Using chaotic dynamics to characterize the complexity of rough surfaces.

In this work, we use the basic ingredients of chaotic dynamics (stretching and folding of phase space points) for the characterization of the complexity of microscopy images of rough surfaces. The key idea is to use an image as the initial condition of a chaotic discrete dynamical system, such as the Arnold cat map, and track its transformations during the first iterations of the map. Since the basic effects of the Arnold map are the stretching and folding of image texture, the application of the map leads to an enhancement of the high frequency content of images along with an increase of discontinuities in pixel intensities. We exploit these effects to quantify the complexity of S type (lying between homogeneity and randomness) of the image texture since the first (enhancement of high frequencies) can be used to quantify the distance of texture from randomness and noise and the second (the proliferation of discontinuities) the distance from order and homogeneity. The method is validated in synthetic images which are generated from computer generated surfaces with controlled correlation length and fractal dimension and it is applied in real images of nanostructured surfaces obtained from a scanning electron microscope with very interesting results.

Ultra-high aspect ratio Si nanowires fabricated with plasma etching: plasma processing, mechanical stability analysis against adhesion and capillary forces and oleophobicity.

Room-temperature deep Si etching using time-multiplexed deep reactive ion etching (DRIE) processes is investigated to fabricate ultra-high aspect ratio Si nanowires (SiNWs) perpendicular to the silicon substrate. Nanopatterning is achieved using either top-down techniques (e.g. electron beam lithography) or colloidal polystyrene (PS) sphere self-assembly. The latter is a faster and more economical method if imperfections in diameter and position can be tolerated. We demonstrate wire radii from below 100 nm to several micrometers, and aspect ratios (ARs) above 100:1 with etching rates above 1 µm min(-1) using classical mass flow controllers with pulsing rise times of seconds. The mechanical stability of these nanowires is studied theoretically and experimentally against adhesion and capillary forces. It is shown that above ARs of the order of 50:1 for spacing 1 µm, SiNWs tend to bend due to adhesion forces between them. Such large adhesion forces are due to the high surface energy of silicon. Wetting the SiNWs with water and drying also gives rise to capillary forces. We find that capillary forces may be less important for SiNW collapse/bending compared to adhesion forces of dry SiNWs, contrary to what is observed for polymeric nanowires/nanopillars which have a much lower surface energy compared to silicon. Finally we show that SiNW arrays have oleophobic and superoleophobic properties, i.e. they exhibit excellent anti-wetting properties for a wide range of liquids and oils due to the re-entrant profile produced by the DRIE process and the well-designed spacing.

Plasma-assisted nanoscale protein patterning on Si substrates via colloidal lithography.

Selective immobilization of proteins in well-defined patterns on substrates has recently attracted considerable attention as an enabling technology for applications ranging from biosensors and BioMEMS to tissue engineering. In this work, a method is reported for low-cost, large scale and high throughput, selective immobilization of proteins on nanopatterned Si, based on colloidal lithography and plasma processing to define the areas (<300 nm) where proteins are selectively immobilized. A close-packed monolayer of PS microparticles is deposited on oxidized Si and, either after microparticle size reduction or alternatively after metal deposition through the PS close-packed monolayer, is used as etching mask to define SiO2 nanoislands (on Si). C4F8 plasma was used to selectively etch and modify the SiO2 nanoislands while depositing a fluorocarbon layer on the Si surface. The plasma-treated surfaces were chemically characterized in terms of functional group identification through XPS analysis and reaction with specific molecules. Highly selective protein immobilization mainly through physical adsorption on SiO2 nanoislands and not on surrounding Si was observed after C4F8 plasma-induced chemical modification of the substrate. The thickness of the immobilized protein monolayer was estimated by means of AFM image analysis. The method reported herein constitutes a cost-efficient route toward rapid, large surface, and high-density patterning of biomolecules on solid supports that can be easily applied in BioMEMS or microanalytical systems.

From superamphiphobic to amphiphilic polymeric surfaces with ordered hierarchical roughness fabricated with colloidal lithography and plasma nanotexturing.

Ordered, hierarchical (triple-scale), superhydrophobic, oleophobic, superoleophobic, and amphiphilic surfaces on poly(methyl methacrylate) PMMA polymer substrates are fabricated using polystyrene (PS) microparticle colloidal lithography, followed by oxygen plasma etching-nanotexturing (for amphiphilic surfaces) and optional subsequent fluorocarbon plasma deposition (for amphiphobic surfaces). The PS colloidal microparticles were assembled by spin-coating. After etching/nanotexturing, the PMMA plates are amphiphilic and exhibit hierarchical (triple-scale) roughness with microscale ordered columns, and dual-scale (hundred nano/ten nano meter) nanoscale texture on the particles (top of the column) and on the etched PMMA surface. The spacing, diameter, height, and reentrant profile of the microcolumns are controlled with the etching process. Following the design requirements for superamphiphobic surfaces, we demonstrate enhancement of both hydrophobicity and oleophobicity as a result of hierarchical (triple-scale) and re-entrant topography. After fluorocarbon film deposition, we demonstrate superhydrophobic surfaces (contact angle for water 168°, compared to 110° for a flat surface), as well as superoleophobic surfaces (153° for diiodomethane, compared to 80° for a flat surface).