Joan M. Redwing

2D Crystal Consortium – Materials Innovation Platform and Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA  USA

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Wafer-scale synthesis of semiconducting transition metal dichalcogenide (TMDs) monolayers is of significant interest for device applications to circumvent size limitations associated with the use of exfoliated flakes. Promising results have been demonstrated for epitaxial films deposited by vapor phase techniques such as chemical vapor deposition (CVD) and metalorganic CVD (MOCVD). However, the three-fold symmetry of TMDs such as MoS2 and WSe2, typically results in two energetically equivalent domain alignments, often referred to as 0o and 60o domains, when grown on substrates such as c-plane sapphire and graphene. The oppositely oriented domains give rise to inversion domain boundaries (IDBs) upon coalescence which exhibit a metallic character and are generally undesirable. In this study, we demonstrate the epitaxial growth of unidirectional TMD monolayers on 2” diameter c-plane sapphire substrates with a significantly reduced density of inversion domains.  Steps on the sapphire surface are shown to break the surface symmetry giving rise to a preferred domain orientation.

   MOCVD was used for the epitaxial growth of WSe2 and WS2 monolayers on c-plane sapphire in a cold-wall horizontal quartz-tube reactor. The as-received sapphire substrates, which are miscut ~0.2o toward <110>, consist of steps with sub-1 nm step height separated by 50-70 nm wide terraces. A three-step nucleation-ripening-lateral growth process, carried out at temperatures ranging from 850oC to 1000oC, was used to achieve epitaxial films using W(CO)6, H2Se and H2S as precursors in a H2 carrier gas.  Nucleation was observed to occur at the terrace edge and the growing domains align epitaxially with the underlying (0001) sapphire lattice. As a result of the nucleation process, the domains grow with a zig-zag edge facing the terrace edge which imparts a preferential direction to the domains. The percentage of domains with a preferred direction ranges from 75%-86% depending on MOCVD growth conditions. Continued lateral growth for times ranging from 10-30 minutes results in fully coalesced TMD monolayers that are epitaxially oriented on the sapphire, as assessed by in-plane x-ray diffraction, with a reduced density of inversion domain boundaries.  The results demonstrate the important role of surface structure in nucleation and epitaxial growth of TMD monolayers.