Molecular Engineering for Enhanced Thermoelectric Performance of Single‐Walled Carbon Nanotubes/π‐Conjugated Organic Small Molecule Hybrids

Hybridizing single‐walled carbon nanotubes (SWCNTs) with π‐conjugated organic small molecules (π‐OSMs) offers a promising approach for producing high‐performance thermoelectric (TE) materials through the facile optimization of the molecular geometry and energy levels of π‐OSMs. Designing a twisted molecular structure for the π‐OSM with the highest occupied molecular orbital energy level comparable to the valence band of SWCNTs enables effective energy filtering between the two materials. The SWCNTs/twisted π‐OSM hybrid exhibits a high Seebeck coefficient of 110.4 ± 2.6 µV K(−1), leading to a significantly improved power factor of 2,136 µW m(−1) K(−2), which is 2.6 times higher than that of SWCNTs. Moreover, a maximum figure of merit over 0.13 at room temperature is achieved via the efficient TE transport of the SWCNTs/twisted π‐OSM hybrid. The study highlights the promising potential of optimizing molecular engineering of π‐OSMs for hybridization with SWCNTs to create next‐generation, efficient TE materials.