Rotating Anisotropic Crystalline Silicon Nanoclusters in Graphene

The atomic structure and dynamics of silicon nanoclusters covalently bonded to graphene are studied using aberration-corrected transmission electron microscopy. We show that as the cluster size increases to 4-10 atoms, ordered crystalline cubic phases start to emerge. Anisotropic crystals are formed due to higher stability of the Si-C bond under electron beam irradiation compared to the Si-Si bond. Dynamics of the anisotropic crystalline Si nanoclusters reveal that they can rotate perpendicular to the graphene plane, with oscillations between the two geometric configurations driven by local volume constraints. These results provide important insights into the crystalline phases of clusters of inorganic dopants in graphene at the intermediate size range between isolated single atoms and larger bulk 2D forms.