Nearly-freestanding supramolecular assembly with tunable structural properties.

The synthesis and design of two-dimensional supramolecular assemblies with specific functionalities is one of the principal goals of the emerging field of molecule-based electronics, which is relevant for many technological applications. Although a large number of molecular assemblies have been already investigated, engineering uniform and highly ordered two-dimensional molecular assemblies is still a challenge. Here we report on a novel approach to prepare wide highly crystalline molecular assemblies with tunable structural properties. We make use of the high-reactivity of the carboxylic acid functional moiety and of the predictable structural features of non-polar alkane chains to synthesize 2D supramolecular assemblies of 4-(decyloxy)benzoic acid (4DBA;C[Formula: see text]H[Formula: see text]O[Formula: see text]) on a Au(111) surface. By means of scanning tunneling microscopy, density functional theory calculations and photoemission spectroscopy, we demonstrate that these molecules form a self-limited highly ordered and defect-free two-dimensional single-layer film of micrometer-size, which exhibits a nearly-freestanding character. We prove that by changing the length of the alkoxy chain it is possible to modify in a controlled way the molecular density of the "floating" overlayer without affecting the molecular assembly. This system is especially suitable for engineering molecular assemblies because it represents one of the few 2D molecular arrays with specific functionality where the structural properties can be tuned in a controlled way, while preserving the molecular pattern.

Empty electron states in cobalt-intercalated graphene.

The dispersion of the electronic states of epitaxial graphene (Gr) depends significantly on the strength of the bonding with the underlying substrate. We report on empty electron states in cobalt-intercalated Gr grown on Ir(111), studied by angle-resolved inverse photoemission spectroscopy and x-ray absorption spectroscopy, complemented with density functional theory calculations. The weakly bonded Gr on Ir preserves the peculiar spectroscopic features of the Gr band structure, and the empty spectral densities are almost unperturbed. Upon intercalation of a Co layer, the electronic response of the interface changes, with an intermixing of the Gr π* bands and Co d states, which breaks the symmetry of π/σ states, and a downshift of the upper part of the Gr Dirac cone. Similarly, the image potential of Ir(111) is unaltered by the Gr layer, while a downward shift is induced upon Co intercalation, as unveiled by the image state energy dispersion mapped in a large region of the surface Brillouin zone.

Zinc(II) tetraphenylporphyrin on Au(111) investigated by scanning tunnelling microscopy and photoemission spectroscopy measurements.

Porphyrins are a versatile class of molecules, which have attracted attention over the years due to their electronic, optical and biological properties. Self-assembled monolayers of porphyrins were widely studied on metal surfaces in order to understand the supramolecular organization of these molecules, which is a crucial step towards the development of devices starting from the bottom-up approach. This perspective could lead to tailor the interfacial properties of the surface, depending on the specific interaction between the molecular assembly and the metal surface. In this study, we revisit the investigation of the assembly of zinc-tetraphenylporphyrins on Au(111) in order to explore the adsorption of the molecular network on the noble metal substrate. The combined analysis of scanning tunneling microscopy (STM) imaging and core levels photoemission spectroscopy measurements support a peculiar arrangement of the ZnTPP molecular network, with Zn atoms occupying the bridge sites of the Au surface atoms. Furthermore, we prove that, at few-layers coverage, the interaction between the deposited layers allows a relevant molecular mobility of the adlayer, as observed by STM and supported by core levels photoemission analysis.

Multiple Coexisting Dirac Surface States in Three-Dimensional Topological Insulator PbBi6Te10.

By means of angle-resolved photoemission spectroscopy (ARPES) measurements, we unveil the electronic band structure of three-dimensional PbBi6Te10 topological insulator. ARPES investigations evidence multiple coexisting Dirac surface states at the zone-center of the reciprocal space, displaying distinct electronic band dispersion, different constant energy contours, and Dirac point energies. We also provide evidence of Rashba-like split states close to the Fermi level, and deeper M- and V-shaped bands coexisting with the topological surface states. The experimental findings are in agreement with scanning tunneling microscopy measurements revealing different surface terminations according to the crystal structure of PbBi6Te10. Our experimental results are supported by density functional theory calculations predicting multiple topological surface states according to different surface cleavage planes.

Interaction of iron phthalocyanine with the graphene/Ni(111) system.

Graphene grown on crystalline metal surfaces is a good candidate to act as a buffer layer between the metal and organic molecules that are deposited on top, because it offers the possibility to control the interaction between the substrate and the molecules. High-resolution angular-resolved ultraviolet photo electron spectroscopy (ARPES) is used to determine the interaction states of iron phthalocyanine molecules that are adsorbed onto graphene on Ni(111). The iron phthalocyanine deposition induces a quenching of the Ni d surface minority band and the appearance of an interface state on graphene/Ni(111). The results have been compared to the deposition of iron phthalocyanine on graphene/Ir(111), for which a higher decoupling of the organic molecule from the underlying metal is exerted by the graphene buffer layer.

Two distinct phases of bilayer graphene films on Ru(0001).

By combining angle-resolved photoemission spectroscopy and scanning tunneling microscopy we reveal the structural and electronic properties of multilayer graphene on Ru(0001). We prove that large ethylene exposure allows the synthesis of two distinct phases of bilayer graphene with different properties. The first phase has Bernal AB stacking with respect to the first graphene layer and displays weak vertical interaction and electron doping. The long-range ordered moiré pattern modulates the crystal potential and induces replicas of the Dirac cone and minigaps. The second phase has an AA stacking sequence with respect to the first layer and displays weak structural and electronic modulation and p-doping. The linearly dispersing Dirac state reveals the nearly freestanding character of this novel second-layer phase.

Large band gap opening between graphene Dirac cones induced by Na adsorption onto an Ir superlattice.

We investigate the effects of Na adsorption on the electronic structure of bare and Ir cluster superlattice-covered epitaxial graphene on Ir(111) using angle-resolved photoemission spectroscopy and scanning tunneling microscopy. At Na saturation coverage, a massive charge migration from sodium atoms to graphene raises the graphene Fermi level by ~1.4 eV relative to its neutrality point. We find that Na is adsorbed on top of the graphene layer, and when coadsorbed onto an Ir cluster superlattice, it results in the opening of a large band gap of Δ(Na/Ir/G) = 740 meV, comparable to the one of Ge and with preserved high group velocity of the charge carriers.

Giant spin splitting through surface alloying.

The long-range ordered surface alloy Bi/Ag(111) is found to exhibit a giant spin splitting of its surface electronic structure due to spin-orbit coupling, as is determined by angle-resolved photoelectron spectroscopy. First-principles electronic structure calculations fully confirm the experimental findings. The effect is brought about by a strong in-plane gradient of the crystal potential in the surface layer, in interplay with the structural asymmetry due to the surface-potential barrier. As a result, the spin polarization of the surface states is considerably rotated out of the surface plane.