Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at temperatures above the corresponding glass transition and chemical deprotection temperatures to yield structured films with exposed carboxylic acid and anhydride groups. Faithful pattern transfer is confirmed by AFM analyses. Transmission-mode FTIR spectra shows a conversion of over 95% of the tert-butyl ester groups after RIL at 230 °C for 5 minutes and a significantly reduced conversion to anhydride compared to thermolysis of neat films with free surfaces in air or nitrogen. An enrichment of the surface layer in PS is detected by angle-resolved X-ray photoelectron spectroscopy (XPS). In order to demonstrate application potentials of the activated platforms, a 7 nm ± 1 nm thick NH2-terminated PEG layer (grafting density of 0.9 chains nm−2) is covalently grafted to RIL-activated substrates. This layer reduces the non-specific adsorption (NSA) of bovine serum albumin by 95% to a residual mass coverage of 9.1 ± 2.9 ng cm−2. As shown by these examples, RIL comprises an attractive complementary approach to produce bio-reactive polymer surfaces with topographic patterns in a one-step process.