Patterned graphene shows substantial potential for applications in future molecular-scale integrated electronics. Environmental effects are a critical issue in a single-layer material where every atom is on the surface. Especially intriguing is the variety of rich chemical interactions shown by molecular oxygen with aromatic molecules. We find that O 2 etching kinetics vary strongly with the number of graphene layers in the sample. Three-layer-thick samples show etching similar to bulk natural graphite. Single-layer graphene reacts faster and shows random etch pits in contrast to natural graphite where nucleation occurs at point defects. In addition, basal plane oxygen species strongly hole dope graphene, with a Fermi level shift of approximately 0.5 eV. These oxygen species desorb partially in an Ar gas flow, or under irradiation by far UV light, and readsorb again in an O 2 atmosphere at room temperature. This strongly doped graphene is very different from "graphene oxide" made by mineral acid attack.

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Mechanically exfoliated graphene mounted on a SiO2/Si substrate was subjected to HF/H(2)O etching or irradiation by energetic protons. In both cases gas was released from the SiO2 and accumulated at the graphene/SiO2 interface resulting in the formation of "bubbles" in the graphene sheet. Formation of these "bubbles" demonstrates the robust nature of single layer graphene membranes, which are capable of containing mesoscopic volumes of gas. In addition, effective mass transport at the graphene/SiO2 interface has been observed.

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