Towards full repair of defects in reduced graphene oxide films by two-step graphitization

The complete restoration of a perfect carbon lattice has been a central issue in the research on graphene derived from graphite oxide since this preparation route was first proposed several years ago, but such a goal has so far remained elusive. Here, we demonstrate that the highly defective structure of reduced graphene oxide sheets assembled into free-standing, paper-like films can be fully repaired by means of high temperature annealing (graphitization). Characterization of the films by X-ray photoelectron and Raman spectroscopy, X-ray diffraction and scanning tunneling microscopy indicated that the main stages in the transformation of the films were (i) complete removal of oxygen functional groups and generation of atomic vacancies (up to 1,500 °C), and (ii) vacancy annihilation and coalescence of adjacent overlapping sheets to yield continuous polycrystalline layers (1,800–2,700 °C) similar to those of highly oriented graphites. The prevailing type of defect in the polycrystalline layers were the grain boundaries separating neighboring domains, which were typically a few hundred nanometers in lateral size, exhibited long-range graphitic order and were virtually free of even atomic-sized defects. The electrical conductivity of the annealed films was as high as 577,000 S·m−1, which is by far the largest value reported to date for any material derived from graphene oxide, and strategies for further improvement without the need to resort to higher annealing temperatures are suggested. Overall, this work opens the prospect of truly achieving a complete restoration of the carbon lattice in graphene oxide materials.