National Institute Of Materials Physics - Romania

Thermally induced changes in the structure and composition of the shell of tightly aggregated cubic ZnS/Zn(OH)(2) core shell quantum dots of 1.9 nm average core size were investigated by multifrequency electron paramagnetic resonance of Mn2+ probing ions. The observed three-steps temperature induced transformation of the Mn2+ surface centers in the 80-450 degrees C temperature range Zn(OH)(2) shell into ZnO, with the formation of the Zn2O(OH)(2) and Zn4O3(OH)(2) intermediate nanocompounds. The presence of a 0.3 to 1.9 nm thick surface layer of disordered nanomaterial separating the cubic ZnS cores and its shrinking to a few atomic layers by mass loss after annealing up to 350 degrees C was observed by high resolution transmission electron microscopy. Unlike the single step dehydration around 120 degrees C of the bulk epsilon-Zn(OH)(2), the complex decomposition of the epsilon-Zn(OH)(2) shell is attributed to its nanosized, disordered structure.

Electroless deposition was successfully applied in developing crystalline particles of zinc oxide onto polyester textile materials; this deposition is here presented in comparison with other materials made from poly(lactic acid), polyamide or hemp. Structural and spectroscopic characterization of the raw and deposited samples has been performed. The structure of zinc oxide particles was that of wurtzite type as indicated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Crystallites were 20-500 nm in diameter and up to 1 mu m in length. The grown particles cover the fibers not only on the fabric surface but in the textile depth. Contact angle measurement by the sessile drop method was used to study the wettability behavior of the investigated composite systems. The hierarchical roughness structure generates superhydrophobic properties onto polyester fabrics, for which water contact angles exceed 150 degrees. The other functionalized samples also become more hydrophobic after deposition. Cassie-Baxter model was found suitable to describe the behavior, though the fraction of surface occupied by the water-solid interface is high enough. The electroless deposition technique applied previously for cotton fabrics was once more proven to be highly reproducible, easy scalable, and cheap, allowing a wide range of applications. (c) 2013 Wiley Periodicals, Inc.

A sandwich structure of four double layers of Ag (5 nm)/As2S3 (82.7 nm) has been prepared by Pulsed Laser Deposition (PLD) method. The effect of broadband light on the multilayer structure has been investigated. The X-ray reflectivity (XRR) patterns after different irradiation times have been measured. Although the fully intermixing of Ag and As2S3 layers should be expected during irradiation with visible light, however even after 5 h of irradiation the intermixing is not completed. The characteristic features of XRR diagrams for long irradiation times have been interpreted by scattering of X-ray radiation on clusters of Ag or Ag-As2S3. (c) 2013 Elsevier B.V. All rights reserved.

Sol-gel route using metal alkoxides and trifluoroacetic acid as precursors has been used to prepare oxyfluoride glass-ceramic containing Eu3+-doped LiYF4 nanocrystals of about tens of nm size embedded in a silica matrix through controlled crystallization at higher temperatures of the xerogel. Photoluminescence spectra and decay curves recorded in the Eu3+-doped LiYF4 polycrystalline pellet and glass ceramic have been discussed using group-theoretical arguments. In the glass-ceramic Eu3+ ions are embedded dominantly inside the LiYF4 nanocrystals most probably as Eu-O center and/or dimer centers in low symmetry (C-2v) sites; oxygen ions were incorporated in their neighborhood during the glass ceramization. (C) 2013 Elsevier B.V. All rights reserved.

Amorphous Ge/SiO2 multilayer structures deposited by magnetron sputtering have been annealed at different temperatures between 650 and 800 degrees C for obtaining Ge nanocrystals in oxide matrix. The properties of the annealed structures were investigated by transmission electron microscopy, Raman spectroscopy, and low temperature photoluminescence. The Ge crystallization is partially achieved at 650 degrees C and increases with annealing temperature. Insight of the Ge nanocrystal formation was acquired by comparing two annealing procedures, i.e., in a conventional tube furnace and by a rapid thermal annealing. By rapid thermal annealing in comparison to conventional furnace one, the Ge crystallization process is faster than Ge diffusion, resulting in the formation of more compact layers of Ge nanocrystals with 8-9.5-nm size as Raman spectroscopy reveals. These findings are important to improve the annealing efficiency in the nanocrystals formation for a precise control of their sizes and location in oxide matrix and for the possibility to create systems with interacting nanoparticles for charge or excitonic transfer. The infrared photoluminescence of Ge nanocrystals at low temperatures shows strong emission with two sharp peaks at about 1,000 meV.

In order to understand the role of ambient humidity on NO2 detection, electrical resistance and work function changes were recorded simultaneously on ZnO-Eu2O3 material. Thus, surface band bending and electron affinity could be evaluated, according to the Schottky model. The lack of electron affinity changes during NO2 exposure in dry air conditions, reveals that only the free charge concentration is affected. Exposure to NO2 in humid background leads to an increase in sensor signals and a significant change in the electron affinity as well. This effect suggests an interaction between NO2 and surface hydroxyl species; thereby additional charge carriers are involved in the overall sensing process. High resolution XPS analysis proves the presence of Eu solely in the 3(+) oxidation state before and after NO2 exposure. A gas-sensing interaction mechanism has been proposed. (C) 2013 Elsevier B.V. All rights reserved.

Nanocrystals (NCs) of II-VI semiconductors of few nanometers average size, called quantum dots (QDs), are now intensely investigated as radiation detectors. Besides the expected quantum confinement and influence of surface states, our electron paramagnetic resonance investigations of cZnS QDs doped with Mn2+ ions, correlated with structural data, underline that other properties should be also taken into consideration in developing the II VI semiconductor QDs as radiation detectors. Thus, the preferential localization of Mn2+ in the core of the cubic ZnS QDs at substitutional Zn2+ cation sites next to a stacking lattice defect is expected to lead, besides changes in the impurity energy levels, to specific aggregation properties. An outer shell of different composition can also influence the structural properties of the QDs core with effects on the optical properties as well. (C) 2013 Elsevier Ltd. All rights reserved.

Nanocomposites based on TiO2 aerogel and Ag nanoparticles have been successfully obtained through different synthesis methods and their specific surface areas have been determined by N-2 sorption (BET method). The photocatalytic potential for salicylic acid degradation has been evaluated. It was found that under visible light irradiation, all synthesized nanocomposites exhibit higher photocatalytic activity than the commercially available Aeroxide P25. By correlating the structural parameters with the photocatalytic performances, it has been found that the Ag nanoparticles and brookite phase presence alongside the anatase play important roles on the visible photocatalysts behavior. For the Ag containing samples with mixed anatase brookite phases, it has been observed that the visible photocatalytic performance decreases with the increase in brookite crystalline phase content. On the other hand, the addition of Ag nanoparticles results, as expected, in a clear enhancement of the visible photocatalytic activity. (C) 2013 Elsevier B.V. All rights reserved.

We report results of noncellular tests, revealing the occurrence of photocatalytic interactions between titanium dioxide (TiO2, titania) nanoparticles and the MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium-bromide] cytotoxicity indicator. These interactions induce the reduction of MTT and formation of purple formazan under biologically relevant conditions. Classical MU assays have been performed to evaluate the production of formazan in DMEM-F12 and RPMI-1640 cell culture media (containing 10% fetal bovine serum-FBS) treated with Degussa-P25 TiO2 nanoparticles, in the absence of cells. The colorimetric determinations revealed the noncellular MU to formazan transformation induced by TiO2 nanoparticles, under conditions commonly used for in vitro cytotoxicity testing of nanomaterials. The formazan precipitation was found to be proportional to the TiO2 concentration, being enhanced under laboratory daylight exposure. The photocatalytic nature of the studied effect was assessed under UV irradiation at 365 nm. The biological significance of the reported reaction was established with respect to cellular reference experiments performed on V79-4, HeLa and B16 cell lines. The results show false viability increases with up to 14% (for TiO2 concentrations generally higher than 50 mu g/ml), induced by the TiO2-MTT reaction. This type of artifacts may lead to underestimated toxicity or false proliferation results. (C) 2013 Elsevier Ltd. All rights reserved.

High aspect ratio nanowires of Ni-Cu alloys have been synthesized by potentiostatic electrochemical deposition in etched ion-track membranes. The nickel-to-copper ratio in the nanowires was controlled via the deposition potential and electrochemical bath composition. We present a detailed study of nanowire properties including morphology, composition, and magnetic behavior. We report the magnetic configurations measured as function of the nanowire composition and discuss domain formation, anisotropy aspects, and local easy axis distributions.