Positive-tone nanopatterning of chemical vapor deposited polyacrylic thin films

Terpolymers of methyl alpha-chloroacrylate (MCA), methacrylic acid (MAA), and methacrylic anhydride (MAH) were synthesized by initiated chemical vapor deposition (iCVD) of MCA and MAA followed by low-temperature annealing that partially converts MAA into MAH. The MAA composition in the iCVD copolymer can be systematically varied between 37 and 85 mol % by adjusting the gas feed fractions of monomers. Study of the monomer reactivity ratios and the copolymer molecular weights supports the hypothesis of a surface propagation mechanism during the iCVD copolymerization. The carboxylic dehydration reaction at the annealing temperature of 160 degrees C is dominated by a mechanism of intramolecular cyclization, resulting in intramolecular MAH anhydride formation while preventing crosslink formation. The incorporation of highly electron-withdrawing anhydride functionality enhances chain scission susceptibility under electron-beam irradiation. P(MCA-MAA-MAH) terpolymer thin films can be completely developed at dosages as low as 20 microC/cm2 at 50 kV. High-quality positive-tone patterns were created with 60 nm feature size achieved in the vapor deposited films.