Two-Dimensional to Three-Dimensional Growth of Transition Metal Diselenides by Chemical Vapor Deposition: Interplay between Fractal, Dendritic, and Compact Morphologies

We investigate the role of growth temperature and metal/chalcogen flux in atmospheric pressure chemical vapor deposition growth of MoSe2 and WSe2 on Si/SiO2 substrates. Using scanning electron microscopy and atomic force microscopy, we observe that the growth temperature and transition metal flux strongly influence the domain morphology, and the compact triangular or hexagonal domains ramify into branched structures as the growth temperature (metal flux) is decreased (increased). The competition between adatom attachment to the domain edges and diffusion of adatoms along the domain boundary determines the evolution of the observed growth morphology. Depending on the growth temperature and flux, two different branched structures- fractals and dendrites-grow. The fractals (with a dimension of similar to 1.67) obey a diffusion-limited aggregation mechanism, whereas the dendrites with a higher fractal dimension of similar to 1.80 exhibit preferential growth along the symmetry-governed directions. The effect of chalcogen environment is studied, where a Se-rich condition helps restrict Mo-rich nucleus formation, promoting lateral growth. For a Se-deficient environment, several multilayer islands cluster on two-dimensional domains, suggesting a transition from lateral to vertical growth because of insufficient Se passivation. X-ray photoelectron spectroscopy analysis shows a near perfect stoichiometry (Mo/Se = 1:1.98) of MoSe2 grown in a Se-rich environment, whereas in the Se-deficient condition, a ratio of Mo/Se = 1:1.68 is observed. This also supports the formation of metal-rich nuclei (Mo1+xSe2-x) under Se-deficient conditions, leading to three-dimensional clustering. Tuning the growth temperature and metal/chalcogen flux, we propose an optimized CVD growth window for synthesizing large-area Mo(W) selenide.