Dirk Hauschild

Complete determination of molecular orbitals by measurement of phase symmetry and electron density

Several experimental methods allow measuring the spatial probability density of electrons in atoms, molecules and solids, that is, the absolute square of the respective single-particle wave function. But it is an intrinsic problem of the measurement process that the information about the phase is generally lost during the experiment. The symmetry of this phase, however, is a crucial parameter for the knowledge of the full orbital information in real space. Here, we report on a key experiment that demonstrates that the phase symmetry can be derived from a strictly experimental approach from the circular dichroism in the angular distribution of photoelectrons. In combination with the electron density derived from the same experiment, the full quantum mechanical wave function can thus be determined experimentally.

Building block picture of the electronic structure of aqueous cysteine derived from resonant inelastic soft X-ray scattering.

The electronic structure of the amino acid L-cysteine in an aqueous environment was studied using resonant inelastic soft X-ray scattering (RIXS) in a 2D map representation and analyzed in the framework of a building block approach. The element selectivity of RIXS allows a local investigation of the electronic structure of the three functional groups of cysteine, namely, the carboxyl, amino, and thiol groups, by measuring at the O K, N K, and S L2,3 edges, respectively. Variation of the pH value allows an investigation of molecules with protonated and deprotonated functional groups, which can then be compared with simple reference molecules that represent the isolated functional groups. We find that such building blocks can provide an excellent description of X-ray emission spectroscopy (XES) and RIXS spectra, but only if all nearest-neighbor atoms are included. This finding is analogous to the building block principle commonly used in X-ray absorption spectroscopy. The building blocks show a distinct spectral character (fingerprint) and allow a comprehensive interpretation of the cysteine spectra. This simple approach opens the path to investigate the electronic structure of more complex biological molecules in aqueous solutions using XES and RIXS.

Impact of environmental conditions on the chemical surface properties of Cu(In,Ga)(S,Se)2 thin-film solar cell absorbers

Environmentally driven aging effects play a crucial role in thin-film solar cells based on Cu(In,Ga)(S,Se)2, both for long-term stability and short air exposure during production. For a better understanding of such effects, Cu(In,Ga)(S,Se)2 absorber surfaces were investigated by x-ray photoelectron and Auger electron spectroscopy after exposure to different environmental conditions. Identical absorbers were stored in a nitrogen atmosphere, in damp heat, and under ambient conditions for up to 14 days. We find varying degrees of diffusion of sulfur, copper, and sodium towards the surface, with potential impact on the electronic surface structure (band gap) and the properties of the interface to a buffer layer in a solar cell device. Furthermore, we observe an oxidation (in decreasing order) of indium, copper, and selenium (but no oxidation of sulfur). And finally, varying amounts of carbon- and oxygen-containing adsorbates are found. In particular, the findings suggest that, for ambient air exposure, sodium carbonate is formed at the surface.

A closer look at initial CdS growth on high-efficiency Cu(In, Ga)Se 2 absorbers using surface-sensitive methods

In this contribution we present further evidence that the post-deposition treatment with alkali elements (PDT) on Cu(In,Ga)Se2 (CIGS) films can positively influence the initial growth of chemical-bath-deposited CdS. We investigate the surface of CIGS films with and without PDT during initial growth of CdS by various surface-sensitive methods — x-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and high-resolution scanning electron microscopy — in order to gather information about the growth rate and coverage of CdS on the two surface types. We find that the CdS film deposited for 180 seconds on PDT-CIGS is mostly closed, while samples without PDT show very inhomogeneous coverage. Furthermore, for growth on PDT-CIGS, the effective CdS film thickness is determined to be higher by both XPS and SE. Finally, we present a discussion of the information content of the methods employed here.

Isotope Effects in the Resonant Inelastic Soft X-ray Scattering Maps of Gas-Phase Methanol

The electronic structure of gas-phase methanol molecules (H3COH, H3COD, and D3COD) at atmospheric pressure was investigated using resonant inelastic soft X-ray scattering (RIXS) at the O K and C K edges. We observe strong changes of the relative emission intensities of all valence orbitals as a function of excitation energy, which can be related to the symmetries of the involved orbitals causing an angularly anisotropic RIXS intensity. Furthermore, all observed emission lines are subject to strong spectator shifts of up to -0.9 eV at the O K edge and up to -0.3 eV at the C K edge. At the lowest O K resonance, we find clear evidence for dissociation of the methanol molecule on the time scale of the RIXS process, which is illustrated by comparing X-ray emission spectra of regular and deuterated methanol.

Band-Gap Widening at the Cu(In,Ga)(S,Se)2 Surface: A Novel Determination Approach Using Reflection Electron Energy Loss Spectroscopy

Using reflection electron energy loss spectroscopy (REELS), we have investigated the optical properties at the surface of a chalcopyrite-based Cu(In,Ga)(S,Se)2 (CIGSSe) thin-film solar cell absorber, as well as an indium sulfide (InxSy) buffer layer before and after annealing. By fitting the characteristic inelastic scattering cross-section λK(E) to cross sections evaluated by the QUEELS-ε(k,ω)-REELS software package, we determine the surface dielectric function and optical properties of these samples. A comparison of the optical values at the surface of the InxSy film with bulk ellipsometry measurements indicates a good agreement between bulk- and surface-related optical properties. In contrast, the properties of the CIGSSe surface differ significantly from the bulk. In particular, a larger (surface) band gap than for bulk-sensitive measurements is observed, providing a complementary and independent confirmation of earlier photoelectron spectroscopy results. Finally, we derive the inelastic mean free path λ for electrons in InxSy, annealed InxSy, and CIGSSe at a kinetic energy of 1000 eV.

X-ray Emission Spectroscopy of Proteinogenic Amino Acids at All Relevant Absorption Edges

Nonresonant N K, O K, C K, and S L2,3 X-ray emission spectra of the 20 most common proteinogenic amino acids in their solid zwitterionic form are reported. They represent a comprehensive database that can serve as a reliable basis for the X-ray absorption spectroscopy (XES) studies of peptides and proteins. At the most important N and O K edges, clear similarities and differences between the spectra of certain amino acids are observed and associated with the specific chemical structure of these molecules and their functional groups. Analysis of these spectra allows the generation of spectral fingerprints of the protonated amino group, the deprotonated carboxylic group, and, using a building block approach, the specific nitrogen- and oxygen-containing functional groups in the side chains of the amino acids. Some of these fingerprints are compared to the spectra of reference compounds with the respective functional groups; they exhibit reasonable similarity, underlining the validity of the spectral fingerprint approach. The C K and S L2,3 XES spectra are found to be specific for each amino acid, in accordance with the different local environments of the involved C and S atoms, respectively.

Titanium Dioxide Nanoparticles: Synthesis, X-Ray Line Analysis and Chemical Composition Study

TiO2 nanoparticleshave been synthesized by the sol-gel method using titanium alkoxide and isopropanolas a precursor. The structural properties and chemical composition of the TiO2 nanoparticles were studied usingX-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy.The X-ray powder diffraction pattern confirms that the particles are mainly composed of the anatase phase with the preferential orientation along [101] direction.The physical parameters such as strain, stress and energy density were investigated from the Williamson- Hall (W-H) plot assuming a uniform deformation model (UDM), and uniform deformation energy density model (UDEDM). The W-H analysis shows an anisotropic nature of the strain in nanopowders. The scanning electron microscopy image shows clear TiO2 nanoparticles with particle sizes varying from 60 to 80nm. The results of mean particle size of TiO2 nanoparticles show an inter correlation with the W-H analysis and SEM results. Our X-ray photoelectron spectroscopy spectra show that nearly a complete amount of titanium has reacted to TiO2.

Quantitative analysis of electron energy loss spectra and modelling of optical properties of multilayer systems for extreme ultraviolet radiation regime

Ruthenium capped multilayer coatings for use in the extreme ultraviolet (EUV) radiation regime have manifold applications in science and industry. Although the Ru cap shall protect the reflecting multilayers, the surface of the heterostructures suffers from contamination issues and surface degradation. In order to get a better understanding of the effects of these impurities on the optical parameters, reflection electron energy loss spectroscopy (REELS) measurements of contaminated and H cleaned Ru multilayer coatings were taken at various primary electron beam energies. Experiments conducted at low primary beam energies between 100u2009eV and 1000u2009eV are very surface sensitive due to the short inelastic mean free path of the electrons in this energy range. Therefore, influences of the surface condition on the above mentioned characteristics can be appraised. In this paper, it can be shown that carbon and oxide impurities on the mirror surface decrease the transmission of the Ru cap by about 0.75% and the ove...

Rubidium Fluoride Post-Deposition Treatment: Impact on the Chemical Structure of the Cu(In,Ga)Se2 Surface and CdS/Cu(In,Ga)Se2 Interface in Thin-Film Solar Cells

We present a detailed characterization of the chemical structure of the Cu(In,Ga)Se2 thin-film surface and the CdS/Cu(In,Ga)Se2 interface, both with and without a RbF post-deposition treatment (RbF-PDT). For this purpose, X-ray photoelectron and Auger electron spectroscopy, as well as synchrotron-based soft X-ray emission spectroscopy have been employed. Although some similarities with the reported impacts of light-element alkali PDT (i.e., NaF- and KF-PDT) are found, we observe some distinct differences, which might be the reason for the further improved conversion efficiency with heavy-element alkali PDT. In particular, we find that the RbF-PDT reduces, but not fully removes, the copper content at the absorber surface and does not induce a significant change in the Ga/(Ga + In) ratio. Additionally, we observe an increased amount of indium and gallium oxides at the surface of the treated absorber. These oxides are partly (in the case of indium) and completely (in the case of gallium) removed from the CdS/Cu(In,Ga)Se2 interface by the chemical bath deposition of the CdS buffer.