The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41 Å of the C atoms with their mean height h = (3.38±0.04) Å as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.
On the graphene moiré on Ir(111) a variety of highly perfect cluster superlattices can be grown as shown is for Ir, Pt, W, and Re. Even materials that do not form cluster superlattices upon room temperature deposition may be grown into such by low temperature deposition or the application of cluster seeding through Ir as shown for Au, AuIr, FeIr. Criteria for the suitability of a material to form a superlattice are given and largely confirmed. It is proven that at least Pt and Ir even form epitaxial cluster superlattices. The temperature stability of the cluster superlattices is investigated and understood on the basis of positional fluctuations of the clusters around their sites of minimum potential energy. The binding sites of Ir, Pt, W and Re cluster superlattices are determined and the ability to cover samples macroscopically with a variety of superlattices is demonstrated.
Using X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM) we resolve the temperature-, time-, and flake size-dependent intercalation phases of oxygen underneath graphene on Ir(111) formed upon exposure to molecular oxygen. Through the applied pressure of molecular oxygen the atomic oxygen created on the bare Ir terraces is driven underneath graphene flakes. The importance of substrate steps and of the unbinding of graphene flake edges from the substrate for the intercalation is identified. With the use of CO titration to selectively remove oxygen from the bare Ir terraces the energetics of intercalation is uncovered. Cluster decoration techniques are used as an efficient tool to visualize intercalation processes in real space.
Here we show that it is possible to intercalate CO under graphene grown on Ir(111) already at room temperature when CO pressures in the millibar regime are used. From the interplay of X-ray photoelectron spectroscopy and scanning tunneling microscopy we conclude that the intercalated CO adsorption structure is similar to the (3√3 × 3√3)R30°) adsorption structure that is formed on Ir(111) upon exposure to ∼1 mbar of CO. Further, density functional theory calculations reveal that the structural and electronic properties of CO-intercalated graphene are similar to p-doped freestanding graphene. Finally we characterize nonintercalated stripes and islands that we always observe in the CO-intercalated graphene. We observe these nonintercalated areas predominately in HCP and FCC areas near step edges and suggest that stress release in graphene is the driving force for their formation, while the weak chemical bonds in HCP and FCC areas are the reason for their area selectivity.
Regular Pt cluster arrays grown on the moiré template formed by graphene on Ir(111) were tested for their stability with respect to CO gas exposure. Cluster stability and adsorption-induced processes were analyzed as a function of cluster size, with in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. Small clusters containing fewer than 10 atoms were unstable upon CO adsorption. They sintered through Smoluchowski ripening-cluster diffusion and coalescence-rather than the frequently reported Ostwald ripening mediated by metal-adsorbate complexes. Larger clusters remained immobile upon CO adsorption but became more three-dimensional. Careful analysis of the experimental data complemented by ab initio density functional theory calculations provides insight into the origin of the CO-induced Pt cluster ripening and shape transformations.
Our understanding of metal-atom cluster adsorption on graphene on Ir(111) is based on elementary chemical ideas, rehybridization, and buckling, supported by density functional theory (DFT) calculations. We tested the DFT picture by comparing calculated core level spectra to x-ray photoemission spectroscopy (XPS) measurements. For pristine graphene, which forms a gently undulating moiré on Ir(111), DFT predicts a 140 meV modulation of C 1s core level shifts (CLS), consistent with the measured spectrum. With Pt clusters adsorbed, measured Pt 4f CLS of the adsorbed clusters also support the calculations. The modulation of the C 1s spectrum is strengthened with clusters adsorbed, and C-atom ionization potentials under and in the vicinity of the Pt clusters are shifted enough to be experimentally distinguished as a broad shoulder of positive C 1s CLSs. Furthermore, DFT calculations imply that sp 2 to sp 3 graphene rehybridization of C atoms below the Pt cluster induces a 1.1 eV CLS splitting between Pt-and Ir-bonded C atoms; this prediction is also consistent with the XPS data.
Through intercalation of metals and gases the Dirac cone of graphene on Ir(111) can be shifted with respect to the Fermi level without becoming destroyed by strong hybridization. Here, we use x-ray photoelectron spectroscopy to measure the C 1s core level shift(CLS) of graphene in contact with a number of structurally well-defined intercalation layers (O, H, Eu, and Cs). By analysis of our own and additional literature data for decoupled graphene, the C 1s CLS is found to be a non-monotonic function of the doping level. For small doping levels the shifts are well described by a rigid band model. However, at larger doping levels, a second effect comes into play which is proportional to the transferred charge and counteracts the rigid band shift. Moreover, not only the position, but also the C 1s peak shape displays a unique evolution as a function of doping level. Our conclusions are supported by intercalation experiments with Li, with which, due to the absence of phase separation, the doping level of graphene can be continuously tuned.
We present the atomic structure of Ir nanoparticles with 1.5 nm diameter at half height and three layers average height grown on graphene/Ir(111). Using surface x-ray diffraction, we demonstrate that Ir nanoparticles on graphene/Ir(111) form a crystallographic superlattice with high perfection. The superlattice arrangement allows us to obtain detailed information on the atomic structure of the nanoparticles themselves, such as size, shape, internal layer stacking and strain. Our experiments disclose that the nanoparticles reside epitaxially on top of the graphene moiré structure on Ir(111), resulting in significant lateral compressive intraparticle strain. Normal incidence x-ray standing wave experiments deliver additional information on the particle formation induced restructuring of the graphene layer.
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