Temperature Dependence of the Reconstruction of Zigzag Edges in Graphene

We examine the temperature dependence of graphene edge terminations at the atomic scale using an in situ heating holder within an aberration-corrected transmission electron microscope. The relative ratios of armchair, zigzag, and reconstructed zigzag edges from over 350 frames at each temperature are measured. Below 400 degrees C, the edges are dominated by zigzag terminations, but above 600 degrees C, this changes dramatically, with edges dominated by armchair and reconstructed zigzag edges. We show that at low temperature chemical etching effects dominate and cause deviation to the thermodynamics of the system. At high temperatures (600 and 800 degrees C), adsorbates are evaporated from the surface of graphene and chemical etching effects are significantly reduced, enabling the thermodynamic distribution of edge types to be observed. The growth rate of holes at high temperature is also shown to be slower than at room temperature, indicative of the reduced chemical etching process. These results provide important insights into the role of chemical etching effects in the hole formation, edge sputtering, and edge reconstruction in graphene.