for their unique physiochemical properties, where the highly stretched polymer chains can be used to tune surface properties such as wetting and adhesion, and these system have been demonstrated promise in a wide breadth of applications, including biomaterials, nanotechnology, and thin-film devices. [7] Jeffamine M-2070, a 31:10 copolymer of poly(ethylene oxide) and poly(propylene oxide) with an average molecular weight of 2000 g mol -1 end capped with a primary amine, was used for PPM, which upon reaction with PFPA results in a drastic increase in surface-bound polymer molecular weight (at fixed grafting density) and a subsequent increase in thickness of resulting brushes. [8] Poly(PFPA) brushes are highly reactive toward primary amines, and under confinement, stress from both the large, rapid increase in thickness of the film, and the formation of a bilayer system with a large modulus mismatch (between the bottle-brush structure and the underlying unreacted polymer backbone) results in nanoscale creases. [9] These feature sizes could be mani pulated by changing the pressure on the polydimethylsiloxane (PDMS) stamp and/or the grafting density of the brush. The experimental studies were corroborated using finite element simulations, and it was proposed that the observed pressure dependence was a result of the amount of reactant penetration into the brush, with a greater pressure applied to the stamp equating to more Jeffamine penetration and a larger degree of functionalization in the brush.In order to further elucidate the factors governing crease formation in this system, as well as other polymer brush platforms, we report a surprisingly simple method to form creases on reactive polymer brushes that uses a droplet of Jeffamine on the surface of poly(PFPA) brushes. Furthermore, using this method, experimental variables in crease formation can be isolated and manipulated to better understand the mechanism of crease formation in reactive polymer brushes platforms. In this work, we examined the effect of reaction time as well as the reaction kinetics of aminolysis on crease formation in poly(PFPA) brushes, resulting in a multitude of crease sizes and shapes fabricated with a high degree of control and reproducibility.
Results and DiscussionPoly(PFPA) brushes were made through photoinitiated freeradical polymerization using an asymmetric azo-based silane initiator on silicon/silicon dioxide substrates as previously reported. [6,9b] Each brush was irradiated under 350 nm light Precisely controlling the morphology in thin film coatings has emerged as an important tool used to tune surface properties in a wide variety of applications. Previously, a method is reported to fabricate nanoscale surface creases with a high degree of control over crease size and shape using microcontact printing to perform post-polymerization modification on reactive polymer brush surfaces. In this work, this approach has been expanded to mani pulate crease morphology in reactive thin films, using only a drop of a reactive, viscous polym...