On the Origin of Seebeck Coefficient Inversion in Highly Doped Conducting Polymers. (5th February 2022)

• Record Type: Journal Article
• Authors: Xu, Kai; Ruoko, Tero‐Petri; Shokrani, Morteza; Scheunemann, Dorothea; Abdalla, Hassan; Sun, Hengda; Yang, Chi‐Yuan; Puttisong, Yuttapoom; Kolhe, Nagesh B.; Figueroa, José Silvestre Mendoza; Pedersen, Jonas O.; Ederth, Thomas; Chen, Weimin M.; Berggren, Magnus; Jenekhe, Samson A.; Fazzi, Daniele; Kemerink, Martijn; Fabiano, Simone
• Is Part Of: Advanced functional materials. Volume 32:Number 20(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-02-05
• Subjects: conducting polymers -- organic electrochemical transistor -- Seebeck coefficient -- thermoelectric application; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202112276
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: A common way of determining the majority charge carriers of pristine and doped semiconducting polymers is to measure the sign of the Seebeck coefficient. However, a polarity change of the Seebeck coefficient has recently been observed to occur in highly doped polymers. Here, it is shown that the Seebeck coefficient inversion is the result of the density of states filling and opening of a hard Coulomb gap around the Fermi energy at high doping levels. Electrochemical n‐doping is used to induce high carrier density (>1 charge/monomer) in the model system poly(benzimidazobenzophenanthroline) (BBL). By combining conductivity and Seebeck coefficient measurements with in situ electron paramagnetic resonance, UV–vis–NIR, Raman spectroelectrochemistry, density functional theory calculations, and kinetic Monte Carlo simulations, the formation of multiply charged species and the opening of a hard Coulomb gap in the density of states, which is responsible for the Seebeck coefficient inversion and drop in electrical conductivity, are uncovered. The findings provide a simple picture that clarifies the roles of energetic disorder and Coulomb interactions in highly doped polymers and have implications for the molecular design of next‐generation conjugated polymers. Abstract : An inversion in the sign of the Seebeck coefficient is observed in highly doped conducting polymers, and the sign change typically correlates with a decrease in the electrical conductivity. The Seebeck coefficient inversion and electrical conductivity drop originate from state filling and opening of a hard Coulomb gap around the Fermi energy.