Electron energy loss spectroscopy with parallel readout of energy and momentum

We introduce a high energy resolution electron source that matches the requirements for parallel readout of energy and momentum of modern hemispherical electron energy analyzers. The system is designed as an add-on device to typical photoemission chambers. Due to the multiplex gain, a complete phonon dispersion of a Cu(111) surface was measured in seven minutes with 4 meV energy resolution

a route towards defined surface functionalization

We investigate the surface-catalyzed dissociation of the archetypal molecular switch azobenzene on the Cu(111) surface. Based on X-ray photoelectron spectroscopy, normal incidence X-ray standing waves and density functional theory calculations a detailed picture of the coverage-induced formation of phenyl nitrene from azobenzene is presented. Furthermore, a comparison to the azobenzene/Ag(111) interface provides insight into the driving force behind the dissociation on Cu(111). The quantitative decay of azobenzene paves the way for the creation of a defect free, covalently bonded monolayer. Our work suggests a route of surface functionalization via suitable azobenzene derivatives and the on surface synthesis concept, allowing for the creation of complex immobilized molecular systems

Vertical structure of Sb-intercalated quasi-freestanding graphene on SiC(0001)

Using the normal incidence x-ray standing wave technique as well as low energy electron microscopy we have investigated the structure of quasi-freestanding monolayer graphene (QFMLG) obtained by intercalation of antimony under the $(6\sqrt{3}\times6\sqrt{3})R30^\circ$ reconstructed graphitized 6H-SiC(0001) surface, also known as zeroth-layer graphene. We found that Sb intercalation decouples the QFMLG very well from the substrate. The distance from the QFMLG to the Sb layer almost equals the expected van der Waals bonding distance of C and Sb. The Sb intercalation layer itself is mono-atomic, very flat, and located much closer to the substrate, at almost the distance of a covalent Sb-Si bond length. All data is consistent with Sb located on top of the uppermost Si atoms of the SiC bulk

Simple extension of the plane-wave final state in photoemission: Bringing understanding to the photon-energy dependence of two-dimensional materials

Angle-resolved photoemission spectroscopy (ARPES) is a method that measures orbital and band structure contrast through the momentum distribution of photoelectrons. Its simplest interpretation is obtained in the plane-wave approximation, according to which photoelectrons propagate freely to the detector. The photoelectron momentum distribution is then essentially given by the Fourier transform of the real-space orbital. While the plane-wave approximation is remarkably successful in describing the momentum distributions of aromatic compounds, it generally fails to capture kinetic-energy-dependent final-state interference and dichroism effects. Focusing our present study on quasi-freestanding monolayer graphene as the archetypical two-dimensional (2D) material, we observe an exemplary Ekin-dependent modulation of, and a redistribution of spectral weight within, its characteristic horseshoe signature around the K¯ and K¯′ points: both effects indeed cannot be rationalized by the plane-wave final state. Our data are, however, in remarkable agreement with ab initio time-dependent density functional simulations of a freestanding graphene layer and can be explained by a simple extension of the plane-wave final state, permitting the two dipole-allowed partial waves emitted from the C 2pz orbitals to scatter in the potential of their immediate surroundings. Exploiting the absolute photon flux calibration of the Metrology Light Source, this scattered-wave approximation allows us to extract Ekin-dependent amplitudes and phases of both partial waves directly from photoemission data. The scattered-wave approximation thus represents a powerful yet intuitive refinement of the plane-wave final state in photoemission of 2D materials and beyond

Quantum transport through STM-lifted single PTCDA molecules

Using a scanning tunneling microscope we have measured the quantum conductance through a PTCDA molecule for different configurations of the tip-molecule-surface junction. A peculiar conductance resonance arises at the Fermi level for certain tip to surface distances. We have relaxed the molecular junction coordinates and calculated transport by means of the Landauer/Keldysh approach. The zero bias transmission calculated for fixed tip positions in lateral dimensions but different tip substrate distances show a clear shift and sharpening of the molecular chemisorption level on increasing the STM-surface distance, in agreement with experiment.Comment: accepted for publication in Applied Physics

Determination of the adsorption geometry of PTCDA on the Cu(100) surface

The adsorption geometry, namely the height and the site, of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on the Cu(100) surface was determined by the normal incidence x-ray standing wave (NIXSW) technique including triangulation. The two PTCDA molecules in the superstructure unit cell, which have perpendicular azimuthal orientation, are both located at bridge sites, the long molecular axis being parallel to the bridge. Carboxylic oxygen atoms and several atoms of the carbon backbone are located close to on-top positions. The vertical distortion motif of PTCDA on Cu(100) differs from that on the three low-index Ag surfaces, because significant downward displacement of the carboxylic oxygen atoms is lacking. In particular, the carbon backbone of PTCDA adsorbs closer to the surface than extrapolated from Ag data. This suggests a relative increase of the attractive interactions between the carbon backbone of PTCDA and the Cu(100) surface versus the attractive interactions on the carboxylic oxygen atoms

Direct Evidence of the Temperature-Induced Molecular Reorientation in Tetracene Thin Films on AlO_<i>x</i>/Ni₃Al(111)

Control over the optical properties of the fluorescent organic layer plays a key role in the development of organic light-emitting diodes. A combination of near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy was used to study structural changes in thin films of tetracene on AlO_<i>x</i>/Ni₃Al­(111). It is shown that upon deposition onto the cold (100 K) substrate, a monolayer of tetracene molecules adopts a disordered adsorption configuration with the molecular planes orientated almost parallel to the surface. Upon annealing at 280 K, the molecular packing changes and the tetracene units adopt a more upright orientation. The consequences of this orientational change for the luminescent properties of the molecular adlayer are discussed, in particular with regard to a quenching of the optical excitation by an electronic coupling of occupied and unoccupied molecular states to those of the metal substrate

Quantitative Prediction of Molecular Adsorption: Structure and Binding of Benzene on Coinage Metals

Interfaces between organic molecules and solid surfaces play a prominent role in heterogeneous catalysis, molecular sensors and switches light-emitting diodes, and photovoltaics. The properties and the ensuing function of such hybrid interfaces often depend exponentially on molecular adsorption heights and binding strengths, calling for well-established benchmarks of these two quantities. Here we present systematic measurements that enable us to quantify the interaction of benzene with the Ag(111) coinage metal substrate with unprecedented accuracy (0.02 angstrom in the vertical adsorption height and 0.05 eV in the binding strength) by means of normal-incidence x-ray standing waves and temperature-programed desorption techniques. Based on these accurate experimental benchmarks for a prototypical molecule-solid interface, we demonstrate that recently developed first-principles calculations that explicitly account for the nonlocality of electronic exchange and correlation effects are able to determine the structure and stability of benzene on the Ag(111) surface within experimental error bars. Remarkably, such precise experiments and calculations demonstrate that despite different electronic properties of copper, silver, and gold, the binding strength of benzene is equal on the (111) surface of these three coinage metals. Our results suggest the existence of universal binding energy trends for aromatic molecules on surfaces