Selection of Diacrylate Monomers for Sub-15 nm Ultraviolet Nanoimprinting by Resonance Shear Measurement

In UV nanoimprinting, the selection of monomers suitable for sub-15 nm patterning is difficult because the filling behavior of resin at this scale still remains scientifically unclear. We demonstrate sub-15 nm patterning by UV nanoimprinting using silica molds with 20, 15, and 7 nm diameter holes; however, the 7 nm diameter pillar patterns were not fabricated using hydroxy-containing monomers. The filling behavior into silica holes of around 10 nm depended on the chemical structure of the monomers. Resonance shear measurements revealed the following: (1) The viscosities of hydroxy-containing monomers confined between chlorodimethyl­(3,3,3-trifluoropropyl)­silane (FAS3-Cl)-modified surfaces began to increase at distances shorter than those of the monomers between unmodified surfaces. (2) The monomers confined between tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane-modified surfaces were squeezed out when the surface–surface distance decreased at less than 7 nm. The measured viscosities between the FAS3-Cl-modified silica surfaces were correlated with the insufficient filling behavior into the silica holes of around 10 nm in UV nanoimprinting. Contact angle measurements provided an additional insight that a higher wettability of the monomers onto the antisticking chemisorbed monolayers resulted in imprinted patterns with higher aspect ratios. Considering the increase in the monomer viscosity in the nanospace and the wettability of monomers onto chemisorbed monolayers, we concluded that the monomer showing low viscosity under confinement and high wettability onto the mold surface was suitable for single-digit nanometer UV nanoimprinting.