Nanoporous silicon nitride membranes fabricated from porous nanocrystalline silicon templates.

The extraordinary permeability and manufacturability of ultrathin silicon-based membranes are enabling devices with improved performance and smaller sizes in such important areas as molecular filtration and sensing, cell culture, electroosmotic pumping, and hemodialysis. Because of the robust chemical and mechanical properties of silicon nitride (SiN), several laboratories have developed techniques for patterning nanopores in SiN using reactive ion etching (RIE) through a template structure. These methods however, have failed to produce pores small enough for ultrafiltration (<100 nm) in SiN and involve templates that are prone to microporous defects. Here we present a facile, wafer-scale method to produce nanoporous silicon nitride (NPN) membranes using porous nanocrystalline silicon (pnc-Si) as a self-assembling, defect free, RIE masking layer. By modifying the mask layer morphology and the RIE etch conditions, the pore sizes of NPN can be adjusted between 40 nm and 80 nm with porosities reaching 40%. The resulting NPN membranes exhibit higher burst pressures than pnc-Si membranes while having 5× greater permeability. NPN membranes also demonstrate the capacity for high resolution separations (<10 nm) seen previously with pnc-Si membranes. We further demonstrate that human endothelial cells can be grown on NPN membranes, verifying the biocompatibility of NPN and demonstrating the potential of this material for cell culture applications.

Ballistic and non-ballistic gas flow through ultrathin nanopores.

We show that ultrathin porous nanocrystalline silicon membranes exhibit gas permeance that is several orders of magnitude higher than other membranes. Using these membranes, gas flow obeying Knudsen diffusion has been studied in pores with lengths and diameters in the tens of nanometers regime. The components of the flow due to ballistic transport and transport after reflection from the pore walls were separated and quantified as a function of pore diameter. These results were obtained in pores made in silicon. We demonstrate that changing the pore interior to carbon leads to flow enhancement resulting from a change in the nature of molecule-pore wall interactions. This result confirms previously published flow enhancement results obtained in carbon nanotubes.

An experimental and theoretical analysis of molecular separations by diffusion through ultrathin nanoporous membranes.

Diffusion based separations are essential for laboratory and clinical dialysis processes. New molecularly thin nanoporous membranes may improve the rate and quality of separations achievable by these processes. In this work we have performed protein and small molecule separations with 15 nm thick porous nanocrystalline silicon (pnc-Si) membranes and compared the results to 1- and 3- dimensional models of diffusion through ultrathin membranes. The models predict the amount of resistance contributed by the membrane by using pore characteristics obtained by direct inspection of pnc-Si membranes in transmission electron micrographs. The theoretical results indicate that molecularly thin membranes are expected to enable higher resolution separations at times before equilibrium compared to thicker membranes with the same pore diameters and porosities. We also explored the impact of experimental parameters such as porosity, pore distribution, diffusion time, and chamber size on the sieving characteristics. Experimental results are found to be in good agreement with the theory, and ultrathin membranes are shown to impart little overall resistance to the diffusion of molecules smaller than the physical pore size cutoff. The largest molecules tested experience more hindrance than expected from simulations indicating that factors not incorporated in the models, such as molecule shape, electrostatic repulsion, and adsorption to pore walls, are likely important.

Porous nanocrystalline silicon membranes as highly permeable and molecularly thin substrates for cell culture.

Porous nanocrystalline silicon (pnc-Si) is new type of silicon nanomaterial with potential uses in lab-on-a-chip devices, cell culture, and tissue engineering. The pnc-Si material is a 15 nm thick, freestanding, nanoporous membrane made with scalable silicon manufacturing. Because pnc-Si membranes are approximately 1000 times thinner than any polymeric membrane, their permeability to small solutes is orders-of-magnitude greater than conventional membranes. As cell culture substrates, pnc-Si membranes can overcome the shortcomings of membranes used in commercial transwell devices and enable new devices for the control of cellular microenvironments. The current study investigates the feasibility of pnc-Si as a cell culture substrate by measuring cell adhesion, morphology, growth and viability on pnc-Si compared to conventional culture substrates. Results for immortalized fibroblasts and primary vascular endothelial cells are highly similar on pnc-Si, polystyrene and glass. Significantly, pnc-Si dissolves in cell culture media over several days without cytotoxic effects and stability is tunable by modifying the density of a superficial oxide. The results establish pnc-Si as a viable substrate for cell culture and a degradable biomaterial. Pnc-Si membranes should find use in the study of molecular transport through cell monolayers, in studies of cell-cell communication, and as biodegradable scaffolds for three-dimensional tissue constructs.

Methods for controlling the pore properties of ultra-thin nanocrystalline silicon membranes.

Porous nanocrystalline silicon (pnc-Si) membranes are a new class of solid-state ultra-thin membranes with promising applications ranging from biological separations to use as a platform for electron imaging and spectroscopy. Because the thickness of the membrane is only 15-30 nm, on the order of that of the molecules to be separated, mass transport through the membrane is greatly enhanced. For applications involving molecular separations, it is crucial that the membrane is highly permeable to some species while being nearly impermeable to others. An important approach to adjusting the permeability of a membrane is by changing the size and density of the pores. With pnc-Si, a rapid thermal treatment is used to induce nanopore formation in a thin film of nanocrystalline silicon, which is then released over a silicon scaffold using an anisotropic etchant. In this study, we examine the influence of thin film deposition and thermal treatment parameters on pore size and density.