Structural characterization of SnS crystals formed by chemical vapour deposition.

The crystal and defect structure of SnS crystals grown using chemical vapour deposition for application in electronic devices are investigated. The structural analysis shows the presence of two distinct crystal morphologies, that is thin flakes with lateral sizes up to 50 µm and nanometer scale thickness, and much thicker but smaller crystallites. Both show similar Raman response associated with SnS. The structural analysis with transmission electron microscopy shows that the flakes are single crystals of α-SnS with [010] normal to the substrate. Parallel with the surface of the flakes, lamellae with varying thickness of a new SnS phase are observed. High-resolution transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), first-principles simulations (DFT) and nanobeam diffraction (NBD) techniques are employed to characterise this phase in detail. DFT results suggest that the phase is a strain stabilised ß' one grown epitaxially on the α-SnS crystals. TEM analysis shows that the crystallites are also α-SnS with generally the [010] direction orthogonal to the substrate. Contrary to the flakes the crystallites consist of two to four grains which are tilted up to 15° relative to the substrate. The various grain boundary structures and twin relations are discussed. Under high-dose electron irradiation, the SnS structure is reduced and ß-Sn formed. It is shown that this damage only occurs for SnS in direct contact with SiO2 .

X-ray absorption in pillar shaped transmission electron microscopy specimens.

The dependence of the X-ray absorption on the position in a pillar shaped transmission electron microscopy specimen is modeled for X-ray analysis with single and multiple detector configurations and for different pillar orientations relative to the detectors. Universal curves, applicable to any pillar diameter, are derived for the relative intensities between weak and medium or strongly absorbed X-ray emission. For the configuration as used in 360° X-ray tomography, the absorption correction for weak and medium absorbed X-rays is shown to be nearly constant along the pillar diameter. Absorption effects in pillars are about a factor 3 less important than in planar specimens with thickness equal to the pillar diameter. A practical approach for the absorption correction in pillar shaped samples is proposed and its limitations discussed. The modeled absorption dependences are verified experimentally for pillars with HfO2 and SiGe stacks.

Observation and understanding of anisotropic strain relaxation in selectively grown SiGe fin structures.

The performance of heterogeneous 3D transistor structures critically depends on the composition and strain state of the buffer, channel and source/drain regions. In this paper we used an in-line high resolution x-ray diffraction (HRXRD) tool to study in detail the composition and strain in selectively grown SiGe/Ge fin structures with widths down to 20 nm. For this purpose we arranged fins of identical dimensions into larger arrays which were then analyzed using an x-ray beam several tens of micrometers in size. Asymmetric reciprocal space maps measured both parallel and perpendicular to the fins allowed us to extract the lattice parameters in all three spatial directions. Our results demonstrate an anisotropic in-plane strain state of the selectively grown SiGe buffer in case of narrower fins with significantly reduced relaxation in the direction along the fin. This observation was verified using nano-beam electron diffraction, and is explained based on the reduced probability for dislocation half-loops to evolve in trenches narrower than a few times the critical radius. Moreover, we introduce and discuss in detail a methodology for the determination of the composition in case of an anisotropic in-plane strain state which differs from the procedure commonly used for blanket layers. Our findings verify the importance of in-line HRXRD measurements for process development and monitoring as well as the fundamental study of relaxation and defect formation in confined volumes.

Functionalized luminescent nanocrystals on patterned surfaces obtained by radio frequency glow discharges.

In this work a genuine combination of a bottom-up approach, which is based on synthesis and functionalization of emitting nanocrystals (NCs), with a top-down strategy, which relies on a flexible and versatile cold plasma process, is shown. Luminescent semiconducting colloidal NCs consisting of a CdSe core coated with a ZnS shell (CdSe@ZnS) are directly assembled onto micro-patterned substrates previously functionalized by means of glow discharges performed through physical masks. The NC assembly is driven by electrostatic interactions that led to their successful organization into spatially resolved domains. Two distinct protocols are tested, the former using a plasma deposition process combined with an electrostatic layer-by-layer procedure, the latter based on a two-step plasma deposition/treatment process. The procedures are thoroughly monitored with fluorescence microscopy, atomic force microscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The two-step plasma protocol is demonstrated to be more efficient in directing a uniform and specific assembly of luminescent NCs with respect to the hybrid procedure. The presented 'mix and match' approach offers great potential for integrating NCs, with their unique size-dependent properties, into microstructures, providing a universal platform for the fabrication of sensors, biochips, displays and switches.

Improved osteoblast cell affinity on plasma-modified 3-D extruded PCL scaffolds.

Cellular adhesion and proliferation inside three-dimensional synthetic scaffolds represent a major challenge in tissue engineering. Besides the surface chemistry of the polymers, it is well recognized that scaffold internal architecture, namely pore size/shape and interconnectivity, has a strong effect on the biological response of cells. This study reports for the first time how polycaprolactone (PCL) scaffolds with controlled micro-architecture can be effectively produced via bioextrusion and used to enhance the penetration of plasma deposited species. Low-pressure nitrogen-based coatings were employed to augment cell adhesion and proliferation without altering the mechanical properties of the structures. X-ray photoelectron spectroscopy carried out on different sections of the scaffolds indicates a uniform distribution of nitrogen-containing groups throughout the entire porous structure. In vitro biological assays confirm that plasma deposition sensitively promotes the activity of Saos-2 osteoblast cells, leading to a homogeneous colonization of the PCL scaffolds.

Covalent immobilization of liposomes on plasma functionalized metallic surfaces.

A method was developed to functionalize biomedical metals with liposomes. The novelty of the method includes the plasma-functionalization of the metal surface with proper chemical groups to be used as anchor sites for the covalent immobilization of the liposomes. Stainless steel (SS-316) disks were processed in radiofrequency glow discharges fed with vapors of acrylic acid to coat them with thin adherent films characterized by surface carboxylic groups, where liposomes were covalently bound through the formation of amide bonds. For this, liposomes decorated with polyethylene glycol molecules bearing terminal amine-groups were prepared. After ensuring that the liposomes remain intact, under the conditions applying for immobilization; different attachment conditions were evaluated (incubation time, concentration of liposome dispersion) for optimization of the technique. Immobilization of calcein-entrapping liposomes was evaluated by monitoring the percent of calcein attached on the surfaces. Best results were obtained when liposome dispersions with 5mg/ml (liposomal lipid) concentration were incubated on each disk for 24h at 37°C. The method is proposed for developing drug-eluting biomedical materials or devices by using liposomes that have appropriate membrane compositions and are loaded with drugs or other bioactive agents.

The study of specific and nonspecific hepatoma cells behavior by means of plasma-treated substrates.

Physical-chemical surface modifications represent a formidable tool to drive a suitable cell behavior on materials intended to be used in the biomedical field. Plasma processes are among the more powerful methods utilized to modify the surface of materials without altering their bulk intrinsic properties. In particular, by means of plasma treatment processes it is possible to graft chemical functional groups on polymer substrate. Functional groups grafted on the surface can improve per se cell adhesion and can also represent suitable anchor sites for biomolecule immobilization. The aim of this work was to determine the effect of plasma treatment and biomolecule immobilization on Polystyrene (PS) Petri dishes on the behavior of a human hepatocellular carcinoma cell line (HepG2). For this aim Petri dishes were grafted with N-containing groups in order to obtain grafted N-functionalities, to be used as anchor groups for the immobilization of galactosamine. In this way two different modified surfaces, NH(3) grafted polystyrene (PS-NH(3)) and polystyrene owing galactosamine moieties (PS-NH(3)-GalNH(2)), have been obtained. Differences in cell morphology, urea and plasma Fibronectin (pFN) production were clearly observed on HepG2 seeded on PS-NH(3) and PS-NH(3)-GalNH(2). These results highlight the role of specific and non specific cell response in the in vitro study of materials intended to be used for biomedical purposes.

Biomineralized porous composite scaffolds prepared by chemical synthesis for bone tissue regeneration.

Scaffold design is a key factor in the clinical success of bone tissue engineering grafts. To date, no existing single biomaterial used in bone repair and regeneration fulfils all the requirements for an ideal bone graft. In this study hydroxyapatite/polycaprolactone (HA/PCL) composite scaffolds were prepared by a wet chemical method at room temperature. The physico-chemical properties of the composite materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, while scaffold morphology was investigated by scanning electron microscopy (SEM) with energy-dispersive spectroscopy to validate the process used for synthesis. Finally, the response of bone marrow-derived human mesenchymal stem cells (hMSCs) in terms of cell proliferation and differentiation to the osteoblastic phenotype was evaluated using the Alamar blue assay, SEM and alkaline phosphatase activity. Microstructural analysis indicated that the HA particles were distributed homogeneously within the PCL matrix. The biological results revealed that the HA/PCL composite scaffolds are suitable for the proliferation and differentiation of MSCs in vitro, supporting osteogenesis after 15 days. All the results indicate that these scaffolds meet the requirements of materials for bone tissue engineering and could be used for many clinical applications in orthopaedic and maxillofacial surgery.

Antimicrobial activity of immobilized lysozyme on plasma-treated polyethylene films.

In this study we tested the antimicrobial activity of polyethylene films modified by means of plasma processes that were followed by the chemical immobilization of lysozyme, an antimicrobial enzyme. To chemically immobilize the enzyme in its active form at the surface of polyethylene, substrates that had been plasma treated under different experimental conditions were soaked in lysozyme solutions at different concentrations. The immobilization of the enzyme was checked, and the antimicrobial activity of the films was investigated by observing the death rate of Micrococcus lysodeikticus cells suspended in phosphate buffer in contact with the films. The results clearly indicate that plasma-treated films loaded with lysozyme are active against the selected microorganism. A modified version of the Gompertz equation was used to quantitatively valuate the dependence of the antimicrobial activity of the films under both plasma treatment conditions and lysozyme concentrations.

A nanoscale fluorocarbon coating on PET surfaces improves the adhesion and growth of cultured coronary endothelial cells.

Plasma deposition was applied to deposit smooth and nanostructured fluorocarbon coatings on polyethylene terephthalate substrates, with the aim to obtain surfaces with identical chemical composition but different roughness to improve the endothelialization process on PET surfaces. We found that increased roughness was associated with enhanced endothelial cell response, as shown by the ability of cells to grow and adhere to nanostructures. We also observed specific interaction of filopodia protruding from the cell membrane with individual nanostructures, leading to increased cell attachment, spreading and cell viability. Among the modified surfaces, one termed PET-tfl90 emerged as the one capable of best sustaining the formation of a confluent monolayer of endothelial cells. In conclusion, PET modified by nanostructured fluorocarbon film represents an improved graft material, over conventional PET, for endothelial cell adhesion and growth.

New PVDF membranes: The effect of plasma surface modification on retention in nanofiltration of aqueous solution containing organic compounds.

New nanofiltration membranes were prepared by non-solvent-induced phase inversion from a PVDF/DMF/water system. The effect of exposure time before coagulation on the membrane characteristics (morphology, thickness, overall porosity, tensile strength) was investigated. PVDF membrane prepared at a fixed exposure time of 45s (PF45) was further plasma surface modified (RF 13.56 MHz) (PF45psm), introducing amino groups on the membrane. The performances of PF45, PF45psm and of a commercial nanofiltration membrane (N30F) were tested in the removal of two dyes from aqueous solution, characterized by different charge and molecular weight (congo red and methylene blue). The observed rejections depended more on the charge of the compound than on their molecular weights and results were optimized for the plasma modified membrane (PF45psm) with respect to unmodified (PF45) and commercial N30F membranes. In particular, methylene blue was retained for 100% by PF45psm with a relative flux of 65% compared to 38% of rejection and 59% of relative flux observed for N30F.

Behaviour of SH-SY5Y neuroblastoma cell line grown in different media and on different chemically modified substrates.

Among the parameters that can be tested in experiments on neuronal cell culture the use of different culture media and substrates represents a powerful assay to influence cell adhesion and differentiation. In this work, plasma-enhanced-chemical vapour depositions (PE-CVD) from acrylic acid and allylamine vapours have been performed to deposit coatings bearing oxygen (O)- and nitrogen (N)-containing functional groups on polyethylenetherephtalate (PET) surface. Human neuroblastoma SH-SY5Y cells were grown on plasma modified substrates and in presence of media containing different amount of fetal calf serum (FCS) or in serum-free medium containing cAMP. Our results showed that N-containing substrates improved cell adhesion, while the neurites sprouting was influenced by cell culture media. Interestingly, the presence of carboxylic groups on the modified surface can influence the expression of a differentiation marker, neurofilament-200 (NF-H), in cells grown in serum-containing media.

X-ray photoelectron spectroscopy of plasma-polymerized films from tetramethylsilane-containing feeds.

The chemical composition and the reactivity of films deposited in RF glow discharges fed with Ar-tetramethylsilane and Ar-tetramethylsilane-O2 mixtures have been studied by X-ray photoelectron spectroscopy. The analyses have been performed by means of a spectrometer connected in vacuo to the deposition reactor. This configuration allows to analyze as deposited films without any external contamination of oxygen and moisture. The work has been conducted by studying the detailed Si2p, C1s, and O1s signals at different electron take-off angles, as well as the valence band region. Depth profiling of films by means of Ar+ ion sputtering has also been performed in some cases.