Detecting valley splitting and valley-contrasting spin splitting at single-electron level around atomic defects of graphene

Detecting broken-symmetry states around individual atomic defects (including single carbon vacancy and adatoms) of graphene requires nanometer-scale spatial resolution, which has so far eluded direct observation. Here, we realize the measurement of the subtle broken-symmetry states at the single-electron level around atomic defects of graphene by using edge-free graphene quantum dots, which are generated by combining the electric field of a scanning tunneling microscopy tip with perpendicular magnetic fields. Our experiments detect the largest valley splitting, ~ 43 meV, reported so far around the atomic defects of graphene. More importantly, we are able to measure different spin splitting in the two valleys of graphene for the first time. Large valley-contrasting spin splitting induced by spin-orbit coupling is observed near the defects, revealing unexplored exotic electronic states in graphene induced by the atomic defects.