3D Crystal Construction by Single‐Crystal 2D Material Supercell Multiplying

Abstract 2D stacking presents a promising avenue for creating periodic superstructures that unveil novel physical phenomena. While extensive research has focused on lateral 2D material superstructures formed through composition modulation and twisted moiré structures, the exploration of vertical periodicity in 2D material superstructures remains limited. Although weak van der Waals interfaces enable layer‐by‐layer vertical stacking, traditional methods struggle to control in‐plane crystal orientation over large areas, and the vertical dimension is constrained by unscalable, low‐throughput processes, preventing the achievement of global order structures. In this study, a supercell multiplying approach is introduced that enables high‐throughput construction of 3D superstructures on a macroscopic scale, utilizing artificially stacked single‐crystalline 2D multilayers as foundational repeating units. By employing wafer‐scale single‐crystalline 2D materials and referencing the crystal orientation of substrates, the method ensures precise alignment of crystal orientation within and across each supercell, thereby achieving controllable periodicity along all three axes. A centimeter‐scale 3R‐MoS₂ crystal is successfully constructed, comprising over 200 monolayers of single‐crystalline MoS₂, through a bottom‐up stacking process. Additionally, the approach accommodates the integration of amorphous oxide, enabling the assembly of 3D non‐linear optical crystals with quasi‐phase matching. This method paves the way for the bottom‐up construction of macroscopic artificial 3D crystals with atomic plane precision, enabling tailored optical, electrical, and thermal properties and advancing the development of novel artificial materials and high‐performance applications.