Highly Sensitive, Patternable Organic Films at the Nanoscale Made by Bottom-Up Assembly

Nanoscale patterning of organic thin films is of great interest for next-generation technologies. To keep pace with the demands of state-of-the-art lithography, both the sensitivity and resolution of the patternable thin films need to be improved. Here we report a highly sensitive polyurea film grown by bottom-up assembly via the molecular layer deposition (MLD) technique, which allows for high-resolution patterning at the nanoscale. The MLD process used in this work provides an exceptionally high degree of control over the film thickness and composition and also offers high coating conformality. The polyurea film was formed by urea coupling reactions between 1,4-diisocyanatobutane and 2,2'-(propane-2,2-diyldioxy)diethanamine precursors and deposited in a layer-by-layer fashion. Acid-labile ketal groups were incorporated into the backbone of the polymer chains to ensure chemically amplified cleaving reactions when combined with photoacid, which was generated by electron-beam activation of triphenylsulfonium triflate soaked into the polyurea film. With electron-beam lithography, sub-100 μC/cm(2) sensitivity and sub-100 nm resolution were demonstrated using this new bottom-up assembly approach to resist fabrication.