Electronic and magnetic properties of the graphene densely decorated with 3d metallic adatoms

TL;DR

This study investigates how decorating graphene with 3d transition metal adatoms like Ni, Co, Cu, and Zn affects its electronic and magnetic properties, revealing charge transfer, induced magnetism, and band structure modifications.

Contribution

It provides a detailed first-principles analysis of how metallic adatoms influence graphene's electronic structure, including gap openings and spin-orbit effects, for different adsorption configurations.

Findings

Charge transfer from adatoms to graphene causes n-doping.

Adatoms induce magnetic moments and modify graphene's magnetic state.

Band structure analysis shows gap openings and symmetry breaking effects.

Abstract

The electronic properties of graphene decorated with Ni, Co, Cu and Zn adatoms is studied with the density functional theory approach. Within the analysis the spin-orbit interaction is taken into account. We focus on the case when the indicated $3d$ metallic adatoms form a perfect, close-packed single-atomic layer above the graphene surface. The two configurations are examined, namely the adatoms in the on-top, and the hollow positions on graphene. First, we verify that the metallic adatoms in the close-packed structure do not form a covalent bonds with the graphene substrate. However, due to the proximity of the metallic adatoms to the graphene, the charge transfer from the adatom layer to the graphene takes place, and in consequence the graphene becomes $n$-doped. The observed charge transfer results from the arising hybridization between the graphene $2p$ and transition metal $3d$ orbitals. The proximity of metallic adatoms modifies the magnetic state of the graphene. This effect is especially pronounced for the decoration with magnetic atoms, when the magnetic moments on the graphene sublattices are induced. The analysis of the band structure demonstrates that the charge transfer, as well as the induced magnetism on graphene, modify the graphene electronic properties near high symmetry points, especially the Dirac cones. The presence of the metallic adatoms breaks graphene $K-K^{'}$ symmetry and splits the bands due to the exchange coupling. We show that for the hollow configuration the gap opening arises at the $K(K^{'})$-point due to the Rashba-like spin-orbit interaction, while in the case of the on-top configuration the energy gap opens mainly due to the staggered potential. We also mapped the parameters of an effective Hamiltonian on the results obtained with the density functional theory approach.