In situ Electrochemical Monitoring of Selective Etching in Ordered Mesoporous Block-Copolymer Templates

We present a simple in situ electrochemical probe for the selective etching of the PLA component of thin film poly(4-fluorostyrene)-b-poly(D,L-lactide) (PFS-b-PLA) mesoporous block copolymer templates with a range of highly ordered microphase morphologies. Etching rates between 0.6 and 0.9 nm s⁻¹ were measured in electric-field aligned standing PLA cylinders 12 nm wide and up to 800 nm long. The etching rate within a bicontinuous gyroid network morphology is comparable to that of the hexagonally ordered cylindrical array. A microphase-separated, nonaligned but film-spanning PLA pore structure is found in cylinder forming PFS-b-PLA films immediately after spin coating that could have applications in patterning of functional nanostructured arrays. Cross-film percolation of the PLA phase is confirmed electrochemically, with an etching rate approximately half that of the highly ordered morphologies. The etching rate is independent of template thickness in all three morphologies.