Epitaxial graphene on Ir(111) prepared in excellent structural quality is investigated by angle-resolved photoelectron spectroscopy. It clearly displays a Dirac cone with the Dirac point shifted only slightly above the Fermi level. The moiré resulting from the overlaid graphene and Ir(111) surface lattices imposes a superperiodic potential giving rise to Dirac cone replicas and the opening of minigaps in the band structure.

Properties of many layered materials, including copper- and iron-based superconductors, topological insulators, graphite and epitaxial graphene, can be manipulated by the inclusion of different atomic and molecular species between the layers via a process known as intercalation. For example, intercalation in graphite can lead to superconductivity and is crucial in the working cycle of modern batteries and supercapacitors. Intercalation involves complex diffusion processes along and across the layers; however, the microscopic mechanisms and dynamics of these processes are not well understood. Here we report on a novel mechanism for intercalation and entrapment of alkali atoms under epitaxial graphene. We find that the intercalation is adjusted by the van der Waals interaction, with the dynamics governed by defects anchored to graphene wrinkles. Our findings are relevant for the future design and application of graphene-based nano-structures. Similar mechanisms can also have a role for intercalation of layered materials.

Angle-resolved photoelectron spectroscopy (ARPES) is extensively used to characterize the dependence of the electronic structure of graphene on Ir(111) on the preparation process. ARPES findings reveal that temperature-programmed growth alone or in combination with chemical vapor deposition leads to graphene displaying sharp electronic bands. The photoemission intensity of the Dirac cone is monitored as a function of the increasing graphene area. Electronic features of the moir\'e superstructure present in the system, namely, minigaps and replica bands are examined and used as robust features to evaluate graphene uniformity. The overall dispersion of the $\pi${} band is analyzed. Finally, by the variation of photon energy, relative changes of the $\pi${} and $\sigma${} band intensities are demonstrated.

The intercalation of Eu underneath Gr on Ir(111) is comprehensively investigated by microscopic, magnetic, and spectroscopic measurements, as well as by density functional theory. Depending on the coverage, the intercalated Eu atoms form either a $(2\times 2)$ or a $(\sqrt{3}\times \sqrt{3})R{30}^{\circ }$ superstructure with respect to Gr. We investigate the mechanisms of Eu penetration through a nominally closed Gr sheet and measure the electronic structures and magnetic properties of the two intercalation systems. Their electronic structures are rather similar. Compared to Gr on Ir(111), the Gr bands in both systems are essentially rigidly shifted to larger binding energies resulting in $n$ doping. The hybridization of the Ir surface state $S_1$ with Gr states is lifted, and the moiré superperiodic potential is strongly reduced. In contrast, the magnetic behavior of the two intercalation systems differs substantially, as found by x-ray magnetic circular dichroism. The $(2\times 2)$ Eu structure displays plain paramagnetic behavior, whereas for the $(\sqrt{3}\times \sqrt{3})R{30}^{\circ }$ structure the large zero-field susceptibility indicates ferromagnetic coupling, despite the absence of hysteresis at 10 K. For the latter structure, a considerable easy-plane magnetic anisotropy is observed and interpreted as shape anisotropy.