Layer-by-layer construction of diamond devices for spin-sensing
calls for the atomistic understanding of the nitrogen species on diamond
surfaces. Motivated by recent experiments, we used density functional
theory simulations to examine the adsorption of nitrogen species (N,
NH, and NH2) on bare and hydrogenated diamond(001) surfaces.
On the bare substrate, we find that nitrogen species favor to attack
the CC dimers at low coverages, forming N(ad) and NH(ad) in
a bridge configuration and NH2(ad) in a terminal configuration.
At increasing coverages up to one full monolayer, the computed adsorption
geometries and energetics suggest that the adsorbate–adsorbate
interactions are attractive for N(ad), but repulsive for NH(ad) and
NH2(ad). On the hydrogenated substrate, the adsorbed nitrogen
species are subject to structural modification, as resulted from the
weakened adsorbate–substrate interactions. Further, we calculated
the vibration of nitrogen species and the 1s core-level shift of surface
carbons, providing atomistic insights into the nature of surface bonding.
Lastly, we simulated images of representative nitrogen species adsorbed
on diamond(001), guiding future work using scanning tunneling microscopy.