Netlike Knitting of Polyelectrolyte Multilayers on Honeycomb-Patterned Substrate

The pH-amplified exponential growth layer-by-layer (LBL) self-assembly process was directly performed on honeycomb-patterned substrate for achievement of "guided patterning" of polyelectrolyte multilayers. Polyethylenimine (PEI) and poly(acrylic acid) (PAA) were used as polyanions, and their pH were carefully tuned to achieve pH-enhanced exponential growth. Guided by underlying hexagonally patterned islandlike poly(dimethylsiloxane) (PDMS) arrays, the diffusive polyelectrolytes rapidly interweaved into linear, multilayered structures distributed along the grooves between the patterned protuberate and formed a regular network of multilayered film with uniform mesh size. Netlike "knitting" of polyelectrolyte multilayers on honeycomb-patterned substrate has been realized by following this procedure. Superhydrophobic surfaces could be readily obtained after several bilayers of LBL assembly (with thermal cross-linking and surface fluorination by chemical vapor deposition), indicating that successful fabrication of functional micro- and nanoscale hierarchical structures can be achieved. Both high- and low-adhesion superhydrophobic surfaces ("petal effect" and "lotus effect") can be obtained with different bilayers of assembly, proving that different levels of nano- to microstructural hierarchy can be realized using this method. Furthermore, we were able to get topographically asymmetric, free-standing, polyelectrolyte multilayer films in the case that we performed more than eight bilayers of assembly. This research reported template-directed LBL patterning assembly for the first time. It provides a beneficial exploration for the surface patterning technique for the LBL assembly process.