Green Nanocoatings Prepared by Crosslinking Self-Assembled Fatty Acids on Metals.

Self-assembled monolayers (SAMs) are an important element of modern nanotechnology and surface functionalization. However, their application is still limited because they are easily removed from the surface of the object in corrosive environments. Crosslinking would make SAMs more resistant to the corrosive environment they are exposed to. In this work, how to strongly crosslink SAMs made of non-toxic and biodegradable fatty acids on metal surfaces using ionizing radiation has been demonstrated for the first time. The crosslinked nanocoatings are stable over time and have significantly improved properties compared to SAMs. Thus, crosslinking opens up the possibility of using SAMS in a variety of different systems and on different materials for surface functionalization to achieve stable and durable surface properties such as biocompatibility or selective reactivity.

Surface Morphology of Textured Transparent Conductive Oxide Thin Film Seen by Various Probes: Visible Light, X-rays, Electron Scattering and Contact Probe.

Fluorine-doped tin oxide thin films (SnO2:F) are widely used as transparent conductive oxide electrodes in thin-film solar cells because of their appropriate electrical and optical properties. The surface morphology of these films influences their optical properties and therefore plays an important role in the overall efficiencies of the solar cells in which they are implemented. At rough surfaces light is diffusely scattered, extending the optical path of light inside the active layer of the solar cell, which in term improves light absorption and solar cell conversion efficiency. In this work, we investigated the surface morphology of undoped and doped SnO2 thin films and their influence on the optical properties of the films. We have compared and analysed the results obtained by several complementary methods for thin-film surface morphology investigation: atomic force microscopy (AFM), transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS). Based on the AFM and TEM results we propose a theoretical model that reproduces well the GISAXS scattering patterns.

High-Energy Heavy Ion Irradiation of Al2O3, MgO and CaF2.

High-energy heavy ion irradiation can produce permanent damage in the target material if the density of deposited energy surpasses a material-dependent threshold value. It is known that this threshold can be lowered in the vicinity of the surface or in the presence of defects. In the present study, we established threshold values for Al2O3, MgO and CaF2 under the above-mentioned conditions, and found those values to be much lower than expected. By means of atomic force microscopy and Rutherford backscattering spectrometry in channelling mode, we present evidence that ion beams with values of 3 MeV O and 5 MeV Si, despite the low density of deposited energy along the ion trajectory, can modify the structure of investigated materials. The obtained results should be relevant for radiation hardness studies because, during high-energy ion irradiation, unexpected damage build-up can occur under similar conditions.

Stress Evolution during Ge Nanoparticles Growth in a SiO2 Matrix.

Superstructures are explored that were obtained by multilayer magnetron deposition at room temperature of 20 SiO2 and SiO2:Ge bilayers, each 2 × 4 nm thick, and subsequently annealed in inert N2 atmosphere at different temperatures in the range of 500-750 °C. The structural and optical changes induced by annealing and the formation and growth of Ge nanoparticles (nps) from early clusters to their full growth and final dissolution were studied by the simultaneous grazing-incidence small- and wide-angle X-ray scattering, transmission electron microscopy, and (time-resolved) photoluminescence (PL). It is shown that in as-deposited multilayers aggregation of small clusters already occurred, and the clusters were reasonably well intercorrelated in the lateral plane. During annealing at Ta = 550 °C or higher temperatures, Ge nps start to form and remain partly amorphous at lower Ta but crystallize completely at about 600 °C. At even higher temperatures, the Ge nps dissolve and Ge diffuses out almost completely, leaving voids in the SiO2 matrix. Visible PL from the samples was detected and attributed to defects in the nps/matrix interface layers rather than to the nps itself because PL persisted even after Ge nps dissolution.

GISAXS Analysis of the In-Depth Morphology of Thick PS-b-PMMA Films.

The morphological evolution of cylinder-forming poly(styrene)-b-poly(methyl methacrylate) block copolymer (BCP) thick films treated at high temperatures in the rapid thermal processing (RTP) machine was monitored by means of in-depth grazing-incidence small-angle X-ray scattering (GISAXS). The use of this nondisruptive technique allowed one to reveal the formation of buried layers composed of both parallel- and perpendicular-oriented cylinders as a function of the film thickness (24 ≤ h ≤ 840 nm) and annealing time (0 ≤ t ≤ 900 s). Three distinct behaviors were observed depending on the film thickness. Up to h ≤ 160 nm, a homogeneous film consisting of perpendicular-oriented cylinders is observed. When h is between 160 and 700 nm, a decoupling process between both the air-BCP and substrate-BCP interfaces takes place, leading to the formation of mixed orientations (parallel and perpendicular) of the cylinders. Finally, for h > 700 nm, the two interfaces are completely decoupled, and the formation of a superficial layer of about 50 nm composed of perpendicular cylinders is observed. Furthermore, the through-film morphology affects the nanodomain long-range order, which substantially decreases in correspondence with the beginning of the decoupling process. When the thick samples are exposed to longer thermal treatments, an increase in the long-range order of the nanodomains occurs, without any sensible variation of the thickness of the superficial layer.

In and ex situ studies of the formation of layered microspherical hydrozincite as precursor for ZnO.

Layered ZnO microspheric particles were prepared by the thermal decomposition of layered hydrozincite (LZnHC), which was synthesized from zinc nitrate and urea in a water/PEG400 mixture. The influence of the starting reagents, their concentrations, and the amount of PEG in the water/PEG400 mixture on the particle growth was observed. The chemical aspect of the particle growth was proposed in the frame of the partial charge model (PCM), and the formation of [Zn(OH)(2)(OH(2))(4)](0) and [Zn(OH)(HCO(3))(OH(2))(3)](0) was predicted for the solid phase. The assumed growth mechanism, which follows the "nonclassical crystallization" concept of a self-assembling mechanism, was observed in situ by small-angle X-ray scattering (SAXS) and predicts the rapid formation of approximately 6 nm sized building units. The size of these nano building units, stable only in the reaction medium, remains nearly constant during the synthesis, as the concentration of the nano building units increases throughout the reaction. The nano building units connect into leaves of LZnHC with a thickness of 20 nm. These leaves of LZnHC are further agglomerated into porous, microsphere-like particles with sizes up to 4 µm.

SAXS Studies of TiO2 Nanoparticles in Polymer Electrolytes and in Nanostructured Films.

Polymer electrolytes as nanostructured materials are very attractive components for batteries and opto-electronic devices. (PEO)8ZnCl2 polymer electrolytes were prepared from PEO and ZnCl2. The nanocomposites (PEO)8ZnCl2/TiO2 themselves contained TiO2 nanograins. In this work, the influence of the TiO2 nanograins on the morphology and ionic conductivity of the nanocomposite was systematically studied by transmission small-angle X-ray scattering (SAXS) simultaneously recorded with wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) at the synchrotron ELETTRA. Films containing nanosized grains of titanium dioxide (TiO2) are widely used in the research of optical and photovoltaic devices. The TiO2 films, prepared by chemical vapor deposition and e-beam epitaxy, were annealed in hydrogen atmospheres in the temperature range between 20 °C and 900 °C in order to study anatase-rutile phase transition at 740 °C. Also, grazing-incidence small angle X-ray scattering (GISAXS) spectra for each TiO2 film were measured in reflection geometry at different grazing incident angles. Environmentally friendly galvanic cells, as well as solar cells of the second generation, are to be constructed with TiO2 film as working electrode, and nanocomposite polymer as electrolyte.