Self‐doping has emerged as an effective strategy to tailor the electronic properties of organic materials, especially for n‐type semiconductors based on perylene diimide (PDI) and naphthalene diimide (NDI). This review summarizes recent progress in the molecular design and application of self‐doped PDI/NDI systems. Representative self‐doping groups such as amines, ammonium salts, and other anionic species are introduced and classified. The effects of doping group connecting site selection, including the imide position, aromatic core, and side substitutes, on molecular and electronic properties are then discussed. The application of self‐doped PDI/NDI materials in organic electronic devices is also highlighted, covering thin‐film solar cells, organic field‐effect transistors, and organic thermoelectrics. These materials have shown the ability to improve charge injection, enhance device stability, and regulate interfacial processes. Overall, self‐doping is a promising strategy for developing high‐performance n‐type organic semiconductors. With ongoing improvements in molecular design and device engineering, self‐doped PDI/NDI materials are expected to contribute significantly to the advancement of next‐generation electronic materials and devices.
Chen et al. (Wed,) studied this question.