To investigate the effect of a side chain on the electrical properties of a conjugated polymer (CP), we designed two different CPs containing alkyl and ethylene glycol (EG) derivatives as side chains on the same conjugated backbone with an electron donor-acceptor (D-A) type chain configuration. PTQ-T with an alkyl side chain showed typical p-type semiconducting properties, whereas PTQ-TEG with an EG-based side chain exhibited electrically conductive behavior. Both CPs generated radical species owing to their strong D-A type conjugated structure; however, the spin density was much greater in PTQ-TEG. X-ray photoelectron spectroscopy analysis revealed that the O atoms of the EG-based side chains in PTQ-TEG were intercalated with the conjugated backbone and increased the carrier density. Upon application to a field-effect transistor sensor for PTQ-T and resistive sensor for PTQ-TEG, PTQ-TEG exhibited a better NO₂ detection capability with faster signal recovery characteristics than PTQ-T. Compared with the relatively rigid alkyl side chains of PTQ-T, the flexible EG-based side chains in PTQ-TEG have a higher potential to enlarge the free volume as well as improve NO₂-affinity, which promotes the diffusion of NO₂ in and out of the PTQ-TEG film, and ultimately resulting in better NO₂ detection capabilities.

To explore a highly conductive flexible platform, this study develops PIDF-BT@SWCNT by wrapping single-walled carbon nanotubes (SWCNTs) with a conjugated polymer, PIDF-BT, known for its effective doping properties. By evaluating the doping behaviors of various dopants on PIDF-BT, appropriate dopant combinations for cascade doping are selected to improve the doping efficiency of PIDF-BT@SWCNT. Specifically, using F4TCNQ or F6TCNNQ as the first dopant, followed by AuCl₃ as the second dopant, demonstrates remarkable doping efficiency, surpassing that of the individual dopants and yielding an exceptional electrical conductivity exceeding 6000 S/cm. Characterization using X-ray photoelectron spectroscopy and Raman spectroscopy elucidates the doping mechanism, revealing an increase in the proportion of electron-donating atoms and the ratio of quinoid structures upon F4TCNQ/AuCl₃ cascade doping. These findings offer insights into optimizing dopant combinations for cascade doping, showcasing its advantages in enhancing doping efficiency and resulting electrical conductivity compared with single dopant processes.

This review provides a comprehensive overview of molecular doping in organic semiconductors (OSCs), with particular emphasis on the mechanistic understanding of doping processes, rational material design strategies, and processing approaches for achieving high doping efficiency and stability. We discuss fundamental doping mechanisms, including integer charge transfer and orbital hybridization models, and highlight how molecular structure, polymer design, and dopant–host interactions influence electrical performance. Recent advances in processing strategies—such as sequential, vapor-phase, and hybrid doping methods—are also summarized in relation to microstructural control and charge transport optimization. In addition, the implications of molecular doping for emerging organic thermoelectric applications are addressed, emphasizing the interplay between dopant distribution, morphology, and device performance. By integrating mechanistic insights, material design principles, and application perspectives, this review aims to provide a unified framework for researchers in organic electronics, materials science, and thermoelectric device engineering seeking to develop highly efficient and stable molecularly doped organic conductors.