Highly Conductive and Conformal Poly(3,4-ethylenedioxythiophene) (PEDOT) Thin Films via Oxidative Molecular Layer Deposition

This work introduces oxidative molecular layer deposition (oMLD) as a chemical route to synthesize highly conductive and conformal poly­(3,4-ethylenedioxythiophene) (PEDOT) thin films via sequential vapor exposures of molybdenum­(V) chloride (MoCl₅, oxidant) and ethylene dioxythiophene (EDOT, monomer) precursors. The growth temperature strongly affects PEDOT’s crystalline structure and electronic conductivity. Films deposited at ∼150 °C exhibit a highly textured crystalline structure, with {010} planes aligned parallel with the substrate. Electrical conductivity of these textured films is routinely above 1000 S cm^–1, with the most conductive films exceeding 3000 S cm^–1. At lower temperatures (∼100 °C) the films exhibit a random polycrystalline structure and display smaller conductivities. Compared with typical electrochemical, solution-based, and chemical vapor deposition techniques, oMLD PEDOT films achieve high conductivity without the need for additives or postdeposition treatments. Moreover, the sequential-reaction synthesis method produces highly conformal coatings over high aspect ratio structures, making it attractive for many device applications