Understanding the graphitization and growth of free-standing nanocrystalline graphene using in situ transmission electron microscopy

Graphitization of polymers is an effective way to synthesize nanocrystalline graphene on different substrates with tunable shape, thickness and properties. The catalyst free synthesis results in crystallite sizes on the order of a few nanometers, significantly smaller than commonly prepared polycrystalline graphene. Even though this method provides the flexibility of graphitizing polymer films on different substrates, substrate free graphitization of freestanding polymer layers has not been studied yet. We report for the first time the thermally induced graphitization and domain growth of free-standing nanocrystalline graphene thin films using in situ TEM techniques. High resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) techniques were used to analyze the graphitization and the evolution of nanocrystalline domains at different temperatures by characterizing the crystallinity and domain size, further supported by ex situ Raman spectroscopy. The graphitization was comparable to the substrate supported heating and the temperature dependence of graphitization was analyzed. In addition, the in situ analysis of the graphitization enabled direct imaging of some of the growth processes taking place at different temperatures