Towards twin-free molecular beam epitaxy of 2D chalcogenides explained by stronger interlayer van der Waals coupling

Defect-free epitaxial growth of 2D materials is one of the holy grails for a successful integration of van der Waals (vdW) materials in the semiconductor industry. The large-area (quasi-)vdW epitaxy of layered 2D chalcogenides is consequently carefully being researched since these materials hold very promising properties for future nanoelectronic applications. The formation of defects such as stacking faults like 60o twins and consequently 60o grain boundaries is still of major concern for the defect-free epitaxial growth of 2D chalcogenides. Although growth strategies to overcome the occurrence of these defects are currently being considered, more fundamental understanding on the origin of these defects at the initial stages of the growth is highly essential. Therefore this work focuses on the understanding of 60o twin formation in (quasi-)vdW epitaxy of 2D chalcogenides relying on systematic molecular beam epitaxy (MBE) experiments supported by density functional theory (DFT) calculations. The MBE experiments reveal the striking difference in 60o twin formation between WSe2 and Bi2Se3 in both quasi-vdW heteroepitaxy and vdW homoepitaxy, which from our DFT calculations links to the difference in interlayer vdW coupling strength. The stronger interlayer vdW coupling in Bi2Se3 compared to WSe2 results in a striking enhanced control on twin formation and hence shows significantly more promise for defect-free epitaxial integration. This interesting aspect of (quasi-)vdW epitaxy reveals that the strength of interlayer vdW coupling is key for functional 2D materials and opens perspectives for other vdW materials sharing strong interlayer interactions.