Tuning adlayer-substrate interactions of graphene/h-BN heterostructures on Cu(111)–Ni and Ni(111)–Cu surface alloys

The evolution of the interface and interaction of h-BN and graphene/h-BN (Gr/h-BN) on Cu(111)–Ni and Ni(111)–Cu surface alloys versus the Ni/Cu atomic percentage on the alloy surface were comparatively studied by the DFT-D2 method, including the critical long-range van der Waals forces. Our results showed that the interaction strength and interface distance of Gr/h-BN/metal can be distinctly tuned by regulating the chemical composition of the surface alloy at the interface. The initially weak interaction of h-BN/Cu(111)–Ni increased linearly with increasing Ni atomic percentage, and the interface distances decreased from ∼3.10 to ∼2.10 Å. For the h-BN/Ni(111)–Cu interface, the strong interaction of the N(top)B(fcc/hcp) stacking decreased sharply with increasing Cu atomic percentage from 0% to 50%, and the interface distances increased from ∼2.15 to ∼3.00 Å; meanwhile, the weak interaction of the B(top)N(fcc/hcp) stacking decreased slightly with increasing Cu atomic percentage. The absorption of graphene on h-BN/Cu(111)–Ni with B(top)N(hollow)/N(top)B(fcc) and B(top)N(hollow)/B(top)N(fcc) stacking was more energetically favorable than that with N(top)B(hollow)/N(top)B(fcc) and N(top)B(hollow)/B(top)N(fcc) at Ni atomic percentages under 75%, while the interaction energy of graphene on h-BN/Cu(111)–Ni increased sharply at Ni atomic percentages higher than 75% for the B(top)N(hollow)/N(top)B(fcc) and N(top)B(hollow)/N(top)B(fcc) stacking. In contrast, the interaction between graphene and the h-BN/Ni(111)–Cu surface increased sharply at Cu atomic percentages lower than 25% and decreased sharply at Cu atomic percentages higher than 75%. The interaction energies were higher when the percentage of Cu atom was between 25% and 75%. The analysis of charge transfer and density of states provided further details on the changing character and evolution trends of the interactions among graphene, h-BN, and Cu–Ni surface alloy versus the Ni/Cu atomic percentage.