Peculiar alignment and strain of 2D WSe₂ grown by van der Waals epitaxy on reconstructed sapphire surfaces

The increasing scientific and industry interest in 2D MX₂ materials within the field of nanotechnology has made the single crystalline integration of large area van der Waals (vdW) layers on commercial substrates an important topic. The c-plane oriented (3D crystal) sapphire surface is believed to be an interesting substrate candidate for this challenging 2D/3D integration. Despite the many attempts that have been made, the yet incomplete understanding of vdW epitaxy still results in synthetic material that shows a crystallinity far too low compared to natural crystals that can be exfoliated onto commercial substrates. Thanks to its atomic control and in situ analysis possibilities, molecular beam epitaxy (MBE) offers a potential solution and an appropriate method to enable a more in-depth understanding of this peculiar 2D/3D hetero-epitaxy. Here, we report on how various sapphire surface reconstructions, that are obtained by thermal annealing of the as-received substrates, influence the vdW epitaxy of the MBE-grown WSe₂ monolayers (MLs). The surface chemistry and the interatomic arrangement of the reconstructed sapphire surfaces are shown to control the preferential in-plane epitaxial alignment of the stoichiometric WSe₂ crystals. In addition, it is demonstrated that the reconstructions also affect the in-plane lattice parameter and thus the in-plane strain of the 2D vdW-bonded MLs. Hence, the results obtained in this work shine more light on the peculiar concept of vdW epitaxy, especially relevant for 2D materials integration on large-scale 3D crystal commercial substrates.