Probing hydrogen bonding orbitals: resonant inelastic soft X-ray scattering of aqueous NH3.

To probe the influence of hydrogen bonding on the electronic structure of ammonia, gas phase and aqueous NH3 have been investigated using soft X-ray absorption (XAS), resonant inelastic soft X-ray scattering (RIXS), and electronic structure calculations including dynamical effects. Strong spectral differences in the XAS scans as well as in the RIXS spectra between gas phase and aqueous NH3 are attributed to orbital mixing with the water orbitals, dipole-dipole interactions, differences in vibronic coupling, and nuclear dynamics on the time-scale of the RIXS process. All of these effects are consequences of hydrogen bonding and the impact of the associated orbitals, demonstrating the power of XAS and RIXS as unique tools to study hydrogen bonding in liquids.

The Be K-edge in beryllium oxide and chalcogenides: soft x-ray absorption spectra from first-principles theory and experiment.

We have carried out a theoretical and experimental investigation of the beryllium K-edge soft x-ray absorption fine structure of beryllium compounds in the oxygen group, considering BeO, BeS, BeSe, and BeTe. Theoretical spectra are obtained ab initio, through many-body perturbation theory, by solving the Bethe-Salpeter equation (BSE), and by supercell calculations using the core-hole approximation. All calculations are performed with the full-potential linearized augmented plane-wave method. It is found that the two different theoretical approaches produce a similar fine structure, in good agreement with the experimental data. Using the BSE results, we interpret the spectra, distinguishing between bound core-excitons and higher energy excitations.

First experimental proof for aberration correction in XPEEM: resolution, transmission enhancement, and limitation by space charge effects.

The positive effect of double aberration correction in x-ray induced Photoelectron Emission Microscopy (XPEEM) has been successfully demonstrated for both, the lateral resolution and the transmission, using the Au 4f XPS peak for element specific imaging at a kinetic energy of 113 eV. The lateral resolution is improved by a factor of four, compared to a non-corrected system, whereas the transmission is enhanced by a factor of 5 at a moderate resolution of 80 nm. With an optimized system setting, a lateral resolution of 18 nm could be achieved, which is up to now the best value reported for energy filtered XPEEM imaging. However, the absolute resolution does not yet reach the theoretical limit of 2 nm, which is due to space charge limitation. This occurs along the entire optical axis up to the contrast aperture. In XPEEM the pulsed time structure of the exciting soft x-ray light source causes a short and highly intense electron pulse, which results in an image blurring. In contrast, the imaging with elastically reflected electrons in the low energy electron microscopy (LEEM) mode yields a resolution clearly below 5 nm. Technical solutions to reduce the space charge effect in an aberration-corrected spectro-microscope are discussed.

Ultrafast proton dynamics in aqueous amino acid solutions studied by resonant inelastic soft X-ray scattering.

Resonant inelastic soft X-ray scattering (RIXS) has been used to study the electronic structure of glycine and lysine in aqueous solution. Upon variation of the pH value of the solution from acidic to basic, major changes of the nitrogen K edge RIXS data are observed for both amino acids, which are associated with the protonation and deprotonation of the amino groups. The experimental results are compared with simulations based on density functional theory, yielding a detailed understanding of the spectral changes, as well as insights into the ultrafast proton dynamics in the intermediate core-excited/ionized state of the RIXS process.

Electron-hole correlation effects in core-level spectroscopy probed by the resonant inelastic soft x-ray scattering map of C60.

We have employed a unique spectroscopic approach, a resonant inelastic soft x-ray scattering (RIXS) map, to identify and separate electron-hole correlation effects in core-level spectroscopy. With this approach, we are able to derive a comprehensive picture of the electronic structure, separating ground state properties (such as the HOMO-LUMO separation) from excited state properties (such as the C 1s core-exciton binding energy of C(60)). In particular, our approach allows us to determine the difference between core- and valence exciton binding energies in C(60) [0.5 (±0.2) eV]. Furthermore, the RIXS map gives detailed insight into the symmetries of the intermediate and final states of the RIXS process.

Double aberration correction in a low-energy electron microscope.

The lateral resolution of a surface sensitive low-energy electron microscope (LEEM) has been improved below 4 nm for the first time. This breakthrough has only been possible by simultaneously correcting the unavoidable spherical and chromatic aberrations of the lens system. We present an experimental criterion to quantify the aberration correction and to optimize the electron optical system. The obtained lateral resolution of 2.6 nm in LEEM enables the first surface sensitive, electron microscopic observation of the herringbone reconstruction on the Au(111) surface.

Disordering of an organic overlayer on a metal surface upon cooling.

Inverse melting or disordering, in which the disordered phase forms upon cooling, is known for a few cases in bulk systems under high pressure. We show that inverse disordering also occurs in two dimensions: For a monolayer of 1,4,5,8-naphthalene-tetracarboxylic dianhydride on Ag(111), a completely reversible order-disorder transition appears upon cooling. The transition is driven by strongly anisotropic interactions within the layer versus with the metal substrate. Spectroscopic data reveal changes in the electronic structure of the system corresponding to a strengthening of the interface bonding at low temperatures. We demonstrate that the delicate, temperature-dependent balance between the vertical and lateral forces is the key to understanding this unconventional phase transition.

High-resolution, high-transmission soft x-ray spectrometer for the study of biological samples.

We present a variable line-space grating spectrometer for soft x-rays that covers the photon energy range between 130 and 650 eV. The optical design is based on the Hettrick-Underwood principle and tailored to synchrotron-based studies of radiation-sensitive biological samples. The spectrometer is able to record the entire spectral range in one shot, i.e., without any mechanical motion, at a resolving power of 1200 or better. Despite its slitless design, such a resolving power can be achieved for a source spot as large as (30 x 3000) microm2, which is important for keeping beam damage effects in radiation-sensitive samples low. The high spectrometer efficiency allows recording of comprehensive two-dimensional resonant inelastic soft x-ray scattering (RIXS) maps with good statistics within several minutes. This is exemplarily demonstrated for a RIXS map of highly oriented pyrolytic graphite, which was taken within 10 min.

Solid and liquid spectroscopic analysis (SALSA)--a soft x-ray spectroscopy endstation with a novel flow-through liquid cell.

We present a novel synchrotron endstation with a flow-through liquid cell designed to study the electronic structure of liquids using soft x-ray spectroscopies. In this cell, the liquid under study is separated from the vacuum by a thin window membrane, such that the sample liquid can be investigated at ambient pressure. The temperature of the probing volume can be varied in a broad range and with a fast temperature response. The optimized design of the cell significantly reduces the amount of required sample liquid and allows the use of different window membrane types necessary to cover a broad energy range. The liquid cell is integrated into the solid and liquid spectroscopic analysis (SALSA) endstation that includes a high-resolution, high-transmission x-ray spectrometer and a state-of-the-art electron analyzer. The modular design of SALSA also allows the measurement of solid-state samples. The capabilities of the liquid cell and the x-ray spectrometer are demonstrated using a resonant inelastic x-ray scattering map of a 25 wt % NaOD solution.

Electronic relaxation effects in condensed polyacenes: A high-resolution photoemission study.

We present a high-resolution photoelectron spectroscopy investigation of condensed films of benzene, naphthalene, anthracene, tetracene, and pentacene. High spectroscopic resolution and a systematic variation of the molecular size allow a detailed analysis of the fine structures. The line shapes of the C 1s main lines are analyzed with respect to the different contributions of inhomogeneous broadening, vibronic coupling, and chemical shifts. The shake-up satellite spectra reveal trends, which give insight into the charge redistribution within the molecule upon photoexcitation. In particular, the shake-up between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) increases in intensity and moves closer toward the C 1s main line if the size of the aromatic system is increased. An explanation is given on the basis of the delocalization of the aromatic system and its capability in screening the photogenerated core hole. A comparison of the HOMO-LUMO shake-up position to the optical band gap gives additional insight into the reorganization of the electronic system upon photoexcitation.

Electron lifetime in a Shockley-type metal-organic interface state.

The lifetimes of electrons at the interface between 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) and Ag(111) have been studied by means of time- and angle-resolved two-photon photoemission. We observe a dispersing unoccupied state 0.6 eV above the Fermi level with an effective electron mass of 0.39m{e} at the Gamma[over ] point. The short lifetime of 54 fs is indicative of a large penetration of the wave function into the metal. Supported by model calculations this interface state is interpreted as predominantly arising from an upshift of the occupied Shockley surface state of the clean metal due to the interaction with the PTCDA overlayer.

Role of intermolecular interactions on the electronic and geometric structure of a large pi-conjugated molecule adsorbed on a metal surface.

The organic semiconductor molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) exhibits two adsorption states on the Ag(111) surface: one in a metastable disordered phase, prepared at low temperatures, the other in the long-range ordered monolayer phase obtained at room temperature. Notably, the two states differ substantial in their vertical bonding distances, intramolecular distortions, and electronic structures. The difference is explained by intermolecular interactions, which are particularly relevant for the long-range ordered phase, and which hence require attention.

Isotope and temperature effects in liquid water probed by x-ray absorption and resonant x-ray emission spectroscopy.

High-resolution x-ray absorption and emission spectra of liquid water exhibit a strong isotope effect. Further, the emission spectra show a splitting of the 1b1 emission line, a weak temperature effect, and a pronounced excitation-energy dependence. They can be described as a superposition of two independent contributions. By comparing with gas phase, ice, and NaOH/NaOD, we propose that the two components are governed by the initial state hydrogen bonding configuration and ultrafast dissociation on the time scale of the O 1s core hole decay.

A high-resolution near-edge x-ray absorption fine structure investigation of the molecular orientation in the pentacene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) pentacene/system.

We present x-ray photoemission spectroscopy and highly resolved near-edge x-ray absorption fine structure spectroscopy measurements taken on pentacene thin films of different thicknesses deposited on a spin coated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) substrate. Thin films of pentacene were prepared by using organic molecular beam deposition in situ using strictly controlled evaporation conditions. Our investigations show that pentacene thin films on PEDOT:PSS are characterized by upright standing molecules. Due to the strong dichroic behavior, the calculated values of the molecular orientation give a clear indication not only of the real molecular arrangement in the films but also of a high orientational order. This high degree of molecular orientation order is a characteristic already of the first layer. The films show the tendency to grow on the PEDOT:PSS substrate following an island-fashion mode, with a relatively narrow intermixing zone at the interface between the pentacene and the polymer blend. The peculiarity of the growth of pentacene on PEDOT:PSS is due to the fact that the substrate does not offer any template for the nucleated films and thus exerts a lateral order toward the crystal structure arrangement. Under these conditions, the upright orientation of the molecules in the films minimizes the energy required for the system stability.

Influence of the preparation conditions on the morphology of perylene thin films on Si(111) and Si(100).

Thin films of perylene on Si(111) and Si(100) substrates have been investigated using a variety of experimental techniques. We find that the structural and morphological properties as well as the growth modes strongly depend on the preparation parameters. In general, we observe the existence of a relatively weak coupling between perylene and the two single crystal substrates. However, under special preparation conditions, it is possible to obtain a multilayer phase on the Si(111) substrate that is characterized by flat-lying, parallel-oriented molecules, and strong coupling with the substrate in the first layer. This phase has different structural, electronic, and intermolecular bonding properties as compared to the known crystalline phases. On Si(100), by varying the deposition rate between 0.1 and 10 nm/min, it is possible to observe a transition from island growth mode, with large and isolated crystallites, to homogeneous film growth. These findings contribute to the basic knowledge for film engineering. Thus, the film morphology could be designed ranging from the growth of very large single grains suitable for a complete nanodevice to homogenous films for application in large displays.

High-resolution inner-shell excitation spectroscopy of H2-phthalocyanine.

We report on a combined experimental and theoretical carbon and nitrogen K-edge near-edge x-ray absorption fine structure investigation on condensed metal-free phthalocyanine (H2Pc). Based on the results from improved virtual orbital calculations, all resonances in the experimental high-resolution data can be assigned to various electronic transitions. The comparison between experiments and calculations further shows that a significant influence of the core hole, which affects both the transition energies and the cross sections, is present and must be considered in theoretical approaches. Moreover, additional fine structure is clearly resolved for the first N 1s-->pi* transition, which can be interpreted as vibronic coupling to the electronic core excitation.

Spectroscopic investigation of the deeply buried Cu(In,Ga)(S,Se)2/Mo interface in thin-film solar cells.

The Cu(In,Ga)(S,Se)(2)Mo interface in thin-film solar cells has been investigated by surface-sensitive photoelectron spectroscopy, bulk-sensitive x-ray emission spectroscopy, and atomic force microscopy. It is possible to access this deeply buried interface by using a suitable lift-off technique, which allows us to investigate the back side of the absorber layer as well as the front side of the Mo back contact. We find a layer of Mo(S,Se)(2) on the surface of the Mo back contact and a copper-poor stoichiometry at the back side of the Cu(In,Ga)(S,Se)(2) absorber. Furthermore, we observe that the Na content at the Cu(In,Ga)(S,Se)(2)Mo interface as well as at the inner grain boundaries in the back contact region is significantly lower than at the absorber front surface.

Structure determination of CdS and ZnS nanoparticles: direct modeling of synchrotron-radiation diffraction data.

We introduce a modified method of powder-diffraction data analysis to obtain precise structural information on freestanding ZnS and CdS nanoparticles with diameters well below 5 nm, i.e., in a range where common bulk-derived approaches fail. The method is based on the Debye equation and allows us to access the crystal structure and the size of the particles with high precision. Detailed information on strain, relaxation effects, stacking faults, and the shape of the particles becomes available. We find significant size differences between our new results and those obtained by established methods, and conclude that a mixed zinc-blende/wurtzite stacking and significant lattice distortions occur in our CdS nanoparticles. Our approach should have direct impact on the understanding and modeling of quantum size effects in nanoparticles.

A comparison of fine structures in high-resolution x-ray-absorption spectra of various condensed organic molecules.

We report on a high-resolution C-K and O-K near-edge x-ray-absorption fine-structure (NEXAFS) study of large aromatic molecules in condensed thin films, namely, anhydrides 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride, 3,4,9,10-perylene-tetracarboxylic acid dianhydride, benzoperylene-(1,2)-dicarboxylic acid anhydride, and 1,8-naphthalene-dicarboxylic acid anhydride and the quinoic acenaphthenequinone. Due to the high-energy resolution of the third-generation synchrotron source BESSY II we observe large differences in the NEXAFS fine structures even for very similar molecules, resulting in a wealth of new information. The rich fine structure can unambiguously be assigned to the coupling of electronic transitions to vibronic excitations. Backed by ab initio calculations we present a detailed analysis of the spectra that allows the complete interpretation of the near-edge features. It also yields information on the vibronic properties in the electronically excited state as well as on the response of the electronic system upon core excitation. The strong differences in the electron-vibron coupling for different molecules are discussed.