Effects of thermal disorder on the electronic properties of ordered polymers

Abstract

The effects of thermal disorder on the electronic properties of crystalline polymers were investigated. Atomic configurations of the material were obtained using classical Monte Carlo simulations at room temperature, while electronic structure calculations were performed using the density functional theory based charge patching method and the overlapping fragment method. We investigated two different stable configurations of crystalline poly(3-hexylthiophene) (P3HT) and calculated the density of electronic states and the wave function localisation. We found that the effect of disorder in side chains is more pronounced in the more stable configuration of P3HT than in the other one due to the larger conformational freedom of side chains. The results show that disorder in main chains has a strong effect on the electronic structure and leads to the localisation of the wave functions of the highest states in the valence band, similar to localisation that occurs in amorphous polymers. The presence of such states is one possible origin of thermally activated electrical transport in ordered polymers at room temperature.