Contrasting diffusion behaviors of O and F atoms on graphene and within bilayer graphene

TL;DR

This study compares the diffusion behaviors of oxygen and fluorine atoms on and within graphene layers using first-principles calculations, revealing contrasting diffusion barriers linked to their bonding nature.

Contribution

It provides a detailed first-principles analysis of how O and F atoms diffuse differently on graphene and in bilayer graphene, highlighting the role of bonding characteristics.

Findings

O and F atoms have lower binding energies between layers than on graphene.

Diffusion barrier for O slightly increases from graphene to bilayer.

Diffusion barrier for F significantly decreases from graphene to bilayer.

Abstract

The chemical modification of graphene with adatoms is of importance for nanoelectronics applications. Based on first-principles density-functional theory calculations with including van der Waals interactions, we present a comparative study of the diffusion characteristics of oxygen (O) and fluorine (F) atoms both on graphene and between the layers of bilayer graphene. We find that O and F atoms have lower binding energies between the layers of bilayer graphene compared to on graphene. Interestingly, the calculated diffusion barrier for the O atom slightly increases from 0.81 eV on graphene to 0.85 eV within bilayer graphene, while that for the F atom significantly decreases from 0.30 eV on graphene to 0.18 eV within bilayer graphene. Such contrasting behaviors of the O and F diffusions within bilayer graphene can be traced to their different bonding natures: i.e., the O adatom that has a strongly covalent C$-$O$-$C bonding on the bridge site of the C$-$C bond diffuses on one graphene layer with a slight interference of the other layer, while the F adatom that has a weakly ionic F$-$C bonding on top of a C atom easily diffuses by hopping between two graphene layers with accepting more electron charges from the two layers. The present findings have important implications for understanding the diffusion processes of F and O atoms on graphene and within bilayer graphene.