Shaping and Edge Engineering of Few-Layered Freestanding Graphene Sheets in a Transmission Electron Microscope

Full exploitation of graphene’s superior properties requires the ability to precisely control its morphology and edge structures. We present such a structure-tailoring approach via controlled atom removal from graphene edges. With the use of a graphitic-carbon-capped tungsten nanoelectrode as a noncontact “milling” tool in a transmission electron microscope, graphene edge atoms approached by the tool tip are locally evaporated, thus allowing a freestanding graphene sheet to be tailored with high precision and flexibility. A threshold for the tip voltage of 3.6 ± 0.4 V, independent of polarity, is found to be the determining factor that triggers the controlled etching process. The dominant mechanisms involve weakening of carbon–carbon bonds through the interband excitation induced by tunneling electrons, assisted with a resistive-heating effect enhanced by high electric field, as elaborated by first-principles calculations. In addition to the precise shape and size control, this tip-based method enables fabrication of graphene edges with specific chiralities, such as “armchair” or “zigzag” types. The as-obtained edges can be further “polished” to become entirely atomically smooth via edge evaporation/reconstruction induced by in situ TEM Joule annealing. We finally demonstrate the potential of this technique for practical uses through creating a graphene-based point electron source, whose field emission characteristics can effectively be tuned via modifying its geometry.