Using the X-ray standing wave method, scanning tunneling microscopy, low energy electron diffraction, and density functional theory, we precisely determine the lateral and vertical structure of hexagonal boron nitride on Ir(111). The moiré superstructure leads to a periodic arrangement of strongly chemisorbed valleys in an otherwise rather flat, weakly physisorbed plane. The best commensurate approximation of the moiré unit cell is (12 × 12) boron nitride cells resting on (11 × 11) substrate cells, which is at variance with several earlier studies. We uncover the existence of two fundamentally different mechanisms of layer formation for hexagonal boron nitride, namely, nucleation and growth as opposed to network formation without nucleation. The different pathways are linked to different distributions of rotational domains, and the latter enables selection of a single orientation only.

Low energy ion beam pattern formation on Si with simultaneous co-deposition of Ag, Pd, Pb, Ir, Fe or C impurities was investigated by in situ scanning tunneling microscopy as well as ex situ atomic force microscopy, scanning electron microscopy, transmission electron microscopy and Rutherford backscattering spectrometry. The impurities were supplied by sputter deposition. Additional insight into the mechanism of pattern formation was obtained by more controlled supply through e-beam evaporation. For the situations investigated, the ability of the impurity to react with Si, i.e. to form a silicide, appears to be a necessary, but not a sufficient condition for pattern formation. Comparing the effects of impurities with similar mass and nuclear charge, the collision kinetics is shown to be not of primary importance for pattern formation. To understand the observed phenomena, it is necessary to assume a bi-directional coupling of composition and height fluctuations. This coupling gives rise to a sensitive dependence of the final morphology on the conditions of impurity supply. Because of this history dependence, the final morphology cannot be uniquely characterized by a steady state impurity concentration.

The moiré of a monolayer of hexagonal boron nitride on Ir(111) is found to be a template for Ir, C, and Au cluster superlattices. Using scanning tunneling microscopy, the cluster structure and epitaxial relation to the substrate, the cluster binding site, the role of defects, as well as the thermal stability of the cluster lattice are investigated. The Ir and C cluster superlattices display a high thermal stability, before they decay by intercalation and Smoluchowski ripening. Ab initio calculations explain the extraordinarily strong Ir cluster binding through selective sp rehybridization of boron nitride involving B-Ir cluster bonds and a strengthening of the nitrogen bonds to the Ir substrate in a specific, initially only chemisorbed valley area within the moiré.

Motivated by the relevance of Pt clusters in heterogeneous catalysis, ordered Pt cluster superlattices are templated by the moiréof monolayer hexagonal boron nitride (h-BN) with Ir(111). Using X-ray photoelectron spectroscopy, scanning tunneling microscopy, and scanning tunneling spectroscopy, we provide a comprehensive picture for the mechanism of cluster binding, the thermal stability of clusters, cluster superlattice decay, the morphological evolution of cluster shape with size, and finally Pt cluster decoupling and internal electronic structure. The key findings are that the Pt cluster superlattices on h-BN on Ir(111) are thermally more stable than any other Pt cluster superlattice, are well decoupled from their substrate, and display a discrete cluster height-dependent electronic structure.

Iridium cluster superlattices on the graphene moiré with Ir(111) are embedded with elemental carbon through vapor-phase deposition. Using scanning tunneling microscopy and spectroscopy, we find that carbon embedding is conformal and does not deteriorate the excellent order of the iridium clusters. The thermal and mechanical stability of the embedded clusters is greatly enhanced. Smoluchowski ripening as well as cluster pick-up by the scanning tunneling microscopy tip are both suppressed. The only cluster decay path left takes place at an elevated temperature of around 1050 K. The cluster material penetrates through the graphene sheet, whereby it becomes bound to the underlying metal. It is argued that conformal carbon embedding is an important step towards the formation of a new type of sintering-resistant cluster lattice material for nanocatalysis and nanomagnetism.

Annealing of a monolayer of hexagonal boron nitride destroyed by Xe ion irradiation gives rise to rich structural phenomena investigated here through a combination of scanning tunneling microscopy, low-energy electron diffraction, x-ray photoelectron spectroscopy, and density functional theory calculations. We find selective pinning of vacancy clusters at a single specific location within the moiré formed by hexagonal boron nitride (h-BN) and the Ir substrate, crystalline Xe at room temperature of monolayer and bilayer thickness sealed inside h-BN blisters, standalone blisters only bound to the metal at temperatures where boron nitride on Ir (111) decomposes, and finally a pronounced threefold symmetry of all morphological features due to the preferential formation of boron-terminated zigzag edges that firmly bind to the substrate. The investigations give clear insight into the relevance of the substrate for the damage creation and annealing in a two-dimensional layer material.

Cluster superlattice membranes consist of a two-dimensional hexagonal lattice of similar-sized nanoclusters sandwiched between single-crystal graphene and an amorphous carbon matrix. The fabrication process involves three main steps, the templated self-organization of a metal cluster superlattice on epitaxial graphene on Ir(111), conformal embedding in an amorphous carbon matrix, and subsequent lift-off from the Ir(111) substrate. The mechanical stability provided by the carbon-graphene matrix makes the membrane stable as a free-standing material and enables transfer to other substrates. The fabrication procedure can be applied to a wide variety of cluster materials and cluster sizes from the single-atom limit to clusters of a few hundred atoms, as well as other two-dimensional layer/host matrix combinations. The versatility of the membrane composition, its mechanical stability, and the simplicity of the transfer procedure make cluster superlattice membranes a promising material in catalysis, magnetism, energy conversion, and optoelectronics.

With the goal to delevop the fabrication of a new type of Pt-nanoparticle carbon–support electrocatalyst, we investigate the carbon embedding of Pt cluster superlattices grown on the moiré of a monolayer of hexagonal boron nitride (h-BN) on Ir(111). Our combined scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) study establishes conformal C embedding of the Pt clusters on h-BN/Ir(111) without deterioration of superlattice order, preferential and strong binding of the embedding carbon to the Pt clusters, and upon annealing the formation of a homogeneous amorphous carbon (a-C) matrix. There are indications that while the a-C matrix and the Pt clusters bind strongly to each other, upon annealing both weaken their binding to h-BN.