Despite the growing interest in dynamic behaviors at the frequency domain, there exist very few studies on molecular orientation-dependent transient responses of organic mixed ionic–electronic conductors. In this research, we investigated the effect of ion injection directionality on transient electrochemical transistor behaviors by developing a model mixed conductor system. Two polymers with similar electrical, ionic, and electrochemical characteristics but distinct backbone planarities and molecular orientations were successfully synthesized by varying the co-monomer unit (2,2’-bithiophene or phenylene) in conjunction with a novel 1,4-dithienylphenylene-based monomer. The comprehensive electrochemical analysis suggests that the molecular orientation affects the length of the ion-drift pathway, which is directly correlated with ion mobility, resulting in peculiar OECT transient responses. These results provide the general insight into molecular orientation-dependent ion movement characteristics as well as high-performance device design principles with fine-tuned transient responses.
C.B.N. and M.-H.Y. acknowledge support from the Medical Research Council and the Korea Health Industry Development Institute (UK-Korean Partnering Award MC_PC_18066). C.B.N. acknowledges the European Commission for financial support through the MITICS H2020-EU-FET Open project (No. 964677). M.-H.Y. acknowledges a National Research Foundation (NRF) grant funded by the Korean government (MSIT) (NRF-2018M3A7B4070988, NRF-2021R1A2C1013015, NRF-2020M3D1A1030660, NRF-2020M1A2A2080748, and NRF-2017K1A1A2013153).