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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Differences in Printed Contacts Lead to Susceptibility of Silicon Cells to Series Resistance Degradation

Here, in this case study, we investigate a degradation mode occurring at the cell level in fielded multi-Si modules. The modules exhibit a mix of affected and unaffected cells. Affected cells show a progressive, series-resistance-related power degradation as shown via module- and cell-level IV curves, along with electroluminescence (EL) and PL imaging at the module, cell, and cell core sample scales. Scanning electron microscopy and energy-dispersive X-ray spectroscopy reveal a difference in the oxides in the silver paste used in screen printing of the gridline contacts. The paste in the affected cells is lead rich, whereas the paste in the unaffected cells is zinc rich. This suggests that the cells were screen printed with different silver paste compositions and possibly firing conditions, and that the different composition correlates with the susceptibility to degradation. Our results indicate degradation of the contact at the oxide-silver interface, causing a severe increase in series resistance across the cell that continues to progress over time.

14 SOLAR ENERGY↗
NASA NTRS1982

XPS Study of SiO2 and the Si/SiO2 Interface

X-ray photoelectron spectroscopy (XPS) is analytical technique for understanding electronic structure of atoms close to surface in solids, in preference to bulk structure of material. Study found evidence for core-level chemical shifts arising from changes in local structural environment in amorphous SiO2 and at Si/SiO2 interface. Observed XPS spectra may be understood as sequential convolution of several functions, each with well-defined physical interpretation.

Grunthaner, F. J.↗
DOE OSTI2023

Using electron energy-loss spectroscopy to measure nanoscale electronic and vibrational dynamics in a TEM

Electron energy-loss spectroscopy (EELS) can measure similar information to x-ray, UV–Vis, and IR spectroscopies but with atomic resolution and increased scattering cross-sections. Recent advances in electron monochromators have expanded EELS capabilities from chemical identification to the realms of synchrotron-level core-loss measurements and to low-loss, 10–100 meV excitations, such as phonons, excitons, and valence structures. EELS measurements are easily correlated with electron diffraction and atomic-scale real-space imaging in a transmission electron microscope (TEM) to provide detailed local pictures of quasiparticle and bonding states. This perspective provides an overview of existing high-resolution EELS (HR-EELS) capabilities while also motivating the powerful next step in the field—ultrafast EELS in a TEM. Ultrafast EELS aims to combine atomic-level, element-specific, and correlated temporal measurements to better understand spatially specific excited-state phenomena. Ultrafast EELS measurements also add to the abilities of steady-state HR-EELS by being able to image the electromagnetic field and use electrons to excite photon-forbidden and momentum-specific transitions. We discuss the technical challenges ultrafast HR-EELS currently faces, as well as how integration with in situ and cryo measurements could expand the technique to new systems of interest, especially molecular and biological samples.

Chemistry↗
DOE OSTI2021

Strain and ligand effects in Pt-Ni alloys studied by valence-to-core X-ray emission spectroscopy

Experimental detection of the Pt 5d densities of states in the valence band is conducted on a series of Pt-Ni alloys by high energy resolution valence-to-core X-ray emission spectroscopy (VTC-XES) at the Pt L 3 -edge. VTC-XES measurements reveal that the Pt d-band centroid shifts away from the Fermi level upon dilution, accompanied by concentration-dependent Pt d-band width. The competition between the strain effect and ligand effect is observed experimentally for the first time. It is found that the d-band widths in Pt 3 Ni and PtNi are broader than that of Pt metal due to compressive strain which overcompensates the effect of dilution, while it is narrower in PtNi 3 where the ligand effect dominates. VTC-XES is demonstrated to be a powerful tool to study the Pt d-band contribution to the valence band of Pt-based bimetallic. The implication for the enhanced activity of Pt-Ni catalysts in oxygen reduction reaction is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Spin-selective evolution of the Zhang-Rice state in binary transition metal oxide MnO(001) film

Here, the Zhang-Rice (ZR) state is a strongly hybridized bound state formed by transition-metal and oxygen atoms. The spin fluctuations within the ZR state are known to play an important role in high-T c superconductivity in cuprates. Here, we employ a combination of angle-resolved photoemission spectroscopy (ARPES), x-ray photoemission spectroscopy (XPS), and ab initio embedded dynamical mean-field theory (eDMFT) to investigate the influence of magnetic ordering on the spectral characteristics of the valence band and Mn 2⁢p core-level in MnO (001) ultrathin films. Our results demonstrate that a complex spin-selective evolution of Mn 3⁢d-O2⁢p hybridization develops due to the long-range antiferromagnetic (AFM) ordering. This hybridization significantly alters the spectral shape and weight of the ZR state. Specifically, in the AFM phase, we observed the sharpening of the ZR state and band folding with the periodicity of the AFM unit cell of MnO(001). We also demonstrated a strong connection between the spectral evolution of the ZR state and the non-local screening channels of the photoexcited core holes. Further, our detailed temperature-dependent study reveals the presence of short-range antiferromagnetic correlations that exist at much higher temperatures than Neel temperature (T N ) and shows the evolution of the ZR state across the magnetic transitions and its implication to the core-hole screening in 3⁢d binary transition metal oxides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Core-excited states of SF 6 probed with soft-x-ray femtosecond transient absorption of vibrational wave packets

A vibrational wavepacket in SF 6 is created by impulsive stimulated Raman scattering with a few-cycle infrared pulse and mapped simultaneously onto five sulfur core-excited states using table-top soft x-ray transient absorption spectroscopy between 170 to 200 eV. The femtosecond vibrations induce real-time energy shifts of the x-ray absorption, whose amplitude depend strongly on the nature of the core-excited state. The pump laser intensity is used to control the number of vibrational states in the superposition, thereby accessing core-excited levels for various extensions of the S-F stretching motion. This enables the determination of the relative core-level potential energy gradients for the symmetric stretching mode, in good agreement with TDDFT calculations. This experiment demonstrates a new means of characterizing core-excited potential energy curves.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Photoelectrochemically Self Improving Si/GaN Photocathode: Figure 3c Raw Data

XPS after 0hr of chronoampometry. Surface chemical composition and valence band structure of GaN were obtained by X-ray photoemission spectroscopy (XPS) on a Kratos Axis Ultra DLD system at a takeoff angle of 0° relative to the surface normal. An Al Kα source (hν = 1486.6 eV) was used to excite the core level electrons. Pass energy of 20 eV was used for the narrow scan of core levels and valence band spectra, and step size of 0.05 eV and 0.025 eV, respectively. The Spectral fitting was conducted using CasaXPS analysis software. The binding energy scales of all core levels were corrected to the N 1s of Ga – N bond at 397.8 eV. XPS O1s core level spectra from as-received Si/GaN sample, and deconvolution shows O - Ga bond and OH - H2O bond.

photocathode↗
DOE OSTI2021

Photoelectrochemically Self Improving Si/GaN Photocathode: Figure 3f Raw Data

XPS of Si/GaN photocathode after 10 hour chronoamperometry (CA) testing. Surface chemical composition and valence band structure of GaN were obtained by X-ray photoemission spectroscopy (XPS) on a Kratos Axis Ultra DLD system at a takeoff angle of 0° relative to the surface normal. An Al Kα source (hν = 1486.6 eV) was used to excite the core level electrons. Pass energy of 20 eV was used for the narrow scan of core levels and valence band spectra, and step size of 0.05 eV and 0.025 eV, respectively. The Spectral fitting was conducted using CasaXPS analysis software. The binding energy scales of all core levels were corrected to the N 1s of Ga – N bond at 397.8 eV. XPS O1s core level spectra from 10 hours CA tested Si/GaN sample, and deconvolution shows O - Ga bond, O - N - Ga bond and OH - H2O bond.

photocathode↗
DOE OSTI2021

Photoelectrochemically Self Improving Si/GaN Photocathode: Figure 3e Raw Data

XPS of Si/GaN photocathode after 4 hour chronoamperometry (CA) testing. Surface chemical composition and valence band structure of GaN were obtained by X-ray photoemission spectroscopy (XPS) on a Kratos Axis Ultra DLD system at a takeoff angle of 0° relative to the surface normal. An Al Kα source (hν = 1486.6 eV) was used to excite the core level electrons. Pass energy of 20 eV was used for the narrow scan of core levels and valence band spectra, and step size of 0.05 eV and 0.025 eV, respectively. The Spectral fitting was conducted using CasaXPS analysis software. The binding energy scales of all core levels were corrected to the N 1s of Ga – N bond at 397.8 eV. XPS O1s core level spectra from 4 hour CA tested Si/GaN sample, and deconvolution shows O - Ga bond, O - N - Ga bond and OH - H2O bond.

photocathode↗
DOE OSTI2025

First-Principles-Based Study of the Decomposition of Phenol and Hydroquinone on Pt(111) Combined with Quantitative Information from XPS Spectra to Address the Impact of Coverage and Number of Hydroxyl Functional Groups

A combined first-principles-based and experimental X-ray photoelectron spectroscopy approach was used to investigate the thermal decomposition of two model biofuel compounds, phenol and hydroquinone, on Pt(111) at both low and high coverages. The DFT-based approach yields adsorption geometries and energies, activation barriers and core-level binding energy shifts for C 1s and O 1s. Increasing the coverage in the theoretical model leads to slight shifts in core-level binding energies─toward higher values for C 1s and lower values for O 1s. It also alters the energy profiles of the decomposition reaction pathway, resulting in weaker adsorption energies and changes in both reaction and activation barriers. At low temperatures, we observe a multilayer for phenol and hydroquinone upon adsorption, with desorption occurring at 200 and 270 K, respectively. Following desorption of the multilayer, decomposition proceeds via initial O–H bond scission, followed by two parallel pathways involving either C–H or C–C bond scission, whereby in the case of phenol C–H bond scission occurs first. Here, we further provide characteristic core level binding energies by theoretical calculations that are subsequently used in experimental analyses, establishing a reference database for key spectra of phenolic functionalities applicable to a range of catalytic reactions.

09 BIOMASS FUELS↗
DOE OSTI2020

Reactivity of a Zirconia–Copper Inverse Catalyst for CO 2 Hydrogenation

Copper–zirconia catalysts have been shown to be effective for methanol synthesis via CO 2 hydrogenation, yet the active phases and reaction mechanism remain uncertain. Here, an inverse model catalyst ZrO 2 /CuO 2 /Cu(111) was prepared by mass-selected ion deposition and tested for CO 2 hydrogenation under near-ambient pressure (AP) reaction conditions by using X-ray photoelectron spectroscopy (NAP-XPS) and infrared reflection–absorption spectroscopy (NAP-IRAS). The spatial resolution afforded by the small entrance cone of the AP-XPS spectrometer was used to resolve regions of the surface with and without Zr deposition. Carbon 1s core level spectra of the ZrO 2 /Cu 2 O/Cu(111) regions of the surface under 500 mTorr of CO 2 + H 2 (1:3 ratio) show evidence for reaction intermediates including carbonate (CO 3 *), formate (HCOO*), and H x CO* species, with methoxy having the highest surface concentration at 500–600 K. These intermediates are confirmed by IRAS vibrational spectra. In regions of the surface without Zr, the Cu 2 O/Cu(111) is reduced to metallic Cu, and the surface intermediates are different and are present at much lower concentrations. The observed surface intermediates and their temperature dependence suggest a mechanism in which CO 2 is adsorbed on zirconia as carbonate (CO 3 *) and then converted to HCOO* and H x CO* hydrogenated intermediates that ultimately lead to methoxy (CH 3 O*), the final surface-bound precursor for methanol. Overall, the results clearly demonstrate the promotional effects of small ZrO 2 particles for enhancing the reactivity of Cu surfaces for CO 2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigating the electronic structure of high explosives with X-ray Raman spectroscopy

Abstract We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures ( $$\approx$$ ≈ 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Time-Resolved Optical Pump-Resonant X-ray Probe Spectroscopy of 4-Thiouracil: A Simulation Study

We theoretically monitor the photoinduced ππ* → nπ* internal conversion process in 4-thiouracil (4TU), triggered by an optical pump. The element-sensitive spectroscopic signatures are recorded by a resonant X-ray probe tuned to the sulfur, oxygen, or nitrogen K-edge. We employ high-level electronic structure methods optimized for core-excited electronic structure calculation combined with quantum nuclear wavepacket dynamics computed on two relevant nuclear modes, fully accounting for their quantum nature of nuclear motions. We critically discuss the capabilities and limitations of the resonant technique. For sulfur and nitrogen, we document a pre-edge spectral window free from ground-state background and rich with ππ* and nπ* absorption features. The lowest sulfur K-edge shows strong absorption for both ππ* and nπ*. In the lowest nitrogen K-edge window, we resolve a state-specific fingerprint of the ππ* and an approximate timing of the conical intersection via its depletion. A spectral signature of the nπ* transition, not accessible by UV–vis spectroscopy, is identified. The oxygen K-edge is not sensitive to molecular deformations and gives steady transient absorption features without spectral dynamics. Here, the ππ*/nπ* coherence information is masked by more intense contributions from populations. Altogether, element-specific time-resolved resonant X-ray spectroscopy provides a detailed picture of the electronic excited-state dynamics and therefore a sensitive window into the photophysics of thiobases.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS2018

Constraints on the chemical enrichment history of the Perseus Cluster of galaxies from high-resolution X-ray spectroscopy

High-resolution spectroscopy of the core of the Perseus Cluster of galaxies, using the Hitomi satellite above 2 keV and the XMM–Newton Reflection Grating Spectrometer at lower energies, provides reliable constraints on the abundances of O, Ne, Mg, Si, S, Ar, Ca, Cr, Mn, Fe, and Ni. Accounting for all known systematic uncertainties, the Ar/Fe, Ca/Fe, and Ni/Fe ratios are determined with a remarkable precision of less than 10 per cent, while the constraints on Si/Fe, S/Fe, and Cr/Fe are at the 15 per cent level, and Mn/Fe is measured with a 20 percent uncertainty. The average biases in determining the chemical composition using archival CCD spectra from XMM–Newton and Suzaku typically range from 15 to 40 per cent. A simple model in which the enrichment pattern in the Perseus Cluster core and the protosolar nebula are identical gives a surprisingly good description of the high-resolution X-ray spectroscopy results, with X^2=10.7 for 10 degrees of freedom. However, this pattern is challenging to reproduce with linear combinations of existing supernova nucleosynthesis calculations, particularly given the precise measurements of intermediateα-elements enabled by Hitomi. We discuss in detail the degeneracies between various supernova progenitor models and explosion mechanisms, and the remaining uncertainties in these theoretical models. We suggest that including neutrino physics in the core-collapse supernova yield calculations may improve the agreement with the observed pattern ofα-elements in the Perseus Cluster core. Our results provide a complementary benchmark for testing future nucleosynthesis calculations required to understand the origin of chemical elements.

A Simionescu↗
DOE OSTI2021

Carrier-specific dynamics in 2H-MoTe2 observed by femtosecond soft x-ray absorption spectroscopy using an x-ray free-electron laser

Femtosecond carrier dynamics in layered 2H-MoTe2 semiconductor crystals have been investigated using soft x-ray transient absorption spectroscopy at the x-ray free-electron laser (XFEL) of the Pohang Accelerator Laboratory. Following above-bandgap optical excitation of 2H-MoTe2, the photoexcited hole distribution is directly probed via short-lived transitions from the Te 3d5/2 core level (M5-edge, 572–577 eV) to transiently unoccupied states in the valence band. The optically excited electrons are separately probed via the reduced absorption probability at the Te M5-edge involving partially occupied states of the conduction band. A 400 ± 110 fs delay is observed between this transient electron signal near the conduction band minimum compared to higher-lying states within the conduction band, which we assign to hot electron relaxation. Additionally, the transient absorption signals below and above the Te M5 edge, assigned to photoexcited holes and electrons, respectively, are observed to decay concomitantly on a 1–2 ps timescale, which is interpreted as electron–hole recombination. The present work provides a benchmark for applications of XFELs for soft x-ray absorption studies of carrier-specific dynamics in semiconductors, and future opportunities enabled by this method are discussed.

2D materials↗
NASA NTRS2003

Ultrasonic Spectroscopy of Stainless Steel Sandwich Panels

Enhanced, lightweight material systems, such as 17-4PH stainless steel sandwich panels are being developed for use as fan blades and fan containment material systems for next generation engines. In order to improve the production for these systems, nondestructive evaluation (NDE) techniques, such as ultrasonic spectroscopy, are being utilized to evaluate the brazing quality between the 17-4PH stainless steel face plates and the 17-4PH stainless steel foam core. Based on NDE data, shear tests are performed on sections representing various levels of brazing quality from an initial batch of these sandwich structures. Metallographic characterization of brazing is done to corroborate NDE findings and the observed shear failure mechanisms.

Cosgriff, Laura M.↗
DOE OSTI2022

Technical and personal remembrances of David A. Shirley in studies of surface magnetism, photoelectron spectroscopy, EUV lithography, and hydrogen storage

This article describes the influence of Professor David A. Shirley on the research science of one of his Ph.D. students in the diverse areas of surface magnetism, x-ray photoelectron spectroscopy (XPS), spin-resolved XPS (SRXPS), extreme ultraviolet (EUV) lithography, and hydrogen storage materials science. Examples are given from the author's work on Cr(001) surface magnetism, XPS, and SRXPS studies of multiplet-splitting in core-level photoemission from Fe. In addition, Dave's influence in understanding the radiation-induced deposition of carbon on EUV optics is described, along with the use of XPS in deciphering how hydrogen storage materials are modified by repeated hydrogen adsorption/desorption cycling. The current status of these particular topics is briefly summarized. These technical remembrances are combined with some fond personal stories about Dave, in recognition of his passing on March 29, 2021.

Klebanoff, L. E.↗
NASA NTRS1988

(1 + 1) resonant enhanced multiphoton ionization via the A2Sigma(+) state of NO - Ionic rotational branching ratios and their intensity dependence

Rotational branching ratios resulting from the (1 + 1) resonant enhanced multiphoton ionization spectroscopy of NO via the 0-0 transition of the A-X band for the four possible branches that can be assigned as R(21.5) are explored using calculation performed in the frozen-core approximation at the Hartree-Fock level. The four different branches, of which three are distinctly different in the perturbative limit, have rather different branching ratios. The mixed R12 + Q22(21.5) branch, which is not intense and has the lowest transition energy, appears to give the best agreement with experimental branching ratio for parallel detection. The agreement is less satisfactory for perpendicular detection. Neither the effect of finite-acceptance angle of the photoelectron detector nor high intensities can explain the discrepancy.

Rudolph, H.↗