Cryo scanning transmission x-ray microscope optimized for spectrotomography.

A cryo scanning transmission X-ray microscope, the cryo-STXM, has been designed and commissioned at the Canadian Light Source synchrotron. The instrument is designed to operate from 100 to 4000 eV (λ = 12.4 - 0.31 nm). Users can insert a previously frozen sample, through a load lock, and rotate it ±70° in the beam to collect tomographic data sets. The sample can be maintained for extended periods at 92 K primarily to suppress radiation damage and a pressure on the order of 10-9 Torr to suppress sample contamination. The achieved spatial resolution (30 nm) and spectral resolution (0.1 eV) are similar to other current soft X-ray STXMs, as demonstrated by measurements on known samples and test patterns. The data acquisition efficiency is significantly more favorable for both imaging and tomography. 2D images, 3D tomograms, and 4D chemical maps of automotive hydrogen fuel cell thin sections are presented to demonstrate current performance and new capabilities, namely, cryo-spectrotomography in the soft X-ray region.

Silicon 1s near edge X-ray absorption fine structure spectroscopy of functionalized silicon nanocrystals.

Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3-100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed silicon nanocrystals that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.

Binding geometry of hydrogen-bonded chain motif in self-assembled gratings and layers on Ag(111).

Upon adsorption on the (111) facet of Ag, 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid (PVBA) self-assembles into a highly ordered, chiral twin chain structure at submonolayer coverages with domains that can extend for micrometers in one dimension. Using polarization-dependent measurements of C and N K-shell excitations in near-edge X-ray absorption fine structure (NEXAFS) spectra, we determine the binding geometry of single PVBA molecules within this unique ensemble for both low and high coverage regimes. At submonolayer coverage, the molecule is twisted to facilitate the formation of hydrogen bonds. The gas-phase planarity is gradually recovered as the coverage is increased, with complete planarity coinciding with loss of order in the overlayer. Thermal treatment of the PVBA film results in deprotonation of the carboxyl tail of the molecule, but despite the suppression of the stabilizing hydrogen-bonds, the overlayer remains ordered.

Substituent effects in the iron 2p and carbon 1s edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of ferrocene compounds.

The iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3)5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hückel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

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.

Electron-vibron coupling in high-resolution X-Ray absorption spectra of organic materials: NTCDA on Ag(111).

We report additional rich fine structures in high-resolution near-edge x-ray-absorption fine structure (NEXAFS) spectra of large organic molecules using NTCDA on Ag(111) as an example. These fine structures are completely interpreted as vibronic coupling to electronic core excitations. The coupling is mode selective; predominantly one vibronic mode couples to each excitation. The fit results suggest the occurrence of a Davydov splitting, first observed for core excitons. Morphological differences substantially influence the electron-vibron coupling, indicating a strong intermolecular interaction. Thus NEXAFS becomes a more subtle probe for organic solids.

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.