National Institute Of Materials Physics - Romania

In this work, the ferroelectric characteristics of ZrO2 thin films grown on ITO-coated glass have been investigated. The ferroelectric nature of the ZrO2 films has been studied by polarization-electric field (P-E) hysteresis loops and found to be optimum for the films processed by rapid thermal annealing at 600 degrees C. The increase in the annealing temperature improves the ferroelectric properties through the increase of the in-plane strain that causes the formation of the ferroelectric orthorhombic phase. The formation of the orthorhombic phase was confirmed through high-resolution transmission electron microscopy. The effect of the electric field on the polarization switching kinetics of ZrO2 films has been investigated revealing that the switching kinetics follows the nucleation limited switching (NLS) model. The activation fields estimated from the peak values of the polarization currents (im) and the time (tm) at which im occurs are in good agreement with the values obtained from the switching characteristic time of the NLS model. This work paves the way towards the integration of (pseudo)binary oxide thin films on cheap substrates like glass for the next-generation of non-volatile memories.

Phosphate and tellurite glasses can be used in optics, optoelectronics, magneto-optics, and nuclear and medical fields. Two series of phosphate-tellurite glasses, (50-x)ZnO-10Al(2)O(3)-40P(2)O(5)-xTeO(2) and (40-x)Li2O-10Al(2)O(3)-5TiO(2)-45P(2)O(5)-xTeO(2) (x = 5, 10), were synthesized by a non-conventional wet-route, and the mechanical properties as key performance measures for their application in optoelectronics were investigated. X-ray Diffraction (XRD) measurements revealed the vitreous nature of the investigated materials. Instrumented indentation tests allowed the calculation of hardness (H) and Young's modulus (E) using the Oliver and Pharr model. The influence of increasing the TeO2 content, as well as the substitution of ZnO by Li2O-TiO2, on the variation of hardness, Young's modulus, penetration depth (PD), and fracture toughness (FT) was evaluated in both series. As a general trend, there is a decrease in the hardness and Young's modulus with increasing penetration depth. The addition of Li2O and TiO2 instead of ZnO leads to improved hardness and elastic modulus values. Regarding the H/E ratio, it was found that the samples with lower TeO2 content should be significantly more crack-resistant compared to the higher TeO2 content samples. The H-3/E-2 ratio, being lower than 0.01, revealed a poor resistance of these glasses to plastic deformation. At the same time, a decrease of the fracture toughness with increasing TeO2 content was noticed for each glass series. Based on dilatometry measurements, the thermal expansion coefficient as well as the characteristic temperatures of the glasses were measured. Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray analysis (FESEM-EDX) revealed a uniform distribution of the elements in the bulk samples. The mechanical properties of these vitreous materials are important in relation to their application as magneto-optical Faraday rotators in laser cavities.

Silver doped hydroxyapatite [AgHAp, Ca10-xAg(PO4)(6)(OH)(2)], due to its antimicrobial properties, is an advantageous material to be used for various coatings. The AgHAp thin films with x(Ag) = 0.05 and x(Ag) = 0.1 were achieved using the spin-coating method. The resulting samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XRD analysis revealed that the particles of both samples are ellipsoidal. Also, in agreement with the results obtained by XRD measurements, the results of the SEM studies have shown that the particles shape is ellipsoidal. Optical properties of silver doped hydroxyapatite thin films deposited on Si substrate were investigated through Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The results obtained by the two complementary techniques highlighted that the molecular structure of the studied samples is not influenced by the increase of the silver concentration in the samples. Our studies revealed that the surface morphology of the obtained samples consist of uniform and continuous layers. The biocompatibility of the obtained thin films was also evaluated with the aid of human osteosarcoma MG63 (ATCC CRL 1427) cell line. Moreover, the in vitro antifungal activity against Candida albicans fungal strain of the AgHAp thin films was studied and the obtained results revealed their antifungal effect. The results of the biological assays showed that the AgHAp thin films are a very promising material for biomedical applications.

In this work, the thermally stimulated current (TSC) technique has been used to investigate the properties of the radiation-induced interstitial boron and interstitial oxygen defect complex by 23-GeV (E-kin) protons, including activation energy, defect concentration, as well as the annealing behavior. At first isothermal annealing (at 80 degrees C for 0-180 min) followed by isochronal annealing (for 15 min between 100 degrees C and 190 degrees C in steps of 10 degrees C), studies had been performed in order to get information about the thermal stability of the interstitial boron and interstitial oxygen defect in 50-Omega cm material after irradiation with 23-GeV protons to a fluence of 6.91 x 10(13) p/cm(2). The results are presented and discussed. Furthermore, the extracted data from TSC measurements are compared with the macroscopic properties derived from current-voltage and capacitance-voltage characteristics. In addition, the introduction rate of interstitial boron and interstitial oxygen defect as a function of the initial doping concentration was determined by exposing diodes with different resistivities (10, 50, 250, and 2 k Omega cm) to 23-GeV protons. These results are compared with data from TSC and deep-level transient spectroscopy measurements achieved by the team of the CERN-RD50 "Acceptor removal project."

This work presents the preparation of W and V co-doped TiO2 nanoparticles (W:TiO2 and W:V:TiO2) using laser pyrolysis technique subsequently modified with noble metals Pt or Pd using chemical impregnation method. By using well defined TiO2 nanoparticles, the enhancement of catalytic activity is expected mainly due to their higher surface area and density defects relative to bulk material. Structural, morphological and optical properties of the as-obtained nanopowders have been characterized by transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, UV-VIS diffuse reflectance spectroscopy and photoluminescence techniques. The phase composition analysis reveals the preponderance of anatase (95%) in addition to ruffle phase, its particle average size ranging from 25 to 30 nm. The TiO 2 based nanomaterials were supplementary modified by noble metals deposition (Pt particles with dimensions of 3-4 nm and spherical Pd crystallites with a diameter between 3 and 9 nm) and their photocatalytic activity was tested in oxidative photo degradation of CH3OH, under simulated solar light. The metal modified samples displayed higher specific surface areas (3-6 times) and improved photocatalytic properties, the W:V:TiO2@Pt material showing better conversion efficiency of CH3OH to CH2O than the reference Degussa P25 sample (1.54 versus 0.90%).

MoO2-Fe2O3 nanoparticle systems were successfully synthesized by mechanochemical activation of MoO2 and alpha-Fe2O3 equimolar mixtures throughout 0-12 h of ball-milling. The role of the long-range ferromagnetism of MoO2 on a fraction of more defect hematite nanoparticles supporting a defect antiferromagnetic phase down to the lowest temperatures was investigated in this work. The structure and the size evolution of the nanoparticles were investigated by X-ray diffraction, whereas the magnetic properties were investigated by SQUID magnetometry. The local electronic structure and the specific phase evolution in the analyzed system versus the milling time were investigated by temperature-dependent Mossbauer spectroscopy. The substantially shifted magnetic hysteresis loops were interpreted in terms of the unidirectional anisotropy induced by pinning the long-range ferromagnetic order of the local net magnetic moments in the defect antiferromagnetic phase, as mediated by the diluted magnetic oxide phase of MoO2, to those less defect hematite nanoparticles supporting Morin transition. The specific evolutions of the exchange bias and of the coercive field versus temperature in the samples were interpreted in the frame of the specific phase evolution pointed out by Mossbauer spectroscopy. Depending on the milling time, a different fraction of defect hematite nanoparticles is formed. Less nanoparticles supporting the Morin transition are formed for samples exposed to a longer milling time, with a direct influence on the induced unidirectional anisotropy and related effects.

Titanium dioxide nanoparticles (TiO2 NPs) are found in several products on the market that include paints, smart textiles, cosmetics and food products. Besides these, TiO2 NPs are intensively researched for their use in biomedicine, agriculture or installations to produce energy. Taking into account that several risks have been associated with the use of TiO2 NPs, our aim was to provide TiO2 NPs with improved qualities and lower toxicity to humans and the environment. Pure TiO2 P25 NPs and the same NPs co-doped with iron (1%) and nitrogen atoms (P25-Fe(1%)-N NPs) by hydrothermal treatment to increase the photocatalytic activity in the visible light spectrum were in vitro evaluated in the presence of human lung cells. After 24 and 72 h of incubation, the oxidative stress was initiated in a time- and dose-dependent manner with major differences between pure P25 and P25-Fe(1%)-N NPs as revealed by malondialdehyde and reactive oxygen species levels. Additionally, a lower dynamic of autophagic vacuoles formation was observed in cells exposed to Fe-N-doped P25 NPs compared to the pure ones. Therefore, our results suggest that Fe-N doping of TiO2 NPs can represent a valuable alternative to the conventional P25 Degussa particles in industrial and medical applications.

A series of cobalt-iron mixed oxides, CoxFe3-xO4 (x = 0; 0.05; 0.1; 0.15), were synthesized by coprecipitation and tested for oxidative decarboxylation of malic acid to pyruvic or malonic acid. The characterization of catalysts was performed by different techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT) and Ultraviolet-visible spectroscopy (UV-Vis). Among studied catalysts, Co0.15Fe2.85O4 sample (denoted Co3Fe) showed the highest malic acid conversion in oxidative decarboxylation reaction as well as the highest pyruvic acid yield. This behavior can be due to the fact that this sample has the highest content of tetrahedral Co2+ that replaces Fe3+ from octahedral position that determine an increased number of defects that play a crucial role for the malic acid conversion.

To enhance the spectral response of solar cells, an experimental study on LaPO4:0.01Ce(3+)/xNd(3+) (x = 0, 2, 4 mol%) was carried out, where structural and morphological properties of the prepared samples were well characterized by the means of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electronic microscope. Additionally, the photoluminescence behavior of phosphors in ultraviolet-visible (UV-VIS) and Near-infrared (NIR) regions were investigated to confirm the energy transfer (ET) from Ce3+ to Nd3+. Moreover, the quantum efficiency of Ce3+/Nd3+-co-doped samples was estimated as high as similar to 172% and the possible ET process was described. Accordingly, the LaPO4:Ce3+/Nd3+ phosphors can convert the UV light (275 nm) into NIR photons (approx. 1059 nm) through the possible two-pathway energy transfer processes from Ce3+ sensitizer ions to Nd3+ activators. Obtained NIR down-conversion emissions are suitable for improving the conversion efficiency of c-Si solar cells.

Group IV quantum dots (QDs) in HfO2 are attractive for non-volatile memories (NVMs) due to complementary metal-oxide semiconductor (CMOS) compatibility. Besides the role of charge storage centers, SiGeSn QDs have the advantage of a low thermal budget for formation, because Sn presence decreases crystallization temperature, while Si ensures higher thermal stability. In this paper, we prepare MOS capacitors based on 3-layer stacks of gate HfO2/floating gate of SiGeSn QDs in HfO2/tunnel HfO2/p-Si obtained by magnetron sputtering deposition followed by rapid thermal annealing (RTA) for nanocrystallization. Crystalline structure, morphology, and composition studies by cross-section transmission electron microscopy and X-ray diffraction correlated with Raman spectroscopy and C-V measurements are carried out for understanding RTA temperature effects on charge storage behavior. 3-layer morphology and Sn content trends with RTA temperature are explained by the strongly temperature-dependent Sn segregation and diffusion processes. We show that the memory properties measured on Al/3-layer stack/p-Si/Al capacitors are controlled by SiGeSn-related trapping states (deep electronic levels) and low-ordering clusters for RTA at 325-450 degrees C, and by crystalline SiGeSn QDs for 520 and 530 degrees C RTA. Specific to the structures annealed at 520 and 530 degrees C is the formation of two kinds of crystalline SiGeSn QDs, i.e., QDs with low Sn content (2 at.%) that are positioned inside the floating gate, and QDs with high Sn content (up to 12.5 at.%) located at the interface of floating gate with adjacent HfO2 layers. The presence of Sn in the SiGe intermediate layer decreases the SiGe crystallization temperature and induces the easier crystallization of the diamond structure in comparison with 3-layer stacks with Ge-HfO2 intermediate layer. High frequency-independent memory windows of 3-4 V and stored electron densities of 1-2 x 10(13) electrons/cm(2) are achieved.