Black Phosphorus for Directed Molecular Assembly with Weak Electronic Coupling

Abstract The combination of 2D materials with organic molecules offer the possibility to obtain low dimensional hybrid materials with tailored properties. Black phosphorus is a monoelemental semiconducting material with a nonplanar puckered atomic structure. Here, porphyrin molecules on black phosphorus are studied and it is shown that they self‐assemble with an epitaxial relationship indicating that the molecule‐surface interaction largely dominates the molecule–molecule interaction. The atomic structure of black phosphorus is found to be at the origin of the substrate driven self‐assembly. Despite this strong interaction with molecules, the electronic coupling is found to be weak allowing the molecules to maintain the properties of their gas phase, which is the usual behavior for van der Waals materials. Therefore, the combination of the peculiar puckered structure with the van der Waals nature of black phosphorus provides this material with the ability to interact strongly enough with adsorbed molecules to drive their assembly but weakly enough to keep their electronic properties intact.