Tuesday, November 6, 2007 - 5:10 PM
310d

Nanoporous Silicon Nitride Membranes Via Triblock Terpolymer Templating

Eric E. Nuxoll, Department of Pharmaceutics, University of Minnesota, 9-177 Weaver Densford Hall, 308 Harvard St. SE, Minneapolis, MN 55455, Marc A. Hillmyer, Dept. of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, and Ronald A. Siegel, Departments of Pharmaceutics and Biomedical Engineering, University of Minnesota, 9-177 Weaver Densford Hall, 308 Harvard St. SE, Minneapolis, MN 55455.

One strategy for protecting the mass transport interface of an implantable drug delivery device or sensor from antibodies and serum proteins is the use of a size exclusion membrane. The pores of such a membrane must be less than 50 nm across to block immunoproteins, but the membrane must still be highly porous and extremely thin to facilitate free transport of smaller pharmaceutical agents and analytes. Low-stress silicon nitride (LSN) is an attractive candidate material for such a membrane, being both mechanically robust and chemically inert. We are developing a process for patterning densely packed, uniform nanoscale pores in LSN films using specialized triblock terpolymers.

A silicon wafer is coated with 50 nm of LSN and windows are patterned on the backside of the wafer using photolithography and reactive ion etching. These windows are then etched through the silicon wafer by either KOH wet etching or Bosch-process directional reactive ion etching. Next the LSN is subjected to an organochlorosilane vapor, modifying the LSN surface to enhance polymer adhesion.

A poly(styrene)-poly(isoprene)-poly(lactide) (PS-PI-PLA) triblock terpolymer is then spin-coated onto this LSN surface and annealed under vacuum at 150 °C for 15 hrs. The PLA block self-assembles into cylinders perpendicular to the coating, nearly spanning it. The PLA cylinders are then removed with 0.05M NaOH in a 60:40 v/v water methanol solution, leaving densely packed 30 nm pores in the polymer film. The membrane is then subjected to reactive ion etching with an oxygen-free plasma for several minutes, during which time the nitride beneath the now-vacant cylinders is removed, while the rest of the LSN is protected by the polymer film. A subsequent oxygen plasma etch removes residual polymer, leaving a nanoporous silicon nitride film.

We have demonstrated effective patterning of high porosity silicon nitride films up to 50 nm thick. Such membranes could provide immuno-isolation without retarding small molecule transport and should integrate well with the growing number of BioMEMS devices under development.