Descriptor-Based Classification of Interfacial Electronic Coupling in Janus XP3-Based 2D Heterostructures

Abstract

Understanding and controlling interfacial electronic coupling in two-dimensional (2D) heterostructures is essential for designing functional materials for electronic, optoelectronic, and catalytic applications. Here, we investigate vertical heterobilayers constructed from two distinct XP3 monolayers (X = As, Ge, Sb, Bi, Sn, Al, Ga, and Pb) using first-principles density functional theory. The resulting Janus heterobilayers are energetically favorable and elastically stable, with electronic band gaps ranging from metallic and near-metallic to semiconducting regimes. Interlayer interactions induce significant band renormalization, including transitions between type I and type II alignment upon structural relaxation. To rationalize these effects, we establish a descriptor-based framework based on the metal metal interlayer distance, interfacial electron localization, and Bader charge redistribution. This combined analysis discriminates vdW-like, polar covalent, and ionic interaction regimes, with systematic trends governed by the average atomic number of the constituent elements. Optical absorption calculations indicate visible-to-near-infrared activity in selected systems, and band-edge alignment identifies promising candidates for selective redox processes. Overall, the proposed descriptor-based strategy provides a physically grounded route for identifying and engineering interfacial coupling in XP3 heterostructures and can be extended to other classes of two-dimensional material interfaces.