Interfacial Coupling Controls Molecular Epitaxy of HMTP on Graphene/SiC.

Epitaxial growth critically influences the structural and electronic properties of organic semiconductors. Graphene serves as a prominent van der Waals template for molecular self-assembly; however, graphene on SiC is intrinsically heterogeneous, with decoupled monolayer graphene coexisting with residuals of a covalently bound buffer layer, which may affect molecular ordering. Here, we track the ordering of the molecular donor, 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), from the first layer to thin films, combining low-energy electron microscopy and diffraction with X-ray diffraction. HMTP forms highly ordered epitaxial layers on single-layer graphene, whereas growth on the buffer layer initiates as amorphous and evolves into polycrystalline films with weak orientation with respect to the substrate. Crucially, hydrogen intercalation decouples the buffer layer, converting it into quasi-freestanding monolayer graphene and restoring epitaxial growth. These findings demonstrate that interfacial coupling governs molecular epitaxy on graphene/SiC, and interface engineering via hydrogen intercalation provides a scalable route to control organic thin-film crystallinity on graphene.