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X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a SrTiO_{3} (001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three hkl substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Overall, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.

Physical review materials 4(5), 056002 (2020). doi:10.1103/PhysRevMaterials.4.056002, We report a model-independent atomic-mapping technique for quantum dots (QDs) by combining Bragg reflection x-ray standing wave (XSW) and grazing incidence diffraction (GID) measurements. In this study, we choose GaAs capped InGaAs QDs/GaAs(001) as a model system to show the locations and arrangements of indium atoms within the QDs along various [hkl] directions. This technique directly reveals the actual amount of positional anisotropy and ordering fraction of indium atoms within the QDs by probing the (¯111), (111), (311), (¯131), (113), and (¯113) crystallographic planes. We find that indium atoms are outwardly shifted along the [001] direction by small fractions of the lattice constant, 0.04aGaAs and 0.06aGaAs from Ga sites for 50- and 150-Å GaAs capped InGaAs QDs, respectively. We observe that an improved coherency factor of the indium atoms within the QDs by 45–60% along the [001] and [011] directions reduces the photoluminescence linewidth by 22%, thus making the QDs efficient for QD-laser and optoelectronic device applications. We also find that the position and ordering of In atoms along the (113) and (¯113) planes are most sensitive to the thickness of the GaAs cap layer. Our XSW-based results are supported by numerical calculations using a QD-macroscopic structural model based on our GID study. We thus show that this atomic-mapping technique will be useful for studying various quantum structures and tuning their properties., Published by APS, College Park, MD

The properties of clay slurries (porosity ~ 0.75) impact a wide range of materials such as commercial clay dispersions and sedimentary deposits. Their material behavior, and in particular the gelation of clay slurries, is thought to be governed by clay particle interactions. In the literature, such interactions are rarely directly probed, but rather inferred from structures observed by cryo-electron microscopy. For example, the honeycomb structure is a widely accepted textbook model that is used to rationalize the observed behavior of clay slurries. Using high-pressure freezing, cryo-electron microscopy, and cryo-synchrotron wide-angle X-ray scattering, this study shows that the honeycomb-structure is an artifact of sample preparation. When samples are high-pressure frozen, individual clay particles and aggregates of particles arrange in a random orientation rather than the closed-cell structure dominated by face-face and face-edge contacts observed in plunge frozen samples. These results substantially contribute to the understanding of the gelation mechanism and particle interactions in colloidal clay slurries, and provide valuable input parameters for meso-scale modeling efforts of clay dispersions and sedimentary deposits to upscale their mechanical properties to the macroscale.

Dental caries is a ubiquitous infectious disease with a nearly 100% lifetime prevalence. Rodent caries models are widely used to investigate the etiology, progression and potential prevention or treatment of the disease. To explore the suitability of these models for deeper investigations of intact surface zones during enamel caries, the structures of early-stage carious lesions in rats were characterized and compared with previous reports on white spot enamel lesions in humans. Synchrotron X-ray microcomputed tomography non-destructively mapped demineralization in carious rat molar specimens across a range of caries severity, identifying 52 lesions across the 30 teeth imaged. Of these lesions, 13 were shown to have intact surface zones. Depth profiles of fractional mineral density were qualitatively similar to lesions in human teeth. However, the thickness of the surface zone in the rat model ranges from 10 to 58 µm, and is therefore significantly thinner than in human enamel. These results indicate that a fraction of lesions in rat caries possess an intact surface zone and are qualitatively similar to human lesions at the micrometer scale. This suggests that rat caries models may be a suitable analog through which to investigate the structure of surface zone enamel and its role during dental caries.

Electrically conducting, 3D elastomeric composite foams are fabricated successfully using multiple cycles of infusing polyurethane foams with graphene oxide sheets followed by reduction, to form coatings of reduced graphene oxide up to ∼1260 nm thick. The reduced graphene oxide coating increases the compression modulus of the composite and lowers the electrical resistance significantly compared with polyurethane foam, the extents of which increase with increasing coating thickness. The electrical resistance of the coated foams varies by as much as three orders of magnitude for coating thickness between ∼150 and ∼1200 nm, whereas the capacitance varies by one order of magnitude. Both the stress-strain and the resistance-strain behavior are highly repeatable with compression cycles performed up to 70% strain. Both SEM and X-ray tomography characterization show that deformation is mostly through bending of the pore walls up to about 20% strain, collapse of pore openings to about 60% strain, and densification beyond that. Micro-fractures also develop on the coating during the first few cycles of compression, but no obvious structural changes can be detected afterwards.

This paper presents a structure-property model for carbon fiber derived from a polyethylene (PE) precursor that relates tensile modulus to the elastic properties and angular distribution of constituent graphitic layers, as measured using wide-angle x-ray diffraction of individual carbon fiber filaments. The observed relationship and interpretation of data using a uniform-stress model has revealed fundamental differences in the nature of the microstructure present in carbon fiber produced from polyethylene compared to carbon fiber produced from polyacrylonitrile (PAN) or pitch precursors. Specifically, it was found that the shear modulus, indicative of the shear between adjacent graphitic layers of the carbonized fiber is lower for polyethylene-derived carbon fiber than for PAN- or pitch-derived carbon fiber, suggesting that the covalent C C sp3 crosslink density connecting adjacent graphitic layers in PE-derived carbon fiber is reduced. This structure that is less crosslinked is anticipated to be easier to orient during carbonization and high-temperature graphitization processes, yielding a highly oriented structure necessary for high tensile modulus.

The cross-plane thermal conductivity of InGaZnO (IGZO) thin films was measured using the 3ω technique from 18 to 300 K. The studied morphologies include amorphous (a-IGZO), semicrystalline (semi-c-IGZO), and c-axis-aligned single-crystal-like IGZO (c-IGZO) grown by pulsed laser deposition (PLD) as well as a-IGZO deposited by sputtering and by solution combustion processing. The atomic structures of the amorphous and crystalline films were simulated with ab initio molecular dynamics. The film quality and texturing information was assessed by X-ray diffraction and grazing incidence wide-angle X-ray scattering. X-ray reflectivity was also conducted to quantify film densities and porosities. All the high-density films exhibit an empirical power-law temperature dependence of the thermal conductivity κ ∼ T0.6 in the specified temperature range. Among the PLD dense films, semi-c-IGZO exhibits the highest thermal conductivity, remarkably exceeding both films with more order (c-IGZO) and with less order (a-IGZO) b...

Amorphous metal oxides (AMOs) are important candidate materials for fabricating next-generation thin-film transistors. While much attention has been directed toward the synthesis and electrical properties of AMOs, less is known about growth conditions that allow AMOs to retain their desirable amorphous state when subjected to high operating temperatures. Using in situ x-ray scattering and level-set simulations, we explore the time evolution of the crystallization process for a set of amorphous $\mathrm{I}{\mathrm{n}}_{2}{\mathrm{O}}_{3}$ thin films synthesized by pulsed-laser deposition at deposition temperatures (${T}_{d}$) of \ensuremath{-}50, \ensuremath{-}25, and 0 \ifmmode^\circ\else\textdegree\fi{}C. The films were annealed isothermally and the degree of crystallinity was determined by a quantitative analysis of the time-evolved x-ray scattering patterns. As expected, for films grown at the same ${T}_{d}$, an increase in the annealing temperature ${T}_{A}$ led to a shorter delay prior to the onset of crystallization, and a faster crystallization rate. Moreover, when lowering the deposition temperature by 25 \ifmmode^\circ\else\textdegree\fi{}C, a 40 \ifmmode^\circ\else\textdegree\fi{}C increase in annealing temperature is needed to achieve the same time interval for the crystals to grow from 10 to 90% volume fraction of the sample. Films grown at ${T}_{d}=0{\phantom{\rule{0.16em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$ exhibited strong cubic texture after crystallization. A level-set method was employed to quantitatively model the texture that develops in the microstructures and to determine key parameters, such as the interface growth velocity, the nucleation density, and the activation energy. The differences observed in the crystallization processes are attributed to the changes in the atomic structure of the oxide and possible nanocrystalline inclusions that formed during the deposition of the amorphous phase.

This paper will discuss the structure-property model developed that correlates the tensile modulus to the elastic properties and angular distribution of constituent graphitic layers for carbon fiber derived from a polyethylene precursor. In addition, a high-temperature fiber tensile device was built to enable heating of carbon fiber bundles at a variable rate from 25 °C to greater than ∼2300 °C, while simultaneously applying a tensile stress. This capability combined with synchrotron wide-angle x-ray diffraction (WAXD), enabled observation in situ and in real time of the microstructural transformation from different carbon fiber precursors to high-modulus carbon fiber. Experiments conducted using PAN- and PE-derived fiber precursors reveal stark differences in their carbonization and high-temperature graphitization behavior.

Currently, carbon fibers (CFs) from the solution spinning, air oxidation, and carbonization of polyacrylonitrile impose a lower price limit of ≈$10 per lb, limiting the growth in industrial and automotive markets. Polyethylene is a promising precursor to enable a high-volume industrial grade CF as it is low cost, melt spinnable and has high carbon content. However, sulfonated polyethylene (SPE)-derived CFs have thus far fallen short of the 200 GPa tensile modulus threshold for industrial applicability. Here, a graphitization process is presented catalyzed by the addition of boron that produces carbon fiber with >400 GPa tensile modulus at 2400 °C. Wide angle X-ray diffraction collected during carbonization reveals that the presence of boron reduces the onset of graphitization by nearly 400 °C, beginning around 1200 °C. The B-doped SPE-CFs herein attain 200 GPa tensile modulus and 2.4 GPa tensile strength at the practical carbonization temperature of 1800 °C.

Termination and hydration of the forsteritic (Fo90Fa10) olivine (0 1 0) surface have been investigated with high-resolution specular X-ray reflectivity and Atomic Force Microscopy. The surface was prepared by polishing a naturally grown {0 1 0} face, from which we found the polished surface in acidic (pH 3.5) alumina suspension exhibits regular steps while the basic (pH 9.5) silica polished surface is irregularly roughened, indicating there are two distinguishable mechanochemical processes for the surface dissolution. The quantitative interpretation of the regular steps from the alumina-polished surface suggests that the observed step heights correspond to multiples of crystallographic unit cell. Only this atomically terraced surface is investigated with the high-resolution X-ray reflectivity (HRXR) to determine the surface termination and hydration. The basic silica paste polished surface turned out too rough to measure with X-ray reflectivity. HRXR reveals that the alumina polished olivine (0 1 0) surface in pure water is terminated at a plane including half-occupied metal ion sites (M1), an oxygen vacancy site, and a silicate tetrahedral unit with one of its apices pointing outward with respect to the surface. An ideal termination with the oxygen vacancy would fulfill the stoichiometry of the formula unit; however, in the observation, the vacancy site is filled by an adsorbed water species and about a quarter of the remaining metal ions are further depleted. The terminating plane generates two distinct atomic layers in the laterally averaged electron density profile, on which two highly ordered adsorbed water layers are formed. The first layer formation is likely through the direct interaction with the M1 plane and the second layer is likely through the hydrogen bonding interaction with the first water layer. With this multilayered adsorbed water structure, the surface metal ion is partially hydrated by the vacancy-filling water species and adsorbed water molecules. The bulk water links to these distinct adsorbed water layers, with weak density oscillations that almost completely damp out after the first bulk water layer. The total thickness of the layered water structure including the two distinct adsorbed layers and the first layer of bulk water is slightly less than 1 nm, which corresponds to roughly three molecular layers of water. These results describe the steric constraints of the surface metal ion hydration and the iron redox environment during water–olivine interactions in this particular crystallographic orientation.

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis-azide-functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis-alkyne-functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β-cyclodextrin(CD)-accelerated, cucurbit[6]uril(CB)-templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss-cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.

A new high-temperature fibre tensile cell is described, developed for use at the Advanced Photon Source at Argonne National Laboratory to enable the investigation of the carbonization and graphitization processes during carbon fibre production. This cell is used to heat precursor fibre bundles to temperatures up to ∼2300°C in a controlled inert atmosphere, while applying tensile stress to facilitate formation of highly oriented graphitic microstructure; evolution of the microstructure as a function of temperature and time during the carbonization and higher-temperature graphitization processes can then be monitored by collecting real-time wide-angle X-ray diffraction (WAXD) patterns. As an example, the carbonization and graphitization behaviour of an oxidized polyacrylonitrile fibre was studied up to a temperature of ∼1750°C. Real-time WAXD revealed the gradual increase in microstructure alignment with the fibre axis with increasing temperature over the temperature range 600–1100°C. Above 1100°C, no further changes in orientation were observed. The overall magnitude of change increased with increasing applied tensile stress during carbonization. As a second example, the high-temperature graphitizability of PAN- and pitch-derived commercial carbon fibres was studied. Here, the magnitude of graphitic microstructure evolution of the pitch-derived fibre far exceeded that of the PAN-derived fibres at temperatures up to ∼2300°C, indicating its facile graphitizability.

In this tutorial, we describe X-ray microtomography as a technique to nondestructively characterize material microstructure in three dimensions at a micron level spatial resolution. While commercially available laboratory scale instrumentation is available, we focus our attention on synchrotron-based systems, where we can exploit a high flux, monochromatic X-ray beam to produce high fidelity three-dimensional images. A brief description of the physics and the mathematical analysis behind the technique is followed by example applications to specific materials characterization problems, with a particular focus on the utilization of three-dimensional image processing that can be used to extract a wide range of useful information.

Chemical and morphological changes induced by an X-ray photochemical reaction in tetrachloroauric solutions leading to Au(3+)-to-Au(0) reduction are monitored in real time by X-ray absorption spectroscopy and X-ray small angle scattering. Prior to metal precipitation, the intermediate state, also observed by other techniques, is unambiguously determined for the first time to be the reduction of Au(3+) to Au(1+), whose kinetics is strictly of the zeroth order. The morphological changes occur simultaneously in the solutions, that is, the gold complexes rearrange and aggregate, as unequivocally observed by the correlated changes in the Au L(3) emission and small angle scattering intensities. The experimental evidence indicates that the eventual metal precipitation is strongly influenced by the changing solution acidity under X-ray irradiation. Detailed local structure changes are also described.

Some X-ray instruments require the utilization of large-area windows to provide vacuum barriers. The necessary attributes of the window material include transparency to X-rays, low scattering, and possession of suitable mechanical properties for reliable long-term performance. Kapton is one such material except that it is a polymer and a large window made from Kapton with a pressure differential of one atmosphere across it can undergo substantial deformation at room temperature. In this paper, we report on the mechanical testing of Kapton samples including creep measurements, and comparison with published data. We use of these data together with analytical / numerical models to predict the changes in the profile of Kapton vacuum windows over time, and show good agreement with experimental measurements.

The pore structure of concrete has long been recognized as the key to a wide range of different mechanical, physical and chemical properties. However, the finite range of the different interrogation techniques for measuring pore structure has always limited our overall picture. In order to add to that picture, a high resolution, three-dimensional imaging technique called x-ray microtomography was employed as a way to link measurable microstructural features with alternate measurements of permeability in different concrete systems. Four different concretes were imaged at spatial resolutions between 1 and 4 microns. Using 3D image analysis techniques, the pore system was characterized by size distribution and connectivity. A parameter we termed “disconnected pore distance” correlated well with standard measures of chloride permeability.

High-volume fabrication of nanostructures requires nondestructive metrologies capable of measuring not only the pattern size but also the pattern shape profile. Measurement tool requirements will become more stringent as the feature size approaches 50nm and tolerances of pattern shape will reach a few nanometers. A small angle x-ray scattering (SAXS) based technique has been demonstrated to have the capability of characterizing the average pitch size and pattern width to subnanometer precision. In this study, we report a simple, modeling-free protocol to extract cross-section information such as the average sidewall angle and the pattern height of line grating patterns from the SAXS data. Diffraction peak intensities and reciprocal space positions are measured while the sample is rotated around the axis perpendicular to the grating direction. Linear extrapolations of peak positions in reciprocal space allow a precise determination of both the sidewall angle and the pattern height.

The DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) built and currently manages sector 5 at the Advanced Photon Source (APS), Argonne National Laboratory. One of the principal techniques supported by DND-CAT is Small and Wide-Angle X-ray Scattering (SAXS/WAXS), with an emphasis on simultaneous data collection over a wide azimuthal and reciprocal space range using a custom SAXS/WAXS detector system. A new triple detector system is now in development, and we describe the key parameters and characteristics of the new instrument, which will be faster, more flexible, more robust, and will improve q-space resolution in a critical reciprocal space regime between the traditional WAXS and SAXS ranges.

Studies of carbon nanotube (CNT) based composites have been unable to translate the extraordinary load-bearing capabilities of individual CNTs to macroscale composites such as yarns. A key challenge lies in the lack of understanding of how properties of filaments and interfaces across yarn hierarchical levels govern the properties of macroscale yarns. To provide insight required to enable the development of superior CNT yarns, we investigate the fabrication-structure-mechanical property relationships among CNT yarns prepared by different techniques and employ a Monte Carlo based model to predict upper bounds on their mechanical properties. We study the correlations between different levels of alignment and porosity and yarn strengths up to 2.4 GPa. The uniqueness of this experimentally informed modeling approach is the model's ability to predict when filament rupture or interface sliding dominates yarn failure based on constituent mechanical properties and structural organization observed experimentally. By capturing this transition and predicting the yarn strengths that could be obtained under ideal fabrication conditions, the model provides critical insights to guide future efforts to improve the mechanical performance of CNT yarn systems. This multifaceted study provides a new perspective on CNT yarn design that can serve as a foundation for the development of future composites that effectively exploit the superior mechanical performance of CNTs.

The role of crystallographic texture in determining the fracture behavior of a highly anisotropic ceramic, iron titanate, has been examined. By exploiting the anisotropy in its single crystal magnetic susceptibility, crystallographically textured and untextured iron titanate microstructures were formed by gelcasting in the presence and absence of a strong magnetic field, respectively. The magnetic field-assisted processing imparted a fiber-like texture to the processed ceramic material in which the crystallographic b-axes of the grains aligned parallel to the applied field. Triaxial residual stress and lattice parameter measurements showed that both the untextured and textured materials had undergone significant stress–relaxation, presumably due to spontaneous microcracking. Further, ‘aggregates’ of non-textured material were discovered within textured material that led to a population of meso-scale cracks (meso-cracks) in the microstructure oriented normal to the direction of alignment. Both crack populations were examined using a finite element simulation and confirmed by small angle neutron scattering measurements, and for meso-cracks, by X-ray tomography. Bend strength and R-curve behavior were evaluated as a function of texture and orientation in the magnetically processed materials. Strengths remained within 20% of that of the control material, except for one orientation, for which the strength decreased with increasing degree of texture due to favorably oriented meso-cracks. The R-curve behavior was highly anisotropic, with the peak fracture toughness of the magnetically processed material ranging from approximately equal to 2.5 times that of the control material. Additionally, the peak fracture toughness of each orientation increased with the degree of texture. Anisotropic fracture properties were related to interactions between the test crack and the population of meso-cracks.

The structure of a passivating sulfide layer on Ge(001) was studied using X-ray standing waves and X-ray fluorescence. The sulfide layer was formed by reacting clean Ge substrates in (NH 4 ) 2 S solutions of various concentrations at 80°C. For each treatment, a sulfide layer containing approximately two to three monolayers (ML) of S was formed on the surface, and an ordered structure was found at the interface that contained approximately 0.4 ML of S. Our results suggest the rapid formation of a glassy GeS x layer containing 1.5‐2.5 ML S residing atop a partially ordered interfacial layer of bridge-bonded S. The passivating reaction appears to be self-limited to 2‐3 ML at this reaction temperature. © 2000 Elsevier Science B.V. All rights reserved.

An x-ray-diffraction method that directly senses the phase of the structure factor is demonstrated and used for determining the local polarity of thin ferroelectric films. This method is based on the excitation of an x-ray standing-wave field inside the film as a result of the interference between the strong incident x-ray wave and the weak kinematically Bragg-diffracted x-ray wave from the film. The method is used to sense the displacements of the Pb and Ti sublattices in single-crystal c-domain PbTiO{sub 3} thin films grown by metal-organic chemical-vapor deposition on SrTiO{sub 3}(001) substrates. (c) 2000 The American Physical Society.

A high-resolution 3D scanning technique called X-ray microtomography was applied to measure internal damage and crack growth in small mortar cylinders loaded in compression. Synchrotron-based microtomography allows us to resolve internal features that are only a few microns in size. Multiple tomographic scans were made of the same specimen at different levels of deformation using a custom-built loading frame. 3D image analysis was used to measure internal crack growth during each deformation increment. Measured load-deformation curves were used to calculate the nonrecoverable work of the external load on the specimen. Nonrecoverable work of load was related to measured incremental change in crack surface area to estimate work-of-fracture in three dimensions. Initial results indicate a nearly constant work-of-fracture for the early stages of crack growth. These results show that basic fracture mechanics principles may be applied to concrete in compression; however, we must think in terms of 3D multiple crack systems rather than traditional 2D single crack systems.

The authors describe a novel technique for the nondestructive evaluation of microelectronic components using X-ray microtomography. Existing microtomography systems have spatial resolution of order 1 /spl mu/m but require X-ray source brilliance that would become unachievable at higher resolutions. The authors describe an imaging method that reduces the number of X-ray photons required from the source without degrading the resolution. The feasibility of the technique is demonstrated through a series of computer simulations. The results are verified with real data from synchrotron experiments.

The internal cracking patterns of a series of small mortar specimens were observed using a technique called X-ray microtomography. The experiments were arranged such that three-dimensional images of internal cracks could be made at several different times during the load history of the sample. This arrangement allowed progressive crack growth to be observed at micron-scale resolution in a single specimen. The specimens were loaded in compression. Image processing routines were used to make quantitative measurements of internal crack growth and damage progression. Preliminary measurements indicate that the maximum increase in crack area occurs around the peak load. Three-dimensional renderings qualitatively illustrate features of internal cracking such as the effects of different microstructural features.

The electronic phase diagram of ${\text{PrFeAsO}}_{1\ensuremath{-}x}{\text{F}}_{x}$ $(0\ensuremath{\le}x\ensuremath{\le}0.225)$ has been determined using synchrotron x-ray powder-diffraction, magnetization, and resistivity measurements. The structural transition temperature is suppressed from 154 to $\ensuremath{\approx}120\text{ }\text{K}$ and the magnetic phase transitions of both iron and praseodymium ions are completely suppressed by $x\ensuremath{\approx}0.08$ fluorine doping, coinciding with the emergence of superconductivity. The optimal doping is $x\ensuremath{\approx}0.15$ when ${T}_{C}=47\text{ }\text{K}$ while the maximum solubility of fluorine in ${\text{PrFeAsO}}_{1\ensuremath{-}x}{\text{F}}_{x}$ is reached around $x=0.22$. The structural, magnetic, and superconducting phase diagram is presented.

[1] High resolution synchrotron-based X-ray computed microtomography (X-CMT) was used to identify the morphology of colloidal deposits formed in porous media. We show that difference microtomography - whereby a tomographic reconstruction is performed across an absorption edge - provides valuable information on the nature and location of the aggregates formed by the deposition of colloidal particles. Column experiments were performed using an idealized porous medium consisting of glass beads through which colloidal ZrO2 particles were transported. Tomographic reconstructions of the porous medium and of the aggregate structure provide an unique opportunity to observe colloidal particle deposits and of their morphology. These results show that the local pore geometry controls particle deposition and that deposits tend to form in a rather heterogeneous manner in the porous medium.

The energy-dependent scintillation intensity of Eu-doped fluorozirconate glass-ceramic X-ray detectors has been investigated in the energy range from 10 to 40 keV. The experiments were performed at the Advanced Photon Source, Argonne National Laboratory, USA. The glass ceramics are based on Eu-doped fluorozirconate glasses, which were additionally doped with chlorine to initiate the nucleation of BaCl(2) nanocrystals therein. The X-ray excited scintillation is mainly due to the 5d-4f transition of Eu(2+) embedded in the BaCl(2) nanocrystals; Eu(2+) in the glass does not luminesce. Upon appropriate annealing the nanocrystals grow and undergo a phase transition from a hexagonal to an orthorhombic phase of BaCl(2). The scintillation intensity is investigated as a function of the X-ray energy, particle size and structure of the embedded nanocrystals. The scintillation intensity versus X-ray energy dependence shows that the intensity is inversely proportional to the photoelectric absorption of the material, i.e. the more photoelectric absorption the less scintillation. At 18 and 37.4 keV a significant decrease in the scintillation intensity can be observed; this energy corresponds to the K-edge of Zr and Ba, respectively. The glass matrix as well as the structure and size of the embedded nanocrystals have an influence on the scintillation properties of the glass ceramics.

We are developing a transmission X-ray scattering platform capable of measuring the average cross section and line edge roughness in patterns ranging from 10 nm to 500 nm in width with sub-nm precision. Critical Dimension Small Angle X-ray Scattering (CD-SAXS) measures the diffraction of a collimated X-ray beam with sub-Angstrom wavelength from a repeating pattern, such as those in light scatterometry targets, to determine the pattern periodicity, line width, line height, and sidewall angle. Here, we present results from CD-SAXS with an emphasis on line edge roughness characterization. Line edge roughness measurements from CD-SAXS are compared with top-down scanning electron microscopy values and comparative definitions are discussed.

Hyporheic exchange is known to provide an important control on nutrient and contaminant fluxes across the stream-subsurface interface. Similar processes also mediate interfacial transport in other permeable sediments. Recent research has focused on understanding the mechanics of these exchange processes and improving estimation of exchange rates in natural systems. While the structure of sediment beds obviously influences pore water flow rates and patterns, little is known about the interplay of typical sedimentary structures, hyporheic exchange, and other transport processes in fluvial/alluvial sediments. Here we discuss several processes that contribute to local-scale sediment heterogeneity and present results that illustrate the interaction of overlying flow conditions, the development of sediment structure, pore water transport, and stream-subsurface exchange. Layered structures are shown to develop at several scales within sediment beds. Surface sampling is used to analyze the development of an armor layer in a sand-and-gravel bed, while innovative synchrotron-based X-ray microtomography is used to observe patterns of grain sorting within sand bedforms. We show that layered bed structures involving coarsening of the bed surface increase interfacial solute flux but produce an effective anisotropy that favors horizontal pore water transport while limiting vertical penetration.

Developing non-destructive, high precision characterization methods of pattern cross section is critical to the maturation of sub-65 nm technologies. In this study, Criticial Dimension Small Angle X-ray Scattering (CD-SAXS) data are used to non-destructively characterize the dimensions of dense, high aspect ratio patterns with sub-nm precision. Data are presented for a series of photoresist patterns with varying degrees of footer and sidewall angle. The scattering intensity, I, is measured as a function of the scattering vector, q, and the sample rotation angle, w. The resulting data are transformed to an effective Qx-Qz plane, representing the Fourier transform of the average pattern cross section. From this data, complex features of cross sectional shape can in principle be obtained through systematic analysis of appropriate intensity slices. Here, we demonstrate the protocol for high precision measurements using CD-SAXS. Data are analyzed to extract average values of pitch, line width, line height, sidewall angle, and the size of a foot or undercut. In addition, the ability of the technique to analyze more complex features, such as lines with curved sidewalls and corner rounding, is discussed. The CD-SAXS technique is found to provide dimensions with sub-nm precision and sidewall angles with sub-degree precision in a non-destructive manner, providing an option for characterization of next generation microelectronic and nanofabricated structures.

The primary measure of process quality in nanoimprint lithography (NIL) is the fidelity of pattern transfer, comparing the dimensions of the imprinted pattern to those of the mold. As a potential next generation lithography, NIL is capable of true nanofabrication, producing patterns of sub-10 nm dimensions. Routine production of nanoscale patterns will require new metrologies capable of non-destructive dimensional measurements of both the mold and the pattern with sub-nm precision. In this article, a rapid, non-destructive technique termed Critical Dimension Small Angle X-ray Scattering (CD-SAXS) is used to measure the cross sectional shape of both a pattern master, or mold, and the resulting imprinted films. CD-SAXS data are used to extract periodicity as well as pattern height, width, and sidewall angles. Films of varying materials are molded by thermal embossed NIL at temperatures both near and far from the bulk glass transition (TG). The polymer systems include a photoresist, representing a mixture of a polymer and small molecular components, and two pure homopolymers. Molding at low temperatures (T-TG 30°C. In addition to obtaining basic dimensions, CD-SAXS data are used to assess the origin of loss in pattern fidelity.© (2005) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

The continuing progress of sub‐65 nm patterning technologies highlights the critical need for high precision metrologies capable of characterizing dense, high aspect ratio patterns. We present data from small angle x‐ray scattering measurements of critical dimension and average pattern cross section of photoresist line/space patterns. The technique is non‐destructive and capable of sub‐nm precision in characterizing dimensions and sub‐degree precision in sidewall angle of patterns with regular periodicity. Moreover, the information enabling linewidth, pitch and sidewall angle determination are decoupled. Efforts to probe line edge roughness are also discussed. The technique is applicable to dense structures of arbitrary composition with dimensions of (10 to 500) nm, including lines, vias and contact holes and buried structures.

To study the relationship between surface and internal cracking, 2 high-resolution, non-destructive evaluation techniques were used to measure crack growth caused by compressive loading in the fracture process of cement-based materials. Digital image correlation (DIC) was used to characterize the 2-D, surface fracture pattern, while 3-D, internal behavior was measured with x-ray microtomography (XMT). Rectangular mortar specimens containing both sand and graphite aggregates were examined. These techniques gave complementary information about crack geometry and development: DIC was more effective at determining crack width and location of small cracks, while XMT depicted the shape of larger cracks more successfully and showed the influence of internal features on the fracture process. The effect of aggregate shape and strength and the subsequent influence of increased crack distribution on ductility are discussed.

The fracture process of cement-based material cause by compressive loading is a complex, three-dimensional phenomenon that occurs as a result of material heterogeneity and complicated mixed-mode cracking mechanisms. However, obtaining three-dimensional information describing this process requires equipment-and time-intensive techniques. One such technique is X-ray Microtomography, which provides high resolution data, but is limited to small specimens. A more straightforward technique, Digital Image Correlation (DIC), can be used to characterize the fracture pattern of a wider range of specimens, but only in two dimensions on the surface. In order to determine the relationship between surface and internal cracking mortar specimens were tested in compression and examined using both DIC and X-ray Microtomography. Microtomography is an X-ray technique that can be used to produce three-dimensional images which reveal the full internal structure of the specimen, including cracks and pores. DIC is a Computer Vision technique that compares successive images to measure two-dimensional deformation on the surface of the specimen, providing information on the location and opening of surface cracks. Rectangular mortar specimens (25.4 mm by 12.7 mm by 12.7 mm) were loaded to certain levels past the peak stress to induce significant cracking and then unloaded. Deformations of the unloaded specimen weremore » measured with DIC and used to determine crack shape, size and location. This surface phenomena was compared to the shape and size of internal cracks seen in tomographic reconstructions of the same specimen. It was observed that these techniques give complementary information about crack geometry and development.« less

Damage and failure mechanisms in cement-based materials such as concrete are difficult to comprehend due to the heterogeneous microstructure. Experimental analysis of damage localization and failure has traditionally been a compromise between low resolution three-dimensional techniques, and high resolution surface techniques. In this research program, two emerging experimental techniques, x-ray microtomography and computer vision, were combined toward problems of damage and failure of concrete. X-ray microtomography produces a high resolution three-dimensional picture of internal damage evolution, while speed computer vision allows us to quantitatively evaluate surface cracking characteristics at variable loading rates under multiple stress states. The primary focus of the work under this grant was to explore the feasibility of these two techniques for applications to shock physics. Preliminary results showed that high resolution (micron scale) scans of internal structure can be made at multiple levels of damage using the experimental setup developed for microtomography.

The design of a versatile ultrahigh vacuum (UHV) endstation for use at the Advanced Photon Source is described. The capabilities of the endstation include x-ray scattering and x-ray spectroscopic techniques for the investigation of surfaces, interfaces, and thin films. The UHV analytical chamber also includes facilities for surface preparation, thin film growth, and standard (non-x-ray) surface analyses. The endstation, which is inspired by previous successful implementations for surface scattering, incorporates several novel design features to facilitate the use of both scattering and spectroscopic techniques, and also allows the examination of small samples. Its capabilities include x-ray reflectivity and crystal truncation rod studies, grazing-incidence x-ray diffraction, x-ray standing waves, surface extended x-ray absorption fine structure, x-ray holography, and x-ray photoelectron spectroscopy.

A three-dimensional digitized image of a porous magnetic gel is determined by x-ray microtomographic techniques. The complex connected pore-space topology is quantitatively characterized by measuring a variety of statistical correlation functions, including the chord-length distribution function, the pore-size distribution function, and the lineal-path function. This structural information is then employed to estimate transport properties, such as the fluid permeability and trapping rate, of the gel. \textcopyright{} 1996 The American Physical Society.

A phase with the stoichiometry Ni0.5(Al0.5−xMnx) is observed at heterophase interfaces of Cu-rich precipitates in an α-Fe matrix, utilizing atom-probe tomography. First-principles calculations are utilized to determine the substitutional energies, yielding EMn→Ni=0.916eVatom−1 and EMn→Al=−0.016eVatom−1 indicating that the manganese atoms prefer substituting at Al sublattice sites instead of Ni sites. A synchrotron radiation experiment demonstrates that the identified phase possesses the B2 structure.

A wet metal deposition process on GaAs surfaces is described. The process is induced by high energy x-ray photons and is mediated by photon-generated carriers through the photoelectrochemical mechanism similar to that for light-induced wet etching. The micrometer to submicrometer feature fabrication using this process is demonstrated.

The primary measure of process quality in nanoimprint lithography (NIL) is the fidelity of pattern transfer, comparing the dimensions of the imprinted pattern to those of the mold. Routine production of nanoscale patterns will require new metrologies capable of nondestructive dimensional measurements of both the mold and the pattern with subnanometer precision. In this work, a rapid, nondestructive technique termed critical dimension small angle x-ray scattering (CD-SAXS) is used to measure the cross sectional shape of both a pattern master, or mold, and the resulting imprinted films. CD-SAXS data are used to extract periodicity as well as pattern height, width, and sidewall angles. Films of varying materials are molded by thermal embossed NIL at temperatures both near and far from the bulk glass transition (TG). The polymer systems include a photoresist and two homopolymers. Our results indicate that molding at low temperatures (T-TG 30°C.