Mechanism of liquid-phase metal infiltration into pyridine-containing polymeric thin films

[Display omitted] •Active block copolymer moiety is capable of selective infiltration.•Careful choice of solvent and metal salt leads to effective infiltration.•Block copolymer can act as template for metal oxide layers.•Metal chemistry directly affects the infiltration process.•Metal coordination is observed for metal-pyridinic N interactions. This research studied the liquid-phase selective metal infiltration of a pyridine-containing block copolymer (BCP). The results demonstrated that the metal cations interact differently with the poly(2-vinylpyridine) in polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP); the oxidation state and type of cation play an important role in the infiltration process, which is also affected by the solvent. Silver (Ag+) did not present an effective infiltration, while nickel (Ni2+) and chromium (Cr3+) were able to reproduce the pattern of the BCP. These differences can be associated with the coordination of the pyridinic nitrogen and the metal, in parallel with π-interactions. Furthermore, in the case of chromium, the presence of oxyanions led to an improved infiltration and high fidelity on the formation of the ordered metal oxide layer.