Fluoroalkylated silicon-containing surfaces-estimation of solid-surface energy

The design of robust omniphobic surfaces, which are not wetted by low-surface-tension liquids such as octane (γlv=21.6 mN/m) and methanol (γlv=22.7 mN/m), requires an appropriately chosen surface micro/nanotexture in addition to a low solid-surface energy (γsv). 1H,1H,2H,2H-Heptadecafluorodecyl polyhedral oligomeric silsesquioxane (fluorodecyl POSS) offers one of the lowest solid-surface energy values ever reported (γsv≈10 mN/m) and has become the molecule of choice for coating textured surfaces. In this work, we synthesize and evaluate a series of related molecules that either retain the POSS cage and differ in fluoroalkyl chain length or that retain the fluorodecyl chains surrounding a linear or cyclic molecular structure. The solid-surface energy (γsv) of these molecules was estimated using contact angle measurements on flat spin-coated silicon wafer surfaces. Zisman analysis was performed using a homologous series of n-alkanes (15.5≤γlv≤27.5 mN/m), whereas Girifalco-Good analysis was performed using a set of polar and nonpolar liquids with a wider range of liquid surface tension (15.5≤γlv≤72.1 mN/m). The hydrogen-bond-donating, hydrogen-bond-accepting, polar, and nonpolar (dispersion) contributions to the solid-surface energy of each compound were determined by probing the surfaces using a set of three liquid droplets of either acetone, chloroform, and dodecane or diiodomethane, dimethyl sulfoxide, and water.