An Efficiently Doped PEDOT:PSS Ink Formulation via Metastable Liquid−Liquid Contact for Capillary Flow‐Driven, Hierarchically and Highly Conductive Films

Abstract With commercial electronics transitioning toward flexible devices, there is a growing demand for high‐performance polymers such as poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). Previous breakthroughs in promoting the conductivity of PEDOT:PSS, which mainly stem from solvent‐treatment and transfer‐printing strategies, remain as inevitable challenges due to the inefficient, unstable, and biologically incompatible process. Herein, a scalable fabrication of conducting PEDOT:PSS inks is reported via a metastable liquid−liquid contact (MLLC) method, realizing phase separation and removal of excess PSS simultaneously. MLLC‐doped inks are further used to prepare ring‐like films through a compromise between the coffee‐ring effect and the Marangoni vortex during evaporation of droplets. The specific control over deposition conditions allows for tunable ring‐like morphologies and preferentially interconnected networks of PEDOT:PSS nanofibrils, resulting in a high electrical conductivity of 6,616 S cm −1 and excellent optical transparency of the film. The combination of excellent electrical properties and the special morphology enables it to serve as electrodes for touch sensors with gradient pressure sensitivity. These findings not only provide new insight into developing a simple and efficient doping method for commercial PEDOT:PSS ink, but also offer a promising self‐assembled deposition pattern of organic semiconductor films, expanding the applications in flexible electronics, bioelectronics as well as photovoltaic devices.