The development of n-type conjugated polymers with high electrical conductivity (σ) has continued to pose a massive challenge in organic thermoelectrics (OTEs). New structural insights into the charge-carrier transport are necessitated for the realization of high-performance OTEs. In this study, three new n-type copolymers, named pNB, pNB-Tz, and pNB-TzDP, consisting of naphthodithiophenediimide (NDTI) and bithiopheneimide (BTI) units, are synthesized by direct arylation polymerization. The backbone orientation is altered by incorporating thiazole units into the backbone and tuning the branching point of the side chain. The alteration of the backbone orientation from face-on to bimodal orientation with both face-on and edge-on fractions significantly impacts the σ and the power factors (PFs) of the polymers. As a result, pNB-TzDP, with the bimodal orientation, demonstrates a high σ of up to 11.6 S cm−1 and PF of up to 53.4 µW m−1 K−2, which are among the highest in solution-processed n-doped conjugated polymers reported so far. Further studies reveal that the bimodal orientation of pNB-TzDP introduces 3D conduction channels and leads to better accommodation of dopants, which should be the key factors for the excellent thermoelectric performance.
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