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Graphene is an intriguing material in view of its unique Dirac quasi-particles, and the manipulation of its electronic structure is important in material design and applications. Here, we theoretically investigate the electronic band structure of epitaxial graphene on SiC with intercalation of rare earth metal ions (e.g., Yb and Dy) using first-principles calculations. The intercalation can be used to control the coupling of the constituent components (buffer layer, graphene, and substrate), resulting in strong modification of the graphene band structure. It is demonstrated that the metal-intercalated epitaxial graphene has tunable band structures by controlling the energies of Dirac cones as well as the linear and quadratic band dispersion depending on the intercalation layer and density. Therefore, the metal intercalation is a viable method to manipulate the electronic band structure of the epitaxial graphene, which can enhance the functional utility and controllability of the material. [ABSTRACT FROM AUTHOR]

SiC-supported graphene intercalated by a two-dimensional Pb monolayer can provide an appealing platform for spintronic applications. Such a monolayer structure is thermodynamically ultrastable, as observed in recent experiments. However, important fundamentals such as the structure of intercalated phases, locations of intercalated atoms, thermodynamic preference for intercalation, and intercalation pathways for this system have not yet been understood conclusively. In this work, extensive density functional theory calculations are performed to assess Pb intercalation thermodynamics and kinetics under graphene on SiC(0001). We find that intercalation of isolated Pb atoms is strongly disfavored over adsorption on top of graphene. However, intercalation of complete Pb layers in the gallery between SiC and graphene buffer layer is strongly favored over supported Pb monolayers and moderately favored over formation of supported large three-dimensional Pb islands. We also find that initiation of intercalation either by individual Pb atoms directly penetrating graphene or by hopping under a static graphene step edge is energetically prohibitive at experimental temperatures. Consequently, more complex intercalation pathways are operative and further analyzed. We demonstrated that once an intercalated Pb monolayer forms around a graphene step edge, a facile Pb mass transport by Pb vacancy-mediated diffusion can be triggered for continued growth of the intercalated monolayer. [Display omitted] [ABSTRACT FROM AUTHOR]

The study of functional manipulation of graphene is a critical subject, both for fundamental research and practical applications. In this study, we present that the intercalation of 5 d transition metals into epitaxial graphene on SiC is a promising strategy for the realization of topologically nontrivial phases with a finite band gap in graphene. Employing first-principles calculations, grounded in density functional theory, we demonstrate that Re- and Ta-intercalated graphene evolve into two-dimensional topological insulators. These exhibit linear Dirac cones and quadratic bands with topological band gaps, respectively. The emergence of these topological states is attributed to the strong spin–orbit coupling strength of the intercalants. We show that the corresponding topological edge states persist within the finite bulk band gap, aligning with the bulk-boundary correspondence. Furthermore, we explore the spin splitting of the band structure, brought about by the inversion symmetry breaking and the spin–orbit coupling. Our study underscores that the intercalation of graphene is an effective and a feasible approach for manipulating the band gap and the topological nature of graphene. Such intercalated graphene systems hold potential utility for spintronics and low-dimensional quantum device applications. • Topological band gaps appear in the Re-intercalated epitaxial graphene on SiC. • Topological band gaps appear in the Ta-intercalated epitaxial graphene on SiC. • Spin-split valence bands in the Re-intercalated epitaxial graphene on SiC. • Rashba-type spin-split bands in the Ta-intercalated epitaxial graphene on SiC. [ABSTRACT FROM AUTHOR]

• DFT generates precise surface and adhesion energies in Cu + graphite/graphene systems. • PBEsol is effective for Cu, and optB88 for graphite/graphene and Cu-C systems. • DFT energies facilitate Winterbottom construction for 3D Cu island shape on graphite. We have generated precise values for several key energies that are relevant to Cu-graphene or Cu-graphite systems. Such systems may find technological applications that range from graphene synthesis, to condensation heat transfer, to electrical contacts to graphene, to composites. Using density functional theory, we have calculated surface energies of the three low-index faces of bulk Cu. We find that these surface energies, calculated with the PBEsol functional, are significantly higher than with the more common PBE functional and agree more closely with experiment. We have also calculated the surface energies of graphene and graphite, the exfoliation energy between graphene and graphite, and the adhesion energies between graphene or graphite and a Cu(111) slab. The adhesion energy between a carbon layer and Cu(111) is close to the exfoliation energy and cleavage energy of graphite, the four sets of values spanning a range of only 0.394–0.456 J/m2. Our results are consistent with the earlier experimental observation of three-dimensional growth of Cu on top of graphite. The energies are also used to perform a continuum Winterbottom analysis and also discrete (atomistic) variants of this analysis to predict the equilibrium shapes of Cu particles supported on graphite. Image, graphical abstract [ABSTRACT FROM AUTHOR]

We show that 3 metals – Dy, Ru, and Cu – can form multilayer intercalated (encapsulated) islands at the graphite (0001) surface if 2 specific conditions are met: Defects are introduced on the graphite terraces to act as entry portals, and the metal deposition temperature is well above ambient. Focusing on Dy as a prototype, we show that surface encapsulation is much different than bulk intercalation, because the encapsulated metal takes the form of bulk-like rafts of multilayer Dy, rather than the dilute, single-layer structure known for the bulk compound. Carbon-covered metallic rafts even form for relatively unreactive metals (Ru and Cu) which have no known bulk intercalation compound. [ABSTRACT FROM AUTHOR]

We have determined the magnetic properties of epitaxially grown Dy islands on graphene/SiC(0001) that are passivated by a gold film (deposited in the ultra-high vacuum growth chamber) for ex-situ X-ray magnetic circular dichroism (XMCD). Our sum-rule analysis of the Dy M 4 , 5 XMCD spectra at low temperatures ( T = 15 K) as a function of magnetic field assuming Dy 3 + (spin configuration 6 H 15 / 2 ) indicate that the projection of the magnetic moment along an applied magnetic field of 5 T is 3.5(3) μ B . Temperature dependence of the magnetic moment (extracted from the M 5 XMCD spectra) shows an onset of a change in magnetic moment at about 175 K in proximity of the transition from paramagnetic to helical magnetic structure at T H = 179 K in bulk Dy. No feature at the vicinity of the ferromagnetic transition of hcp bulk Dy at T c = 88 K is observed. However, below ∼130 K, the inverse magnetic moment (extracted from the XMCD) is linear in temperature as commonly expected from a paramagnetic system suggesting different behavior of Dy nano-island than bulk Dy. [ABSTRACT FROM AUTHOR]

Graphene, a single atomic layer of graphite, has been the focus of recent intensive studies due to its novel electronic and structural properties. Metals grown on graphene also have been of interest because of their potential use as metal contacts in graphene devices, for spintronics applications, and for catalysis. All of these applications require good understanding and control of the metal growth morphology, which in part reflects the strength of the metal–graphene bond. Also of importance is whether the interaction between graphene and metal is sufficiently strong to modify the electronic structure of graphene. In this review, we will discuss recent experimental and computational studies related to deposition of metals on graphene supported on various substrates (SiC, SiO 2 , and hexagonal close-packed metal surfaces). Of specific interest are the metal–graphene interactions (adsorption energies and diffusion barriers of metal adatoms), and the crystal structures and thermal stability of the metal nanoclusters. [ABSTRACT FROM AUTHOR]

In this article, we review basic information about the interaction of transition metal atoms with the (0 0 0 1) surface of graphite, especially fundamental phenomena related to growth. Those phenomena involve adatom-surface bonding, diffusion, morphology of metal clusters, interactions with steps and sputter-induced defects, condensation, and desorption. General traits emerge which have not been summarized previously. Some of these features are rather surprising when compared with metal-on-metal adsorption and growth. Opportunities for future work are pointed out. [ABSTRACT FROM AUTHOR]