Hierarchical Nanoflake Surface Driven by Spontaneous Wrinkling of Polyelectrolyte/Metal Complexed Films

A mechanical or physical change observed in nanocomposite thin films has recently offered new opportunities to generate intriguing nanostructures. In this study, we present a novel means of creating a hierarchically developed nanoflake structure by exploiting surface wrinkles that occur during the incorporation process of metallic nanoparticles into layer-by-layer assembled polyelectrolyte multilayer (PEM) thin films. The PEM film composed with linear polyethylenimine (LPEI) and poly(acrylic acid) (PAA) allows for facilitated cationic exchange reaction within the film even after the electrostatic complexation and chemical cross-linking reaction. The subsequent reduction process induces an in situ complexation of metallic nanoparticles with a PEM matrix, causing an accumulation of lateral compressive stress for surface wrinkling. The wrinkling characteristics of the complexed films can be theoretically interpreted by employing the gradationally swollen film model, whereby a gradual change in the elastic property along the axial direction of the film can be appropriately reflected. In addition, wrinkled surfaces are further processed to form vertically aligned and hierarchically ordered nanoflakes after selective removal of the PEM matrix with plasma ashing. Consequently, superhydrophobic surface properties (water contact angle = 170°, sliding angle <1°) can be attained from the hierarchical nanoflake structure. The method presented here is advantageous in that large-scale preparation can be readily implemented by a stepwise dipping process without resorting to specific patterning or a serially applied complex structuring process, which can provide a promising platform technique for various surface engineering applications.