▎ 摘 要
Three-dimensional graphene (3D-graphene) is used in surface-enhanced Raman spectroscopy (SERS) because of its plasmonic nanoresonator structure and good ability to interact with light. However, a thin (3-5 nm) layer of amorphous carbon (AC) inevitably appears as a template layer between the 3D-graphene and object substrate when the 3D-graphene layer is synthesized, weakening the enhancement factor. Herein, two-dimensional graphene (2D-graphene) is employed as a template layer to directly synthesize 3D-graphene on a germanium (Ge) substrate via plasma-assisted chemical vapor deposition, bypassing the formation of an AC layer. The interaction and photoinduced charge transfer ability of the 3D-graphene/Ge heterojunction with incident light are improved. Moreover, the high density of electronic states close to the Fermi level of the heterojunction induces the adsorbed probe molecules to efficiently couple to the 3D-graphene-based SERS substrate. Our experimental results imply that the lowest concentrations of rhodamine 6G and rhodamine B that can be detected on the 3D/2D-graphene/Ge SERS substrate correspond to 10(-)(10) M; for methylene blue, it is 10(-8) M. The detection limits of the 3D/2D-graphene/Ge SERS substrate with respect to 3-hydroxytyramine hydrochloride and melamine (in milk) are both less than 1 ppm. This work may provide a viable and convenient alternative method for preparing 3D-graphene SERS substrates. It also constitutes a new approach to developing SERS substrates with remarkable performance levels.