Revealing and Controlling Energy Barriers and Valleys at Grain Boundaries in Ultrathin Organic Films

Abstract In organic electronics, local crystalline order is of critical importance for the charge transport. Grain boundaries between molecularly ordered domains are generally known to hamper or completely suppress charge transfer and detailed knowledge of the local electronic nature is critical for future minimization of such malicious defects. However, grain boundaries are typically hidden within the bulk film and consequently escape observation or investigation. Here, a minimal model system in form of monolayer‐thin films with sub‐nm roughness of a prototypical n‐type organic semiconductor is presented. Since these films consist of large crystalline areas, the detailed energy landscape at single grain boundaries can be studied using Kelvin probe force microscopy. By controlling the charge‐carrier density in the films electrostatically, the impact of the grain boundaries on charge transport in organic devices is modeled. First, two distinct types of grain boundaries are identified, namely energetic barriers and valleys, which can coexist within the same thin film. Their absolute height is found to be especially pronounced at charge‐carrier densities below 10 ¹² cm ^{– 2} —the regime at which organic solar cells and light emitting diodes typically operate. Finally, processing conditions by which the type or energetic height of grain boundaries can be controlled are identified.