Abstract

We have investigated the phenomena determining the stability reached by first-row transition metals (Sc-Zn) on phosphorene nanostructured materials. In the framework of density functional theory calculations, it is shown that the substitutional doping of phosphorene reaches higher stability in comparison to the adatom doping. To give a guideline to understand this order of relative stabilities between doping schemes, in addition to the specific stability per dopant atom, we conducted further structural, binding, and energy decomposition analyses based on absolutely localized molecular orbitals. Our results reveal that the highest stability of the substitutional doping is a consequence of the strong interplay among charge-transfer, polarization, and Coulombic electrostatic physical effects. In contrast, adatom doping is mainly stabilized by charge-transfer effects. The magnitude of the stabilizing polarization effects also shows a strong correlation to the polar character of the single closed-shell interactions between dopants and phosphorous atoms, while the fulfill of 3d orbitals controls the magnitude of stabilizing charge-transfer energies. Moreover, the magnitude of the physical stabilizing contributions appears associated with the electronic/structural properties of the doped phosphorene nanosheets, e.g., the topology of electron density, coordination environment, and ligand-field exerted on the dopant atom.