Role of Bilayer Graphene Microstructure on the Nucleation of WSe₂ Overlayers

Over the past few years, graphene grown by chemical vapor deposition (CVD) has gained prominence as a template to grow transition metal dichalcogenide (TMD) overlayers. The resulting two-dimensional (2D) TMD/graphene vertical heterostructures are attractive for optoelectronic and energy applications. However, the effects of the microstructural heterogeneities of graphene grown by CVD on the growth of the TMD overlayers are relatively unknown. Here, we present a detailed investigation of how the stacking order and twist angle of CVD graphene influence the nucleation of WSe₂ triangular crystals. Through the combination of experiments and theory, we correlate the presence of interlayer dislocations in bilayer graphene with how WSe₂ nucleates, in agreement with the observation of a higher nucleation density of WSe₂ on top of Bernal-stacked bilayer graphene versus twisted bilayer graphene. Scanning/transmission electron microscopy (S/TEM) data show that interlayer dislocations are present only in Bernal-stacked bilayer graphene but not in twisted bilayer graphene. Atomistic ReaxFF reactive force field molecular dynamics simulations reveal that strain relaxation promotes the formation of these interlayer dislocations with localized buckling in Bernal-stacked bilayer graphene, whereas the strain becomes distributed in twisted bilayer graphene. Furthermore, these localized buckles in graphene are predicted to serve as thermodynamically favorable sites for binding WSe molecules, leading to the higher nucleation density of WSe₂ on Bernal-stacked graphene. Overall, this study explores synthesis-structure correlations in the WSe₂/graphene vertical heterostructure system toward the site-selective synthesis of TMDs by controlling the structural attributes of the graphene substrate.