T. Tyliszczak

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.

X-ray spectromicroscopy of immiscible polymer blends: Polystyrene-poly(methyl methacrylate)

Abstract Spun cast thin films of blends of low and high molecular weight mono-disperse polystyrene (PS) and poly(methyl methacrylate) (PMMA) with nominal compositions ranging from 66/33 wt.%/wt.% (w/w) up to 10/90 w/w PS/PMMA have been studied, as-made and after annealing. Two synchrotron-based X-ray microscopies — scanning transmission X-ray microscopy (STXM) and X-ray photoemission electron microscopy (X-PEEM) — as well as several variants of atomic force microscopy (AFM) were used to probe the composition and morphology of the bulk and surface of these blends. The chemical sensitivities and spatial resolutions of these three techniques are compared. All samples are observed to have a PS signal in the C 1s X-ray absorption spectrum of the surface of the PMMA-rich domains as measured in the X-PEEM. A continuous thin PS layer is not expected at a PMMA surface since neither polymer should wet the other at thermodynamic equilibrium. The likely origin of this PS surface signal is from a bimodal distribution of PS domain sizes with the PS signal arising from domains at the surface which are smaller than the ∼200-nm resolution of the X-PEEM. High resolution AFM and STXM provide direct evidence for this explanation.

Advances in the detection of as in environmental samples using low energy X-ray fluorescence in a scanning transmission X-ray microscope: arsenic immobilization by an Fe(II)-oxidizing freshwater bacteria.

Speciation and quantitative mapping of elements, organic and inorganic compounds, and mineral phases in environmental samples at high spatial resolution is needed in many areas of geobiochemistry and environmental science. Scanning transmission X-ray microscopes (STXMs) provide a focused beam which can interrogate samples at a fine spatial scale. Quantitative chemical information can be extracted using the transmitted and energy-resolved X-ray fluorescence channels simultaneously. Here we compare the relative merits of transmission and low-energy X-ray fluorescence detection of X-ray absorption for speciation and quantitative analysis of the spatial distribution of arsenic(V) within cell-mineral aggregates formed by Acidovorax sp. strain BoFeN1, an anaerobic nitrate-reducing Fe(II)-oxidizing β-proteobacteria isolated from the sediments of Lake Constance. This species is noted to be highly tolerant to high levels of As(V). Related, As-tolerant Acidovorax-strains have been found in As-contaminated groundwater wells in Bangladesh and Cambodia wherein they might influence the mobility of As by providing sorption sites which might have different properties as compared to chemically formed Fe-minerals. In addition to demonstrating the lower detection limits that are achieved with X-ray fluorescence relative to transmission detection in STXM, this study helps to gain insights into the mechanisms of As immobilization by biogenic Fe-mineral formation and to further the understanding of As-resistance of anaerobic Fe(II)-oxidizing bacteria.

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.

Assignment of Polarization-Dependent Peaks in Carbon K-Edge Spectra from Biogenic and Geologic Aragonite

Many biominerals, including mollusk and echinoderm shells, avian eggshells, modern and fossil bacterial sediments, planktonic coccolithophores, and foraminifera, contain carbonates in the form of biogenic aragonite or calcite. Here we analyze biogenic and geologic aragonite using different kinds of surface- and bulk-sensitive X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge, as well as high-resolution scanning transmission X-ray microscopy (STXM). Besides the well-known main pi* and sigma* carbonate peaks, we observed and fully characterized four minor peaks, at energies between the main pi* and sigma* peaks. As expected, the main peaks are similar in geologic and biogenic aragonite, while the minor peaks differ in relative intensity. In this and previous work, the minor peaks appear to be the ones most affected in biomineralization processes, hence the interest in characterizing them. Peak assignment was achieved by correlation of polarization-dependent behavior of the minor peaks with that of the main pi* and sigma* peaks. The present characterization provides the background for future studies of aragonitic biominerals.

Generalized oscillator strengths for inner-shell excitation of SF6 recorded with a high-performance electron energy loss spectrometer

The generalized oscillator strength profiles for S 2p, S 2s and F 1s excited and ionized states of sulfur hexafluoride (SF6) are reported up to very high momentum transfer. These have been measured with a variable impact energy, variable scattering angle electron energy loss spectrometer, which is dedicated to studies of electric dipole (optically allowed) and non-dipole (optically forbidden electric quadrupole and spin-exchange) inner shell electronic transitions of gases, and systematic measurements of their angular and impact energy distributions in order to derive generalized oscillator strength profiles. In addition to presenting the SF6 results, we describe the design, construction and performance of the instrument, as well as data acquisition and analysis procedures. ” 2000 Published by Elsevier Science B.V. All rights reserved.

SOFT X-RAY MICROSCOPY OF SOFT MATTER HARD INFORMATION FROM TWO SOFTS

Scanning transmission X-ray microscopy (STXM) and X-ray photoelectron emission microscopy (X-PEEM) provide quantitative chemical analysis at a spatial resolution well below 100 nm. Soft X-ray absorption or near edge X-ray absorption (NEXAFS) contrast provides sensitive differentiation of species which have similar elemental composition but are chemically distinct. Due to the ability of soft X-rays at wavelengths below the O K-edge to penetrate water, and on account of lower radiation damage, soft X-ray microscopy is an ideal tool for providing quantitative information about soft matter in the context of biological, polymer and environmental studies. Examples are given from recent studies of: phase segregation in polyurethanes and polymer blends, protein adsorption on polymers relating to biomaterial optimization, and metal mapping in biofilms. These examples show that it is indeed possible to get quantitative (hard) information by combining soft X-rays and soft materials.

Generalized oscillator strengths for C 1s excitation of acetylene and ethylene

Abstract The generalized oscillator strength profiles for discrete C 1s excited states of C 2 H 2 and C 2 H 4 have been derived from angle-dependent inelastic electron scattering cross-sections measured with 1300 eV final electron energy. The measured GOS profiles for the strong C 1s→π* transition in each species are compared to theoretical calculations computed within the first Born approximation, using ab-initio generalized multi structural wave functions. These wave functions include relaxation, correlation and hole localization effects. Theory predicts large quadrupole contributions to the π* GOS of each species, analogous to those previously reported for computed GOS profiles for O 1s→π* excitation of CO 2 . We find good agreement between experiment and theory as to the shape of the π* GOS but, when the relative GOS extracted from the experimental data is normalized to the optical oscillator strength at K 2 =0, the magnitude is in better agreement with the GOS computed for only the dipole channel than for the sum of the dipole and quadrupole channels.

Inner-shell electron energy-loss spectroscopy of SF6 at very high momentum transfer

Abstract Non-dipole S 2p and S 2s core excitation of SF 6 has been studied using inelastic electron scattering with variable scattering angles and impact energies (momentum transfer ( K ), 0.9 K 2 −2 ). A non-dipole excitation at 181 eV is found to be the dominant S 2p spectral feature at large momentum transfer. A variable impact energy, fixed- K study shows that the first Born approximation fails under low impact energy, large scattering angle conditions. This study illustrates the importance of exploring a wide range of the inelastic scattering surface to ensure proper understanding of molecular spectroscopy and scattering dynamics.

Local microstructures of Si in GaN studied by x-ray absorption spectroscopy

Si K-edge x-ray absorption spectroscopy (XAFS) has been used to study the local structure of Si dopant in GaN crystalline material. Doping concentrations NSi from 8.0×1016 to 4.4×1019 cm−3 were investigated. It is observed that the near-edge spectra vary significantly as a function of NSi. At low concentrations the Si K-edge spectra exhibit features similar to that obtained from N K-edge measurement, while at high concentrations the near-edge spectra shape is similar to that recorded from Si3N4. We interpret the results as an indication that Si is not randomly distributed. The changes of the near-edge spectra as a function of doping level is explained as due to changes in the magnitude of Si local lattice contraction caused by the formation of various types of Si clusters. The interpretation is further supported by extended XAFS spectra analysis. A Si-induced strain-field near the surface is proposed as the main force for the cluster formation during epitaxial growth.