National Institute Of Materials Physics - Romania

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

Partially-oriented MgB2 bulk discs (13 and 9 %) with the starting compositions of (MgB2)(0.99)(B4C)(0.01) and (MgB2)(0.99)(c-BN)om were fabricated by slip casting under an H-0 = 12 T magnetic field (perpendicular to the disc surface) and subsequent spark plasma sintering. The maximum critical current density and irreversibility field are for H//H-0 (H=applied field). These values are higher or similar to the randomly-oriented samples with the same composition. The maximum volume pinning force (F-p) is lower in the partially-oriented ones than in the randomly-oriented samples. The pinning-force-related parameters depend on the additive and orientation. Assessment of the major pinning mechanism within the scaling and percolation models considering these parameters shows significant limitations. A method to scale F-p is proposed; for the randomly and partially-oriented samples (that show an extra peak in F-p), the single and double Gaussian functions fit well. The results suggest an anisotropic influence of carbon substituting for boron in the MgB2.

The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.

Doping SnO2 with trivalent lanthanide (Ln) metals aiming at optical applications faces several challenges. The elastic and electrostatic misfit between bulkier Ln activators and Sn host cation induces strain in the lattice as well as defects as a result of charge-compensation. These effects can be partially healed by thermal annealing. However, dopant segregation which occurs above a certain temperature drives quenching of Ln emission. In this work, we explore Li co-doping as a vehicle to improve the luminescence of lanthanide (Eu, Sm, Er, Dy and, Tb) doped SnO2 nanoparticles. In case of substitutional Ln dopants (Eu, Sm and Er), Li enhances significantly the Ln luminescence up to 40-46 times. The luminescence enhancement induced by Li co-doping is explained by an interplay of removal of nearby oxygen vacancies (Eu, Sm), improved Ln doping homogeneity (Er) and, improved crystallinity (Eu, Sm, Er). The improved crystallinity caused by Li co-doping accounts for less than 30% of the total enhancement. In the case of surface Ln dopants (Dy and Tb), Li co-doping does not alter the Ln emission, either in shape or intensity. Only a few Dy dopants succeed to substitute for Sn in the rutile lattice as shown by single-photon counting investigations. Collectively, our results show that the extent of luminescence enhancement induced by Li co-doping depend strongly on the Ln type. In SnO2, the common mechanisms that explain the Li induced enhancement of Ln luminescence in various hosts, either contribute partially (improved crystallization) or do not contribute at all (local structure distortion).

The equimolar oxide mixture beta-Ga2O3-alpha-Fe2O3 was subjected to high-energy ball milling (HEBM) with the aim to obtain the nanoscaled GaFeO3 ortho-ferrite. X-ray diffraction, Fe-57 Mossbauer spectroscopy, and transmission electron microscopy were used to evidence the phase structure and evolution of the equimolar nano-system beta-Ga2O3-alpha-Fe2O3 under mechanochemical activation, either as-prepared or followed by subsequent calcination. The mechanical activation was performed for 2 h to 12 h in normal atmosphere. After 12 h of HEBM, only nanoscaled (similar to 20 nm) gallium-doped alpha-Fe2O3 was obtained. The GaFeO3 structure was obtained as single phase, merely after calcination at 950 degrees C for a couple of hours, of the sample being subjected to HEBM for 12 h. This temperature is 450 degrees C lower than used in the conventional solid phase reaction to obtain gallium orthoferrite. The optical and magnetic properties of representative nanoscaled samples, revealing their multifunctional character, were presented.

Two core-double-shell pH-sensitive nanocarriers were fabricated using Fe3O4 as magnetic core, poly(glycidyl methacrylate-PEG) and salep dialdehyde as the first and the second shell, and doxorubicin as the hydrophobic anticancer drug. Two nanocarriers were different in the drug loading steps. The interaction between the first and the second shell assumed to be pH-sensitive via acetal cross linkages. The structure of nanocarriers, organic shell loading, magnetic responsibility, morphology, size, dispersibility, and drug loading content were investigated by IR, NMR, TG, VSM, XRD, DLS, HRTEM and UV-Vis analyses. The long-term drug release profiles of both nanocarriers showed that the drug loading before cross-linking between the first and second shell led to a more pH-sensitive nanocarrier exhibiting higher control on DOX release. Cellular toxicity assay (MTT) showed that DOX-free nanocarrier is biocompatible having cell viability greater than 80% for HEK-293 and MCF-7 cell lines. Besides, high cytotoxic effect observed for drug-loaded nanocarrier on MCF-7 cancer cells. Cellular uptake analysis showed that the nanocarrier is able to transport DOX into the cytoplasm and perinuclear regions of MCF-7 cells. In vitro hemolysis and coagulation assays demonstrated high blood compatibility of nanocarrier. The results also suggested that low concentration of nanocarrier have a great potential as a contrast agent in magnetic resonance imaging (MRI).

Due to its physical and chemical properties, the n-type tungsten oxide (WO3) semiconductor is a suitable photoanode for water decomposition reaction. The responses of the photoelectrochemical PEC water-splitting properties as an effect of structural and optical changes of WO3 thin films, as well as the nature of electrolyte solutions, were studied in this work. The WO3 thins films have been obtained by pulsed laser deposition (PLD) on silicon (Si(001)) covered with platinum substrates using three different laser wavelengths. As the XRD (X-ray diffraction) and XTEM (cross-section transmission electron microscopy) analysis shows, the formation of highly crystalline monocline WO3 phase is formed for the film deposited at 1064 nm wavelength and poor crystalline phases with a large ordering anisotropy, characteristic of 2D structures for the films deposited at 355 nm and 193 nm wavelengths, respectively. The photogenerated current densities J(ph) depend on the laser wavelength, in both alkaline and acidic electrolyte. The maximum values of the photocurrent density have been obtained for the sample prepared with laser emitting at 355 nm. This behavior can be correlated with the coherent crystallized atomic ordering that appear for long distances (10-15 nm) in the (001) plane of the monoclinic WO3 phase structure films obtained at 355 nm laser wavelength. All the samples show poor current density in dark conditions and they are very stable in both acidic and alkaline solutions. The highest photocurrent density value is obtained in acidic solution for the WO3 thin film prepared by 355 nm laser (29 mA/cm(2) at 1.6 V vs. RHE (1.35 V vs. Ag/AgCl)).

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)(2) have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)(2) native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 degrees C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

Commercial nanopowders of MgB2 were characterized from the viewpoint of granulometric distribution, structure, microstructure, and pH behavior in water. The powders are very different: a higher amount of the MgB2 phase with a lower tendency for agglomeration determines a higher rate of pH-increase. A higher rate of pH-increase usually produces a stronger antimicrobial activity against Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Pseudomonas aeruginosa, Candida albicans, and Candida parapsilosis reference strains. The variation of the pH-increase rate suggests the possibility of temporo-spatial control of MgB2 bioactivity, although the contribution of other factors should not be neglected. Remarkably, the efficiency of the MgB2 powders is higher against biofilms than on microbes in the planktonic state. Further, our experiments confirm the antimicrobial efficiency of MgB2 in the in vitro tests against 29 methicillin resistant clinical S. aureus isolates and 33 vancomycin resistant E. faecium/faecalis strains, but in this case the biofilms are more resistant than planktonic cells. The MgB2 treatment of infected mice led to a significant decrease of E. coli colonization in liver, spleen and peritoneal liquid and it also caused changes in the intestinal microbiota. The activity of powders on HeLa and HT-29 tumor cell lines was assessed by inverted microscopy, flow cytometry, and evaluation of the cellular cycle. MgB2 inhibits tumor cell growth influencing DNA synthesis (S-phase). The obtained results indicate that the tested powders could provide promising solutions for the development of large-spectrum multifunctional antimicrobial and anti-biofilm agents, and/or for anti-cancer therapies. (C) 2021 The Authors. Published by Elsevier B.V.

The development of short-wave infrared (SWIR) photonics based on GeSn alloys is of high technological interest for many application fields, such as the Internet of things or pollution monitoring. The manufacture of crystalline GeSn is a major challenge, mainly because of the low miscibility of Ge and Sn. The use of embedded GeSn nanocrystals (NCs) by magnetron sputtering is a cost-effective and efficient method to relax the growth conditions. We report on the use of GeSn/SiO2 multilayer deposition as a way to control the NC size and their insulation. The in situ prenucleation of NCs during deposition was followed by ex situ rapid thermal annealing. The nanocrystallization of 20X(11nm_Ge0.865S0.135/1.5nm_SiO2) multilayers leads to formation of GeSn NCs with similar to 16% Sn concentration and similar to 9 nm size. Formation of GeSn domes that are vertically correlated contributes to the nanocrystallization process. The absorption limit of similar to 0.4 eV in SWIR found by ellipsometry is in agreement with the spectral photosensitivity. The ITO/20x(GeSn NC/SiO2)/p-Si/Al diodes show a maximum value of the SWIR photosensitivity at a reverse voltage of 0.5 V, with extended sensitivity to wavelengths longer than 2200 nm. The multilayer diodes have higher photocurrent efficiency compared to diodes based on a thick monolayer of GeSn NCs.