Stimuli‐Responsive Hybrid Coatings of Polyelectrolyte Multilayers and Nano‐Patterned Polymer Brushes

Abstract

A new type of polymeric hybrid coating is created by layer‐by‐layer deposition of polyelectrolyte multilayers (PEM) onto nano‐patterned polymer brushes (NPB). The PEM is a hydrogen‐bonded multilayer consisting of poly(acrylic acid) and poly(acrylamide) and the NPB is derived from a surface reactive rod‐coil block copolymer, polystyrene‐block‐poly[3‐(triethoxysilyl)propylisocyanate]. The thickness of the PEM coating is optimized with respect to the height of the NPB mounds, to yield PEM/NPB hybrid coatings with unique nano‐embossed or nano‐porous structures that can be interchangeable by heating and moisture annealing. The hybrid coating is patternable by the micro‐contact printing method. The results demonstrate that the combination of surface‐bound, hydrophobic NPB layer with hydrophilic PEM films at the nanoscopic level offers a new organic hybrid coating with novel surface properties.

Layer‐by‐Layer Hydrogen‐Bonded Polymer Films: From Fundamentals to Applications

“…Very recently, the HB LbL films were also deposited onto nanopatterned polymer brushes. [77] Such hybrid nanostructured materials showed reversible transitions from nanoporous to nanoembossed structures upon heating or exposure to moisture. [77] Finally, the ability of HB LbL films to disintegrate at elevated pHs was utilized in their application as release layers for the preparation of free-standing membranes.…”

“…[77] Such hybrid nanostructured materials showed reversible transitions from nanoporous to nanoembossed structures upon heating or exposure to moisture. [77] Finally, the ability of HB LbL films to disintegrate at elevated pHs was utilized in their application as release layers for the preparation of free-standing membranes. [78] Free-standing films of electrostatically assembled PEM LbL films were prepared by first depositing the HB PEO/PAA LbL film at the substrate surface, followed by selective dissolution of these sacrificial layers at a neutral pH value.…”

Holes and Ledges Created by Multilayer Assembly on Polyelectrolyte Brushes: A Novel Route for the Three‐Dimensional Nanoscale Design of Surfaces

“…[15] Interesting topological features of the multilayers on top of patterned brushes have recently been demonstrated. [16] In this work, we describe unusual topologic features occurring when LBL deposition was conducted on polyelectrolyte brushes. We show that the assembly of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sodium sulphonate) (PSS) on poly(sulfo propyl methacrylate) (PSPM) brushes resulted in films with holes and ledges in the nano-and micron-size range.…”

Two-dimensional nanoarchitectonics based on self-assembly

“…For example, SAM structures can be further machined or functionalized with atomic force microscope (AFM) nanolithography [47][48][49], dip-pen nanolithography [50], micro-compact printing [51]. LbL films can also be fabricated with photolithography [52,53], micro-contact printing [54][55][56], and ink-jet printing [57]. Although these combinations of bottom-up assemblies and top-down techniques provide important incremental steps in nanotechnology, molecular or atomic level resolution has not generally been attained.…”