Ordered Reactive Nanomembranes/Nanotemplates from Thin Films of Block Copolymer Supramolecular Assembly

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Abstract
We report on a unique, very simple method of preparation of reactive membranes and nanotemplates with nanoscopic cylindrical channels on the surface of various inorganic and polymeric substrates. Well-ordered nanostructured thin polymer films have been fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-PVP) and 2-(4‘-hydroxybenzeneazo)benzoic acid (HABA), consisting of cylindrical nanodomains formed by PVP-HABA associates surrounded by PS. Alignment of the domains has been shown to be switched upon exposure to vapors of different solvents from the parallel to perpendicular orientation to the confining surface and vice versa. The alignment of the cylindrical nanodomains is insensitive to the composition of the confining surface due to the self-adaptive behavior of the supramolecular PVP-HABA assembly. Extraction of HABA with selective solvent results in nanomembranes with a hexagonal lattice (24 nm in the period) of hollow channels of 8 nm in the diameter crossing the membrane from the top to the bottom. The walls of the channels are constituted from reactive PVP chains. The channels were filled with Ni clusters via the electrodeposition method to fabricate the ordered array of metallic nanodots of 1.2 tera per cm2.