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.