| Summary: | In this study, a benzodithiophene (BDT)-based donor (D)–acceptor (A) polymer containing carbazole segment in the side-chain was designed and synthesized and the thermoelectric composites with 50 wt % of single walled carbon nanotubes (SWCNTs) were prepared via ultrasonication method. Strong interfacial interactions existed in both of the composites before and after immersing into the 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F<sub>4</sub>TCNQ) solution as confirmed by UV-Vis-NIR, Raman, XRD and SEM characterizations. After doping the composites by F<sub>4</sub>TCNQ, the electrical conductivity of the composites increased from 120.32 S cm<sup>−1</sup> to 1044.92 S cm<sup>−1</sup> in the room temperature. With increasing the temperature, the electrical conductivities and Seebeck coefficients of the undoped composites both decreased significantly for the composites; the power factor at 475 K was only 6.8 μW m<sup>−1</sup> K<sup>−2</sup>, which was about nine times smaller than the power factor at room temperature (55.9 μW m<sup>−1</sup> K<sup>−2</sup>). In the case of doped composites, although the electrical conductivity was deceased from 1044.9 S cm<sup>−1</sup> to 504.17 S cm<sup>−1</sup>, the Seebeck coefficient increased from 23.76 μV K<sup>−1</sup> to 35.69 μW m<sup>−1</sup> K<sup>−2</sup>, therefore, the power factors of the doped composites were almost no change with heating the composite films.
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