Electronic Structure Modification of Ion Implanted Graphene: The Spectroscopic Signatures of p- and n-Type Doping

A combination of scanning transmission electron microscopy, electron energy loss spectroscopy, and ab initio calculations is used to describe the electronic structure modifications incurred by free-standing graphene through two types of single-atom doping. The N K and C K electron energy loss transitions show the presence of pi* bonding states, which are highly localized around the N dopant. In contrast, the B K transition of a single B dopant atom shows an unusual broad asymmetric peak which is the result of delocalized pi* states away from the B dopant. The asymmetry of the B K toward higher energies is attributed to highly localized sigma* antibonding states. These experimental observations are then interpreted as direct fingerprints of the expected p- and n-type behavior of graphene doped in this fashion, through careful comparison with density functional theory calculations.