Polymer nanogels grafted from nanopatterned surfaces studied by AFM force spectroscopy

Nanopatterned cross-linked polymers are important for applications with controlled mechanical properties. Grafted linear and cross-linked polydimethylacrylamide gels on micro- and nanopatterns were created using iniferter-driven quasi-living radical polymerization combined with conventional photolithography and nanosphere lithography. Micropatterned linear polymers reproduce the expected scaling behavior at moderate grafting density. The addition of cross-linker to the polymerization solution leads to an increased tendency of early termination as determined by AFM force spectroscopy. Similarly, nanopatterned linear polymers show reduced thickness in agreement with the expected scaling relationship for nanoisland grafts that have reduced lateral confinement. The addition of cross-linker reintroduces some of the lateral confinement for the length of polymers reported here. The mechanical properties of both the micro- and nanopatterned linear as well as cross-linked polymers were analyzed using an algorithm to objectively determine the contact point in AFM force spectroscopy and two independent Hertz-based analysis approaches. The obtained Young's moduli are close to those expected for homogeneous thick polymer films and are independent of pattern size. Our results demonstrate that polymeric nanopillars with controlled elastic modulus can be fabricated using irreversible cross-linkers. They also highlight some of the factors that must be considered for successful fabrication of grafted nanopillars of defined mechanical and structural properties.