Reversible Morphology Locking via Metal Infiltration in a Block Copolymer

Metal infiltration from an acid solution of a metal precursor into the poly­(2-vinylpyridine) (P2VP) microdomains of a polystyrene-b-P2VP block copolymer is shown to reduce the uptake of solvent vapor during a subsequent solvent annealing process, locking the morphology of the self-assembled microdomains. The amount of metal, here Pt, incorporated into the P2VP increases with both metal precursor [PtCl4]2– and hydrochloric acid concentrations, reaching 0.83 Pt atom per pyridine unit. The metal is then exfiltrated using a KOH + ethylenediamine­tetraacetic acid disodium salt dihydrate (Na2EDTA) complexing solution, which restores solvent uptake and unlocks the morphology. The reversibility of the metal infiltration and morphology locking is demonstrated in a multistage annealing process and is confirmed for Fe as well as Pt. Reversible locking and unlocking of block copolymer microdomain morphologies expand their utility for nanofabrication processes by allowing the morphology to be fixed during subsequent process steps.