Porous nanocrystalline silicon (pnc-Si) is a 15 nm thin freestanding membrane material with applications in small-scale separations, biosensors, cell culture and lab-on-a-chip devices. Pnc-Si has already been shown to exhibit high permeability to diffusing species and selectivity based on molecular size or charge. In this report we characterize properties of pnc-Si in pressurized flows. We compare results to long-standing theories for transport through short pores using actual pore distributions obtained directly from electron micrographs. Measurements are in agreement with theory over a wide range of pore sizes and porosities and at orders-of-magnitude higher than those exhibited by commercial ultrafiltration and experimental carbon nanotube membranes. We also show that pnc-Si membranes can be used in dead-end filtration to fractionate gold nanoparticles and protein size ladders with better than 5 nm resolution, insignificant sample loss, and little dilution of the filtrate. These performance characteristics, combined with scalable manufacturing, make pnc-Si filtration a straightforward solution to many nanoparticle and biological separation problems.

We report on the application of scanning electrochemical microscopy (SECM) for the measurement of the ion-selective permeability of porous nanocrystalline silicon membrane as a new type of nanoporous material with potential applications in analytical, biomedical, and biotechnology device development. The reliable measurement of high permeability in the molecularly thin nanoporous membrane to various ions is important for greater understanding of its structure-permeability relationship and also for its successful applications. In this work, this challenging measurement is enabled by introducing two novel features into amperometric SECM tips based on the micropipetsupported interface between two immiscible electrolyte solutions (ITIES) to reveal the important ion-transport properties of the ultrathin nanopore membrane. The tip of a conventional heat-pulled micropipet is milled using focused ion beam (FIB) technique to be smoother, better aligned, and subsequently, approach closer to the membrane surface, which allows for more precise and accurate permeability measurement. The high membrane permeability to small monovalent ions is determined using FIB-milled micropipet tips to establish a theoretical formula for the membrane permeability that is controlled by free ion diffusion across water-filled nanopores. Moreover, the ITIES tips are rendered selective for larger polyions with biomedical importance, i.e., polyanionic pentasaccharide Arixtra and polycationic peptide protamine, to yield the membrane permeability that is lower than the corresponding diffusion-limited permeability. The hindered transport of the respective polyions is unequivocally ascribed to electrostatic and steric repulsions from the wall of the nanopores, i.e., the charge and size effects.The fast and selective transport of molecules across porous nanocrystalline silicon (pnc-Si) membranes 1 is attractive potentially for various important applications such as nanofiltration, 2, 3 biomedical device development, 4, 5 and nanofluidics for medical diagnostics and drug discovery. [6][7][8][9][10] The high permeability of the molecularly thin nanoporous membrane is also essential for its successful applications as cell culture and tissue engineering substrates. 11 This novel solid-state membrane features well-defined nanopores with an average diameter of ~10 nm and a length of ~15 nm. The nanopore membrane is nearly as thin as biological membranes * To whom correspondence should be addressed. amemiya@pitt.edu. # Current address: Shandong Entry-Exit Inspection and Quarantine Bureau, P. R. China SUPPORTING INFORMATION AVAILABLE Additional information as noted in text. This material is available free of charge via the Internet at http://pubs.acs.org. NIH Public Access Author ManuscriptAnal Chem. Author manuscript; available in PMC 2011 September 1. and is ~1000 times thinner than widely used nanopore membranes such as aluminum oxide membranes and polycarbonate track etch membranes. Despite the molecular thickness, the nanopore silicon membrane wi...

We have developed electroosmotic pumps (EOPs) fabricated from 15-nm-thick porous nanocrystalline silicon (pnc-Si) membranes. Ultrathin pnc-Si membranes enable high electroosmotic flow per unit voltage. We demonstrate that electroosmosis theory compares well with the observed pnc-Si flow rates. We attribute the high flow rates to high electrical fields present across the 15-nm span of the membrane. Surface modifications, such as plasma oxidation or silanization, can influence the electroosmotic flow rates through pnc-Si membranes by alteration of the zeta potential of the material. A prototype EOP that uses pnc-Si membranes and Ag/ AgCl electrodes was shown to pump microliter per minute-range flow through a 0.5-mm-diameter capillary tubing with as low as 250 mV of applied voltage. This silicon-based platform enables straightforward integration of low-voltage, on-chip EOPs into portable microfluidic devices with low back pressures.lectroosmotic flow results from the interaction between an electric field and the diffuse layer of ions at a charged surface. In capillaries or pores, the migration of the diffuse layer toward the oppositely charged electrode causes the bulk fluid within the channel to flow through viscous drag. Electroosmotic pumps (EOPs) are designed to generate high flow rates in microchannels using these principles (1, 2). EOPs present a number of advantages over mechanical pumps, including the lack of mechanical parts, pulse-free flows, and ease of control through electrode actuation. EOPs have been suggested as pumps for cooling circuits (3) and microfluidic devices that aid in drug delivery (4, 5) or diagnostics (2, 6). Microfluidic devices enable the miniaturization of multistep laboratory processes into small, low-cost, disposable units (6, 7). The inclusion of multiple steps into a single device increases the need for the precision pumping of fluids on-chip.High voltages (>1 kV) are often required for direct current (dc) EOPs to achieve sufficient flow rates in microchannels (8, 9). However, devices with high-voltage EOPs require bulky external power supplies and a skilled technician to operate, which defeats the ease of use and portability aims of a microfluidic diagnostic tool. For these reasons, the development of a low-voltage EOP is a current focus in the literature. Several recent low-voltage EOPs have been fabricated from porous silicon (10), alumina (11-13), track-etched polymer (14), and carbon nanotube membranes (15). These low-voltage EOPs are much thinner than their highvoltage predecessors (60-350 μm compared with >10 mm). Yao et al. suggest that further thinning of EOPs will enable better voltage-specific characteristics (16). Here, we examine the electroosmotic pumping by nanoporous membranes that are more than two orders of magnitude thinner than any membrane material previously used in an EOP.We have recently developed an ultrathin (15-30 nm), nanoporous membrane material called porous nanocrystalline silicon (pnc-Si) (17). pnc-Si membranes are fabricated on silicon wafers usin...