Growth and Redox Properties of Boron on Al(111): Competing Affinities in the Case of Honeycomb AlB₂.

Abstract

The complexity of the geometric and electronic structure of boron allotropes is associated with the multicentric bonding character and the consequent B polymorphism. When growth is limited to two-dimensions (2D), the structural and electronic confinement yields the borophenes family, where the interaction with the templating substrate actually determines the stability of inequivalent boron phases. We report here a detailed study of the growth of the honeycomb AlB₂ phase on Al(111), followed by an investigation of its oxidation and reduction properties. By means of a combined experimental and theoretical approach, we show that the structure of the B/Al interface is affected by the complex interplay between B, Al, and common reactive agents like oxygen and hydrogen. While kinetic effects associated with diffusion and strain release influence the AlB₂ growth in vacuo, Al, B, O, and H chemical affinities determine its redox behavior. Reduction with atomic hydrogen involves the B layer and yields an ordered honeycomb borophane H/AlB₂ phase. Instead, oxidation takes place at the Al interface, giving origin to buried and 1D surface aluminum oxide phases.