Substrate Induced van der Waals Force Effects on the Stability of Violet Phosphorus

Since the first isolation of graphene, the importance of van der Waals (vdW) interactions has become increasingly recognized in the burgeoning field of layered materials. In this work, infrared nanoimaging techniques and theoretical modeling are used to unravel the critical role played by interfacial vdW interactions in governing the stability of violet phosphorus (VP)—a recently rediscovered wide bandgap p‐type semiconductor—when exfoliated on different substrates. It is demonstrated that vdW interactions with the underlying substrate can have a profound influence on the stability of exfoliated VP flakes and investigate how these interactions are affected by flake thickness, substrate properties (e.g., substrate hydrophilicity, surface roughness), and the exfoliation process. These findings highlight the key role played by interfacial vdW interactions in governing the stability and physical properties of layered materials, and can be used to guide substrate selection in the preparation and study of this important class of materials.