C₆₀self-orientation on hexagonal boron nitride induced by intermolecular coupling

A deep grasp of the properties of the interface between organic molecules and hexagonal boron nitride (h-BN) is essential for the full implementation of these two building blocks in the next generation of electronic devices. Here, using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), we report on the geometric and electronic features of C₆₀evaporated on a single layer of h-BN grown on a Rh(110) surface under ultra-high vacuum. Two different molecular assemblies of C₆₀on the h-BN/Rh(110) surface were observed. The first STM study at room temperature (RT) and at low temperatures (40 K) looked at the molecular orientation of C₆₀on a two-dimensional layered material. Intramolecular-resolution images demonstrate the existence of a phase transition of C₆₀over the h-BN/Rh(110) surface similar to that found on bulk solid C₆₀. At RT molecules exhibit random orientations, while at 40 K such rotational disorder vanishes and they adopt a common orientation over the h-BN/Rh(110) surface. The decrease in thermal energy allows recognition between C₆₀molecules, and they become equally oriented in the configuration at which the van der Waals intermolecular interactions are optimized. Bias-dependent submolecular features obtained by means of high-resolution STM images are interpreted as the highest occupied and lowest unoccupied molecular orbitals. STS data showed that fullerenes are electronically decoupled from the substrate, with a negligible charge transfer effect if any. Finally, the very early stages of multilayer growth were also investigated.