Performance of a hardened x-ray streak camera at Lawrence Livermore National Laboratory's National Ignition Facility.

Electron tubes continue to provide the highest speeds possible for recording dynamics of hot high-energy density plasmas. Standard streak camera drive electronics and CCD readout are not compatible with the radiation environment associated with high DT fusion yield inertial confinement fusion experiments >1013 14 MeV DT neutrons or >109 n cm-2 ns-1. We describe a hardened x-ray streak camera developed for the National Ignition Facility and present preliminary results from the first experiment on which it has participated, recording the time-resolved bremsstrahlung spectrum from the core of an inertial confinement fusion implosion at more than 40× the operational neutron yield limit of the previous National Ignition Facility x-ray streak cameras.

Side-bounce beamlines using single-reflection diamond monochromators at Cornell High Energy Synchrotron Source.

The design and implementation of new beamlines featuring side-bounce (single-reflection) diamond monochromators at Cornell High Energy Synchrotron Source (CHESS) are described. Undulator radiation is monochromated using an interchangeable set of diamond crystal plates reflecting radiation in the horizontal (synchrotron) plane, where each crystal plate is set to one of the low-index Bragg reflections (111, 220, 311 and 400) in either Bragg or Laue reflection geometries. At the nominal Bragg angle of 18° these reflections deliver monochromated X-rays with photon energies of 9.7, 15.9, 18.65 and 22.5 keV, respectively. An X-ray mirror downstream of the diamond monochromator is used for rejection of higher radiation harmonics and for initial focusing of the monochromated beam. The characteristics of the X-ray beam entering the experimental station were measured experimentally and compared with the results of simulations. A reasonable agreement is demonstrated. It is shown that the use of selected high-dislocation-density `mosaic' diamond single-crystal plates produced using the chemical vapor deposition method yields a few-fold enhancement in the flux density of the monochromated beam in comparison with that delivered by perfect crystals under the same conditions. At present, the Functional Materials Beamline at CHESS, which is used for time-resolved in situ characterization of soft materials during processing, has been outfitted with the described setup.

Evolution of lattice distortions in 4H-SiC wafers with varying doping.

Lattice distortions (LD) in 4H-silicon carbide (SiC) wafers were quantified using synchrotron X-ray rocking curve mapping (RCM), and were resolved into their two components of lattice strain (Δd/d) and lattice plane curvature (LPC) for 150 mm diameter wafers. The evolution of these LDs were investigated for three sequential substrates from the same boule, one of which was the substrate reference, and the other two had a 10 µm thick, 1 × 1017 and 4 × 1014 cm-3 n-type doped epitaxial layer. The lattice strain, Δd/d, was highest for the lowest doped wafer due to higher mismatch with the substrate wafer. After epitaxial layer growth, the LPC variation across the wafer increases by a factor of 2, irrespective of doping. The LPC maps indicate presence of a twist in the lattice planes that increases after epitaxial growth. The LPC component has higher influence on wafer shape change, which can reduce device yields. The lattice strain component predominantly affects the glide of basal plane dislocations (BPDs), thereby reducing device reliability. From analysis of peak widths, it was determined that threading dislocations in the top 6 microns of the wafer increase after epitaxial layer growth.

High-dynamic-range transmission-mode detection of synchrotron radiation using X-ray excited optical luminescence in diamond.

Enhancement of X-ray excited optical luminescence in a 100 µm-thick diamond plate by introduction of defect states via electron beam irradiation and subsequent high-temperature annealing is demonstrated. The resulting X-ray transmission-mode scintillator features a linear response to incident photon flux in the range 7.6 × 108 to 1.26 × 1012 photons s-1 mm-2 for hard X-rays (15.9 keV) using exposure times from 0.01 to 5 s. These characteristics enable a real-time transmission-mode imaging of X-ray photon flux density without disruption of X-ray instrument operation.

An Innovative Lithium Ion Battery System Based on a Cu2S Anode Material.

Cu2S is considered as one of the potential anode paradigms for advanced rechargeable batteries because of its high theoretical capacity (∼335 mAh·g-1), high and flat charge/discharge voltage plateaus (∼1.7 V vs Li+/Li), stable cycling performance, and its elemental abundance. However, many studies have shown that Cu2S exhibits a dramatic capacity fade in carbonate-based electrolytes, which has precluded its commercialization when paired with high voltage cathodes in state-of-the-art lithium ion batteries. Here, we report on a fundamental mechanistic study of the electrochemical processes of Cu2S in both ether- and carbonate-based electrolytes employing operando synchrotron X-ray methods. Based on our findings, we developed a Cu2S/C composite material that suppresses its failure mechanism in carbonate-based electrolytes and further demonstrated its feasibility in lithium ion full cells for the first time. Our experiment provides the basis for the utilization of Cu2S in industrial-scale applications for large-scale electrical energy storage.

High Bragg reflectivity of diamond crystals exposed to multi-kW†mm-2 X-ray beams.

X-ray free-electron lasers in the oscillator configuration (XFELO) are future fully coherent hard X-rays sources with ultrahigh spectral purity. X-ray beams circulate in an XFELO optical cavity comprising diamond single crystals. They function as high-reflectance (close to 100%), narrowband (∼10 meV) Bragg backscattering mirrors. The average power density of the X-ray beams in the XFELO cavity is predicted to be as high as ∼10 kW mm-2. Therefore, XFELO feasibility relies on the ability of diamond crystals to withstand such a high radiation load and preserve their high reflectivity. Here the endurance of diamond crystals to irradiation with multi-kW mm-2 power density X-ray beams is studied. It is shown that the high Bragg reflectivity of the diamond crystals is preserved after the irradiation, provided it is performed at ∼1 × 10-8 Torr high-vacuum conditions. Irradiation under 4 × 10-6 Torr results in a ∼1 meV shift of the Bragg peak, which corresponds to a relative lattice distortion of 4 × 10-8, while the high Bragg reflectivity stays intact.

Efficiency and coherence preservation studies of Be refractive lenses for XFELO application.

Performance tests of parabolic beryllium refractive lenses, considered as X-ray focusing elements in the future X-ray free-electron laser oscillator (XFELO), are reported. Single and double refractive lenses were subject to X-ray tests, which included: surface profile, transmissivity measurements, imaging capabilities and wavefront distortion with grating interferometry. Optical metrology revealed that surface profiles were close to the design specification in terms of the figure and roughness. The transmissivity of the lenses is >94% at 8 keV and >98% at 14.4 and 18 keV. These values are close to the theoretical values of ideal lenses. Images of the bending-magnet source obtained with the lenses were close to the expected ones and did not show any significant distortion. Grating interferometry revealed that the possible wavefront distortions produced by surface and bulk lens imperfections were on the level of ∼λ/60 for 8 keV photons. Thus the Be lenses can be succesfully used as focusing and beam collimating elements in the XFELO.

Surface studies of solids using integral X-ray-induced photoemission yield.

X-ray induced photoemission yield contains structural information complementary to that provided by X-ray Fresnel reflectivity, which presents an advantage to a wide variety of surface studies if this information is made easily accessible. Photoemission in materials research is commonly acknowledged as a method with a probing depth limited by the escape depth of the photoelectrons. Here we show that the integral hard-X-ray-induced photoemission yield is modulated by the Fresnel reflectivity of a multilayer structure and carries structural information that extends well beyond the photoelectron escape depth. A simple electric self-detection of the integral photoemission yield and Fourier data analysis permit extraction of thicknesses of individual layers. The approach does not require detection of the reflected radiation and can be considered as a framework for non-invasive evaluation of buried layers with hard X-rays under grazing incidence.

Large-surface-area diamond (111) crystal plates for applications in high-heat-load wavefront-preserving X-ray crystal optics.

Fabrication and results of high-resolution X-ray topography characterization of diamond single-crystal plates with large surface area (10 mm × 10 mm) and (111) crystal surface orientation for applications in high-heat-load X-ray crystal optics are reported. The plates were fabricated by laser-cutting of the (111) facets of diamond crystals grown using high-pressure high-temperature methods. The intrinsic crystal quality of a selected 3 mm × 7 mm crystal region of one of the studied samples was found to be suitable for applications in wavefront-preserving high-heat-load crystal optics. Wavefront characterization was performed using sequential X-ray diffraction topography in the pseudo plane wave configuration and data analysis using rocking-curve topography. The variations of the rocking-curve width and peak position measured with a spatial resolution of 13 µm × 13 µm over the selected region were found to be less than 1 µrad.

Thermally triggered phononic gaps in liquids at THz scale.

In this paper we present inelastic X-ray scattering experiments in a diamond anvil cell and molecular dynamic simulations to investigate the behavior of phononic excitations in liquid Ar. The spectra calculated using molecular dynamics were found to be in a good agreement with the experimental data. Furthermore, we observe that, upon temperature increases, a low-frequency transverse phononic gap emerges while high-frequency propagating modes become evanescent at the THz scale. The effect of strong localization of a longitudinal phononic mode in the supercritical phase is observed for the first time. The evidence for the high-frequency transverse phononic gap due to the transition from an oscillatory to a ballistic dynamic regimes of motion is presented and supported by molecular dynamics simulations. This transition takes place across the Frenkel line thermodynamic limit which demarcates compressed liquid and non-compressed fluid domains on the phase diagram and is supported by calculations within the Green-Kubo phenomenological formalism. These results are crucial to advance the development of novel terahertz thermal devices, phononic lenses, mirrors, and other THz metamaterials.

Revealing the Mechanism of the Viscous-to-Elastic Crossover in Liquids.

In this work, we report on inelastic X-ray scattering experiments combined with the molecular dynamics simulations on deeply supercritical Ar. The presented results unveil the mechanism and regimes of sound propagation in the liquid matter and provide compelling evidence for the adiabatic-to-isothermal longitudinal sound propagation transition. We introduce a Hamiltonian predicting low-frequency transverse sound propagation gaps, which is confirmed by experimental findings and molecular dynamics calculations. As a result, a universal link is established between the positive sound dispersion (PSD) phenomenon and the origin of transverse sound propagation revealing the viscous-to-elastic crossover in liquids. The PSD and transverse phononic excitations evolve consistently with theoretical predictions. Both can be considered as a universal fingerprint of the dynamic response of a liquid, which is also observable in a subdomain of supercritical phase. The simultaneous disappearance of both these effects at elevated temperatures is a manifestation of the Frenkel line. We expect that these findings will advance the current understanding of fluids under extreme thermodynamic conditions.

Performance of a beam-multiplexing diamond crystal monochromator at the Linac Coherent Light Source.

A double-crystal diamond monochromator was recently implemented at the Linac Coherent Light Source. It enables splitting pulses generated by the free electron laser in the hard x-ray regime and thus allows the simultaneous operations of two instruments. Both monochromator crystals are High-Pressure High-Temperature grown type-IIa diamond crystal plates with the (111) orientation. The first crystal has a thickness of ~100 µm to allow high reflectivity within the Bragg bandwidth and good transmission for the other wavelengths for downstream use. The second crystal is about 300 µm thick and makes the exit beam of the monochromator parallel to the incoming beam with an offset of 600 mm. Here we present details on the monochromator design and its performance.

High-contrast sub-millivolt inelastic X-ray scattering for nano- and mesoscale science.

Photon and neutron inelastic scattering spectrometers are microscopes for imaging condensed matter dynamics on very small length and time scales. Inelastic X-ray scattering permitted the first quantitative studies of picosecond nanoscale dynamics in disordered systems almost 20 years ago. However, the nature of the liquid-glass transition still remains one of the great unsolved problems in condensed matter physics. It calls for studies at hitherto inaccessible time and length scales, and therefore for substantial improvements in the spectral and momentum resolution of the inelastic X-ray scattering spectrometers along with a major enhancement in spectral contrast. Here we report a conceptually new spectrometer featuring a spectral resolution function with steep, almost Gaussian tails, sub-meV (≃620 µeV) bandwidth and improved momentum resolution. The spectrometer opens up uncharted space on the dynamics landscape. New results are presented on the dynamics of liquid glycerol, in the regime that has become accessible with the novel spectrometer.

Hard x-ray monochromator with milli-electron volt bandwidth for high-resolution diffraction studies of diamond crystals.

We report on design and performance of a high-resolution x-ray monochromator with a spectral bandwidth of ΔE(X) ≃ 1.5 meV, which operates at x-ray energies in the vicinity of the backscattering (Bragg) energy E(H) = 13.903 keV of the (008) reflection in diamond. The monochromator is utilized for high-energy-resolution diffraction characterization of diamond crystals as elements of advanced x-ray crystal optics for synchrotrons and x-ray free-electron lasers. The monochromator and the related controls are made portable such that they can be installed and operated at any appropriate synchrotron beamline equipped with a pre-monochromator.

Nanoradian angular stabilization of x-ray optical components.

An x-ray free-electron laser oscillator (XFELO) has been recently proposed [K. Kim et al., Phys. Rev. Lett. 100, 244802 (2008)]. Angular orientation and position in space of Bragg mirrors of the XFELO optical cavity must be continuously adjusted to compensate for the instabilities and maximize the output intensity. An angular stability of about 10 nrad (rms) is required [K. Kim and Y. Shvyd'ko, Phys. Rev. ST Accel. Beams 12, 030703 (2009)]. To approach this goal, a feedback loop based on a null-detection principle was designed and used for stabilization of a high-energy-resolution x-ray monochromator (DeltaE/E approximately 4 x 10(-8), E=23.7 keV) and a high-heat-load monochromator. Angular stability of about 13 nrad (rms) has been demonstrated for x-ray optical elements of the monochromators.

Thermal expansion of diamond at low temperatures.

Temperature variation of a lattice parameter of a synthetic diamond crystal (type IIa) was measured using high-energy-resolution x-ray Bragg diffraction in backscattering. A 2 order of magnitude improvement in the measurement accuracy allowed us to directly probe the linear thermal expansion coefficient at temperatures below 100 K. The lowest value measured was 2x10{-9} K-1. It was found that the coefficient deviates from the expected Debye law (T3) while no negative thermal expansion was observed. The anomalous behavior might be attributed to tunneling states due to low concentration impurities.

Influence of Adsorbate-Free Atoms on Δ-XANES Signatures.

The use of differential X-ray Absorption Near Edge Spectroscopy (Δ-XANES) for analysis of site specific adsorption on metallic electrodes relies on theoretical Δ-XANES signatures for analysis of experimental Δ-XANES fingerprints. A simple model, currently used in the analysis, considers changes in X-ray absorption properties of adsorbing atoms only. This model has been extended to include changes in X-ray absorption for other atoms of the same type that remain adsorbate-free. Configurational averaging has been applied to calculate difference spectra of a Pt6 cluster with an oxygen atom adsorbed at different sites. The extended theory shows that contribution of the adsorbate-free atoms might become significant as it affects the shape profiles of the theoretical signatures. The effect, most prominent at the absorption edge energy, is interpreted in terms of change in the electronic structure of the cluster due to oxygen adsorption. In addition to model dependence of the theoretical signatures, challenges to the application of Δ-XANES to the experimentally obtained fingerprints are discussed.

Structural analysis of sonochemically prepared PtRu versus Johnson Matthey PtRu in operating direct methanol fuel cells.

Sonochemically prepared PtRu (3 : 1) and Johnson Matthey PtRu (1 : 1) were analyzed by X-ray absorption spectroscopy in operating liquid feed direct methanol fuel cells. The total metal loadings were 4 mg cm(-2) unsupported catalysts at the anode and cathode of the membrane electrode assembly. Ex situ XRD lattice parameter analysis indicates partial segregation of the Ru from the PtRu fcc alloy in both catalysts. A comparison of the in situ DMFC EXAFS to that of the as-received catalyst shows that catalyst restructuring during DMFC operation increases the total metal coordination numbers. A combined analysis of XRD determined grain sizes and lattice parameters, ex situ and in situ EXAFS analysis, and XRF of the as-received catalysts enables determination of the catalyst shell composition. The multi-spectrum analysis shows that the core size increases during DMFC operation by reduction of Pt oxides and incorporation of Pt into the core. This increases the mole fraction of Ru in the catalyst shell structure.

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.