A model system has been created to shuttle electrons through a metal-insulator-metal (MIM) structure to induce the formation of a CO2 anion radical from adsorbed gas-phase carbon dioxide that subsequently reacts to form an oxalate species. The process is completely reversible, and thus allows the elementary steps involved to be studied at the atomic level. The oxalate species at the MIM interface have been identified locally by scanning tunneling microscopy, chemically by IR spectroscopy, and their formation verified by density functional calculations.

Self‐assembly of functional supra‐molecular nanostructures is among the most promising strategies for further development of organic electronics. However, a poor control of the interactions driving the assembling phenomena still hampers the tailored growth of designed structures. Here exploration of how non‐covalent molecule‐substrate interactions can be modified on a molecular level is described. For that, mixtures of DIP and F16CuPc, two molecules with donor and acceptor character, respectively are investigated. A detailed study of their structural and electronic properties is performed. In reference to the associated single‐component layers, the growth of binary layers results in films with strongly enhanced intermolecular interactions and consequently reduced molecule‐substrate interactions. This new insight into the interplay among the aforementioned interactions provides a novel strategy to balance the critical interactions in the assembly processes by the appropriate choice of molecular species in binary supra‐molecular assemblies, and thereby control the self‐assembly of functional organic nanostructures.

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

Vicinal surfaces of the (111) plane of noble metals are characterized by free-electron-like surface states that scatter at one-dimensional step edges, making them ideal model systems to test the electronic properties of periodic lateral nanostructures. Here we use high-resolution, angle-resolved photoemission to analyse the evolution of the surface state on a variety of vicinal surface structures where both the step potential barrier and the superlattice periodicity can vary. A transition in the electron dimensionality is found as we vary the terrace size in single-phase step arrays. In double-phase, periodic faceted surfaces, we observe surface states that characterize each of the phases.

We report a comprehensive study of the self-assembly of a diindenoperylene (DIP) monolayer on Au(111) single crystals exploiting different electron probes ranging from STM and LEED to photoelectron spectroscopy and NEXAFS. By this multitechnique approach, we obtain a full picture of the crystallographic and electronic structure of the DIP layer as well as an insight into the assembly process and the role of the DIP−Au interactions. We contrast these experimental findings with theoretical calculations.

Alkali-antimonide photocathodes were grown on Si(100) and studied by means of XPS and UHV-AFM to validate the growth procedure and morphology of this material. The elements were evaporated sequentially at elevated substrate temperatures (first Sb, second K, third Cs). The generated intermediate K-Sb compound itself is a photocathode and the composition of K2.4Sb is close to the favored K3Sb stoichiometry. After cesium deposition, the surface layer is cesium enriched. The determined rms roughness of 25 nm results in a roughness domination of the emittance in the photoinjector already above 3 MV/m

We present an analysis of the electronic structure of C60 adsorbed on a vicinal Au(111) surface at different fullerene coverages using photoemission, x-ray absorption, and scanning tunneling microscopy/spectroscopy (STS). STS provides a straightforward determination of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels with respect to the Fermi energy. At C60 coverages of 0.5 and 1 ML a 2.7 eV wide HOMO-LUMO gap is found. The near-edge x-ray absorption fine structure (NEXAFS) spectrum for the 0.5 ML C60 nanomesh structure displays a significant intensity at the low energy side of the LUMO exciton peak, which is explained as due to absorption into HOMO-LUMO gap states localized at individual C60 cluster edges. From 0.5 to 1 ML we observe a rigid shift of the HOMO-LUMO peaks in the STS spectra and an almost complete quenching of the gap states feature in NEXAFS.

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