Unraveling the Mechanism of Maskless Nanopatterning of Black Silicon by CF4/H2 Plasma Reactive-Ion Etching.

The process of deep texturization of the crystalline silicon surface is intimately related to its promising diverse applications, such as bactericidal surfaces for integrated lab-on-chip devices and absorptive optical layers (black silicon-BSi). Surface structuring by a maskless texturization appeals as a cost-effective approach, which is up-scalable for large-area production. In the case of silicon, it occurs by means of reactive plasma processes (RIE-reactive-ion etching) using fluorocarbon CF4 and H2 as reaction gases, leading to self-assembled cylindrical and pyramidal nanopillars. The mechanism of silicon erosion has been widely studied and described as it is for the masked RIE process. However, the onset of the erosion and the reaction kinetics leading to defined maskless patterning have not been unraveled to date. In this work, we specifically tackle this issue by analyzing the results of three different RIE recipes, specifically designed for the purpose. The mechanism of surface self-nanopatterning is revealed by deeply investigating the physical chemistry of the etching process at the nanoscale and the evolution of surface morphology. We monitored the progress in surface patterning and the composition of the etching plasma at different times during the RIE process. We confirm that nanopattering issues from a net erosion, as contributed by chemical etching, physical sputtering, and by the synergistic plasma effect. We propose a qualitative model to explain the onset, the evolution, and the stopping of the process. As the RIE process is started, a high density of surface defects is initially created at the free silicon surface by energetic ion sputtering. Contextually, a polymeric overlayer is synthesized on the Si surface, as thick as 5 nm on average, and self-aggregates into nanoclusters. The latter phenomenon can be explained by considering that the initial creation of surface defects increases the activation energy for surface diffusion of deposited CF and CF2 species and prevents them from aggregating into a continuous Volmer-Weber polymeric film. The clusterization of the polymer provides the self-masking effect since the beginning, which eventually triggers surface patterning. Once started, the maskless texturing proceeds in analogy with the masked case, that is, by combined chemical etching and ion sputtering, and ceases because of the loss of ion energy. In the case of CF4/H2 RIE processes at 10% of H2 and by supplying 200 W of RF power for 20 min, nanopillars of 200 nm in height and 100 nm in width were formed. We therefore propose that a precise assessment of surface defect formation and density in dependence on the initial RIE process parameters can be the key to open a full control of outcomes of maskless patterning.

Effect of materials for micro-electro-mechanical systems on PCR yield.

In this study we analyzed the surface properties of different silicon-based materials used for micro-electro-mechanical systems (MEMS) production, such as thermally grown silicon oxide, plasma-enhanced chemical vapor deposition (PECVD)-treated silicon oxide, reactive-ion etch (RIE)-treated silicon oxide, and Pyrex. Substrates were characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) to define the surface chemical and morphological properties, and by fluorescence microscopy to directly assess the absorption of the different polymerase chain reaction (PCR) components. By using microchips fabricated with the same materials we investigated their compatibility with PCR reactions, exploiting the use of different enzymes and reagents or proper surface treatments. We established the best conditions for DNA amplification in silicon/Pyrex microdevices depending on the type of device and fabrication method used and the quality of reagents, rather than on the passivation treatment or increment in standard Taq polymerase concentration.

Human plasma protein adsorption on carbon-based materials.

In this study the initial reactions of different carbon-based materials with human blood were investigated by short-time exposure to platelet poor plasma (PPP). Extent of protein adsorption and conformational changes of proteins adsorbed on material surfaces are known to be keys factors affecting further biological reactions. Plasma protein adsorption on multi-walled carbon nanotubes (MWCNTs), highly oriented pyrolytic graphite (HOPG) and nanocrystalline graphite (NG) were investigated and the results obtained on these materials were compared with those obtained studying pyrolytic carbon (PyC), a material showing good anti-trombogenic properties. The quantification of adsorbed plasma proteins on sample surfaces was obtained by Micro BCA Protein Assay, while immunofluorescence analysis was employed to monitor the surface density and distribution of two selected proteins, namely fibrinogen (Fg) and Hageman factor (FXII), proteins playing a leading role in mediating platelet adhesion. The dependence of the biological response on the surface chemical and morphological properties were also investigated and data obtained using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) are presented. After PPP incubation PyC is characterized by the presence of low level of whole proteins and FXII adsorption, in contrast to a high adhesion of Fg. Compared to PyC the analysis of the other carbon-based materials result in a higher whole protein adsorption with an increasing trend moving from MWCNTs, NG and HOPG respectively. The Fg surface density on PyC, NG and MWCNTs is about four times higher than on HOPG while only HOPG show a detectable fluorescent signal of FXII. If AFM data indicate that surface morphology does not play a crucial role in protein adhesion, XPS analysis show chemical differences that can be correlated with this biological response.

Covalently anchored lipid structures on amine-enriched polystyrene.

The study of the adhesion of lipid vesicles on surfaces is of increasing interest in the field of medical implants and tissue engineering (protein-resistant surfaces), drug delivery, biosensors, and biochips. In this work, lipid coverage was developed from PEG-coated vesicles (with sizes from 100 to 300 nm) by covalently binding poly(ethylene glycol)-alpha-disteroylphosphatidylethanolamine-omega-benzotriazole carbonate (DSPE-PEG-BTC) molecules onto the surface amine groups by carbamate chemistry. Lipid surface density and the surface structure of multilamellar (MLVs) and extruded unilamellar (LUVs) vesicles deposited on three types of polystyrene (PS) well-plates were probed by fluorescence and atomic force microscopy (AFM) imaging. A significant difference in the vesicle surface coverage of PS substrates was observed with a substantial increase in lipid multilayers on the amine-enriched PS surface using both unilamellar and multilamellar vesicles.