Direct tuning of graphene work function via chemical vapor deposition control

Besides its unprecedented physical and chemical characteristics, graphene is also well known for its formidable potential of being a next-generation device material. Work function (WF) of graphene is a crucial factor in the fabrication of graphene-based electronic devices because it determines the energy band alignment and whether the contact in the interface is Ohmic or Schottky. Tuning of graphene WF, therefore, is strongly demanded in many types of electronic and optoelectronic devices. Whereas study on work function tuning induced by doping or chemical functionalization has been widely conducted, attempt to tune the WF of graphene by controlling chemical vapor deposition (CVD) condition is not sufficient in spite of its simplicity. Here we report the successful WF tuning method for graphene grown on a Cu foil with a novel CVD growth recipe, in which the CH₄/H₂ gas ratio is changed. Kelvin probe force microscopy (KPFM) verifies that the WF-tuned regions, where the WF increases by the order of ~250 meV, coexist with the regions of intrinsic WF within a single graphene flake. By combining KPFM with lateral force microscopy (LFM), it is demonstrated that the WF-tuned area can be manipulated by pressing it with an atomic force microscopy (AFM) tip and the tuned WF returns to the intrinsic WF of graphene. A highly plausible mechanism for the WF tuning is suggested, in which the increased graphene-substrate distance by excess H₂ gases may cause the WF increase within a single graphene flake. This novel WF tuning method via a simple CVD growth control provides a new direction to manipulate the WF of various 2-dimensional nanosheets as well as graphene.