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Realizing high-performance nanoelectronics requires control of materials atthe nanoscale. Methods to produce high quality epitaxial graphene (EG)nanostructures on silicon carbide are known. The next step is to grow Van derWaals semiconductors on top of EG nanostructures. Hexagonal boron nitride(h-BN) is a wide bandgap semiconductor with a honeycomb lattice structure thatmatches that of graphene, making it ideally suited for graphene-basednanoelectronics. Here, we describe the preparation and characterization ofmultilayer h-BN grown epitaxially on EG using a migration-enhanced metalorganicvapor phase epitaxy process. As a result of the lateral epitaxial deposition(LED) mechanism, the grown h-BN/EG heterostructures have highly orderedepitaxial interfaces, as desired in order to preserve the transport propertiesof pristine graphene. Atomic scale structural and energetic details of theobserved row-by-row, growth mechanism of the 2D epitaxial h-BN film areanalyzed through first-principles simulations, demonstrating one-dimensionalnucleation-free-energy-barrierless growth. This industrially relevant LEDprocess can be applied to a wide variety of van der Waals materials.

Highly Ordered Boron Nitride/Epigraphene Epitaxial Films on Silicon Carbide by Lateral Epitaxial Deposition