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This study was motivated by earlier observations. It is a systematic examination of the adequacy of reporting of information (metadata) necessary to understand x-ray photoelectron spectroscopy (XPS) data collection and data analysis in the scientific literature. The information for this study was obtained from papers published in three high-quality journals over a six-month period in 2019 and throughout 2021. Each paper was evaluated to determine whether the authors had reported (percentages of the papers properly providing the information are given in parentheses) the spectrometer (66%), fitting software (15%), x-ray source (40%), pass energy (10%), spot size (5%), synthetic peak shapes in fits (10%), backgrounds in fits (10%), whether the XPS data are shown in the main body of the paper or in the supporting information (or both), and whether fitted or unfitted spectra were shown (80% of published spectra are fit). The Shirley background is the most widely used background in XPS peak fitting. The Al Kα source is the most widely used x-ray source for XPS data collection. casaxps is the most widely used fitting program for XPS data analysis. There is good agreement between the results gathered during the two years of our survey. There are some hints the situation may be improving. This study also provides a list of the information/parameters that should be reported when XPS is performed.

Due to significant advances in instrumentation, many previously specialized techniques have become “routine” in user facilities. However, detailed knowledge held by experts has often not been relayed to general users, so they often rely on entry-level information, basic principles, and comparison with literature results for data analysis. As a result, major errors in the data analysis of multiple surface and material analysis techniques, including in x-ray photoelectron spectroscopy (XPS), have been appearing in the scientific literature. Representative examples of serious errors in XPS data analysis are shown in this work. We suggest that surface and material analysis, and perhaps even science in general, are in a state of “pre-crisis.” We use two (logistic) models from population biology to suggest that bad analyses self-correct if they remain below a critical number. However, beyond a threshold, the literature can become useless because of the perpetuation of faulty analyses and concomitant loss of its self-correcting ability. XPS is used by scientists in many communities because of the power of the technique and high-quality instrumentation that is commercially available. Those who make new surfaces and materials face unique challenges because of the large number of surface and material analytical techniques that are often needed to characterize their materials. Graduate students and post-docs are often provided with only minimal instruction on using surface and material characterization methods. High fees for instruments may affect both the quality and the quantity of the data people collect. The Prisoner's Dilemma is a model from game theory that describes situations with reward structures that encourage uncooperative behavior and lead to suboptimal outcomes. However, the outcomes of Prisoner's Dilemma are not inevitable—their consequences change if their reward structures change. The current system does not appear to incentivize detailed learning of surface and material characterization techniques and careful material characterization. Prisoner's dilemmas appear to lead to other undesirable consequences in science. The concerns raised in this work suggest that many manuscripts are incompletely reviewed at present. The different stakeholders in this problem, including authors, research advisers, subject matter experts, reviewers, scientists who notice examples of faulty data analysis, editors, journals and publishers, funding agencies, scientific societies, leaders at universities and research centers, and instrument vendors, can improve the current situation. This work provides specific recommendations for each of these stakeholders. For example, we believe that authors are primarily responsible for the correctness of their work, not reviewers or editors; we question the wisdom of listing the names of the editor and reviewers on a paper; we are grateful for the significant contributions that have been made by subject matter experts to produce standards and tutorial information; the high cost of instrument time at some institutions may limit student access and result in suboptimal analyses; staff scientists often need to be better recognized for their intellectual contributions to studies; publishers may wish to allow selective reviewing of specific sections of papers related to material characterization; the reviewing at some open access journals may be inadequate; while it had its shortcomings, the pre-open access model of publishing incentivized the production and publication of high-quality work; audits of the products (scientific papers) of funding agencies may be necessary; collaboration needs to be encouraged to a greater extent at some institutions; and instrument vendors should not suggest to potential customers that surface characterization, e.g., by XPS, is trivial or simple.

Radionuclides and heavy metal ions have become the main harmful pollutants in the environment. Developing sensitive and rapid methods to detect them from natural water or wastewater is important to reduce their exposure risks. In this study, a novel luminescent Tb3+-doped fluorapatite/agar nanocomposite (Tb-FAP/agar) has been synthesized via a facile and green synthetic route through an environmentally friendly biomineralization process using agar as a template. This nanocomposite is the first luminescent fluorapatite for detecting UO22+, Cu2+, and Cr3+ ions in water with high selectivity and sensitivity based on luminescence turn-off effects. The detection limits of the Tb-FAP/agar for UO22+ (7.95 nM), Cu2+ (3.94 nM), and Cr3+ (1.67 nM) are much lower than the permissible limits in drinking water defined by the United States Environmental Protection Agency (USEPA). Furthermore, the luminescence detection mechanisms for UO22+, Cu2+, and Cr3+ ions were speculated. Our study provides insight into developing biodegradable rare earth doped fluorapatite probes for the detection of both radioactive and nonradioactive ions.

The use of peak fitting to extract information from x-ray photoelectron spectroscopy (XPS) data is of growing use and importance. Due to increased instrument accessibility and reliability, the use of XPS instrumentation has significantly increased around the world. However, the increased use has not been matched by the expertise of the new users, and the erroneous application of curve fitting has contributed to ambiguity and confusion in parts of the literature. This guide discusses the physics and chemistry involved in generating XPS spectra, describes good practices for peak fitting, and provides examples of appropriate use along with tools for avoiding mistakes.

All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO2 (LCO) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature using interface-sensitive techniques. X-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS), and energy-dispersive X-ray spectroscopy (EDS) data indicated significant cation interdiffusion and structural changes starting at temperatures as low as 300°C. La2Zr2O7 and Li2CO3 were identified as decomposition products after annealing at 500°C by synchrotron X-ray diffraction (XRD). X-ray absorption spectroscopy (XAS) results indicate the presence of also LaCoO3, in addition to La2Zr2O7 and Li2CO3. Based on electrochemical impedance spectroscopy, and depth profiling of the Li distribution upon potentiostatic hold experiments on symmetric LCO|LLZO|LCO cells, the interfaces exhibited significantly increased impedance, up to 8 times that of the as-deposited samples after annealing at 500°C. Our results indicate that lower-temperature processing conditions, shorter annealing time scales, and CO2-free environments are desirable for obtaining ceramic cathode-electrolyte interfaces that enable fast Li transfer and high capacity.

X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are much used analytical techniques that provide information about the outermost atomic and molecular layers of materials. In this work, we discuss the application of multivariate spectral techniques, including principal component analysis (PCA) and multivariate curve resolution (MCR), to the analysis of XPS and ToF-SIMS depth profiles. Multivariate analyses often provide insight into data sets that is not easily obtained in a univariate fashion. Pattern recognition entropy (PRE), which has its roots in Shannon’s information theory, is also introduced. This approach is not the same as the mutual information/entropy approaches sometimes used in data processing. A discussion of the theory of each technique is presented. PCA, MCR, and PRE are applied to four different data sets obtained from: a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized C3F6 on Si, a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized PNIPAM (poly (N-isopropylacrylamide)) on Si, an XPS depth profile through a film of SiO2 on Si, and an XPS depth profile through a film of Ta2O5 on Ta. PCA, MCR, and PRE reveal the presence of interfaces in the films, and often indicate that the first few scans in the depth profiles are different from those that follow. PRE and backward difference PRE provide this information in a straightforward fashion. Rises in the PRE signals at interfaces suggest greater complexity to the corresponding spectra. Results from PCA, especially for the higher principal components, were sometimes difficult to understand. MCR analyses were generally more interpretable.

Improving photocathode performance by increasing electron emission while lowering the angular spread of emitted electrons can improve particle accelerator performance, expanding the reach of both fundamental and applied science. Materials science expertise is needed to design new photocathodes with these desired properties. In this work, we have undertaken a study of the electronic structure of the interfaces in a multilayer photocathode structure consisting of MgO/Ag/MgO to explore how the fabrication process can lead to nonideal interfaces compared to those constructed in simulations. To study how the fabrication affects the interfaces, hard x-ray photoemission spectroscopy was used to probe the chemistry of the buried interfaces within the thin film multilayer structure of Ag and MgO. In these multilayer structures, we observed that the silver layers were predominantly metallic. A small high binding energy ( ΔE=0.69 eV) peak was also observed in the Ag 3d core level in the samples. This peak is shifted in the opposite direction of the binding energy shift in silver oxides, suggesting that this peak is not due to formation of silver oxides at the interfaces with the MgO. Two possible explanations for the origin of this peak then are charge transfer at the interface from the Ag to the oxide monolayer or the formation of silver nanoparticles during the growth process. Based upon simple depth profiling analysis, we postulate that the former is the more likely explanation but cannot rule out the latter. In addition, the O 1s and Mg 1s core level indicated the presence of Mg(OH) 2. The MgO layers react with H 2O in the vacuum chamber or ideal gas used as a buffer during sample transfer. Since the theory predicts strong dependence upon the number of MgO layers surrounding the Ag, the formation of Mg(OH) 2 likely contributes to the nonideal behavior, even given the similarity in the electronic structure to MgO (large bandgap insulator) and Mg(OH) 2. The speed at which this reaction occurs would significantly limit the lifetime and the utility of the MgO/Ag multilayer photocathodes. In order to custom engineer multilayer photocathodes, complete control over the growth process will be needed to ensure that the ideal surfaces are formed. Using nonreactive materials would greatly increase the lifetime of the engineered photocathodes.

High temperature-ultrafine precipitate strengthened (HT-UPS) steel has potential applications in advanced nuclear reactors as a structural material. However, little is currently known about its response to neutron irradiation. This research provides insight into the neutron irradiation-induced physicochemical changes of the major constituents in HT-UPS steels, including Fe, Cr, and Ni, using synchrotron X-ray absorption near edge structure (XANES) and diffraction. This study is the first known investigation using XANES to characterize HT-UPS steel to analyze the evolution of the atomic level chemistry. It was found that following neutron exposure, radiation-induced nucleation, growth, and/or ballistic dispersion of Cr23C6 precipitates occurred at very low neutron irradiation fluences, from 0.003 displacements per atom (dpa) up to 0.3 dpa, at 600 °C, which were at least an order of magnitude lower than previous studies. Calculations of the angular momentum projected partial density of states and the XANES spectra confirmed the experimental findings of the Cr23C6 precipitate evolution. In contrast, the local atomic structure around Fe and Ni atoms demonstrated irradiation resistance.

Technetium-99 (99Tc) is important to the nuclear fuel cycle as a long-lived radionuclide produced in ∼6% fission yield from 235U or 239Pu. In its most common chemical form, namely, pertechnetate (99TcO4–), it is environmentally mobile. In situ hydrogen sulfide reduction of pertechnetate has been proposed as a potential method to immobilize environmental 99TcO4– that has entered the environment. Reactions of 99TcO4– with sulfide in solution result in the precipitation of Tc2S7 except when olefinic acids, specifically fumaric or maleic acid, are present; a water-soluble 99Tc species forms. NMR (1H, 13C, and 2D methods) and X-ray absorption spectroscopy [XAS; near-edge (XANES) and extended fine structure (EXAFS)] studies indicate that sulfide adds across the olefinic bond to generate mercaptosuccinic acid (H3MSA) and/or dimercaptosuccinic acid (H4DMSA), which then chelate(s) the 99Tc to form [99TcO(MSA)2]3–, [99TcO(DMSA)2]5–, or potentially [99TcO(MSA)(DMSA)]4–. 2D NMR methods allowed identification of the p...

In this study, smaller-grained (hundred nano-meter size grain) and larger-grained (micro-meter size grain) U-10Mo specimens have been irradiated (implanted) with 250 keV Xe + beam and were in situ characterized by TEM. Xe bubbles were not seen in the specimen after an implantation fluence of 2 × 10 20 ions/m 2 at room temperature. Nucleation of Xe bubbles happened during heating of the specimen to a final temperature of 300 °C. By comparing measured Xe bubble statistics, the nucleation and growth behaviors of Xe bubbles were investigated in smaller-grained and larger-grained U-10Mo specimens. A multi-atom kind of nucleation mechanism has been observed in both specimens. X-ray Absorption spectroscopy showed the edge position in the bubbles to be the same as that of Xe gas. The size of Xe bubbles has been shown to be bigger in larger-grained specimens than in smaller-grained specimens at the same implantation conditions.

As a group of subject-matter experts in X-ray photoelectron spectroscopy (XPS) and other material characterization techniques from different countries and institutions, we write this document to raise awareness of an epidemic of poor and incorrect materials data analysis in the literature. This issue is a growing problem with many causes and very undesirable consequences. It contributes to what has been called a "reproducibility crisis", which is a recent concern of the U.S. National Academies of Science (Baker,2016; Harris, 2017; NASE&M, 2019).

We have addressed the issue of improper and unreliable analysis of materials characterization data by developing an artificial intelligence based methodology that can reliably and more efficiently analyze experimental results from extended X-ray absorption fine structure (EXAFS) measurements. Such methods help address growing reproducibility problems that are slowing research progress, discouraging the quest for research excellence, and inhibiting effective technology transfer and manufacturing innovation. We have developed a machine learning system for automated analysis of EXAFS spectroscopy measurements and demonstrated its effectiveness on measurements collected at powerful, third generation synchrotron radiation facilities. Specifically, the system uses a genetic algorithm to efficiently find sets of structural parameters that lead to high quality fits of the experimental spectra. A human analyst suggests a set of chemical compounds potentially present in the sample, used as theoretical standards. The algorithm then searches the large multidimensional space of combinations of these materials to determine the set of structural paths using the theoretical standards that best reproduces the experimental data. The algorithm further calculates a goodness of fit value from the suggested standards that can be used to identify the chemical moieties present in the measured sample.

The microstructural behaviors of materials control material properties and the recovery mechanism is a key to understanding the microstructural changes induced by irradiation. But the recovery mechanism of many metal materials is not fully understood through traditional research methods. By using Extended X-ray absorption fine-structure (EXAFS) measurements combined with Molecular Dynamics (MD) simulations, we studied the stage IV recovery process through investigating the behaviors of irradiation induced defects (caused by 104 MeV xenon ion beam irradiation) at an elevated temperature (~350 °C) in single crystal Molybdenum (Mo). We distinctly characterized self-interstitial dumbbell defect configurations and simulated their behaviors at this elevated temperature. EXAFS measurements, together with MD simulations and TEM observations, revealed that the mechanism of IV stage recovery is the migration of interstitial type defects (including dumbbells) rather than vacancy type defects. We also discussed the possible states of dumbbells after the stage IV recovery. These results further revealed the nature of the irradiated BCC structure (Mo).

Peak fitting is an essential part of X-ray photoelectron spectroscopy (XPS) narrow scan analysis, and the Literature contains both good and bad examples of peak fitting. A common cause of poor peak fitting is the inclusion of too many fit parameters, often without a sound chemical and/or physical basis for them, and/or the failure to reasonably constrain them. Under these conditions, fit parameters are often correlated, and therefore lacking in statistical meaning. Here we introduce the uniqueness plot as a simple graphical tool for identifying bad peak fits in XPS, i.e., fit parameter correlation. These plots are widely used in spectroscopic ellipsometry. We illustrate uniqueness plots with two data sets: a C 1s narrow scan from ozone-treated carbon nanotube forests and an Si 2p narrow scan from an air-oxidized silicon wafer. For each fit, we consider different numbers of parameters and constraints on them. As expected, the uniqueness plots are parabolic when fewer fit parameters and/or more constraints are applied. However, they fan out and eventually become horizontal lines as more unconstrained parameters are included in the fits. Uniqueness plots are generated by plotting the chi squared (χ2) value for a fit vs. a systematically varied value of a parameter in the fit. The Abbe criterion is also considered as a figure of merit for uniqueness plots in the Supporting Information. We recommend that uniqueness plots be used by XPS practitioners for identifying inappropriate peak fits.

Zirconium carbide and zirconium nitride are candidate materials for new fuel applications due to several favorable physicochemical properties. ZrC and ZrN samples were irradiated at the Advanced Test Reactor National Scientific User Facility with neutrons at 800 °C to a dose of 1 dpa. Structural examinations have been made of the ZrC samples using high resolution transmission electron microscopy, and the findings compared with a previous study of ZrC irradiated with protons at 800 °C. The use of X-ray absorption fine structure spectroscopy (XAFS) to characterize the radiation damage was also explored including a model based on spherical crystallites that can be used to relate EXAFS measurements to microscopy observations. A loss of coordination at more distant coordination shells was observed for both ZrC and ZrN, and a model using small spherical crystallites suggested this technique can be used to study dislocation densities in future studies of irradiated materials.

The nickel-base Alloy 617 has been considered as the lead candidate structural material for the intermediate heat exchanger (IHX) of the Very-High-Temperature Reactor (VHTR). In order to assess the long-term performance of Alloy 617, thermal aging experiments up to 10,000 h in duration were performed at 1000 °C. Subsequently, in-situ synchrotron wide-angle X-ray scattering (WAXS) tensile tests were carried out at ambient temperature. M 23 C 6 carbides were identified as the primary precipitates, while a smaller amount of M 6 C was also observed. The aging effects were quantified in several aspects: (1) macroscopic tensile properties, (2) volume fraction of the M 23 C 6 phase, (3) the lattice strain evolution of both the matrix and the M 23 C 6 precipitates, and (4) the dislocation density evolution during plastic deformation. The property–microstructure relationship is described with a focus on the evolution of the M 23 C 6 phase. For aging up to 3000 h, the yield strength (YS) and ultimate tensile strength (UTS) showed little variation, with average values being 454 MPa and 787 MPa, respectively. At 10,000 h, the YS and UTS reduced to 380 MPa and 720 MPa, respectively. The reduction in YS and UTS is mainly due to the coarsening of the M 23 C 6 precipitates. After long term aging, the volume fraction of the M 23 C 6 phase reached a plateau and its maximum internal stress was reduced, implying that under large internal stresses the carbides were more susceptible to fracture or decohesion from the matrix. Finally, the calculated dislocation densities were in good agreement with transmission electron microscopy (TEM) measurements. The square roots of the dislocation densities and the true stresses displayed typical linear behavior and no significant change was observed in the alloys in different aging conditions.

We report on an experimental verification that emission properties of photocathodes can be manipulated through the engineering of the surface electronic structure. Ultrathin multilayered MgO/Ag(0 0 1)/MgO films were grown by pulsed laser deposition, tuning the thickness n of the flanking MgO layers to 0, 2, 3, and 4 monolayers. We observed an increase in quantum efficiency and simultaneous decrease in work function with layer thickness. The scale and trend direction of measurements are in good but not excellent agreement with theory. Angle resolved photoemission data for the multilayered sample n = 3 showed that the emission profile has a metallic-like momentum dispersion. Deviations from theoretical predictions [K. Nemeth et al., PRL 104, 046801 (2010)] are attributed to imperfections of real surfaces in contrast with the ideal surfaces of the calculation. Photoemissive properties of cathodes are critical for electron beam applications such as photoinjectors for Free Electron Lasers (FEL) and Energy Recovery Linacs (ERL). An ideal photoemitter has a high quantum efficiency, low work function, low intrinsic emittance and long lifetime. It has been demonstrated here that emission properties may be systematically tailored by control of layer thickness in ultrathin multilayered structures. The reproducibility of the emission parameters under specific growth conditions is excellent, even though the interfaces themselves have varying degrees of roughness.

Technetium-99 (

Background Interferon-induced transmembrane protein 3 (IFITM3) restricts endocytic fusion of influenza virus. IFITM3 rs12252_C, a putative alternate splice site, has been associated with influenza severity in adults. IFITM3 has not been evaluated in pediatric influenza. Methods The Pediatric Influenza (PICFLU) study enrolled children with suspected influenza infection across 38 pediatric intensive care units during November 2008 to April 2016. IFITM3 was sequenced in patients and parents were genotyped for specific variants for family-based association testing. rs12252 was genotyped in 54 African-American pediatric outpatients with influenza (FLU09), included in the population-based comparisons with 1000 genomes. Splice site analysis of rs12252_C was performed using PICFLU and FLU09 patient RNA. Results In PICFLU, 358 children had influenza infection. We identified 22 rs12252_C homozygotes in 185 white non-Hispanic children. rs12252_C was not associated with influenza infection in population or family-based analyses. We did not identify the Δ21 IFITM3 isoform in RNAseq data. The rs12252 genotype was not associated with IFITM3 expression levels, nor with critical illness severity. No novel rare IFITM3 functional variants were identified. Conclusions rs12252 was not associated with susceptibility to influenza-related critical illness in children or with critical illness severity. Our data also do not support it being a splice site.

X-ray photoelectron spectroscopy (XPS) is widely used in surface and materials laboratories around the world. It is a near surface technique, providing detailed chemical information about samples in the form of survey and narrow scans. To extract the maximum amount of information about materials it is often necessary to peak fit XPS narrow scans. And while indispensable to XPS data analysis, even experienced practitioners can struggle with their peak fitting. In our previous publication, we introduced the equivalent width (EWXPS) as both a possible machine automated method, one that requires less expert judgment for characterizing XPS narrow scans, and as an approach that may be well suited for the analysis of complex spectra. The EWXPS figure of merit was applied to four different data sets. However, as previously noted, other width functions are also regularly employed for analyzing functions. Here we evaluate two other width functions for XPS narrow scan analysis: the autocorrelation width (AWXPS) and the variance ( σ XPS 2 ). These widths were applied to the same four sets of spectra studied before: (a) four C 1s narrow scans of ozone-treated carbon nanotubes (CNTs) (EWXPS: ∼2.11–2.16 eV, AWXPS: ∼3.9–4.1 eV, σ XPS 2 : ∼5.0–5.2 eV, and a modified form of σ XPS 2 , denoted σ XPS 2 * : ∼6.3–6.8 eV), (b) silicon wafers with different oxide thicknesses (EWXPS: ∼1.5–2.9 eV, AWXPS: ∼2.28–4.9, and σ XPS 2 : ∼0.7–4.9 eV), (iii) hydrogen-terminated silicon surfaces, before and after modification with pentyl groups, and after annealing of the pentyl-terminated surface (EWXPS: ∼0.7–1.0 eV, AWXPS: ∼1.2–1.6 eV, and σ XPS 2 : ∼0.12–0.19 eV), and (iv) C 1s narrow scans from five different nanodiamond samples, three of which showed charging (EWXPS: ∼2.6–4.8 eV, AWXPS: ∼3.8–6.9 eV, and σ XPS 2 : ∼1.6–4.2 eV). All three of the width functions showed similar trends, except in the case of the C 1s spectra of the CNT samples, which were the most complex spectra evaluated, where σ XPS 2 showed poor correlation with the corresponding O/C ratios. Accordingly, we favor EWXPS and AWXPS. EWXPS is advantageous because it is conceptually simple, giving the most intuitive results. AWXPS has the advantage of not requiring the user to specify the height of the function at its maximum, which will be affected by noise. Because these functions are based on different mathematical operations/algorithms, best practices may involve the calculation of both widths for a set of narrow scans. The standard deviation, σXPS, i.e., the square root of the variance, was also examined. As expected, it gave results similar to σ XPS 2 .

X-ray Photoelectron Spectroscopy (XPS) is a widely used surface analytical tool that provides information about the near surface regions of materials. And while indispensable for XPS data analysis, peak fitting of narrow scans is often a fairly subjective exercise. Herein we introduce the equivalent width (EW) as an additional and less subjective figure of merit for XPS narrow scans. We believe that this parameter will prove particularly useful for analyzing series of similar or nominally identical spectra, perhaps as a component of an expert software system for the machine interpretation of spectra. It also appears to be useful, shedding light on the chemical state of materials, when additional information about a sample is known. The EW XPS is simply defined as the area of a narrow scan divided by the height of the maximum of its peak envelope. To limit any ambiguity in EW XPS for a series of spectra, we may also list the peak position of the maximum of the envelope (PE max ). The potential usefulness and limitations of the EW XPS and PE max parameters are demonstrated by their application to the narrow scans of: (i) four sets of ozone-treated carbon nanotubes (EW XPS ∼ 2.11–2.16 eV for a Shirley background, and up to 2.88 eV for no background, PE max ∼ 284.4–284.5 eV), (ii) a series of silicon wafers with different oxide thicknesses (EW XPS ∼ 1.5–2.8 eV, PE max ∼ 99–103 eV), (iii) hydrogen-terminated silicon before and after derivatization with pentyl groups, and after annealing of the pentyl-modified material (EW XPS ∼ 0.7–1.0 eV, PE max ∼ 25.9–26.1 eV), and (iv) five nanodiamond samples, where three of the spectra showed charging (EW XPS ∼ 2.6–4.9 eV, PE max ∼ 272.7–293.9 eV). In this final example, EW XPS was plotted against PE max to identify the region corresponding to the materials that showed the least charging. EW XPS and PE max appear to correlate with the expected chemistries of all the systems studied. We calculate EW XPS using a Shirley baseline and with no baseline at all. In setting the baseline limits for EW XPS , we consider the derivative of C 1s narrow scans. We also show the application of EW XPS to single, fitted components within a narrow scan.

δ Pu–Ga alloys and their response to self-irradiation are important scientifically because of the unique complexity of Pu and technologically because of their importance in Science Based Stockpile Stewardship. The local order and structure and the role of the Ga are crucial to understanding the phase stability and the aging effects. X-ray diffraction that gives the long-range average structure of the periodic component of the materials and pair distribution functions analysis and X-ray absorption fine structure that give the overall and the element specific local structure have been used to examine a variety of new and aged materials, including a set of high purity δ Pu1–xGax alloys with 1.7 ≤ x ≤ 6.4 atom % Ga that span the low [Ga] portion of the δ region of the phase diagram across the ∼3.3 atom % Ga metastability boundary, a ∼1.7 atom % Ga alloy that was enriched with Pu238 to accelerate the aging process, and others. We find that metastable alloys contain tens of percents of a novel, “σ”, Pu structur...

The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron spectroscopy, a core electron spectroscopy that is sensitive to oxidation states of elements, generally agrees with his suggestion. We also list the typical (IUPAC) rules for assigning oxidation states, review recent suggestions of Loock and Steinborn that are based on Pauling’s earlier approach, discuss the traditional (IUPAC and Pauling–Loock–Steinborn) assignments of oxidation states to organic molecules, review Calzaferri’s suggestion, introduce X-ray photoelectron spectroscopy (XPS), show the general agreement of Calzaferri’s suggestion with XPS results, provide supporting examples from the literature, and discuss the limitations of Calzaferri’s recommendation v...

Synchrotron extended X-ray absorption fine structure (EXAFS) spectroscopy measurements were performed to study the dose dependence of and alloying effects on irradiation-induced changes in the local atomic environments in a mod.9Cr–1Mo ferritic-martensitic steel. The measurements were carried out at room temperature on non-irradiated and irradiated specimens exposed to 1, 4, and 10 displacement per atom (dpa) at 40–70 °C. The EXAFS data for Fe, Cr, Mo, and Nb K-edges were recorded, and the local structure close to the X-ray absorbing atom was determined. Irradiation caused significant reductions in peak amplitude in the Fe, Mo and Nb K-edge Fourier transformed EXAFS. The data showed a systematic decrease in coordination number of neighbor atoms with increasing irradiation dose, and the dose dependence of the coordination loss was dependent on the specific element. The measured damage around Fe sites can be correlated with the dpa value, while the loss of near neighbors around Mo saturated at ∼1 dpa. The coordination in the Fe matrix was reduced less by irradiation than either the coordination of Mo in solution or Nb in carbides. It was demonstrated that EXAFS can provide a detailed, atomic level description of radiation damage in complex alloy systems.

The gravitational acceleration of antimatter, $\bar g$, has yet to be directly measured but could change our understanding of gravity, the Universe, and the possibility of a fifth force. Three avenues are apparent for such a measurement: antihydrogen, positronium, and muonium, the last requiring a precision atom interferometer and benefiting from a novel muonium beam under development. The interferometer and its few-picometer alignment and calibration systems appear to be feasible. With 100 nm grating pitch, measurements of $\bar g$ to 10%, 1%, or better can be envisioned. This could constitute the first gravitational measurement of leptonic matter, of second-generation matter and, possibly, the first measurement of the gravitational acceleration of antimatter., Comment: Presented at the Seventh Meeting on CPT and Lorentz Symmetry, Bloomington, Indiana, June 20-24, 2016

BACKGROUND: Organ dysfunction scores, based on physiological parameters, have been created to describe organ failure. In a general pediatric intensive care unit (PICU) population, the PEdiatric Logistic Organ Dysfunction-2 score (PELOD-2) score had both a good discrimination and calibration, allowing to describe the clinical outcome of critically ill children throughout their stay. This score is increasingly used in clinical trials in specific subpopulation. Our objective was to assess the performance of the PELOD-2 score in a subpopulation of critically ill children requiring plasma transfusions.METHODS: This was an ancillary study of a prospective observational study on plasma transfusions over a 6-week period, in 101 PICUs in 21 countries. All critically ill children who received at least one plasma transfusion during the observation period were included. PELOD-2 scores were measured on days 1, 2, 5, 8, and 12 after plasma transfusion. Performance of the score was assessed by the determination of the discrimination (area under the ROC curve: AUC) and the calibration (Hosmer-Lemeshow test).RESULTS: Four hundred and forty-three patients were enrolled in the study (median age and weight: 1 year and 9.1 kg, respectively). Observed mortality rate was 26.9 % (119/443). For PELOD-2 on day 1, the AUC was 0.76 (95 % CI 0.71-0.81) and the Hosmer-Lemeshow test was p = 0.76. The serial evaluation of the changes in the daily PELOD-2 scores from day 1 demonstrated a significant association with death, adjusted for the PELOD-2 score on day 1.CONCLUSIONS: In a subpopulation of critically ill children requiring plasma transfusion, the PELOD-2 score has a lower but acceptable discrimination than in an entire population. This score should therefore be used cautiously in this specific subpopulation.

The corrosion of fuel cladding and structural materials by lead and lead-bismuth eutectic in the liquid state at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. In this work, lead corrosion studies of molybdenum were performed to investigate the interaction layer as a function of temperature by X-ray absorption spectroscopy. In situ X-ray absorption measurements on a Mo substrate with a 3-6 {micro}m layer of Pb deposited by thermal evaporation were performed at temperatures up to 900 C and at a 15{sup o} angle to the incident X-rays. The changes in the local atomic structure of the corrosion layer are visible in the difference extended X-ray absorption fine structure and the linear combination fitting of the X-ray absorption near-edge structure to as-deposited molybdenum sample and molybdenum oxide (MoO{sub 2} and MoO{sub 3}) standards. The data are consistent with the appearance of MoO{sub 3} in an intermediate temperature range (650-800 C) and the more stable MoO{sub 2} phase dominating at high and low temperatures.

The reduction of pertechnetate (TcO4−) with freshly prepared amorphous iron sulfide was investigated. The amorphous iron sulfide (FeS) was shown to have an elemental composition of FeS0.97for all of the size fractions and a point of zero charge of pHpzc=7.4. Solubility studies of FeS in various buffers indicated that in the pH range 6.1–9.0, the concentrations of dissociated Fe2+and S2−were negligible. The reductive immobilization of TcO4−with FeS was shown to be accelerated by increasing ionic strength and strongly pH dependent. At pH values below the pHpzc, the positively charged FeS surface reacted much faster with TcO4−and had higher immobilization yields relative to the negatively charged FeS surface at pH values above pHpzc. The TcO4−−FeS reaction is consistent with a surface mediated reaction through ligand exchange. The TcO4−−FeS reductive immobilization reaction product was characterized by X-ray absorption near edge spectroscopy (XANES), extended X-ray absorption fine structure (EXAFS), Fourier transform infrared spectroscopy (FT-IR), and energy dispersive X-ray spectroscopy (EDS) and found to be predominantly TcO2. Studies on the reductive capacity of the FeS and the long term stability of the TcO4−−FeS reaction product under both anaerobic and aerobic environments shows the potential utility of thein situgaseous (hydrogen sulfide gas) immobilization technology in solidification of TcO4−by creating a FeS permeable reaction barrier in the vadose zone.

Improving our knowledge of plant metal metabolism is facilitated by the use of analytical techniques to map the distribution of elements in tissues. One such technique is X-ray fluorescence (XRF), which has been used previously to map metal distribution in both two and three dimensions. One of the difficulties of mapping metal distribution in two dimensions is that it can be difficult to normalize for tissue thickness. When mapping metal distribution in three dimensions, the time required to collect the data can become a major constraint. In this article a compromise is suggested between two- and three-dimensional mapping using multi-angle XRF imaging. A synchrotron-based XRF microprobe was used to map the distribution of K, Ca, Mn, Fe, Ni, Cu and Zn in whole Arabidopsis thaliana seeds. Relative concentrations of each element were determined by measuring fluorescence emitted from a 10 {micro}m excitation beam at 13 keV. XRF spectra were collected from an array of points with 25 or 30 {micro}m steps. Maps were recorded at 0 and 90{sup o}, or at 0, 60 and 120{sup o} for each seed. Using these data, circular or ellipsoidal cross-sections were modelled, and from these an apparent pathlength for the excitation beam was calculatedmore » to normalize the data. Elemental distribution was mapped in seeds from ecotype Columbia-4 plants, as well as the metal accumulation mutants manganese accumulator 1 (man1) and nicotianamine synthetase (nasx). Multi-angle XRF imaging will be useful for mapping elemental distribution in plant tissues. It offers a compromise between two- and three-dimensional XRF mapping, as far as collection times, image resolution and ease of visualization. It is also complementary to other metal-mapping techniques. Mn, Fe and Cu had tissue-specific accumulation patterns. Metal accumulation patterns were different between seeds of the Col-4, man1 and nasx genotypes.« less

We have used the MR-CAT beamline of the Advanced Photon Source at Argonne National Laboratory to study the fine structure in the Cu K-edge X-ray absorption in 3 μm thick polycrystalline films of CdTe on fused silica. About 4 nm of evaporated Cu is diffused either with or without prior vapor CdCl2 treatments in dry air. Cu absorption is monitored through the Cu Kα fluorescence using a 13-element Ge detector. The absorption fine structure indicated predominantly Cu2Te when Cu was diffused into the as-deposited CdTe film but a CuxO environment when Cu was diffused after the vapor CdCl2 treatment. We believe most of the diffused Cu decorates grain boundaries as oxides, consistent with the low doping densities typically observed in CdTe solar cells. The significance for grain boundary passivation will be discussed.

Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (

A highly strained, curved silicon crystal in the Laue geometry has been used as a large-area x-ray fluorescence analyzer for x-ray absorption spectroscopy. The analyzer is able to resolve the Lα fluorescence lines for neighboring actinide elements. A large gain in the signal to background ratio has been demonstrated for small quantities of Np in the presence of U, with the U fluorescence peak approaching 1000 times the magnitude of the off-peak background.

The gravitational acceleration of antimatter, ḡ, has never been directly measured and could bear importantly on our understanding of gravity, the possible existence of a fifth force, and the nature and early history of the universe. Only two avenues for such a measurement appear to be feasible: antihydrogen and muonium. The muonium measurement requires a novel, monoenergetic, low-velocity, horizontal muonium beam directed at an atom interferometer. The precision three-grating interferometer can be produced in silicon nitride or ultrananocrystalline diamond using state-of-the-art nanofabrication. The required precision alignment and calibration at the picometer level also appear to be feasible. With 100 nm grating pitch, a 10% measurement of ḡ can be made using some months of surface-muon beam time, and a 1% or better measurement with a correspondingly larger exposure. This could constitute the first gravitational measurement of leptonic matter, of 2nd-generation matter and, possibly, the first measurement of the gravitational acceleration of antimatter., EPJ Web of Conferences, 95, ISSN:2100-014X, ISSN:2101-6275

Experimental resonant photoemission (ResPes) results for α-Pu and δ-Pu bulk samples are presented and compared to the results of an atomic model calculation. Both Pu samples exhibit limited agreement with the atomic model calculations. As expected, α-Pu appears to have more 5f valence band delocalization than δ-Pu. Evidence of an enhanced sensitivity to surface corruption, by using synchrotron radiation as the excitation, is presented.

Solid-state lithium-ion batteries hold great promise for obtaining higher energy densities but the power density is currently limited by the electrode-electrolyte interfaces. [1] The high resistances at SLIB interfaces are hypothesized to be due to chemical mixing, space charge formation, or secondary phase formation. [2,3] Although several secondary phases have been proposal theoretically, there is no experimental work studying the secondary phase formation as a function of temperature and applied voltage. Extended x-ray absorption fine structure spectroscopy (EXAFS) is a unique capability that allows us to probe the fine structure around the atoms at the electrode-electrolyte interface. Previous interface studies using XRD were not able to identify the secondary phases, either because secondary phases are small in amount or not crystalline. [3] Depth-sensitive x-ray absorption spectroscopy allows us to probe the changes in structure at the interface even if the secondary phases are not crystalline. This work studies the interface between Li7La3Zr2O12 (LLZO) and LiCoO2 (LCO). [1] Cheng, L. et al. Phys. Chem. Chem. Phys. 16, 18294–18300 (2014). [2] Miara, L. J., et al. Chem. Mater. 27, 4040–4047 (2015). [3] Park, K. et al. Chem. Mater. 28, 8051–8059 (2016).

The bonding of alkyl monolayers to Si(111) surfaces has been studied with high-resolution core level photoelectron spectroscopy (PES). Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) Olefin insertion into the H–Si bond of the H–Si(111) surface, and (ii) replacement of Cl on the Cl–Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, PES has revealed a C 1s component shifted to lower binding energy and a Si 2p component shifted to higher binding energy. Both components are attributed to the presence of a C–Si bond at the interface. Along with photoelectron diffraction data [Appl. Phys. Lett. 71, 1056, (1997)], these data are used to show that these two synthetic methods can be used to functionalize the Si(111) surface.