Soft x-ray scattering facility at the Advanced Light Source with real-time data processing and analysis.

We present the development and characterization of a dedicated resonant soft x-ray scattering facility. Capable of operation over a wide energy range, the beamline and endstation are primarily used for scattering from soft matter systems around the carbon K-edge (∼285 eV). We describe the specialized design of the instrument and characteristics of the beamline. Operational characteristics of immediate interest to users such as polarization control, degree of higher harmonic spectral contamination, and detector noise are delineated. Of special interest is the development of a higher harmonic rejection system that improves the spectral purity of the x-ray beam. Special software and a user-friendly interface have been implemented to allow real-time data processing and preliminary data analysis simultaneous with data acquisition.

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.

Calibrated NEXAFS spectra of common conjugated polymers.

Near edge x-ray absorption fine structure (NEXAFS) spectroscopy has evolved into a powerful characterization tool for polymeric materials and is increasingly being used to elucidate composition and orientation in thin films of relevance to organic electronic devices. For accurate quantitative compositional analysis, insight into the electronic structure and the ability to assess molecular orientation, reliable reference spectra with known energy resolution and calibrated energy scale are required. We report a set of such NEXAFS spectra from 23 semiconducting polymers and some related materials that are frequently used in organic device research.

Surface sensitivity in scanning transmission x-ray microspectroscopy using secondary electron detection.

The successful integration of electron detection into an existing scanning transmission x-ray microspectroscope (STXM) at the Swiss Light Source is demonstrated. In conventional x-ray detection using a photomultiplier, STXM offers mainly bulk sensitivity combined with high lateral resolution. However, by implementation of a channeltron electron multiplier, the surface sensitivity can be established by the detection of secondary electrons emitted from the sample upon resonant excitation. We describe the experimental setup and discuss several relevant aspects, in particular the schemes to correct for self-absorption in the specimen due to back illumination in case of thicker films.

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 sample's 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.

Evolution of the nanomorphology of photovoltaic polyfluorene blends: sub-100 nm resolution with x-ray spectromicroscopy.

We investigate the influence of annealing on the morphology of intimately mixed blends of the conjugated polymers poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) with scanning transmission x-ray microscopy (STXM). Through the use of a zone plate with theoretical Rayleigh resolution of 30 nm, we are able to resolve sub-100 nm bulk structure in these films. Surprisingly, for unannealed films spin-coated from chloroform we observe features with an average diameter of 85 nm. The high degree of photoluminescence quenching in these as-spun films (>95%) implies that there is significant intermixing within the 85 nm structures, indicating that a hierarchy of phase separation exists even on the length scale of less than 100 nm. With annealing up to 160 °C, close to the T(g) of the components, there is little change in the feature sizes observed by STXM, although an increase in variation of the composition is observed. With annealing above 160 °C the imaged features begin to evolve in size, increasing to 225 nm in extent, alongside large changes in composition with annealing to 200 °C. Comparing the evolution of morphology imaged by STXM with the change in photoluminescence quenching with annealing, we propose that phase separation first evolves via the evolution of relatively pure phases on the length scale of a few to tens of nanometres within the larger 85 nm structures. Once the length scale of compositional fluctuations exceeds 85 nm (for anneal temperatures above 160 °C) the hierarchy of phase separation is lost and the subsequent morphological evolution is readily imaged by STXM. Applying the results of an exciton diffusion and quenching model, we find good agreement between the size of the domains measured by STXM (above 180 °C) and the results of the model for an exciton diffusion length of 15 nm. The growth in domain size and towards purer structures has also been observed with resonant soft x-ray scattering.

Carbon-13 labeled polymers: an alternative tracer for depth profiling of polymer films and multilayers using secondary ion mass spectrometry.

13C labeling is introduced as a tracer for depth profiling of polymer films and multilayers using secondary ion mass spectrometry (SIMS). Deuterium substitution has traditionally been used in depth profiling of polymers but can affect the phase behavior of the polymer constituents with reported changes in both bulk-phase behavior and surface and interfacial interactions. SIMS can provide contrast by examining various functional groups, chemical moieties, or isotopic labels. 13C-Labeled PS (13C-PS) and unlabeled PS (12C-PS) and PMMA were synthesized using atom-transfer radical polymerization and assembled in several model thin-film systems. Depth profiles were recorded using a Cameca IMS-6f magnetic sector mass spectrometer using both 6.0-keV impact energy Cs+ and 5.5-keV impact energy O2+ primary ion bombardment with detection of negative and positive secondary ions, respectively. Although complete separation of 12C1H from 13C is achieved using both primary ion species, 6.0-keV Cs+ clearly shows improved detection sensitivity and signal-to-noise ratio for detection of 12C, 12C1H, and 13C secondary ions. The use of Cs+ primary ion bombardment results in somewhat anomalous, nonmonotonic changes in the 12C, 12C1H, and 13C secondary ion yields through the PS/PMMA interface; however, it is shown that this behavior is not due to sample charging. Through normalization of the 13C secondary ion yield to the total C (12C + 13C) ion yield, the observed effects through the PS/PMMA interface can be greatly minimized, thereby significantly improving analysis of polymer films and multilayers using SIMS. Mass spectra of 13C-PS and 12C-PS were also analyzed using a PHI TRIFT I time-of-flight mass spectrometer, with 15-keV Ga+ primary ion bombardment and detection of positive secondary ions. The (12)C7(1)H7 ion fragment and its 13C-enriched analogues have significant secondary ion yields with negligible mass interferences, providing an early indication of the potential for future use of this technique for cluster probe depth profiling of high molecular weight 13C-labeled fragments.

Carbon-13 labeling for improved tracer depth profiling of organic materials using secondary ion mass spectrometry.

13C labeling is introduced as an alternative to deuterium labeling for analysis of organic materials using secondary ion mass spectrometry (SIMS). A model macromolecular system composed of polystyrene (PS) and poly(methyl methacrylate) (PMMA) was used to compare the effects of isotopic labeling using both deuterium substitution (dPS) and 13C labeling (13C-PS). Clear evidence is shown that deuterium labeling does introduce changes in the thermodynamic properties of the system, with the observation of segregation of dPS to an hPS:dPS/hPMMA interface. This type of behavior could significantly impact many types of investigations due to the potential for improper interpretation of experimental results as a consequence of labeling-induced artifacts. 13C labeling is shown to provide a true tracer for analysis using SIMS.

Substrate effect on the melting temperature of thin polyethylene films.

Strong dependence of the crystal orientation, morphology, and melting temperature (Tm) on the substrate is observed in the semicrystalline polyethylene thin films. The Tm decreases with the film thickness decrease when the film is thinner than a certain critical thickness, and the magnitude of the depression increases with increasing surface interaction. We attribute the large Tm depression to the decrease in the overall free energy on melting, which is caused by the substrate attraction force to the chains that competes against the interchain force which drives the chains to crystallization.

Attractive migration and coalescence: a significant process in the coarsening of TiSi2 islands on the Si(111) surface.

The dynamics and coarsening of TiSi2 islands on Si(111) surfaces are studied in real time with photoelectron emission microscopy. A significant fraction of events are observed in which nearby islands move attractively toward each other and subsequently coalesce. It is proposed that attractive island migration is due to the growth-decay flow of the island edges driven by a nonuniform surface concentration around the islands. The local surface concentration is induced by the neighboring islands. This coarsening mechanism should significantly affect the evolution of the island distribution.

Interferometer-controlled scanning transmission X-ray microscopes at the Advanced Light Source.

Two new soft X-ray scanning transmission microscopes located at the Advanced Light Source (ALS) have been designed, built and commissioned. Interferometer control implemented in both microscopes allows the precise measurement of the transverse position of the zone plate relative to the sample. Long-term positional stability and compensation for transverse displacement during translations of the zone plate have been achieved. The interferometer also provides low-distortion orthogonal x, y imaging. Two different control systems have been developed: a digital control system using standard VXI components at beamline 7.0, and a custom feedback system based on PC AT boards at beamline 5.3.2. Both microscopes are diffraction limited with the resolution set by the quality of the zone plates. Periodic features with 30 nm half period can be resolved with a zone plate that has a 40 nm outermost zone width. One microscope is operating at an undulator beamline (7.0), while the other is operating at a novel dedicated bending-magnet beamline (5.3.2), which is designed specifically to illuminate the microscope. The undulator beamline provides count rates of the order of tens of MHz at high-energy resolution with photon energies of up to about 1000 eV. Although the brightness of a bending-magnet source is about four orders of magnitude smaller than that of an undulator source, photon statistics limited operation with intensities in excess of 3 MHz has been achieved at high energy resolution and high spatial resolution. The design and performance of these microscopes are described.

Optimization of scanning transmission X-ray microscopy for the identification and quantitation of reinforcing particles in polyurethanes.

The morphology, size distributions, spatial distributions, and quantitative chemical compositions of co-polymer polyol-reinforcing particles in a polyurethane have been investigated with scanning transmission X-ray microscopy (STXM). A detailed discussion of microscope operating procedures is presented and ways to avoid potential artifacts are discussed. Images at selected photon energies in the C 1s, N 1s and O 1s regions allow unambiguous identification of styrene-acrylonitrile-based (SAN) copolymer and polyisocyanate polyaddition product-based (PIPA) reinforcing particles down to particle sizes at the limit of the spatial resolution (50 nm). Quantitative analysis of the chemical composition of individual reinforcing particles is achieved by fitting C 1s spectra to linear combinations of reference spectra. Regression analyses of sequences of images recorded through the chemically sensitive ranges of the C 1s, N 1s and O 1s spectra are used to generate quantitative compositional maps, which provide a fast and effective means of investigating compositional distributions over a large number of reinforcing particles. The size distribution of all particles determined by STXM is shown to be similar to that determined by TEM. The size distributions of each type of reinforcing particle, which differ considerably, were obtained by analysis of STXM images at chemically selective energies.

Illumination for coherent soft X-ray applications: the new X1A beamline at the NSLS.

The X1A soft X-ray undulator beamline at the NSLS has been rebuilt to serve two microscopy stations operating simultaneously. Separate spherical-grating monochromators provide the resolving power required for XANES spectroscopy at the C, N and O absorption edges. The exit slits are fixed and define the coherent source for the experiments. The optical design and the operational performance are described.

Development of scanning X-ray microscopes for materials science spectromicroscopy at the Advanced Light Source.

The development of two zone-plate microscopes for X-ray spectroscopic analysis of materials is described. This pair of instruments will provide imaging NEXAFS analysis of samples in transmission at atmospheric pressure and imaging XPS and NEXAFS analysis of sample surfaces in a UHV environment.

X-ray Linear Dichroism Microscopy.

Chemical-specific x-ray linear dichroism was observed in an x-ray microscope as evidenced by changes in relative contrast upon azimuthal rotation of the sample. As a demonstration, thin sections of a partially ordered polymer fiber were examined with a transmission x-ray microscope near the carbon K-shell absorption edge to provide chemical-specific imaging at 50-nanometer spatial resolution. The observed dichroism and change in contrast upon rotation arise from the polarization dependence of the near-edge x-ray absorption cross section and can be used to image the orientation of specific chemical bonds.

Chemical contrast in X-ray microscopy and spatially resolved XANES spectroscopy of organic specimens.

The scanning transmission x-ray microscope at the National Synchrotron Light Source has been used to record x-ray absorption near-edge structure (XANES) spectra from 0.01-square-micrometer regions of organic specimens. The spectral features observed reflect the molecular structure of the dominant absorbing atoms and provide the contrast mechanism for high-resolution imaging with chemical sensitivity. This technique was used with x-ray energies near the carbon K absorption edge to identify and map separate phases in various polymer blends and to map the DNA distribution in chromosomes with a spatial resolution of 55 nanometers.

Coherent Radiation for X-Ray Imaging-The Soft X-Ray Undulator and the X1A Beamline at the NSLS.

An undulator-based beamline was built and commissioned at the National Synchrotron Light Source to provide tunable coherent radiation in the 200-800 eV range. The low emittance of the storage ring means that the undulator source has high brightness so that a large flux of coherent x rays is delivered to experimental stations. The beamline uses a horizontally dispersing bichromator that allows two experiments to run simultaneously, making use of the first and second harmonics of the undulator output. In addition, the use of horizontally deflecting optics enables the beamline alignment to be insensitive to electron beam motion since the horizontal electron beam size is quite large. The beamline and its performance are discussed with emphasis on the optics and on stability, radiation, and vacuum considerations.

The interior of a whole and unmodified biological object--the zymogen granule--viewed with a high-resolution X-ray microscope.

We report the ability of focused soft X-rays to visualize at spatial resolution well beyond that of the optical microscope (less than 100 nm) the interior of a small, whole biological object without fixation, staining, dehydration or sectioning. Quantitative estimation of its protein content with unique femtogram sensitivity is also reported. The present results represent a significant step towards the goals of natural imaging and chemical mapping of biological structures with soft X-rays.