Silica/Ultraviolet-Cured Resin Nanocomposites for Replica Molds in Ultraviolet Nanoimprinting

Fluid UV-curable composite resins made with methacrylate-modified silica nanoparticles (NPs), a diacrylate monomer, and a photoinitiator without nonreactive solvents were prepared to develop composite replica molds in UV nanoimprinting. 1,4-Bis(acryloyloxy)butane was compatible with NPs up to an inorganic silica component of 60 wt %, and its cured composite films showed a high transmittance of ${>}89$% at an i-line wavelength of 365 nm. The fluorinated antisticking layer obtained from an antisticking reagent was formed effectively on a composite surface at which bare silica surfaces of NPs appeared by photooxidation of the composite film surface. Composite replica molds could be fabricated by putting a droplet of the composite resin on a silica substrate modified with a reactive adhesion layer, filling cavities of a fluorinated master mold with the resin under a pentafluoropropane (PFP) atmosphere, curing the molded resin by exposure to UV light, and treating the surface of the cured resin with the antisticking reagent after demolding. It was confirmed that the composite replica molds were available for step-and-repeat UV nanoimprinting using an acrylate-type UV-curable resin in PFP. The composite replica molds showed remarkably smaller release energies than the replica mold without NPs.