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Air-stable, lightweight, and electrically conductive polymers are highly desired as the electrodes for next-generation electronic devices. However, the low electrical conductivity and low carrier mobility of polymers are the key bottlenecks that limit their adoption. We demonstrate that the key to addressing these limitations is to molecularly engineer the crystallization and morphology of polymers. We use oxidative chemical vapor deposition (oCVD) and hydrobromic acid treatment as an effective tool to achieve such engineering for conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). We demonstrate PEDOT thin films with a record-high electrical conductivity of 6259 S/cm and a remarkably high carrier mobility of 18.45 cm V s by inducing a crystallite-configuration transition using oCVD. Subsequent theoretical modeling reveals a metallic nature and an effective reduction of the carrier transport energy barrier between crystallized domains in these thin films. To validate this metallic nature, we successfully fabricate PEDOT-Si Schottky diode arrays operating at 13.56 MHz for radio frequency identification (RFID) readers, demonstrating wafer-scale fabrication compatible with conventional complementary metal-oxide semiconductor (CMOS) technology. The oCVD PEDOT thin films with ultrahigh electrical conductivity and high carrier mobility show great promise for novel high-speed organic electronics with low energy consumption and better charge carrier transport.

High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment