Insulator to semimetallic transition in conducting polymers

We report a multiscale modeling of electronic structure of a conducting polymer poly(3,4-ethylenedioxythiopehene) (PEDOT) based on a realistic model of its morphology. We show that when the charge carrier concentration increases, the character of the density of states (DOS) gradually evolves from the insulating to the semimetallic, exhibiting a collapse of the gap between the bipolaron and valence bands with the drastic increase of the DOS between the bands. The origin of the observed behavior is attributed to the effect of randomly located counterions giving rise to the states in the gap. These results are discussed in light of recent experiments. The method developed in this work is general and can be applied to study the electronic structure of other conducting polymers.
Funding Agencies|Swedish Energy Agency; Knut and Alice Wallenberg Foundation (The Tail of the Sun); Carl Tryggers Foundation; SeRC; European Research Council (ERC) [307596]