sizes can also be obtained by the 3D printing of polylactic acid filaments embedded with MgB2 powder particles (10 wt.%). Our present work aims to assess antimicrobial activity quantified as viable cells (CFU/mL) vs. time of sintered and 3D-printed materials. In vitro antimicrobial tests were performed against the bacterial strains Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853, Staphylococcus aureus ATCC 25923, Enterococcus faecium DSM 13590, and Enterococcus faecalis ATCC 29212; and the yeast strain Candida parapsilosis ATCC 22019. The antimicrobial effects were found to depend on the tested samples and microbes, with E. faecium being the most resistant and E. coli the most susceptible.

In the field of research for designing and preparing innovative nanostructured systems, these systems are able to reveal the presence of heavy metals in water samples, and can efficiently and selectively interact with them, allowing for future applications in the field of water remediation. We investigated the electronic and molecular structure, as well as the morphology, of silver nanoparticles stabilized by mixed biocompatible ligands (the amino acid L-cysteine and the organic molecule citrate) in the presence of cadmium and arsenic ions. The molecular, electronic, and local structure at the ligands/silver nanoparticles interface was probed by the complementary synchrotron radiation-induced techniques (SR-XPS, NEXAFS and XAS). The optical absorption (in the UV-Vis range) of the nanosystem was investigated in the presence of Cd(II) and As(III) and the observed behavior suggested a selective interaction with cadmium. In addition, the toxicological profile of the innovative nanosystem was assessed in vitro using a human epithelial cell line HEK293T. We analyzed the viability of the cells treated with silver nanoparticles, as well as the activation of antioxidant response.

Orthorhombic HfO2 exhibits nanoscale ferroelectricity that opens the perspective of ultra-scalable CMOS integration of ferroelectric memories. However, many aspects of the metastable orthorhombic crystallization mechanisms still need to be elucidated and new fabrication methods are of high interest. In this paper, the atomically resolved crystal structure of HfO2 is a 3-layer structure with a Ge-rich HfO2 intermediate layer capped by a top (cap) HfO2 layer and cladded by a bottom HfO2 layer. There is a continuity of crystal growth from the top and bottom HfO2 layers into the intermediate layer. A spatial transition from a monoclinic phase to an orthorhombic phase was revealed within a region of a few atomic layers at the interface between capped and intermediate HfO2 layers. This result suggests the mechanism of orthorhombic and monoclinic phase formation by a martensitic-like transformation of the initially grown tetragonal phase. The sample fabrication method we used involved magnetron sputtering deposition of the 3-layer structures, i.e. a stack of top HfO2/Ge-rich HfO2 intermediate/bottom HfO2 layers, followed by rapid thermal annealing. It results in self-optimized orthorhombic crystallization of HfO2 by Ge nanoparticle segregation in the intermediate layer. The ferroelectric effects are revealed by polarization-voltage hysteresis loops and piezoresponse force microscopy measurements. The atomistic computations performed by using the density functional theory support the experimental results by showing that the Ge doping of HfO2 leads to orthorhombic phase stabilization and increased Berry phase polarization.