Insulating hexagonal boron nitride monolayers (hBN) are best known for being resistant to chemical functionalization. This property makes hBN an excellent substrate for graphene heterostructures, but limits
its application as an active element in nanoelectronics where tunable electronic properties are needed. Moreover,
the two-dimensional–materials’ community wishes to learn more about the adsorption and intercalation
characteristics of alkali metals on hBN, which have direct relevance to several electrochemistry experiments
that are envisioned with layered materials. Here we provide results on ionic functionalization of hBN/metal
interfaces with K and Li dopants.
By combining angle-resolved photoemission spectroscopy (ARPES), x-ray photoelectron spectroscopy, and density functional theory calculations, we show that the metallic substrate readily ionizes the alkali dopants and exposes hBN to large electric fields and band-energy shifts. In particular, if hBN is in between the negatively charged substrate and the positive alkali ion, this allows us to directly study, using ARPES, the effects of large electric fields on the electron energy bands of hBN.