Side Chain Engineering toward Chemical Doping of Conjugated Polymers

ConspectusSolution-processable conjugated polymers are typically composed of two distinct structural components: rigid conjugated backbones and flexible side chains, each with unique roles and properties. The conjugated backbone forms the core framework of the polymer and is directly responsible for its optoelectronic properties, such as light absorption, emission, and charge transport. Meanwhile, the conjugated backbone can undergo chemical doping, where molecular dopants introduce charge carriers to modulate the carrier density and electrical conductivity. Therefore, the conjugated backbone is the critical determinant of the resulting optoelectronic performance. However, on the other hand, the flexible side chains, originally introduced to improve solution processability, were long considered chemically inert to the doping reaction. Recent advances have shown that the role of side chains is more than just improving solubility, demonstrating the significant impact of side chains on the packing of the conjugated backbone, film morphology, and electronic properties of conjugated polymers. Side chain engineering has become an essential design strategy for creating high-performance conjugated polymers in various applications.In this Account, we aim to emphasize the importance of side chain engineering toward controllable chemical doping of conjugated polymers, where side chain engineering allows us to tune the molecular packing, doping efficiency, and film morphology, thereby enhancing charge transport and optoelectronic performance. Specifically, the length, branching structures, and functional groups of the side chains can be systematically varied to control the solubility, miscibility, and interactions of conjugated polymers with dopants. For example, longer or branched side chains can improve solubility but may disrupt the π-π stacking between the conjugated backbones, thereby reducing the charge transport efficiency of the polymer. Shorter or linear side chains may enhance backbone packing and electronic coupling, though at the expense of reduced solubility. The impact of side chains on the doping process is particularly noteworthy. Although side chains are chemically inert to doping reactions, their design influences all three critical steps of the doping process: mixing, ionization, and carrierization. Side chains affect the spatial distribution of dopants during mixing, modulate the local environment to facilitate charge transfer during ionization, and influence the dissociation of ion pairs into free charge carriers during carrier generation. Functional side chains with polar groups, for example, can enhance dopant-polymer compatibility, while those with functional groups can modulate the dielectric environment to weaken ion pairing and promote free carrier generation. The interplay between side chains and the conjugated backbone is critical to achieving optimal optoelectronic performance in applications such as organic photovoltaics, field-effect transistors, and thermoelectrics. Rational side chain engineering provides a powerful tool to address these challenges in doping, morphology control, and charge transport, bringing more opportunities to design advanced conjugated polymers and chemical dopants tailored to specific applications.