Morphological design strategies to tailor out-of-plane charge transport in conjugated polymer systems for device applications

The transport of charge carriers throughout an active conjugated polymer (CP) host, characterized by a heterogeneous morphology of locally varying degrees of order and disorder, profoundly influences the performance of CP-based electronic devices, including diodes, photovoltaics, sensors, and supercapacitors. Out-of-plane charge carrier mobilities (μout-of-plane) across the bulk of the active material host and in-plane mobilities (μin-plane) parallel to a substrate are highly sensitive to local morphological features along their migration pathways. In general, the magnitudes of μout-of-plane and μin-plane are very different, in part because these carriers experience different morphological environments along their migration pathways. Suppressing the impact of variations in the morphological order/disorder on carrier migration remains an important challenge. While much is known about μin-plane and its optimization for devices, the current challenges are associated with μout-of-plane and its optimization for device performance. Therefore, this review is devoted to strategies for improving μout-of-plane in neat CP films and the implications for more complex systems, such as D:A blends which are relevant to OPV devices. The specific strategies discussed for improving μout-of-plane include solvent/field processing methods, chemical modification, thickness confinement, chemical additives, and different post-annealing strategies, including annealing with supercritical fluids. This review leverages the most recent fundamental understanding of mechanisms of charge transport and connections to morphology, identifying robust design strategies for targeted improvements of μout-of-plane.