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

Abstract 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.