▎ 摘　　要

The nature of chemical bonding at graphene-metal interfaces is intriguing from a fundamental perspective and has great relevance for contacts to novel spintronics and high-frequency electronic devices. Here, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in conjunction with Raman spectroscopy and first-principles density functional theory to examine chemical bonding and perturbation of the pi-electron cloud at graphene-metal interfaces. Graphene-metal bonding has been contrasted for graphene interfaced with single-crystalline metals, polycrystalline metal foils, and with evaporated metal overlayers and is seen to be strongest at the last noted interface. Strong covalent metal-d-graphene-pi hybridization and hole doping of graphene is observed upon deposition of Ni and Co metal contacts onto graphene/SiO2 and is significantly stronger for these metals in comparison to Cu. Of single-crystalline substrates, the most commensurate (111) facets exhibit the strongest interactions with the graphene lattice. First-principles electronic structure simulations, validated by direct comparison of simulated spectra with NEXAFS measurements, suggest that metal deposition induces a loss of degeneracy between the alpha- and beta-graphene sublattices and that spin-majority and spin-minority channels are distinctly coupled to graphene, contributing to splitting of the characteristic pi* resonance. Finally, the electronic structure of graphene is found to be far less perturbed by metal deposition when the p cloud is pinned to an underlying substrate; this remarkable behaviour of "sandwich" structures has been attributed to electronic accessibility of only one face of graphene and illustrates the potential for anisotropic functionalization.