Nanoscale Surface Creasing Induced by Post-polymerization Modification.

Creasing in soft polymeric films is a result of substantial compressive stresses that trigger instability beyond a critical strain and have been directly related to failure mechanisms in different materials. However, it has been shown that programming these instabilities into soft materials can lead to new applications, such as particle sorting, deformable capillaries, and stimuli-responsive interfaces. In this work, we present a method for fabricating reproducible nanoscale surface instabilities using reactive microcontacting printing (μCP) on activated ester polymer brush layers of poly(pentafluorophenyl acrylate). The sizes and structures of the nanoscale creases can be modulated by varying the grafting density of the brush substrate and pressure applied during μCP. Stress is generated in the film under confinement due to the molecular weight increase of the side chains during post-polymerization modification, which results in substantial in-plane growth in the film and leads to the observed nanoscale creases.