The Intrinsic Thermodynamic Difficulty and a Step‐Guided Mechanism for the Epitaxial Growth of Uniform Multilayer MoS2 with Controllable Thickness

Multilayer MoS2 shows superior performance over the monolayer MoS2 for electronic devices while the growth of multilayer MoS2 with controllable and uniform thickness is still very challenging. It is revealed by calculations that monolayer MoS2 domains are thermodynamically much more favorable than multilayer ones on epitaxial substrates due to the competition between surface interactions and edge formation, leading accordingly to a layer-by-layer growth pattern and non-continuously distributed multilayer domains with uncontrollable thickness uniformity. The thermodynamics model also suggests that multilayer MoS2 domains with aligned edges can significantly reduce their free energy and represent a local minimum with very prominent energy advantage on a potential energy surface. However, the nucleation probability of multilayer MoS2 domains with aligned edges is, if not impossible, extremely rare on flat substrates. Herein, a step-guided mechanism for the growth of uniform multilayer MoS2 on an epitaxial substrate is theoretically proposed. The steps with proper height on sapphire surface are able to guide the simultaneous nucleation of multilayer MoS2 with aligned edges and uniform thickness, and promote the continuous growth of multilayer MoS2 films. The proposed mechanism can be reasonably extended to grow multilayer 2D materials with uniform thickness on epitaxial substrates.