Resolidified Chalcogen‐Assisted Growth of Bilayer Semiconductors with Controlled Stacking Orders

Abstract Bilayer semiconductors have attracted much attention due to their stacking‐order‐dependent properties. However, as both 3R‐ and 2H‐stacking are energetically stable at high temperatures, most of the high‐temperature grown bilayer materials have random 3R‐ or 2H‐stacking orders, leading to non‐uniformity in optical and electrical properties. Here, a chemical vapor deposition method is developed to grow bilayer semiconductors with controlled stacking order by modulating the resolidified chalcogen precursors supply kinetics. Taking tungsten disulfide (WS 2 ) as an example, pure 3R‐stacking (100%) and 2H‐stacking dominated (87.6%) bilayer WS 2 are grown by using this method and both show high structural and optical quality and good uniformity. Importantly, the bilayer 3R‐stacking WS 2 shows higher field effect mobility than 2H‐stacking samples, due to the difference in stacking order‐dependent surface potentials. This method is universal for growing other bilayer semiconductors with controlled stacking orders including molybdenum disulfide and tungsten diselenide, paving the way to exploit stacking‐order‐dependent properties of these family of emerging bilayer materials.