High Anodic-Voltage Focusing of Charge Carriers in Silicon Enables the Etching of Regularly-Arranged Submicrometer Pores at High Density and High Aspect-Ratio.

The anodic dissolution of silicon in acidic electrolytes is a well-known technology enabling the silicon machining to be accurately controlled down to the micrometer scale in low-doped n-type silicon electrodes. Attempts to scale down this technology to the submicrometer scale has shown to be challenging, though it premises to enable the fabrication of meso and nano structures/systems that would greatly impact the fields of biosensors and nanomedicine. In this work, we report on the electrochemical etching at high anodic voltages (up to 40 V) of two-dimensional regular arrays of millions pores per square centimeter (up to 30 × 106 cm-2) with sub-micrometric diameter (down to ~860 nm), high depth (up to ~40 µm), and high aspect-ratio (up to ~45) using low-doped n-type silicon electrodes (resistivity 3-8 Ω cm). The use of high anodic voltages, which are over one order of magnitude higher than that commonly used in electrochemical etching of silicon, tremendously improves hole focusing at the pore tips during the etching and enables, in turn, the control of electrochemical etching of submicrometer-sized pores when spatial period reduces below 2 µm. A theoretical model allows experimental results to be interpreted in terms of an electric-field-enhanced focusing of holes at the tip apex of the pores at high anodic voltages, with respect to the pore base, which leads to a smaller curvature radius of the tip apex and enables, in turn, the etching of pore tips to be preferentially sustained over time and space.

Layer-by-layer biofunctionalization of nanostructured porous silicon for high-sensitivity and high-selectivity label-free affinity biosensing.

Nanostructured materials premise to revolutionize the label-free biosensing of analytes for clinical applications, leveraging the deeper interaction between materials and analytes with comparable size. However, when the characteristic dimension of the materials reduces to the nanoscale, the surface functionalization for the binding of bioreceptors becomes a complex issue that can affect the performance of label-free biosensors. Here we report on an effective and robust route for surface biofunctionalization of nanostructured materials based on the layer-by-layer (LbL) electrostatic nano-assembly of oppositely-charged polyelectrolytes, which are engineered with bioreceptors to enable label-free detection of target analytes. LbL biofunctionalization is demonstrated using nanostructured porous silicon (PSi) interferometers for affinity detection of streptavidin in saliva, through LbL nano-assembly of a bi-layer of positively-charged poly(allylamine hydrochloride) (PAH) and negatively-charged biotinylated poly(methacrylic acid) (b-PMAA). High sensitivity in streptavidin detection is achieved, with high selectivity and stability, down to a detection limit of 600 fM.

A minimally invasive microchip for transdermal injection/sampling applications.

The design, fabrication, and characterization of a minimally invasive silicon microchip for transdermal injection/sampling applications are reported and discussed. The microchip exploits an array of silicon-dioxide hollow microneedles with density of one million needles cm(-2) and lateral size of a few micrometers, protruding from the front-side chip surface for one hundred micrometers, to inject/draw fluids into/from the skin. The microneedles are in connection with independent reservoirs grooved on the back-side of the chip. Insertion experiments of the microchip in skin-like polymers (agarose hydrogels with concentrations of 2% and 4% wt) demonstrate that the microneedles successfully withstand penetration without breaking, despite their high density and small size, according to theoretical predictions. Operation of the microchip with different liquids of biomedical interest (deionized water, NaCl solution, and d-glucose solution) at different differential pressures, in the range 10-100 kPa, highlights that the flow-rate through the microneedles is linearly dependent on the pressure-drop, despite the small section area (about 13 µm(2)) of the microneedle bore, and can be finely controlled from a few ml min(-1) up to tens of ml min(-1). Evaporation (at room temperature) and acceleration (up to 80 g) losses through the microneedles are also investigated to quantify the ability of the chip in storing liquids (drug to be delivered or collected fluid) in the reservoir, and result to be of the order of 70 nl min(-1) and 1300 nl min(-1), respectively, at atmospheric pressure and room temperature.

Fibrillogenesis of human ß2 -microglobulin in three-dimensional silicon microstructures.

The authors describe the interaction of biological nanostructures formed by ß(2) -microglobulin amyloid fibrils with three-dimensional silicon microstructures consisting in periodic arrays of vertical silicon walls (≈3 µm-thick) separated by 50 µm-deep air gaps (≈5 µm-wide). These structures are of great interest from a biological point of view since they well mimic the interstitial environment typical of amyloid deposition in vivo. Moreover, they behave as hybrid photonic crystals, potentially applicable as optical transducers for label-free detection of the kinetics of amyloid fibrils formation. Fluorescence and atomic force microscopy (AFM) show that a uniform distribution of amyloid fibrils is achieved when fibrillogenesis occurs directly on silicon. The high resolution AFM images also demonstrate that amyloid fibrils grown on silicon are characterized by the same fine structure typically ensured by fibrillogenesis in solution.

Optical characterization of alcohol-infiltrated one-dimensional silicon photonic crystals.

In this work, experimental results on the optical characterization of alcohol-infiltrated silicon/air one-dimensional photonic crystals (1D-PhCs), fabricated by electrochemical micromachining of silicon, are presented. The spectral reflectivity of high-order hybrid 1D-PhCs with a spatial period of 8 microm was measured, in the wavelength range 1.0-1.7 microm, when alcohols (ethanol and isopropanol) substitute air inside the trenches. A reliable redshift is observed in the presence of alcohols, with respect to air, which allows one to discriminate the refractive index difference between the alcohols. Experimental data are in good agreement with numerical results calculated by using the characteristic matrix method, modified to take into account surface roughness of silicon walls.