Linking Electronic and Structural Disorder Parameters to Carrier Transport in a Modern Conjugated Polymer.

Understanding charge transport in conjugated polymers is crucial for the development of next-generation organic electronic applications. It is presumed that structural disorder in conjugated polymers originating from their semicrystallinity, processing, or polymorphism leads to a complex energetic landscape that influences charge carrier transport properties. However, the link between polymer order parameters and energetic landscape is not well established experimentally. In this work, we successfully link statistical surveys of the local polymer electronic structure with paracrystalline structural disorder, a measure of statistical fluctuations away from the ideal polymer packing structure. We use scanning tunneling microscopy/spectroscopy to measure spatial variability in electronic band edges in PM6 films, a high-performance conjugated polymer, and find that films with higher paracrystallinity exhibit greater electronic disorder, as expected. In addition, we show that macroscopic charge carrier mobility in field effect transistors and and trap influence in hole-only diode devices is positively correlated with these microscopic structural and electronic parameters.