High-Resolution Photolithographic Patterning of Conjugated Polymers via Reversible Molecular Doping

Organic field-effect transistors (OFETs) require reliable micro- and nanoscale patterning of semiconducting layers, yet conjugated polymers have long been considered incompatible with photolithography due to dissolution and chemical damage from photoresist solvents. Here, we present a photolithography-compatible strategy based on doping-induced solubility conversion (DISC), demonstrated using poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT). AuCl₃ doping reversibly modulates the benzoid/quinoid resonance balance, lamellar stacking, and π-π interactions, suppressing solubility during lithographic exposure, while dedoping restores the intrinsic electronic properties. Using this approach, micropatterns with linewidths as small as 2 µm were fabricated in diverse geometries-including line arrays, concentric rings, dot arrays, and curved channels-with high fidelity; quantitative analysis of dot arrays yielded mean absolute errors of 48-66 nm and coefficients of variation of 2.0-3.9%, confirming resolution and reproducibility across large areas. Importantly, OFETs based on patterned PBTTT exhibited charge-carrier mobility, threshold voltage, and on/off ratios comparable to spin-coated devices, despite undergoing multiple photolithography steps, indicating preservation of transport characteristics. Furthermore, the same DISC-assisted lithography was successfully applied to other representative p-type conjugated polymers, including P3HT and PDPP-4T, confirming the universality of the method. This scalable strategy thus combines the precision of established lithography with the functional advantages of organic semiconductors, providing a robust platform for high-density organic electronic integration in flexible circuits, biointerfaces, and active-matrix systems.