In contrast to photolithography where particular wavelengths of light can couple to specific photochemistries, electron-beam lithography can drive competing chemistries. To separate surface-grafting, cross-linking, and chemical functionality, we studied the effects of 2 keV electrons on thin films of poly(ethylene glycol) end-functionalized with hydroxyls (PEG-OH) or biotins (PEG-B). Similarities in the dose-dependent thickness changes of the patterned PEGs indicate that surface grafting and cross-linking primarily involve the ethylene oxide main chain. While higher doses create thicker patterns with more biotin, the concurrent increase in thiol reactivity indicates that cross-linking competes with biotin degradation. The dose window for optimal e-beam patterning of biotinylated PEG is very narrow. Biotin is entirely consumed at higher doses. Its modified functionality is reactive with 5-((2-(and-3)--(acetylmercapto) succinoyl) amino) (SAMSA). This effect creates a dose-dependent orthogonal functionality that can be patterned from a single precursor thin film.
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