Molecular Self-Assembly in a Poorly Screened Environment: F₄TCNQ on Graphene/BN

We report a scanning tunneling microscopy and noncontact atomic force microscopy study of close-packed 2D islands of tetrafluoro­tetracyanoquinodimethane (F₄TCNQ) molecules at the surface of a graphene layer supported by boron nitride. While F₄TCNQ molecules are known to form cohesive 3D solids, the intermolecular interactions that are attractive for F₄TCNQ in 3D are repulsive in 2D. Our experimental observation of cohesive molecular behavior for F₄TCNQ on graphene is thus unexpected. This self-assembly behavior can be explained by a novel solid formation mechanism that occurs when charged molecules are placed in a poorly screened environment. As negatively charged molecules coalesce, the local work function increases, causing electrons to flow into the coalescing molecular island and increase its cohesive binding energy