Micromolding Surface‐Initiated Polymerization: A Versatile Route for Fabrication of Coatings with Microscale Surface Features of Tunable Height

This article introduces a process termed micromolding surface‐initiated polymerization (μMSIP) as a versatile route to provide surface‐bound, partially fluorinated polymer coatings with a homogeneous array of microscale surface features. The process employs hard‐polydimethylsiloxane (h‐PDMS) to mold the surface structure of master substrates exhibiting patterned microscale features. Upon filling the mold with the monomer 5‐(perfluorooctyl)norbornene (NBF8) and placing against a surface that is pre‐activated for surface‐initiated ring‐opening metathesis polymerization (SI‐ROMP), a partially fluorinated polymer film propagates from the surface with features that grow into the recesses of the mold to produce the final microtextured coating. The heights of these features can be tuned from 20–100% of the full height of the mold features based on the amount of initiator employed as well as the polymerization time and temperature. Reproduced topographies include pyramidal and inverted pyramidal structures. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images show that the final polymer film exhibits a homogeneously microstructured surface that resembles that of its corresponding master.