High Performing Ambipolar Organic Electrochemical Transistors and Solid‐State Inverters Enabled by Hydrophilic/Hydrophobic Side Chains Integration

Abstract Progress in solid‐state organic electrochemical transistors (SS‐OECTs) and complementary circuits is limited by the lack of high‐performance single component ambipolar mixed ionic‐electronic conductors (AMIECs). Herein, two DPP‐V‐based terpolymers, p(gDPP‐V‐B05) and p(gDPP‐V‐B20) are designed, featuring an ambipolar backbone and tunable integrated hydrophilic/hydrophobic side‐chain engineering to optimize mixed conduction. Both polymers exhibited state‐of‐the‐art ambipolar performance in aqueous OECTs, with p(gDPP‐V‐B05) demonstrating the record µ C * values of 384.8 F cm ⁻¹ V ⁻¹ s ⁻¹ (n‐type) and 691.7 F cm ⁻¹ V ⁻¹ s ⁻¹ (p‐type), along with a state‐of‐the‐art normalized transconductance of 72.6 S cm ⁻¹ for n‐type. These exceptional performances are attributed to the synergistic enhancement of electronic mobility and optimized ion capacity. Aqueous inverters based on single‐component p(gDPP‐V‐B05) delivered a high voltage gain of 393 V V ⁻¹ , benefiting from well‐balanced n/p‐type characteristics. Notably, this material also enabled high‐performing SS‐OECTs, which retained strong transconductance and current output, and exhibited typical antiambipolar behavior. Furthermore, single‐component solid‐state inverters (SS‐inverters) achieved a record‐high voltage gain of 163 V V ⁻¹ , representing the first SS‐inverters based on AMIECs and the highest value reported for SS‐inverter systems to date. These results underscore the effectiveness of the molecular design strategy and highlight the promise of ambipolar polymeric mixed ionic‐electronic conductors (PMIECs) for scalable, solid‐state, bio‐integrated electronic circuits.