Unravelling the Epitaxial Growth Mechanism of Hexagonal and Nanoporous Boron Nitride: A First‐Principles Microkinetic Model

Abstract Understanding the chemical and physical mechanisms at play in 2D materials growth is critical for effective process development of methods such as chemical vapor deposition (CVD) as a toolbox for processing more complex nanostructures and 2D materials. A combination of density functional theory and microkinetic modeling is employed to comprehensively investigate the reaction mechanism governing the epitaxial growth of hexagonal boron nitride (hBN) on Ru(0001) from borazine. This analysis encompasses four key stages prior to the formation of the complete hBN overlayer: (i) adsorption, diffusion and deprotonation of borazine, (ii) dimerization and microkinetic modeling (iii) stability of larger borazine polymers and (iv) formation of nanoporous intermediates. In doing so, the exact deprotonation sequence is followed for the first time, illustrating its crucial role for the formation of nanostructures. These findings not only provide insights into the epitaxial growth of hBN and the stability of intermediate overlayers, which are strongly dependent on surface temperature and the amount of precursor exposures, they offer also crucial guidance for producing high‐quality hBN monolayers with regular patterns or functionalisation. Importantly, these results align with experimental data and provide a detailed model which explains temperature‐dependent, in‐situ surface measurements during hBN growth on Ru and other substrates.