Film Confinement Induced "Jump-Percolation" Wetting Transition in Amphiphilic Block Copolymer Films

We report a first-order like sharp surface wettability transition with varying film thickness dependent morphology in cast films of an amphiphilic triblock copolymer. Films composed of poly(2-(N-ethylperfluorooctanesulfonamido) ethyl methyl acrylate), poly(FOSM), and poly(N,N'-dimethyl acrylamide), poly(DMA), with thickness (h) in the transition-range, 200 < h < 300 nm, exhibited an abrupt hydrophobic to hydrophilic dynamic water contact angle transition. After an induction time, t_i ≈ 40 to 180 s, water contact angle varied as θ_c ≈ 116° to 40° with an ultrafast contact angle decay time constant, [Formula: see text] ≈ -18°/s. This behavior is a result of competing heterogeneous and antagonistic effects of bumpy poly(DMA) wetting domains against a nonwetting planar poly(FOSM) background, with a "jump percolation" wetting transition when the poly(DMA) domain density reaches unity. Outside of this film thickness range, relatively shallow decreasing water contact angle gradients were observed with a monotonically increasing poly(DMA) domain area coverage with increasing film thickness in the overall range of 40 nm (hydrophobic, θ_c ≈ 118°) < h < 500 nm (hydrophilic, θ_c ≈ 8°). The optical diffuse reflectance properties of these rough surfaces exhibit an onset of diffuse reflectance maxima correlated to the transition morphology film thickness.