Nanoscale Electron Beam Patterning of <scp>PEDOT</scp>:<scp>PSS</scp> Free‐Standing Films for Enhanced Thermoelectric Performance

The growing demand for flexible, lightweight, and highly processable electronic devices makes high‐functionality conducting polymers such as poly (3,4‐ethylene dioxythiophene): polystyrene sulfonate (PEDOT:PSS) an attractive alternative to conventional inorganic materials for various applications including thermoelectrics. However, considerable improvements are necessary to make conducting polymers a commercially viable choice for thermoelectric applications. This study explores nanopatterning as an effective and unique strategy for enhancing polymer functionality to optimize thermoelectric parameters, such as electrical conductivity, Seebeck coefficient, and thermal conductivity. Introducing nanopatterning into thermoelectric polymers is challenging due to intricate technical hurdles and the necessity for individually manipulating the interdependent thermoelectric parameters. Here, array nanopatterns with different pattern spacings are imposed on free‐standing PEDOT:PSS films using direct electron beam irradiation, thereby achieving selective control of electrical and thermal transport in PEDOT:PSS. Electron beam irradiation transformed PEDOT:PSS from a highly ordered quinoid to an amorphous benzoid structure. Optimized pattern spacing resulted in a remarkable 70% reduction in thermal conductivity and a 60% increase in thermoelectric figure of merit compared to non‐patterned PEDOT:PSS. The proposed nanopatterning methodology demonstrates a skillful approach to precisely manipulate the thermoelectric parameters, thereby improving the thermoelectric performance of conducting polymers, and promising utilization in cutting‐edge electronic applications.