Hydrogen-free graphene edges

Abstract

Graphene edges and their functionalization influence the electronic and magnetic properties of graphene nanoribbons. Theoretical calculations predict saturating graphene edges with hydrogen lower its energy and form a more stable structure. Despite the importance, experimental investigations of whether graphene edges are always hydrogen-terminated are limited. Here we study graphene edges produced by sputtering in vacuum and direct measurements of the C-C bond lengths at the edge show ~86% contraction relative to the bulk. Density functional theory reveals the contraction is attributed to the formation of a triple bond and the absence of hydrogen functionalization. Time-dependent images reveal temporary attachment of a single atom to the arm-chair C-C bond in a triangular configuration, causing expansion of the bond length, which then returns back to the contracted value once the extra atom moves on and the arm-chair edge is returned. Our results provide confirmation that non-functionalized graphene edges can exist in vacuum.