Understanding transport phenomena in conducting polymers (CP) is a main issue in order to optimize their performance and despite intense investigations, the influence of their microstructure remains controversial. By analyzing the thermoelectric measurements performed on highly oriented and non-oriented CP films, we show that an Heterogeneous Oriented Structure (HOSt) model considering both ordered and disordered domains is able to account for the thermoelectric transport in CP. This model unveils the key role of the crystallinity, the anisotropy and the alignment degree of these domains. It points out the importance of the thermal conductivity in the interpretation of the thermopower [Formula: see text] and explains the frequently observed electrical conductivity [Formula: see text] cut-off in the [Formula: see text] curves due to the disordered domains. By varying the alignment degree depending on the orientation and the anisotropy according to the face-on or the edge-on polymers conformation, the HOSt model successfully describes the overall measured thermoelectric properties by demonstrating its applicability to a wide variety of both oriented and non-oriented CP.
© 2023. The Author(s).