A method for forming a single, few-layer, or multi-layer graphene and structure is described incorporating selecting a substrate having a buried layer of carbon underneath a metal layer, providing an ambient and providing a heat treatment to pass carbon through the metal layer to form a graphene layer on the metal layer surface or incorporating a metal-carbon layer which is heated to segregate carbon in the form of graphene to the surface or chemically reacting the metal in the metal-carbon layer with a substrate containing Si driving the carbon to the surface whereby graphene is formed.