R. Fink

Polarized X-ray scattering reveals non-crystalline orientational ordering in organic films

Molecular orientation critically influences the mechanical, chemical, optical and electronic properties of organic materials. So far, molecular-scale ordering in soft matter could be characterized with X-ray or electron microscopy techniques only if the sample exhibited sufficient crystallinity. Here, we show that the resonant scattering of polarized soft X-rays (P-SoXS) by molecular orbitals is not limited by crystallinity and that it can be used to probe molecular orientation down to size scales of 10 nm. We first apply the technique on highly crystalline small-molecule thin films and subsequently use its high sensitivity to probe the impact of liquid-crystalline ordering on charge mobility in polymeric transistors. P-SoXS also reveals scattering anisotropy in amorphous domains of all-polymer organic solar cells where interfacial interactions pattern orientational alignment in the matrix phase, which probably plays an important role in the photophysics. The energy and q-dependence of the scattering anisotropy allows the identification of the composition and the degree of orientational order in the domains.

PolLux: A new facility for soft x-ray spectromicroscopy at the Swiss Light Source

We report on the successful installation and operation of a scanning transmission x-ray microspectroscope (STXM) at the PolLux facility at the Swiss Light Source. This integration of an advanced STXM with improved sample handling capabilities and a novel beamline provides unique capabilities. PolLux uses linearly or circularly polarized x-rays from a bending magnet with an extended photon energy range (200-1400 eV). It is therefore well suited to determine a samples quantitative chemical composition, molecular orientation, or thickness of organic as well as condensed matter materials. The local magnetic state of magnetic thin films is accessible through fast helicity switching by steering the electron beam off axis through the bending magnet. Ex vacuo girder movers allow fast and highly reproducible (<1 microm) alignment of the instrument with respect to the photon beam. The present spatial resolution is approximately 20 nm, limited by the zone plates utilized. The instrument has the stability and positional resolution to operate with much higher resolution optics as it becomes available. In addition to characterization experiments, we present several typical examples from materials research and environmental science to exemplify the capabilities.

SMART: a planned ultrahigh-resolution spectromicroscope for BESSY II

Abstract A new UHV spectromicroscope called SMART (spectromicroscope for all relevant techniques) is currently under construction for a soft X-ray undulator beamline at BESSY II. The instrument consists of a plane-grating monochromator with an aspherical focusing mirror and an ultrahigh-resolution, low-energy electron microscope containing an energy filter. It can be used as a photoemission microscope for a variety of electron spectroscopies (XAS, XPS, UPS, XAES) and has a calculated spatial resolution of better than 1 nm. A maximum energy resolution of about 0.1 eV will be provided by a corrected omega filter. The high lateral resolution of the electron microscope will be achieved through the correction of the chromatic and spherical aberrations of the objective lens by means of an electrostatic mirror in combination with a corrected magnetic beam separator. An additional electron source placed on the other side of the beam separator opposite the electrostatic mirror will also allow LEEM, MEM and small-spot LEED investigations to be carried out. The basic ideas, the various modes of operation and the electron optical design of the instrument are outlined.

Substrate-interaction, long-range order, and epitaxy of large organic adsorbates

Large and symmetric organic molecules (>200 amu) can form highly-ordered adsorbate layers and thin films when they are deposited by vacuum sublimation on clean reactive surfaces. In such cases covalent bonding often occurs via the molecular π-system leading to a parallel orientation of the adsorbate as shown for oligothiophenes and PTCDA on Ag(1 1 1). A proper choice of the substrate and/or a preadsorbate may also cause an upright orientation with bonding via a reactive group of the molecule (example: NDCA/Ni(1 11)). Most of the used molecules yield long-range ordered monolayers with large, almost defect-free domains. The stronger the bonding and the smaller the molecule the more likely is the formation of commensurate superstructures which indicate site-specific adsorption even for such large molecules as PTCDA or EC4T. Organic epitaxy is discussed and shown for a particular system, PTCDA on Ag(1 1 1), for which the structure of the monolayer is nearly identical to that of theβ-modification of PTCDA crystals, whereas on other substrates (e.g. Si(1 1 1), Ge(1 0 0)) a disordered interface and hence no true epitaxy is found.

Observation of intermixing at the buried CdS/Cu(In, Ga)Se2 thin film solar cell heterojunction

A combination of x-ray emission spectroscopy and x-ray photoelectron spectroscopy using high brightness synchrotron radiation has been employed to investigate the electronic and chemical structure of the buried CdS/Cu(In, Ga)Se2 interface, which is the active interface in highly efficient thin film solar cells. In contrast to the conventional model of an abrupt interface, intermixing processes involving the elements S, Se, and In have been identified. The results shed light on the electronic structure and interface formation processes of semiconductor heterojunctions and demonstrate a powerful tool for investigating buried interfaces in general.

Investigations on chemically capped CdS, ZnS and ZnCdS nanoparticles

CdS, ZnS and ZnCdS nanoparticles of various sizes (1-10 nm) are synthesized using a wet chemical route including passivation by organic capping molecules. The particles can also be doped with transition metal ions. The optical properties of the particles are investigated using UV absorption and photoluminescence spectroscopies. High resolution photoelectron spectroscopy using variable photon energy from a synchrotron source is performed to obtain detailed information about the nanoparticle surfaces. These investigations are able to reveal the termination of the nanoparticles and the nature of bonding between the surface atoms and stabilizing organic molecules.

Advanced thin film technology for ultrahigh resolution X-ray microscopy

Further progress in the spatial resolution of X-ray microscopes is currently impaired by fundamental limitations in the production of X-ray diffractive lenses. Here, we demonstrate how advanced thin film technologies can be applied to boost the fabrication and characterization of ultrahigh resolution X-ray optics. Specifically, Fresnel zone plates were fabricated by combining electron-beam lithography with atomic layer deposition and focused ion beam induced deposition. They were tested in a scanning transmission X-ray microscope at 1.2 keV photon energy using line pair structures of a sample prepared by metal organic vapor phase epitaxy. For the first time in X-ray microscopy, features below 10nm in width were resolved.

Line shapes and satellites in high-resolution x-ray photoelectron spectra of large π-conjugated organic molecules

We present a high-resolution C1s and O1 s x-ray photoemission (XPS) study for condensed films of pi-conjugated organic molecules, namely, of the anhydrides 3,4,9,10-perylene-tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride, 1,8-naphthalene dicarboxylic acid anhydride, and benzoperylene-(1,8)-dicarboxylic acid anhydride as well as the quinoic acenaphthenequinone. Although the functional groups are identical for the anhydrides, the molecules show very different photoemission fine structure thus providing a detailed fingerprint. A simultaneous peak fit analysis of the XPS spectra of all molecules allows to consistently determine the ionization potentials of all chemically different carbon and oxygen atoms. Additional structures in the C1s and O1s spectra are interpreted as shakeup satellites and assigned with the help of singles and doubles configuration interaction calculations. These satellites provide further information on multielectron excitations and must be taken into account for quantitative investigations.

Detailed investigation of CdS nanoparticle surfaces by high-resolution photoelectron spectroscopy

Abstract Direct and detailed information about the surface of differently sized CdS nanoparticles has been obtained from high-resolution X-ray photoelectron spectroscopy using tunable synchrotron radiation. We identify up to four distinct components in the S 2p core level spectra. Two of them are assigned to bulk and surface S-species of the nanoparticles, the latter arising from a surface core level shift due to their S-termination. The remaining S 2p components stem from S-atoms of the stabilizer thiol group bound to Cd and to S–S-bonds formed by thiol groups which are attached to surface S-atoms. In the latter case, the oxidation of the nanoparticle surface is drastically reduced.

Enhancement of photoluminescence in manganese-doped ZnS nanoparticles due to a silica shell

Zinc sulphide nanoparticles doped with manganese (ZnS:Mn) have been stabilized using thioglycerol [HSCH2CH(OH)CH2OH] molecules. The nanoparticles (∼1.7 nm) are highly stable and exhibit photoluminescence at ∼600 nm when excited with ultraviolet light. For increasing luminescence and stability the particles are further treated with tetraethylorthosilicate (TEOS)[Si(C2H5O)4] in an aqueous medium, yielding either a disordered silica matrix or spherical core-shell particles of up to ∼900 nm size with strongly enhanced luminescence under certain conditions. Photoluminescence, excitation spectroscopy, transmission electron microscopy, energy dispersive analysis of x-rays, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy measurements have been performed for the characterization of the ZnS:Mn nanoparticles alone, in the silica matrix as well as in spherical silica shells. Among other things, the analysis indicates that the thioglycerol capping has been affected by the coating neither in...