Fabrication of Oriented n‐Type Thermoelectric Polymers by Polarity Switching in a DPP‐Based Donor–Acceptor Copolymer Doped with FeCl3

Abstract n‐Type‐doped polymers are key elements to fabricate all‐polymer thermoelectric generators but they are challenging to produce. Herein, a new strategy is proposed, which is based on polarity switching upon doping of a donor–acceptor (D–A) copolymer based on diketopyrrolopyrrol (DPP) and quintethiophene (5T) with FeCl 3 . Polarity switching from p‐type to n‐type is observed upon increasing the doping concentration of FeCl 3 . An analysis based on nonmonotonic density of states is proposed, which accounts for the main experimental trends and demonstrates that the polarity switch is governed by the electronic band filling that is determined by the dopant concentration. The influence of the curvature of the density of states is in addition discussed and a complete description of the doping induced transport regimes is proposed. This polarity switching depends on the molecular weight M n of the polymer and shifts to higher FeCl 3 concentrations with increasing M n . This behavior is attributed to the change of the width of the density of states with M n . The combination of polarity switching and alignment is a means to produce n‐type‐like oriented and conducting polymers with enhanced power factors up to 10 µW K −2 m −1 along the chain direction.