A new sputtered process for cadmium sulfide (CdS) has been developed that boosted efficiency of a PV device baseline (with single-stage, coevaporated CIGS) by similar to 2.7% (absolute) to an average of similar to 10%. The process is highly scalable to a roll-to-roll environment, with the maximum efficiency effect occurring at 0.1 mbar (similar to 75 mTorr) sputtering pressure. The efficiency improvement is thought to be due to two main factors: composition and defects. The CdS film deposited at high pressure (HP) contains more oxygen (primarily as CdO) than one deposited at typical pressures, with oxygen content higher towards the CdS-CIGS interface. The HP process produces an interface with less CdS-CIGS intermixing, which results in a junction with similar to 5x fewer defects as measured by admittance spectroscopy. The performance improvement due to HP CdS occurs even with a very thin CdS layer (< 15 nm), thus greatly reducing the total amount of cadmium contained in the cells.

We report on the design and construction of a higher energy Scanning Transmission X-ray Microscope on a new bend magnet beam line at the Advanced Light Source. Previously we have operated such an instrument on a bend magnet for C, N and O 1s NEXAFS spectroscopy. The new instrument will have similar performance at higher energies up to and including the S 1s edge at 2472eV. A new microscope configuration is planned. A more open geometry will allow a fluorescence detector to count emitted photons from the front surface of the sample. There will be a capability for zone plate scanning in addition to the more conventional sample scanning mode. This will add the capability for imaging a massive sample at high resolution over a limited field of view, so that heavy reaction cells may be used to study processes in-situ, exploiting the longer photon attenuation length and the longer zone plate working distances available at higher photon energy. The energy range will extend down to include the C1s edge at 300eV, to allow high energy NEXAFS microscopic studies to correlate with the imaging of organics in the same sample region of interest.

Three-dimensional chemical mapping using angle scan nanotomography in a soft X-ray scanning transmission X-ray microscope (STXM) has been used to investigate the spatial distributions of a low density polyacrylate polyelectrolyte ionomer inside submicron sized polystyrene microspheres. Acquisition of tomograms at multiple photon energies provides true, quantifiable 3-d chemical sensitivity. Both pre-O 1s and C 1s results are shown. The study reveals aspects of the 3-d distribution of the polyelectrolyte that were inferred indirectly or had not been known prior to this study. The potential and challenges for extension of the technique to studies of other polymeric and to biological systems is discussed.

The C 1s, Si 2p, Si 2s, and O 1s inner-shell excitation spectra of vinyltriethoxysilane, trimethylethoxysilane, and vinyltriacetoxysilane have been recorded by electron energy loss spectroscopy under scattering conditions dominated by electric dipole transitions. The spectra are converted to absolute optical oscillator strength scales and interpreted with the aid of ab initio calculations of the inner-shell excitation spectra of model compounds. Electron energy loss spectra recorded in a transmission electron microscope on partly cured adhesion promoter, atomic force micrographs, and images and X-ray absorption spectra from X-ray photoemission electron microscopy of as-spun and cured vinyltriacetoxysilane-based adhesion promoter films on silicon are presented. The use of these measurements in assisting chemistry studies of adhesion promoters for electronics applications is discussed.

High energy resolution C 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of ethylene-1-alkene copolymers with systematic variations in comonomer content and thus systematic changes in branch length, branching ratio, and degree of crystallinity are presented. Spectral changes of the σ*C–H/Rydberg and σ*C–C features in these ideal model systems provide unambiguous experimental evidence for intermolecular interactions with profound effects on the spectral intensity, but only very small energy shifts. Ab initio calculations reproduce the experimental results in detail. The intermolecular interaction observed suggests that interpretation of NEXAFS spectra based on calculations of isolated molecules can be insufficient even in relatively weakly interacting macromolecules.

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.

We report the visualization and quantitative analysis of the cross-link structure in model core/shell hydrogel polymers on the microscopic scale, in a fully swollen state, using soft X-ray microscopy. The cross-link density in these materials and their microscopic or even nanoscopic variation critically influence materials characteristics, yet the cross-link density is difficult to characterize by conventional methods. By the use of soft X-ray microscopy, one can investigate these materials in a fully swollen state and thus directly visualize and quantitatively determine the cross-link structure on a microscopic scale. Materials that were cross-linked by different methods were shown to give rise to differently shaped profiles. Abrupt and gradient cross-link density profiles have been investigated, and the spatial variation in their cross-link density has been determined quantitatively.

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.

The successful application of X-ray spectromicroscopy to chemical analysis of polymers is reviewed and a detailed application to quantitative analysis of polyurethanes is presented. Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is the basis of chemical sensitive X-ray imaging, as well as qualitative and quantitative micro-spectroscopy. These capabilities are demonstrated by a review of recent work, and by presentation of new results outlining a methodology for quantitative speciation of polyurethane polymers. C 1s inner-shell excitation spectra of a series of molecular and polymeric model compounds, recorded by gas phase inelastic electron scattering (ISEELS) and solid phase NEXAFS techniques, are used to understand the spectroscopic basis for chemical analysis of polyurethanes. These model species contain the aromatic urea, aromatic urethane (carbamate) and aliphatic ether functionalities that are the main constituents of polyurethane polymers. Ab initio calculations of several of the model molecular compounds are used to support spectral assignments and give insight into the origin and relative intensities of characteristic spectral features. The model polymer spectra provide reference standards for qualitative identification and quantitative analysis of polyurethane polymers. The chemical compositions of three polyurethane test polymers with systematic variation in urea/urethane content are measured using the spectra of model toluene diisocyanate (TDI) urea, TDI-carbamate, and poly(propylene oxide) polymers as reference standards.

Superabsorbent polymers are often designed with increased density of crosslinking in the outer layer of the particles in order to improve liquid retention under load. For efficient product design, it is desirable to directly measure the spatial variation in crosslink density. Typically employed techniques (such as solvent uptake or measuring the changes in various mechanical properties such as the modulus) do not provide spatially resolved crosslink density information. We have applied Scanning Transmission X-ray Microscopy to examine the swelling of inhomogenously crosslinked superabsorbent polymers in deionized water and salt water solution. Scanning Transmission X-ray Microscopy (STXM) is an effective way to study the chemical and morphological character of polymers on a sub micron spatial scale.1 STXM image contrast is based on core electron excitation by x-ray absorption; an interaction that has remarkable chemical sensitivity. Beam damage is less than in TEM microscopes and samples can be examined in wet and in ambient conditions.