An n‐type Polymer with High‐Performance Thermoelectric Properties by Solvent‐Mediated Oxidation

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Abstract Organic thermoelectric (OTE) materials are interesting because they can have the merits of high mechanical flexibility, lightweight, and low or no toxicity over inorganic thermoelectric (TE) materials. Both p ‐ and n ‐type OTE materials are required for efficient TE conversion. But the performance of n ‐type OTE materials lags well behind their p ‐type counterparts. Herein, the great enhancement in the TE properties of poly(benzodifurandione) (PBFDO) films through a treatment with a solution of FeCl 3 with dimethyl sulfoxide (DMSO) as the solvent is reported. This can greatly enhance the Seebeck coefficient and thus the power factor of PBFDO. The optimal power factor is 306.1 ± 8.7 µW m −1 K −2 , and the corresponding electrical conductivity and Seebeck coefficient are 970 ± 26 S cm −1 and −56.2 ± 1.6 µV K −1 , respectively. This is the highest power factor for n ‐type OTEs. The corresponding ZT value is 0.27 ± 0.01 at room temperature. The TE properties depend on the solvent of the FeCl 3 solution. A solvent with a high donor number, like DMSO, can share its electrons with PBFDO. It can hinder the dedoping of PBFDO by Fe 3+ and thus greatly enhance the Seebeck coefficient while not lowering the electrical conductivity too much.

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