Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition

We report the selective growth of large-area bilayered graphene film and multilayered graphene film on copper. This growth was achieved by introducing a reciprocal chemical vapor deposition (CVD) process that took advantage of an intermediate h-BN layer as a sacrificial template for graphene growth. A thin h-BN film, initially grown on the copper substrate using CVD methods, was locally etched away during the subsequent graphene growth under residual H2 and CH4 gas flows. Etching of the h-BN layer formed a channel that permitted the growth of additional graphene adlayers below the existing graphene layer. Bilayered graphene typically covers an entire Cu foil with domain sizes of 10–50 μm, whereas multilayered graphene can be epitaxially grown to form islands a few hundreds of microns in size. This new mechanism, in which graphene growth proceeded simultaneously with h-BN etching, suggests a potential approach to control graphene layers for engineering the band structures of large-area graphene for electronic device applications.