Despite the great efforts to unveil the charge carrier behavior at the semiconductor/dielectric interface of organic field-effect transistors, an examination of the interfacial carrier distribution and the correlation with the charge transport in molecular crystalline semiconductors remains fundamental for understanding the nature of the microscopic carrier motion. Hence, an effective approach to accurately tune the carrier distribution with molecular-layer precision is essential. Here, we find that the carrier accumulation is strictly modulated in highly ordered, few-layer molecular crystalline semiconducting films by tuning the polaronic coupling between the charge carriers and dielectric. The admittance method reveals that the carriers distribute only within a monolayer with stronger localization on a high-κ dielectric and extend to a second layer with better delocalization on a low-κ dielectric. Furthermore, a unique dimensional transition in the charge transport at the dielectric interface is evidenced under a transistor architecture by temperature-dependent measurements. The presented microscopic nature of charge carriers with layer-defined precision in molecular crystalline films should provide an unprecedented opportunity in organic electronics in terms of interface engineering, quantum transport, and device physics.
Keywords: carrier distributions; charge transport dimension; few-layer molecular crystalline films; metal-oxide-semiconductor capacitors; organic field-effect transistors.