Epitaxial single-crystal hexagonal boron nitride multilayers on Ni (111)

Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene^1-3, hexagonal boron nitride (hBN)^4-6 and transition metal dichalcogenides^7,8 have been grown. hBN is considered to be the 'ideal' dielectric for 2D-materials-based field-effect transistors (FETs), offering the potential for extending Moore's law^9,10. Although hBN thicker than a monolayer is more desirable as substrate for 2D semiconductors^11,12, highly uniform and single-crystal multilayer hBN growth has yet to be demonstrated. Here we report the epitaxial growth of wafer-scale single-crystal trilayer hBN by a chemical vapour deposition (CVD) method. Uniformly aligned hBN islands are found to grow on single-crystal Ni (111) at early stage and finally to coalesce into a single-crystal film. Cross-sectional transmission electron microscopy (TEM) results show that a Ni₂₃B₆ interlayer is formed (during cooling) between the single-crystal hBN film and Ni substrate by boron dissolution in Ni. There are epitaxial relationships between hBN and Ni₂₃B₆ and between Ni₂₃B₆ and Ni. We also find that the hBN film acts as a protective layer that remains intact during catalytic evolution of hydrogen, suggesting continuous single-crystal hBN. This hBN transferred onto the SiO₂ (300 nm)/Si wafer acts as a dielectric layer to reduce electron doping from the SiO₂ substrate in MoS₂ FETs. Our results demonstrate high-quality single-crystal  multilayered hBN over large areas, which should open up new pathways for making it a ubiquitous substrate for 2D semiconductors.