Patricia A. Thiel

The front cover artwork is provided by Dr. Peter Spurgeon, Dr. Da‐Jiang Liu, and Prof. Jim Evans at Ames Laboratory USDOE and Iowa State University. The top images show the decay of a 2D Au island on Au(111) in the presence of 24 milli‐monolayers of S. The enhancement of island decay with increasing S coverage is quantified in the lower left image for ∼85 nm² Au islands. The Au‐S complexes implicated as facile mass carriers enhancing decay are also illustrated. Read the full text of the Article at 10.1002/cphc.202000884.

Metal nanoclusters encapsulated beneath the graphite surface present novel surface nanostructures and open opportunities to investigate and control interfacial properties.

Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages,θ_S, of a few hundredths of a monolayer (ML), and is most pronounced for 0.1–0.3 ML where the decay rate is increased by a factor of around 30. Forθ_Sclose to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lowerθ_Sis attributed to the formation and diffusion across terraces of Au−S complexes, particularly AuS₂and Au₄S₄, with some lesser contribution from Au₃S₄. This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers.

Paradoxically a very broad diffraction background, named the Bell-Shaped-Component (BSC), has been established as a feature of graphene growth. Although the BSC has been present in the earlier literature it has been ignored. Recent diffraction studies as a function of electron energy have shown that the BSC is not related to scattering interference. The BSC is a very strong effect, but its origin is still unclear. Here, additional experiments are carried out as a function of temperature while monitoring changes in the intensity of different spots over the range that single-layer-graphene (SLG) grows. Quantitative fitting of the profiles shows that the BSC follows the increase of the G(10) spot, proving directly that BSC is an indicator of high quality graphene. Additional metal deposition experiments provide more information about the BSC. The BSC is insensitive to metal deposition and it increases with metal intercalation, because a more uniform interface forms between graphene and SiC. These experiments support the conclusion that the BSC originates from electron spatial confinement within SLG and surprisingly it is an excellent measure of graphene uniformity, instead of film disorder.

Using scanning tunneling microscopy, we show that Pt clusters can be encapsulated beneath the surface of graphite, whereas Ag and Au cannot. This is in complete agreement with independent predictions from density functional theory, which show that surface intercalation of single metal atoms is favorable for Pt, but unfavorable for Ag and Au. This supports the validity of using single-metal-atom energetics for predicting encapsulation of metal nanoparticles at the graphite surface. We also demonstrate that the optimal temperature for encapsulation scales with the cohesive energy of the metal.

Ordering of different chalcogens, S, Se, and Te, on Au(111) exhibit broad similarities but also some distinct features, which must reflect subtle differences in relative values of the long-range pair and many-body lateral interactions between adatoms. We develop lattice-gas (LG) models within a cluster expansion framework, which includes about 50 interaction parameters. These LG models are developed based on density functional theory (DFT) analysis of the energetics of key adlayer configurations in combination with the Monte Carlo (MC) simulation of the LG models to identify statistically relevant adlayer motifs, i.e., model development is based entirely on theoretical considerations. The MC simulation guides additional DFT analysis and iterative model refinement. Given their complexity, development of optimal models is also aided by strategies from supervised machine learning. The model for S successfully captures ordering motifs over a broader range of coverage than achieved by previous models, and models for Se and Te capture the features of ordering, which are distinct from those for S. More specifically, the modeling for all three chalcogens successfully explains the linear adatom rows (also subtle differences between them) observed at low coverages of ∼0.1 monolayer. The model for S also leads to a new possible explanation for the experimentally observed phase with a (5 × 5)-type low energy electron diffraction (LEED) pattern at 0.28 ML and to predictions for LEED patterns that would be observed with Se and Te at this coverage.

We use a variety of experimental techniques to characterize Cu clusters on bulk MoS₂ formed via physical vapor deposition of Cu in ultrahigh vacuum, at temperatures ranging from 300 K to 900 K. We find that large facetted clusters grow at elevated temperatures, using high Cu exposures. The cluster size distribution is bimodal, and under some conditions, large clusters are surrounded by a denuded zone. We propose that defect-mediated nucleation, and coarsening during deposition, are both operative in this system. At 780 K, a surprising type of facetted cluster emerges, and at 900 K this type predominates: pyramidal clusters with a triangular base, exposing (311) planes as side facets. This is a growth shape, rather than an equilibrium shape.

We describe and analyze in detail the shapes of Fe islands encapsulated under the top graphene layers in graphite. Shapes are interrogated using scanning tunneling microscopy. The main outputs of the shape analysis are the slope of the graphene membrane around the perimeter of the island, and the aspect ratio of the central metal cluster. Modeling primarily uses a continuum elasticity (CE) model. As input to the CE model, we use density functional theory to calculate the surface energy of Fe, and the adhesion energies between Fe and graphene or graphite. We use the shaft-loaded blister test (SLBT) model to provide independent stretching and bending strain energies in the graphene membrane. We also introduce a model for the elastic strain in which stretching and bending are treated simultaneously. Measured side slopes agree very well with the CE model, both qualitatively and quantitatively. The fit is optimal for a graphene membrane consisting of 2–3 graphene monolayers, in agreement with experiment. Analysis of contributions to total energy shows that the side slope depends only on the properties of graphene/graphite. This reflects delamination of the graphene membrane from the underlying graphite, caused by upward pressure from the growing metal cluster. This insight leads us to evaluate the delamination geometry in the context of two related, classic models that give analytic results for the slope of a delaminated membrane. One of these, the point-loaded circular blister test model, reasonably predicts the delamination geometry at the edge of an Fe island. The aspect ratio also agrees well with the CE model in the limit of large island size, but not for small islands. Previously, we had speculated that this discrepancy was due to lack of coupling between bending and stretching in the SLBT model, but the new modeling shows that this explanation is not viable.