Toward Achieving Highly Ordered Fluorinated Surfaces of Spin-Coated Polymer Thin Films by Optimizing the Air/Liquid Interfacial Structure of the Casting Solutions

Thin polymer films with well-assembled fluorinated groups on their surfaces are not easily achieved via spin-coating film-fabrication methods because the solution solidifies very rapidly during spin-coating, which hinders the fluorinated moieties from segregating and organizing on the film surface. In this contribution, we have proposed a comprehensive strategy toward achieving well-ordered fluorinated thin films surfaces by optimizing the molecular organization at air/liquid interface of the film-formation solutions. To validate such a route, poly(methyl methacrylate) (PMMA) end-capped with several 2-perfluorooctylethyl methacrylate (FMA) units was employed as the model polymer for investigations. The air/solution interfacial structures were optimized by systematically changing the polymer chain structures and properties of the casting solvents. It was found that the polymers that form loosely associated aggregates (e.g., FMA1-ec-PMMA65-ec-FMA1) and a solvent with better solubility to FMA while having no...