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Thin films of poly-3,4-ethylene dioxythiophene (PEDOT) were electrodeposited on transparent electrodes of indium tin oxide (ITO) using potentiostatic regime. These films had thicknesses ranging from 15 nm to 60 nm and were studied using UV-vis absorption and chronoamperometric techniques in monomer-free tetrabutylammonium perchlorate/acetonitrile solutions. The charge transfer diffusion coefficient (D) of the films were calculated using Cottrell model for a wide range of potential steps from −1.60 to 1.60 V vs. Ag°/AgNO3. For p-doped films, the highest diffusion coefficients were obtained when a potential of 0.70 V was applied. Moreover, a direct relationship between film thickness and their diffusion coefficients was found for thin PEDOT films showing D values up to 1.4 × 10−9 cm2 s−1 for 60 nm thickness films. These values are remarkably higher than the D of 1.8 × 10−11 cm2 s−1 obtained for spin-coated PEDOT: PSS films of similar thickness.

Relationship between Charge Transfer Diffusion Coefficients and Doping Level for electro generated thin PEDOT films on ITO