Understanding the growth mechanisms of 2D van der Waals (vdW) heterostructures is of great importance in exploring their functionalities and device applications. A custom-built system integrating physical vapor deposition and optical microscopy/Raman spectroscopy is employed to study the dynamic growth processes of 2D vdW heterostructures in situ. This allows the identification of a new growth mode with a distinctly different growth rate and morphology from those of the conventional linear growth mode. A model that explains the difference in morphologies and quantifies the growth rates of the two modes by taking the role of surface diffusion into account is proposed. A range of material combinations including CdI 2 /WS 2 , CdI 2 /MoS 2 , CdI 2 /WSe 2 , PbI 2 /WS 2 , PbI 2 /MoS 2 , PbI 2 /WSe 2 , and Bi 2 Se 3 /WS 2 is systematically investigated. These findings may be generalized to the synthesis of many other 2D heterostructures with controlled morphologies and physical properties, benefiting future device applications.

Realizing van der Waals (vdW) epitaxy in the 80's represents a breakthrough that circumvents the stringent lattice matching and processing compatibility requirements in conventional covalent heteroepitaxy. However, due to the weak vdW interactions, there is little control over film qualities by the substrate. Typically, discrete domains with a spread of misorientation angles are formed, limiting the applicability of vdW epitaxy. Here we report the epitaxial growth of monocrystalline, covalent Cr5Te8 2D crystals on monolayer vdW WSe2 by chemical vapor deposition, driven by interfacial dative bond formation. The lattice of Cr5Te8, with a lateral dimension of a few ten microns, is fully commensurate with that of WSe2 via 3 × 3 (Cr5Te8)/7 × 7 (WSe2) supercell matching, forming a single-crystalline moiré superlattice. Our work has established a conceptually distinct paradigm of thin film epitaxy termed "dative epitaxy", which takes full advantage of covalent epitaxy with chemical bonding for fixing the atomic registry and crystal orientation, while circumventing its stringent lattice matching and processing compatibility requirements; conversely, it ensures the full flexibility of vdW epitaxy, while avoiding its poor orientation control. Cr5Te8 2D crystals grown by dative epitaxy exhibit square magnetic hysteresis, suggesting minimized interfacial defects that can serve as pinning sites.

In this work, a chemical vapor deposition (CVD) method was developed for the synthesis of transition metal dichalcogenide alloy monolayers, with a composition gradient in the radial direction. The composition gradient was achieved by controlling the substrate cooling rate during the CVD growth. The two types of alloys, namely, WS2(1−x)Se2x and MoS2(1−x)Se2x, were found to exhibit an opposite composition gradient. This is attributed to their different cohesive energies. A two-dimensional Ising model is used to explain the growth mechanism, where two ends of the composition were modeled as a magnetically ordered phase and a paramagnetic phase. The composition as a function of substrate temperature is then represented by the thermal magnetization curve.