Tuning Valleys and Wave Functions of van der Waals Heterostructures by Varying the Number of Layers: A First‐Principles Study

Abstract In van der Waals heterostructures of 2D transition‐metal dichalcogenides (2D TMDCs) electron and hole states are spatially localized in different layers forming long‐lived interlayer excitons. Here, the influence of additional electron or hole layers on the electronic properties of a MoS₂/WSe₂ heterobilayer (HBL), which is a direct bandgap material, is investigated from first principles. Additional layers modify the interlayer hybridization, mostly affecting the quasiparticle energy and real‐space extend of hole states at the Γ and electron states at the Q valleys. For a sufficient number of additional layers, the band edges move from K to Q or Γ, respectively. Adding electron layers to the HBL leads to more delocalized K and Q states, while Γ states do not extend much beyond the HBL, even when more hole layers are added. These results suggest a simple and yet powerful way to tune band edges and the real‐space extent of the electron and hole wave functions in TMDC heterostructures, potentially affecting strongly the lifetime and dynamics of interlayer excitons.