Fast Electrochemical Netting of Composite Chains for Transferable Highly Conductive Polymeric Nanofilms

Broad applications of electropolymerized conducting polymers (CPs) often prefer thinner soft electrodes to comply with downscaling of the fabrication resolution. However, high conductivity of existing CP films vanishes as thickness decreases to the nanoscale (i.e., below 100 nm), with an unclear mechanism so far. In this study, with an unprecedented family of polypyrrole (PPy) nanofilms that can be easily transferred in a fast and contamination-free manner, we are able to trace the initial development of electrical conductance along with chains' arrangement starting from the very early electrochemical deposition. Our results evidence that the classical nodular polymeric aggregation fundamentally accounts for the persistent losses of interchain connectivity and macroscopic conductivity at a limited thickness. Surprisingly, this seemingly disadvantageous structure can be altered into a large conjugated network to robustly restore the conductivity back to over 80 S cm^-1 even below 100 nm, while the controllable formation, growth, and collapse of such networks radically vary the conductivity over a range of 3 orders of magnitude (0.8-129 S cm^-1). These observations depict the first physical picture detailing how the long-range conductivity builds up in a growing conjugated network, which opens a route to fast synthesis and diverse applications of such highly conductive CP nanofilms.