Mixed Ionic and Electronic Conduction in Small-Molecule Semiconductors

Small-molecule organic semiconductors have displayed remarkable electronic properties with a multitude of π-conjugated structures developed and fine-tuned over recent years to afford highly efficient hole- and electron-transporting materials. Already making a significant impact on organic electronic applications including organic field-effect transistors and solar cells, this class of materials is also now naturally being considered for the emerging field of organic bioelectronics. In efforts aimed at identifying and developing (semi)conducting materials for bioelectronic applications, particular attention has been placed on materials displaying mixed ionic and electronic conduction to interface efficiently with the inherently ionic biological world. Such mixed conductors are conveniently evaluated using an organic electrochemical transistor, which further presents itself as an ideal bioelectronic device for transducing biological signals into electrical signals. Here, we review recent literature relevant for the design of small-molecule mixed ionic and electronic conductors. We assess important classes of p- and n-type small-molecule semiconductors, consider structural modifications relevant for mixed conduction and for specific interactions with ionic species, and discuss the outlook of small-molecule semiconductors in the context of organic bioelectronics.