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Hexagonal boron nitride (hBN) is an essential component in van der Waalsheterostructures as it provides high quality and weakly interacting interfacesthat preserve the electronic properties of adjacent materials. While exfoliatedflakes of hBN have been extensively studied using electron transport andoptical probes, detailed experimental measurements of the energy- and momentum-dependent electronic excitation spectrum are lacking. Here, we directlydetermine the full valence band (VB) electronic structure of micron-sizedexfoliated flakes of hBN using angle-resolved photoemission spectroscopy withmicrometer spatial resolution. We identify the {\pi}- and {\sigma}-banddispersions, the hBN stacking order and determine a total VB bandwidth of 19.4eV. We compare these results with electronic structure data for epitaxial hBNon graphene on silicon carbide grown in situ using a borazine precursor. Theepitaxial growth and electronic properties are investigated using photoe-mission electron microscopy. Our measurements show that the fundamentalelectronic properties of hBN are highly dependent on the fabrication strategy.

Electronic Structure of Exfoliated and Epitaxial Hexagonal Boron Nitride