Structural Modifications for Tuning Performance and Operational Modes in n-Type Organic Electrochemical Transistors.

Organic mixed ionic-electronic conductors (OMIECs) are crucial in defining the operational modes and performance of organic electrochemical transistors (OECTs). However, studies on the design and structure-performance correlations of small-molecule n-type OMIECs remain scarce. Herein, we designed and synthesized a series of naphthalene diimide (NDI)-based n-type small molecules by extending π-conjugation and increasing the number of electron-withdrawing groups, achieving performance optimization and even changes in operational modes through structural regulations. OECTs based on exhibit a low threshold voltage of -0.022 V, which is the lowest reported for n-type channel materials to date. , synthesized through π-expansion of , maintains a low threshold voltage of -0.041 V and achieves 2 orders of magnitude improvement in electron mobility (1.04 × 10 cm V s) owing to its mixed edge-on and face-on orientation. Specifically, by further increasing the number of electron-withdrawing groups, attains a sufficiently low LUMO energy level (-4.51 eV), enabling a spontaneous reduction in 0.1 M NaCl solution without external bias, thereby achieving self-doping. Consequently, it exhibits n-depletion-mode characteristics with a transconductance value of 287 μS. Moreover, devices made with show exceptional stability, retaining 98% of the initial drain current after 150 min operation. These results provide insights into the understanding and design of n-type mixed ionic-electronic conductor materials.