Morphology of conducting polymer blends at the interface of conducting and insulating phases: insight from PEDOT:PSS atomistic simulations

Having phase-separated conductive and less-conductive domains is a common morphology in semiconducting polymer blends as it exists in the case of PEDOT:PSS, which is a representative example with a wide range of applications. In this paper, we constructed atomistic models for the interface between the PEDOT-rich (conductive) grains and the PSS-rich (less-conductive) phase through molecular dynamics simulations. Our models are obtained from experimentally relevant compositions, based on precise force field parameters, and through a robust relaxation procedure. We show that both PEDOT-rich and PSS-rich phases consist of PEDOT lamellae embedded in PSS chains. The size of these lamellae depends on the PEDOT concentration in each phase and our model predictions are in quantitative agreement with the experimental data. Furthermore, our models suggest that neither the phases nor the interfaces are entirely connected by π–π stacking. Thus, inter-lamellae tunnelling is essential for both intra- and inter-grain charge transport. We also show that a small increase (≈8 wt%) in the PEDOT concentration results in rather larger lamellae sizes, considerably more oriented lamellae, and slightly better inter-lamellae connectivity, which result in enhanced intra-grain conductivity. Moreover, we show how enhancing phase separation between PEDOT-rich and PSS-rich domains (similar to the effect of polar co-solvents), i.e., pulling out PEDOT from the PSS-rich phase and adding it in the PEDOT-rich phase, highly enhances the intra-grain connectivity but decreases the inter-grain conduction paths through the interface. Our results explain how the marginal extra degree of phase separation (based on experimentally obtained values) could result in a great enhancement in the overall film conductivity.