A high-throughput screening system has been developed to rapidly produce, screen, and assess the usefulness of organically modified silane (ORMOSIL)-based xerogel films formed on the surface of porous silicon (pSi) surfaces. The ORMOSILs tested include methyltriethoxysilane, <i>n</i>-octyltriethoxysilane, <i>n</i>-hexyltriethoxysilane, <i>n</i>-propyltriethoxysilane, 2-cyanoethyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, vinyltriethoxysilane, tetraethoxysilane, and hexafluoroethyltriethoxysilane. Xerogel microarrays were pin-printed on the surface of O<sub>3</sub> oxidized pSi using a computer-controlled robotic pin-printer. The fragile pSi required careful pin-printing parameter optimization to simultaneously ensure sufficient sol application and limit pin-induced damage. These multi-functional xerogel-pSi microarrays were exposed to harsh conditions (0.1 mM NaOH, 15 min) to determine the extent to which the xerogel protected the pSi. Microarray assessment included multispectral photoluminescence and infrared imaging. Results demonstrate that the more hydrophobic/nonpolar xerogel films (<i>n</i>-octyltriethoxysilane, <i>n</i>-hexyltriethoxysilane) protect the pSi surface the most and maintained the pSi photoluminescence. Also, unlike xerogel material doped with a reporter molecule, the uniformity of the printed feature plays a role in the protection of the pSi material underneath. Areas with thinner xerogel distributions allowed the permeation of NaOH whereas the thicker areas prohibit pSi exposure to NaOH.

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