National Institute Of Materials Physics - Romania

Cu2ZnSnS4 (CZTS) is an economically and environmentally friendly alternative to other toxic and expensive materials used for photovoltaics, however, the variation in the composition during synthesis is often followed by the occurrence of the secondary binary and ternary crystalline phases. These phases produce changes in the optical absorption edge important in cell efficiency. We explore here the secondary phases that emerge in a combinatorial Cu2S-ZnS-SnS2 thin films library. Thin films with a composition gradient were prepared by simultaneous magnetron sputtering from three binary chalcogenide targets (Cu2S, SnS2 and ZnS). Then, the samples were crystallized by sulfurization annealing at 450 degrees C under argon flow. Their composition was measured by energy dispersive X-ray spectroscopy (EDX), whereas the structural and optical properties were investigated by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and optical transmission measurements. As already known, we found that annealing in a sulfur environment is beneficial, increasing the crystallinity of the samples. Raman spectroscopy revealed the presence of CZTS in all the samples from the library. Secondary crystalline phases such as SnS2, ZnS and Cu-S are also formed in the samples depending on their proximity to the binary chalcogenide targets. The formation of ZnS or Cu-S strongly correlates with the Zn/Sn and Cu/Zn ratio of the total sample composition. The presence of these phases produces a variation in the bandgap between 1.41 eV and 1.68 eV. This study reveals that as we go further away from CZTS in the composition space, in the quasi-ternary Cu2S-ZnS-SnS2 diagram, secondary crystalline phases arise and increase in number, whereas the bandgap takes values outside the optimum range for photovoltaic applications.

Hydroxyapatite (HAp) and samarium doped hydroxyapatite, Ca10-xSmx(PO4)(6)(OH)(2),x(Sm)= 0.05, (5SmHAp), coatings were prepared by sol-gel process using the dip coating method. The stability of 5SmHAp suspension was evaluated by ultrasound measurements. Fourier transform infrared spectroscopy (FTIR) was used to examine the optical characteristics of HAp and 5SmHAp nanoparticles in suspension and coatings. The FTIR analysis revealed the presence of the functional groups specific to the structure of hydroxyapatite in the 5SmHAp suspensions and coatings. The morphology of 5SmHAp nanoparticles in suspension was evaluated by transmission electron microscopy (TEM). Moreover, scanning electron microscope (SEM) was used to evaluate the morphology of nanoparticle in suspension and the morphology of the surface on the coating. The SEM and TEM studies on 5SmHAp nanoparticles in suspension showed that our samples consist of nanometric particles with elongated morphology. The SEM micrographs of HAp and 5SmHAp coatings pointed out that the coatings are continuous and homogeneous. The surface morphology of the 5SmHAp coatings was also assessed by Atomic Force Microscopy (AFM) studies. The AFM results emphasized that the coatings presented the morphology of a uniformly deposited layer with no cracks and fissures. The crystal structure of 5SmHAp coating was characterized by X-ray diffraction (XRD). The surface composition of 5SmHAp coating was analyzed by X-ray photoelectron spectroscopy (XPS). The XRD and XPS analysis shown that the Sm(3+)ions have been incorporated into the 5SmHAp synthesized material. The antifungal properties of the 5SmHAp suspensions and coatings were studied usingCandida albicansATCC 10231 (C. albicans) fungal strains. The quantitative results of the antifungal assay showed that colony forming unity development was inhibited from the early phase of adherence in the case of both suspensions and coatings. Furthermore, the adhesion, cell proliferation and biofilm formation of theC. albicanswere also investigated by AFM, SEM and Confocal Laser Scanning Microscopy (CLSM) techniques. The results highlighted that theC. albicansadhesion and cell development was inhibited by the 5SmHAp coatings. Moreover, the data also revealed that the 5SmHAp coatings were effective in stopping the biofilm formation on their surface. The toxicity of the 5SmHap was also investigated in vitro using HeLa cell line.

This study develops, for the first time, composite coatings based on silver and zinc doped hydroxyapatite in chitosan matrix (AgZnHApCs). The AgZnHApCs composite coatings were prepared by dip coating method. The hydroxyapatite (HAp), biocompatible material for regenerating and strengthening damaged bones were doped with silver and zinc ions and coated with chitosan in order to produce a uniform and homogenous coating with biocompatibility and antimicrobial properties. The stability of AgZnHApCs suspensions was evaluated by ultrasound measurements. The value of stability parameters of AgZnHApCs suspension is in good agreement with the value of bidistilled water used as reference fluid. Homogeneously dispersed solutions of AgZnHApCs were synthesized to endeavor to optimize the physico-chemical and biological characteristics of the coatings obtained at room temperature. The AgZnHApCs composite suspension and coatings were analyzed using various investigation techniques, such as X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenylte-2H-tetrazolium bromide) assay and antimicrobial studies. The optical spectroscopy, atomic force microscopy (AFM), metallographic examination and X-ray photoelectron spectroscopy (XPS) on AgZnHApCs composite coatings were also conducted. Cell culture and MTT assays demonstrate that AgZnHApCs composite suspension and coatings have no negative effect on the cell viability and proliferation. The cell morphology was not affected in presence of AgZnHApCs composite suspension and coatings. The antimicrobial assays conducted againstStaphylococcus aureusATCC 25923,Escherichia coliATCC 25922, andCandida albicansATCC 90029 microbial strains revealed that both the AgZnHApCs composite suspension and coatings exhibited great antimicrobial properties.

The first electrochemical immunosensor for the determination of the 20S proteasome (P20S) was developed, entailing the immobilization of an antibody on an aminophenylboronic/poly-indole-6-carboxylic acid-modified electrode. The proposed electrochemical bioplatform is a simple and feasible analytical tool applicable for the determination of P20S in human plasma, considering its high clinical and biological relevance. Cyclic voltammetry, electrochemical impedance spectroscopy, and square wave voltammetry (SWV) were used to determine the optimal step-by-step process to obtain the electrochemical immunosensor. The interaction of P20S with the recognition layer of the immobilized antibody on the nanostructured surface took place by incubating the electrode in a P20S solution at 20 degrees C for 2 h. Using SWV as an electro-analytical technique, this immunosensor can quantify P20S. The current was linear with the P20S concentration within two dynamic concentration ranges from 20.0 to 80.0 and 80.0 to 200.0 ng.mL(-1) (r(2) = 0.992 and 0.98, respectively) with a limit of detection and quantification of 6 and 18 ng.mL(-1), respectively. Moreover, the immunosensor showed considerable repeatability and reproducibility, when the determination was done in human serum, which confirms that it is a promising alternative for direct detection of P20S in biological fluids with minimal interference.

In this work, the effects of graphene oxide (GO) concentrations (1.5 wt.%, 2.5 wt.%, and 5 wt.%) on the structural, morphological, optical, and luminescence properties of zinc oxide nanorods (ZnO NRs)/GO nanocomposites, synthesized by a facile hydrothermal process, were investigated. X-ray diffraction (XRD) patterns of NRs revealed the hexagonal wurtzite structure for all composites with an average coherence length of about 40-60 nm. A scanning electron microscopy (SEM) study confirmed the presence of transparent and wrinkled, dense GO nanosheets among flower-like ZnO nanorods, depending on the GO amounts used in preparation. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, and photoluminescence (PL) measurements revealed the impact of GO concentration on the optical and luminescence properties of ZnO NRs/GO nanocomposites. The energy band gap of the ZnO nanorods was independent of GO concentration. Photoluminescence spectra of nanocomposites showed a significant decrease in the intensities in the visible light range and red shifted suggesting a charge transfer process. The nanocomposites' chromaticity coordinates for CIE 1931 color space were estimated to be (0.33, 0.34), close to pure white ones. The obtained results highlight the possibility of using these nanocomposites to achieve good performance and suitability for optoelectronic applications.

Polymer-based nanocomposites have recently received considerable attention due to their unique properties, which makes them feasible for applications in optics, sensors, energy, life sciences, etc. The present work focuses on the synthesis of nanocomposites consisting of a polytetrafluorethylene-like matrix in which metallic nano-silver are embedded, by using multiple magnetron plasmas. By successively exposing the substrate to separate RF magnetrons using as combination of target materials polytetrafluorethylene (PTFE) and silver, individual control of each deposition process is insured, allowing obtaining of structures in which silver nanoparticles are entrapped in-between two PTFE layers with given thicknesses. The topographical and morphological characteristics investigated by means of Scanning Electron Microscopy and Atomic Force Microscopy techniques evidenced the very presence of Ag nanoparticles with typical dimension 7 nm. The chemical composition at various depositing steps was evaluated through X-ray Photoelectron Spectroscopy. We show that the presence of the top PTFE layer prevents silver oxidation, while its thickness allows the tailoring of optical properties, as evidenced by spectroellipsometry. The appearance of chemical bonds between silver atoms and PTFE atoms at interfaces is observed, pointing out that despite of pure physical deposition processes, a chemical interaction between the polymeric matrix and metal is promoted by plasma.

Iron oxides such as magnetite and maghemite coated with cetyltrimethylammonium bromide (CTAB) are very promising materials for wastewater treatment because iron oxide can be easily separated from solutions using the magnetic separation procedure Iron oxide (IO) coated CTAB was synthesized by an adapted co-precipitation method. In the present study, the IO-CTAB was used for removing arsenic from water for the first time. In the present study, the performance of iron oxide coated CTAB biocomposites as an adsorbent for arsenic removal from aqueous solutions was examined. X-ray diffraction (XRD) analysis and the results revealed a cubic phase Fd-3 m of Fe(3)O(4)with lattice a = 8.40 angstrom and average crystal size equal to 17.26 +/- 3 nm. The mean particle size calculated from transmission electron microscopy (TEM) was 19.86 +/- 1.7 nm. The results of the adsorption batch experiments and the data determined using the Langmuir and Freundlich models emphasized that IO-CTAB nanoparticles were favorable for the adsorption of As(III) ions from aqueous solutions. Ultrasound measurements have shown that IO-CTAB is a cost-effective biocomposite for removing arsenic from contaminated solutions. Moreover, x-ray photoelectron spectroscopy (XPS) has shown that during the process of arsenic absorption, there is oxidation from As(III) to As(V), which leads to a decrease in toxicity during this process. The results of the cytotoxic assays confirmed that the IO-CTAB nanoparticles did not induce any morphological changes in the HeLa cells and did not affect their proliferation after 24 h of incubation.

GeSn alloys have the potential of extending the Si photonics functionality in shortwave infrared (SWIR) light emission and detection. Epitaxial GeSn layers were deposited on a relaxed Ge buffer on Si(100) wafer by using high power impulse magnetron sputtering (HiPI-MS). Detailed X-ray reciprocal space mapping and HRTEM investigations indicate higher crystalline quality of GeSn epitaxial layers deposited by Ge HiPI-MS compared to commonly used radio frequency magnetron sputtering (RF-MS). To obtain a rectifying heterostructure for SWIR light detection, a layer of GeSn nanocrystals (NCs) embedded in oxide was deposited on the epitaxial GeSn one. Embedded GeSn NCs are obtained by cosputtering deposition of (Ge1-xSnx)(1-y)(SiO2)(y) layers and subsequent rapid thermal annealing at a low temperature of 400 degrees C. Intrinsic GeSn structural defects give p-type behavior, while the presence of oxygen leads to the n-character of the embedded GeSn NCs. Such an embedded NCs/epitaxial GeSn p-n heterostructure shows superior photoelectrical response up to 3 orders of magnitude increase in the 1.2-2.5 mu m range, as compared to performances of diode based only on embedded NCs.

The effects of 4-(2-hydroxyphenyl)-2-(morpholin-4-yl)-1,3-thiazole (Pr02), 1-(3,5-dibromo-2-hydroxyphenyl)-1-oxoethan-2-yl-N,N-diethyldithiocarbamate (Pr04) and 1-(5-bromo-2-hydroxy-3-methylphenyl)-1-oxoethan-2-yl-O- ethyl xanthate (Pr06) on the aqueous oxidation of chalcopyrite (CuFeS2) in air-equilibrated solution at a temperature of 25 degrees C and a pH of 2.5 were studied. The effects were investigated by using potentiodynamic polarization, electro-chemical impedance spectroscopy (EIS), scanning electron microscopy coupled with energy dispersive X-ray (SEM/EDX) analysis, aqueous batch experiments, Fourier transform infrared (FTIR) spectroscopy, Raman scattering and quantum chemical calculations. It is found that the anodic current densities decrease in the order of EtOH Pr02 > Pr04 > Pr06. These results, along with those of the EIS measurements, show that Pr02, Pr04 and Pr06 are effective anodic inhibitors of chalcopyrite aqueous oxidation. Both Raman scattering and FTIR spectroscopy indicate that the elemental sulfur, polysulfide and ferric oxyhydroxides that form on the surface of the mineral are not responsible when it comes to the aqueous oxidation inhibition of chalcopyrite. Quantum chemical calculations show that the adsorption of the tested compounds on the chalcopyrite surface is energetically favorable and so, it can explain the inhibiting effects that were observed.

In this study, we report on the structural, magnetic, and optical properties of Tb3+-doped CeF(3)nanocrystals prepared via a polyol-assisted route, followed by calcination. X-ray diffraction analysis and electron microscopy investigations have shown the formation of a dominant Ce(0.75)F(3)nanocrystalline phase (of about 99%), with a relatively uniform distribution of nanocrystals about 15 nm in size. Magnetization curves showed typical paramagnetic properties related to the presence of Ce(3+)and Tb(3+)ions. The magnetic susceptibility showed a weak inflexion at about 150 K, assigned to the cerium ions' crystal field splitting. Under UV light excitation of the Ce(3+)ions, we observed Tb(3+)green luminescence with a quantum yield of about 20%.