Thermoelectric (TE) materials are important for the sustainable development because they enable the direct harvesting of low‐quality heat into electricity. Among them, conducting polymers have attracted great attention arising from their advantages, such as flexibility, nontoxicity, easy availability, and intrinsically low thermal conductivity. In this work, a novel and facile method is reported to significantly enhance the TE property of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films through sequential post‐treatments with common acids and bases. Compared with the as‐prepared PEDOT:PSS, both the Seebeck coefficients and electrical conductivities can be remarkably enhanced after the treatments. The oxidation level, which significantly impacts the TE property of the PEDOT:PSS films, can also be well tuned by controlling the experimental conditions during the base treatment. The optimal PEDOT:PSS films can have a Seebeck coefficient of 39.2 µV K−1 and a conductivity of 2170 S cm−1 at room temperature, and the corresponding power factor is 334 µW (m−1 K−2). The enhancement in the TE properties is attributed to the synergetic effect of high charge mobility by the acid treatment and the optimal oxidation level tuned by the base treatment.
PSS films were studied as the transparent electrode of polymer solar cells. The photovoltaic efficiency is comparable to that with an ITO transparent electrode.
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