Electrochemical Fabrication and Characterization of Organic Electrochemical Transistors Using poly(3,4-ethylenedioxythiophene) with Various Counterions

Organic electrochemical transistors (OECTs) are promising bioelectronic devices, especially because of their ability to transport charge both ionically and electronically. Conductive polymers are typically used as the active materials of OECTs. Crosslinked, cast, and dried films of commercially available poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) suspensions are commonly and widely used for OECTs so far. Electrochemical polymerization of PEDOT from 3,4-ethylenedioxythiophene (EDOT) monomer can also be used to fabricate OECTs; however, this approach has not been investigated in as much detail. In particular, the role of various counterions that can be incorporated into the PEDOT films of OECTs has not been systematically studied. Here, we report the electrochemical fabrication and characterization of OECTs using PEDOT with several different counterion salts including lithium perchlorate (LiClO₄), sodium p-toluene sulfonate (pTS), and poly(sodium 4-styrene sulfonate) (PSS). We found that the characteristic dimensions of PEDOT films deposited on the electrodes could be precisely controlled by total charge density, with a nominal thickness of about one micron requiring a current density of about 0.6 C/cm² regardless of the choice of counterion. The films with the PSS counterion were relatively smooth, while PEDOT films prepared with the pTS and LiClO₄ were much rougher due to the sizes of counterions. The PEDOT films with pTS and PSS grew along the substrate surface (in-plane direction) much faster than with LiClO₄. The maximum transconductance (g_m) of a PEDOT OECT was 46 mS with pTS as the counterion with the high on-current level (>10 mA) based on the large channel area. These results provide an effective and efficient way to fabricate OECTs with various monomers and additives as active materials in order to modify the device characteristics for further applications.