First-Principles High-Throughput Inverse Design of Direct Momentum-Matching Band Alignment van der Waals Heterostructures Utilizing Two-Dimensional Indirect Semiconductors.

Two-dimensional (2D) van der Waals (vdW) heterostructures have attracted widespread attention in photocatalysis. Herein, we employ a novel strategy utilizing first-principles high-throughput inverse design of 2D Z-scheme heterojunctions for photocatalysis. This approach is anchored in high-throughput screening conditions, which are fundamentally based on the characteristics of carrier mechanisms influenced significantly by Z-scheme heterojunctions. A pivotal element of our screening process is the integration of the indirect-to-direct bandgap transition with momentum-matching band alignment in k -space, guiding us to combine two 2D indirect bandgap monolayers into direct Z-scheme heterojunctions characterized by pronounced interlayer excitons. Various stacking modes introduce extra and distinct degrees of freedom that can be useful for tuning the properties of heterostructures, encompassing factors such as components, stacking patterns, and sequences. We demonstrate that various stacking modes can facilitate the indirect-to-direct bandgap transition and the emergence of interlayer excitons. These findings provide exciting opportunities for designing Z-scheme heterojunctions in photocatalysis.