Effective Model Reduction Scheme for the Electronic Structure of Highly Doped Semiconducting Polymers

Highly doped organic polymers have emerged as prominent candidates within novel technological disciplines, yet the fundamental correlation between structure and charge transport characteristics still remains missing. Toward this objective, an efficient model reduction scheme for highly doped polymer chains is developed considering the paradigmatic case of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS). The reduced model accounts for the chemical and structural details of the conducting polymer chain in addition to the long-range Coulombic interactions between charge carriers (holes) and dopant ions and the Coulombic repulsion between holes residing on the PEDOT chain. The model is shown to reproduce the intrachain hole-density profile of bulk polymer chains within a mean-field description. Furthermore, and critically, the model is adept at determining the energy distribution of doped PEDOT samples that in effect, influences the hole distribution among polymer chains. The hole distribution so obtained broadly upholds the approximation of a homogeneous charge-carrier distribution in doped polymers commonly found in the literature. In addition, it is observed that the spin configuration of the charge carriers dictates the energetics of the doped chains while it is a critical function of the chain length, carrier density, and disorder parameters.