In this review, we discuss electrochemical applications of electrode-supported thin films derived from microphase-separated block copolymers (BCPs). In contrast to conventional homopolymers used for electrode modification, BCPs afford periodic nanoscale structures (microdomains) of uniform dimensions (5–100 nm) and predictable morphologies, which can be controlled by adjusting the lengths of individual homopolymer segments. BCPs usable for electrochemical applications consist of two or more segments that form solute-permeable, redox-active or etchable microdomains and a chemically inert matrix. The resulting microdomains afford nanoscale molecular/charge transport pathways toward the underlying electrode, whereas the matrix serves as a scaffold to improve film stability in solution. These polymeric thin films provide a unique means for fabricating nanowire arrays via template-based electrochemical synthesis, designing electrochemical sensors with unique selectivity, and constructing electrochemically-tunable functional materials.
