Reversible hydrogenation and band gap opening of graphene and graphite surfaces probed by scanning tunneling spectroscopy

The effect of hydrogenation on the topography and the electronic properties of graphene and graphite surfaces are studied by scanning tunneling microscopy and spectroscopy. The surfaces are chemically modified using Ar/H2 plasma. Analyzing thousands of scanning tunneling spectroscopy measurements we determine that the hydrogen chemisorption on the surface of graphite/graphene opens on average an energy band gap of 0.4 eV around the Fermi level. We find that although the plasma treatment modifies the surface topography in a non-reversible way, the change in the electronic properties can be reversed by a moderate thermal annealing and the samples can be hydrogenated again yielding a similar, but slightly reduced, semiconducting behavior after the second hydrogenation.