Modifying the geometric and electronic structure of hexagonal boron nitride on Ir(111) by Cs adsorption and intercalation

Abstract

Epitaxial hexagonal boron nitride on Ir(111) is significantly modified by adsorption and intercalation of alkali-metal atoms. Regarding geometry, intercalation lifts the two-dimensional layer from its substrate and reduces the characteristic corrugation imprinted by direct contact with the metal substrate. Moreover, the presence of charged species in close proximity to the hexagonal boron nitride (hBN) layer strongly shifts the electronic structure (valence bands and core levels). We used scanning tunneling microscopy, low-energy electron diffraction, x-ray photoelectron spectroscopy (XPS), and the x-ray standing wave technique to study changes in the atomic structure induced by Cs adsorption and intercalation. Depending on the preparation, the alkali-metal atoms can be found on top and underneath the hexagonal boron nitride in ordered and disordered arrangements. Adsorbed Cs does not change the morphology of hBN/Ir(111) significantly, whereas an intercalated layer of Cs decouples the two-dimensional sheet and irons out its corrugation. XPS and angle-resolved photoelectron spectroscopy reveal a shift of the electronic states to higher binding energies, which increases with increasing density of the adsorbed and intercalated Cs. In the densest phase, Cs both intercalates and adsorbs on hBN and shifts the electronic states of hexagonal boron nitride by 3.56 eV. As this shift is not sufficient to move the conduction band below the Fermi energy, the electronic band gap must be larger than 5.85 eV.