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The chemical shift of core level binding energies makes electron spectroscopy for chemical analysis (ESCA) a workhorse analytical tool for science and industry. For some elements, close lying and overlapping spectral features within the natural life time broadening restrict applications. We establish how the core level binding energy chemical shift can be picked up experimentally by the additional selectivity through Auger electron photoelectron coincidence spectroscopy (APECS). Coincident measurement of Ni 3p photoemission with different MVV Auger regions from specific decay channels, narrows the 3p core-levels to a width of 1.2 eV, resolves the spin-orbit splitting of 1.6 eV and determines the chemical shift of Ni 3p levels of a Ni(111) single crystal and its oxidized surface layer to 0.6 eV.

In this work, we present the CoESCA station for electron-electron coincidence spectroscopy from surfaces, built in a close collaboration between Uppsala University and Helmholtz-Zentrum Berlin at the BESSY II synchrotron facility in Berlin, Germany. We start with a detailed overview of previous work in the field of electron-electron coincidences, before we describe the CoESCA setup and its design parameters. The system is capable of recording shot-to-shot resolved 6D coincidence datasets, i.e. the kinetic energy and the two take off angles for both coincident electrons. The mathematics behind extracting and analysing these multi-dimensional coincidence datasets is introduced, with a focus on coincidence statistics, resulting in fundamental limits of the signal-to-noise ratio and its implications for acquisition times and the size of the raw data stream. The functionality of the CoESCA station is demonstrated for the example of Auger electron-photoelectron coincidences from silver surfaces for photoelectrons from the Ag 3d core levels and their corresponding MNN Auger electrons. The Auger spectra originating from the different core levels, 3d3/2 and 3d5/2 could be separated and further, the two-hole state energy distributions were determined for these Auger decay channels.

An investigation of the unoccupied electronic structure of the transition-metal dichalcogenide tin disulphide has been conducted using core-hole clock spectroscopy. Polarization-dependent x-ray absorption in the tender x-ray regime at the S K edge and maps of the resonant Auger spectra in the S KLL Auger kinetic energy range have been recorded. Supported with ab initio calculations of the unoccupied electronic structure, these allow us to relate resonances in the absorption cross section to excitations along various directions in the Brillouin zone. We observe anisotropy in the x-ray absorption cross section in polarization directions in plane and out of plane of the crystal. There is also anisotropy in the charge transfer dynamics as inferred from the coherent and noncoherent parts of the resonant Auger spectra. This approach can be generally used to interpret dynamics in unoccupied states, e.g., in layered structure or heterogenous interfaces.

Black phosphorus (BPh) is a layered material with strong in-plane anisotropy of its structural and electronic properties; in spite of the great potential of BPh for conceptually new devices in optoelectronics and plasmonics, its fundamental electronic excitations have not yet been fully elucidated. In order to discriminate collective (plasmons) and single-particle (inter band transitions) excitations, we investigate the energy-loss distribution of P 1s photoelectrons in hard X-ray photoelectron spectra of BPh over a wide energy range. The energy-loss function (ELF), averaged over the principal directions of the BPh crystal, has been retrieved by using a Fourier Transform analysis to eliminate multiple inelastic scattering events. At low loss energies (1-8 eV), weak unresolved energy loss peaks are well described by DFT calculated inter band transitions, showing some anisotropy in the dielectric function epsilon(omega, q) tensor of BPh. At high loss energies, the ELF is dominated by the collective excitation of valence electrons with a peak energy at 20.1 +/- 0.2 eV, and weak anisotropy is found in the DFT calculated Im(- 1/epsilon) tensor. The anomalously small peak energy (9.0 +/- 0.5 eV) of a weak surface plasmon resonance is attributed either to low surface electron density in the terminal phosphorene layer or to some anisotropic surface plasmon propagation.

The temperature dependent dehydrogenation of naphthalene on Ni(111) has been investigated using vibrational sum-frequency generation spectroscopy, X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory with the aim of discerning the reaction mechanism and the intermediates on the surface. At 110 K, multiple layers of naphthalene adsorb on Ni(111); the first layer is a flat lying chemisorbed monolayer, whereas the next layer(s) consist of physisorbed naphthalene. The aromaticity of the carbon rings in the first layer is reduced due to bonding to the surface Ni-atoms. Heating at 200 K causes desorption of the multilayers. At 360 K, the chemisorbed naphthalene monolayer starts dehydrogenating and the geometry of the molecules changes as the dehydrogenated carbon atoms coordinate to the nickel surface; thus, the molecule tilts with respect to the surface, recovering some of its original aromaticity. This effect peaks at 400 K and coincides with hydrogen desorption. Increasing the temperature leads to further dehydrogenation and production of H-2 gas, as well as the formation of carbidic and graphitic surface carbon. Published under license by AIP Publishing.

Ge nanoparticles embedded in thin films have attracted a lot of attention due to their promising optical and electronic properties that can be tuned by varying the particle size and choice of matrix material. In this study, Ge nanoparticle formation was investigated for Al-Ge-N based thin films by simultaneous measurements of HAXPES and grazing incidence XRD during in situ annealing in vacuum conditions. As-deposited Al-Ge-N thin films, synthesized by reactive dc magnetron sputtering, consisted of a nanocrystalline (Al1–xGex)Ny solid solution and an amorphous tissue phase of Ge3Ny. Upon annealing to 750 °C, elemental Ge was formed shown by both HAXPES and XRD measurements, and N2 gas was released as measured by a mass spectrometer. Postannealed ex situ analysis by SEM and TEM showed that the elemental Ge phase formed spherical nanoparticles on the surface of the film, with an average size of 210 nm. As the annealing temperature increased further to 850 °C, the Ge particles on the film surface evaporated, while the phase segregation of Ge still could be observed within the film. Thus, these results show the possibility for a controlled synthesis of Ge nanoparticles through annealing of Al-Ge-N thin films to produce materials suitable for use in electronic or optoelectronic devices.