Extending Schottky–Mott rule to van der Waals heterostructures of 2D Janus materials: Influence of intrinsic dipoles

The Schottky–Mott (S–M) limit based on the S–M rule is often used to evaluate the Schottky barrier height (SBH) at metal–semiconductor (MS) van der Waals (vdW) contacts but fails at the polar interfaces. In order to extend the S–M rule to the polar interfaces, we here modify the S–M equation to predict the SBH at vdW interfaces of 2D Janus materials, taking into account the effects of intrinsic and interface dipoles. The modified S–M equation is verified based on the first-principles calculations of the MoSi2As2P2/HTaSe2F vdW interfaces, showing a sharp dependence of SBH on the dipole amplitude and direction. Specifically, n-type Schottky barriers tend to form when a semiconductor contacts with a low-work-function surface of Janus metal or a metal interfaces to the high-electron-affinity surface of Janus semiconductor; otherwise, a p-type one is preferable. Interestingly, the smallest n(p)-type SBH could be attained when both intrinsic dipole directions are the same. This work demonstrates that the S–M rule can be extended to the polar interfaces and dipole engineering is an effective strategy to tune the SBH at the MS interface.