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The capabilities of soft x-ray absorption (XAS), soft x-ray emission spectroscopy (XES), resonant inelastic soft x-ray scattering (RIXS), and their application to characterization of solar energy materials are presented. We have discussed some recent developments of in-situ soft x-ray spectroscopy cells, which enable the investigation of critical solid/liquid or solid/gas interfaces in chemical and electrochemical processes under real-world practical conditions. In particular, in-situ soft x-ray spectroscopies can be utilized to probe the formation of intermediate species, charge separation upon illumination of sunlight and electron transfer to the interfacial reactions. A number of examples using soft x-ray spectroscopies to study these solar energy and catalytic materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the energy conversion and energy storage systems.

The capabilities of soft x-ray absorption (XAS), soft x-ray emission spectroscopy (XES), resonant inelastic soft x-ray scattering (RIXS), and their application to characterization of solar energy materials are presented. We have discussed some recent developments of in-situ soft x-ray spectroscopy cells, which enable the investigation of critical solid/liquid or solid/gas interfaces in chemical and electrochemical processes under real-world practical conditions. In particular, in-situ soft x-ray spectroscopies can be utilized to probe the formation of intermediate species, charge separation upon illumination of sunlight and electron transfer to the interfacial reactions. A number of examples using soft x-ray spectroscopies to study these solar energy and catalytic materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the energy conversion and energy storage systems.

A Na-ion battery (NIB) device is a promising solution for mid-/large-scale energy storage, with the advantages of material abundance, low cost, and environmental benignity. To improve the NIB capacity and retainability, extensive efforts have been put into the developments of NIB electrode materials. The redox activities of the transition metal (TM)-based NIB electrodes are critical in defining the capacity and stability. Here, we provide a comprehensive review on recent studies of the redox mechanisms of NIB cathodes through synchrotron-based soft X-ray absorption spectroscopy (sXAS) and mapping of resonant inelastic X-ray scattering (mRIXS). These soft X-ray techniques are direct and effective tools to fingerprint the TM-3d and O-p states with both bulk and surface sensitivities. Particularly, 3d TM L-edge sXAS has been used to quantify the cationic redox contributions to the electrochemical property; however, it suffers from lineshape distortion for the bulk sensitive signals in some scenarios. With the new dimension of information along the emitted photon energy, mRIXS can address the distortion issue of in TM-L sXAS; moreover, it also breaks through the limitation of conventional sXAS on detecting unconventional TM and O states, e.g., Mn(I) in NIB anode and oxidized oxygen in NIB cathodes. The mRIXS fingerprint of the oxidized oxygen state enables the detection of the reversibility of the oxygen redox reaction through the evolution of feature intensity upon electrochemical cycling and thus clarifies various misunderstandings in our conventional wisdom. We conclude that, with mRIXS established as a powerful tool, its potential and power will continue to be explored for characterizing novel chemical states in NIB electrodes.

The ever-increasing demand for large-scale energy storage has driven the prosperous investigation of sodium-ion batteries (NIBs). As a promising cathode candidate for NIBs, P2-type Na2/3Ni1/3Mn2/3O2 (NaNMO), a prototype sodium-layered oxide, has attracted extensive attention because of its high operating voltage and high capacity density. Although its electrochemical properties have been extensively investigated, the fundamental charge compensation mechanism, that is, the cationic and anionic redox reactions, is still elusive. In this report, we have systematically investigated the transition metal and oxygen redox reactions of NaNMO nanoflakes using bulk-sensitive soft X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering from an atomic-level view. We show that the bulk Mn3+/Mn4+ redox couple emerges from the first discharge process with the increment of inactive Mn3+ upon cycling, which may have a negative effect on the cyclability. In contrast, the bulk Ni redox mainly stems from the Ni2+/Ni3+ redox couple, in contrast to the conventional wisdom of the Ni2+/Ni4+ redox couple. The quantitative analysis provides unambiguous evidence for the continuous reduction of the average valence state of Mn and Ni over extended cycles, leading to the voltage fading. In addition, we reveal that the oxygen anions also participate in the charge compensation process mainly through irreversible oxygen release rather than reversible lattice oxygen redox. Such understanding is vital for the precise design and optimization of NaNMO electrodes for rechargeable NIBs with outstanding performance.

Resonant inelastic X-ray scattering in the XUV-regime has been implemented at BESSY II, pushing for a few-meV bandwidth in inelastic X-ray scattering at transition metal M-edges, rare earth N-edges and the K-edges of light elements up to carbon with full polarization control. The new dedicated low-energy beamline UE112-PGM1 has been designed to provide 1 µm vertical and 20 µm horizontal beam dimensions that serve together with sub-micrometre solid-state sample positioning as the source point for a high-resolution plane grating spectrometer and a high-transmission Rowland spectrometer for rapid overview spectra. The design and commissioning results of the beamline and high-resolution spectrometer are presented. Helium autoionization spectra demonstrate a resolving power of the beamline better than 10 000 at 64 eV with a 300 lines mm−1 grating while the measured resolving power of the spectrometer in the relevant energy range is 3000 to 6000.

The observation of a spontaneous electron enrichment at the apexes of bismuth vanadate (BiVO4) nanopyramidal arrays is achieved by performing synchrotron-based angular dependent X-ray absorption spectroscopy. In accordance with density function theory calculations, the formation of (112) facets enriched apexes is proposed. Such intrinsically electron-enriched (112) facets at the apexes produce a potential facilitating the diffusion of photoexcited holes, which not only mitigates the recombination with the photoexcited electrons, but also provide an active reaction site for the photoassisted selective growth of cobalt phosphate (CoPi), a well known and highly active co-catalyst for water oxidation at the apex of BiVO4 nanopyramids. Benefiting from the element-resolved properties of synchrotron-based X-ray spectroscopy, 3d electrons on the vanadium site are directly resolved by resonant inelastic X-ray scattering measurements. Due to this unique morphology, the charge at the apex is expected to induce a strong interaction with CoPi, as a result of the metal-to-ligand charge transfer spectroscopy feature observed from the cobalt site. Substantial evidences are collected by means of comprehensive soft X-ray spectroscopy techniques with high spectral resolution revealing the atomic-scale origin and the nature of the synergy as well as the strong correlation between its unique structural properties and the electronic structure of this novel highly-ordered hybrid photocatalyst and its significantly improved photoelectrochemical performance.

The observation of a spontaneous electron enrichment at the apexes of bismuth vanadate (BiVO4) nanopyramidal arrays is achieved by performing synchrotron-based angular dependent X-ray absorption spectroscopy. In accordance with density function theory calculations, the formation of (112) facets enriched apexes is proposed. Such intrinsically electron-enriched (112) facets at the apexes produce a potential facilitating the diffusion of photoexcited holes, which not only mitigates the recombination with the photoexcited electrons, but also provide an active reaction site for the photoassisted selective growth of cobalt phosphate (CoPi), a well known and highly active co-catalyst for water oxidation at the apex of BiVO4 nanopyramids. Benefiting from the element-resolved properties of synchrotron-based X-ray spectroscopy, 3d electrons on the vanadium site are directly resolved by resonant inelastic X-ray scattering measurements. Due to this unique morphology, the charge at the apex is expected to induce a strong interaction with CoPi, as a result of the metal-to-ligand charge transfer spectroscopy feature observed from the cobalt site. Substantial evidences are collected by means of comprehensive soft X-ray spectroscopy techniques with high spectral resolution revealing the atomic-scale origin and the nature of the synergy as well as the strong correlation between its unique structural properties and the electronic structure of this novel highly-ordered hybrid photocatalyst and its significantly improved photoelectrochemical performance.

We present a detailed characterization of the chemical structure of the Cu(In,Ga)Se2 thin-film surface and the CdS/Cu(In,Ga)Se2 interface, both with and without a RbF post-deposition treatment (RbF-PDT). For this purpose, X-ray photoelectron and Auger electron spectroscopy, as well as synchrotron-based soft X-ray emission spectroscopy have been employed. Although some similarities with the reported impacts of light-element alkali PDT (i.e., NaF- and KF-PDT) are found, we observe some distinct differences, which might be the reason for the further improved conversion efficiency with heavy-element alkali PDT. In particular, we find that the RbF-PDT reduces, but not fully removes, the copper content at the absorber surface and does not induce a significant change in the Ga/(Ga + In) ratio. Additionally, we observe an increased amount of indium and gallium oxides at the surface of the treated absorber. These oxides are partly (in the case of indium) and completely (in the case of gallium) removed from the CdS/Cu(In,Ga)Se2 interface by the chemical bath deposition of the CdS buffer.

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

• Soft X-ray surface spectroscopy end-stations we built at the PF are reviewed. • Case studies on in situ/operando observations for catalytic surfaces are introduced. • In each study, critical findings emerged, while clear challenges remain. • Future perspective to address these challenges are discussed. This minireview provides an overview of recent advancements in in situ/operando soft X-ray surface spectroscopy, particularly focusing on the development and application of techniques such as near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and soft X-ray absorption spectroscopy (SXAS) conducted at the Photon Factory. These techniques enable us to observe catalytic surfaces under working conditions, which provides new insights into catalytic mechanisms by probing the chemical states of reactive species as well as catalytic surfaces. The review highlights three case studies: the reduction of nitrogen oxide (NO) on rhodium (Rh) catalysts, ethylene epoxidation on silver (Ag) catalysts, and water-splitting photocatalysis using SrTiO 3 with co-catalysts. Each study shows how these techniques reveal critical aspects about surface reactions, structures of intermediate species, and photoinduced processes, which contributes to a deeper understanding of reactive species and reaction pathways. I also discuss about the challenges in operando kinetic analyses, structure analyses and extension of applicable catalytic phenomena and suggest future improvements in operando spectroscopy to enhance the capability of these analyses. [Display omitted] [ABSTRACT FROM AUTHOR]

Oxide heterostructures and superlattices (SLs) have attracted a great deal of attention in recent years owing to the rich exotic properties encountered at their interfaces. We focus on the potential of tunable correlated oxides by investigating the spectral function of the prototypical correlated metal SrVO3, using soft x-ray absorption spectroscopy and resonant inelastic soft x-ray scattering to access both unoccupied and occupied electronic states, respectively. We demonstrate a remarkable level of tunability in the spectral function of SrVO3 by varying its thickness within the SrVO3/SrTiO3 SL, showing that the effects of electron correlation can be tuned from dominating the energy spectrum in a strongly correlated Mott–Hubbard insulator, towards a correlated metal. We show that the effects of dimensionality on the correlated properties of SrVO3 are augmented by interlayer coupling, yielding a highly flexible correlated oxide that may be readily married with other oxide systems.

The mixed transition-metal layered compound, LiNi0.5Mn0.3Co0.2O2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni2+, Ni3+ and Ni4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Additionally, about 20% of Ni2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

The mixed transition-metal layered compound, LiNi0.5Mn0.3Co0.2O2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni2+, Ni3+ and Ni4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Additionally, about 20% of Ni2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

Resonant inelastic X-ray scattering in the XUV-regime has been implemented at BESSY II, pushing for a few-meV bandwidth in inelastic X-ray scattering at transition metal M-edges, rare earth N-edges and the K-edges of light elements up to carbon with full polarization control. The new dedicated low-energy beamline UE112-PGM1 has been designed to provide 1 µm vertical and 20 µm horizontal beam dimensions that serve together with sub-micrometre solid-state sample positioning as the source point for a high-resolution plane grating spectrometer and a high-transmission Rowland spectrometer for rapid overview spectra. The design and commissioning results of the beamline and high-resolution spectrometer are presented. Helium autoionization spectra demonstrate a resolving power of the beamline better than 10 000 at 64 eV with a 300 lines mm-1 grating while the measured resolving power of the spectrometer in the relevant energy range is 3000 to 6000. [ABSTRACT FROM AUTHOR]

Resonant Soft X-ray Scattering (RSoXS) was developed over the last a few years, and the first dedicated resonant soft X-ray scattering beamline for soft materials was constructed at the Advanced Light Source, LBNL. RSoXS combines soft X-ray spectroscopy with X-ray scattering and thus offers statistical information for 3D chemical morphology over a large length scale range from nanometers to micrometers. Using RSoXS to characterize multi-length scale soft materials with heterogeneous chemical structures, we have demonstrated that soft X-ray scattering is a unique complementary technique to conventional hard X-ray and neutron scattering. Its unique chemical sensitivity, large accessible size scale, molecular bond orientation sensitivity with polarized X-rays, and high coherence have shown great potential for chemically specific structural characterization for many classes of materials.

Resonant Soft X-ray Scattering (RSoXS) was developed over the last a few years, and the first dedicated resonant soft X-ray scattering beamline for soft materials was constructed at the Advanced Light Source, LBNL. RSoXS combines soft X-ray spectroscopy with X-ray scattering and thus offers statistical information for 3D chemical morphology over a large length scale range from nanometers to micrometers. Using RSoXS to characterize multi-length scale soft materials with heterogeneous chemical structures, we have demonstrated that soft X-ray scattering is a unique complementary technique to conventional hard X-ray and neutron scattering. Its unique chemical sensitivity, large accessible size scale, molecular bond orientation sensitivity with polarized X-rays, and high coherence have shown great potential for chemically specific structural characterization for many classes of materials.

A Na-ion battery (NIB) device is a promising solution for mid-/large-scale energy storage, with the advantages of material abundance, low cost, and environmental benignity. To improve the NIB capacity and retainability, extensive efforts have been put into the developments of NIB electrode materials. The redox activities of the transition metal (TM)-based NIB electrodes are critical in defining the capacity and stability. Here, we provide a comprehensive review on recent studies of the redox mechanisms of NIB cathodes through synchrotron-based soft X-ray absorption spectroscopy (sXAS) and mapping of resonant inelastic X-ray scattering (mRIXS). These soft X-ray techniques are direct and effective tools to fingerprint the TM-3d and O-p states with both bulk and surface sensitivities. Particularly, 3d TM L-edge sXAS has been used to quantify the cationic redox contributions to the electrochemical property; however, it suffers from lineshape distortion for the bulk sensitive signals in some scenarios. With the new dimension of information along the emitted photon energy, mRIXS can address the distortion issue of in TM-L sXAS; moreover, it also breaks through the limitation of conventional sXAS on detecting unconventional TM and O states, e.g., Mn(I) in NIB anode and oxidized oxygen in NIB cathodes. The mRIXS fingerprint of the oxidized oxygen state enables the detection of the reversibility of the oxygen redox reaction through the evolution of feature intensity upon electrochemical cycling and thus clarifies various misunderstandings in our conventional wisdom. We conclude that, with mRIXS established as a powerful tool, its potential and power will continue to be explored for characterizing novel chemical states in NIB electrodes.

The crystal structure of magnetite nanoparticles may be transformed to maghemite by complete oxidation, but under many relevant conditions the oxidation is partial, creating a mixed-valencematerial with structural and electronic properties that are poorly characterized. We used X-ray diffraction, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, and soft X-rayabsorption and emission spectroscopy to characterize the products of oxidizing uncoated and oleic acid-coated magnetite nanoparticles in air. The oxidization of uncoated magnetite nanoparticlescreates a material that is structurally and electronically indistinguishable from maghemite. By contrast, while oxidized oleic acid-coated nanoparticles are also structurally indistinguishable frommaghemite, Fe L-edge spectroscopy revealed the presence of interior reduced iron sites even after a 2-year period. We used X-ray emission spectroscopy at the O K-edge to study the valence bands (VB)of the iron oxide nanoparticles, using resonant excitation to remove the contributions from oxygen atoms in the ligands and from low-energy excitations that obscured the VB edge. The bonding in allnanoparticles was typical of maghemite, with no detectable VB states introduced by the long-lived, reduced-iron sites in the oleic acid-coated sample. However, O K-edge absorption spectroscopyobserved a 0.2 eV shift in the position of the lowest unoccupied states in the coated sample, indicating an increase in the semiconductor band gap relative to bulk stoichiometric maghemite that wasalso observed by optical absorption spectroscopy. The results show that the ferrous iron sites within ferric iron oxide nanoparticles coated by an organic ligand can persist under ambient conditionswith no evidence of a distinct interior phase and can exert an effect on the global electronic and optical properties of the material. This phenomenon resembles the band gap enlargement caused byelectron accumulation in the conduction band of TiO2.

Material functionalities strongly depend on the stoichiometry, crystal structure, and homogeneity. Here we demonstrate an approach of amorphous nonstoichiometric inhomogeneous oxides to realize tunable ferromagnetism and electrical transport at room temperature. In order to verify the origin of the ferromagnetism, we employed a series of structural, chemical, and electronic state characterizations. Combined with electron microscopy and transport measurements, synchrotron-based grazing incident wide angle X-ray scattering, soft X-ray absorption and circular dichroism clearly reveal that the room-temperature ferromagnetism originates from the In 0.23 Co 0.77 O 1− v amorphous phase with a large tunable range of oxygen vacancies. The room-temperature ferromagnetism is tunable from a high saturation magnetization of 500 emu cm−3 to below 25 emu cm−3, with the evolving electrical resistivity from 5 × 103 μΩ cm to above 2.5 × 105 μΩ cm. Inhomogeneous nano-crystallization emerges with decreasing oxygen vacancies, driving the system towards non-ferromagnetism and insulating regime. Our work unfolds the novel functionalities of amorphous nonstoichiometric inhomogeneous oxides, which opens up new opportunities for developing spintronic materials with superior magnetic and transport properties. [ABSTRACT FROM AUTHOR]

We report on the first experimental results obtained with a newly designed instrument for high-resolution soft X-ray spectroscopy, using reflection zone plates (RZPs) on a spherical substrate. The spectrometer was tested with a fluorescence source. High-resolution flat field spectra within ±50% around the design energies were measured at an interval of 150–750 eV, using only two RZPs: the first RZP, with its design energy of 277 eV, covered the band of 150–370 eV, and the second RZP, with a design energy of 459 eV, covered the band of 350–750 eV, where the upper boundary of this energy range was defined by the Ni coating of the RZPs. The absolute quantum efficiency of the spectrometer, including the optical element and the detector, was, on average, above 10%, and reached 20% at the designed energies of the RZPs. The resolving power E/∆E exceeded 600 for energies E inside the core range of 200–550 eV. [ABSTRACT FROM AUTHOR]

Recent developments in solid‐state lighting lead to a demand for new phosphors with excellent thermal stability, exhibiting large bandgaps for highly efficient emission. A detailed characterization of the luminescent material AELi2Be4O6:Eu2+ (AE = Ba, Sr) is presented using soft X‐ray absorption spectroscopy, X‐ray emission spectroscopy, X‐ray excited optical luminescence (XEOL) spectroscopy, and density functional theory (DFT) calculations. The experimental indirect bandgap for both BaLi2Be4O6:Eu2+ (BLBO:Eu) and SrLi2Be4O6:Eu2+ (SLBO:Eu) is found to be 6.5 ± 0.3 eV, which agrees well with the DFT calculations (6.8 eV for BLBO:Eu and 7.4 eV for SLBO:Eu). The crucial Eu2+ 5d to conduction band energy separation is determined to be 0.21 ± 0.10 and 0.25 ± 0.10 eV for BLBO:Eu and SLBO:Eu, respectively, using resonant inelastic X‐ray scattering. These measured values are in good agreement with the thermal quenching measurements (0.20 ± 0.03 eV for BLBO:Eu and 0.26 ± 0.03 eV for SLBO:Eu). Finally, the XEOL measurement confirms the Eu2+ 5d14f6 → 4f7 transition, which is responsible for the ultranarrow band (full width at half‐maximum: 25 nm) blue optical luminescence at 455–457 nm for both compounds. With these measurements and calculations, deep insights are gained into the key properties of those two phosphors. [ABSTRACT FROM AUTHOR]

The performance of the recently commissioned spectrometer PEAXIS for resonant inelastic soft X‐ray scattering (RIXS) and X‐ray photoelectron spectroscopy and its hosting beamline U41‐PEAXIS at the BESSY II synchrotron are characterized. The beamline provides linearly polarized light from 180 eV to 1600 eV allowing for RIXS measurements in the range 200–1200 eV. The monochromator optics can be operated in different configurations to provide either high flux with up to 1012 photons s−1 within the focal spot at the sample or high energy resolution with a full width at half maximum of <40 meV at an incident photon energy of ∼400 eV. The measured total energy resolution of the RIXS spectrometer is in very good agreement with theoretically predicted values obtained by ray‐tracing simulations. PEAXIS features a 5 m‐long RIXS spectrometer arm that can be continuously rotated about the sample position by 106° within the horizontal photon scattering plane, thus enabling the study of momentum‐transfer‐dependent excitations. Selected scientific examples are presented to demonstrate the instrument capabilities, including measurements of excitations in single‐crystalline NiO and in liquid acetone employing a fluid cell sample manipulator. Planned upgrades of the beamline and the RIXS spectrometer to further increase the energy resolution to ∼100 meV at 1000 eV incident photon energy are discussed. [ABSTRACT FROM AUTHOR]

We used the DV-X alpha method to analyze the high-resolution soft X-ray emission and absorption spectra in the CK region of titanium carbide (TiC). The spectral profiles of the X-ray emission and absorption can be ssuscfucelly reproduced by the occupied and unoccupied density of states (DOS), respectively, in the C2p orbitals of the center carbon atoms in a Ti62C63 cluster model, suggesting that the center carbon atom in a large cluster model expanded to the cubic-structured 53 (= 125) atoms provides sufficient DOS for the X-ray spectral analysis of rock-salt structured metal carbides.

Free‐electron lasers (FELs) based on superconducting accelerator technology and storage ring facilities operate with bunch repetition rates in the MHz range, and the need arises for bunch‐by‐bunch electron and photon diagnostics. For photon‐pulse‐resolved measurements of spectral distributions, fast one‐dimensional profile monitors are required. The linear array detector KALYPSO (KArlsruhe Linear arraY detector for MHz‐rePetition rate SpectrOscopy) has been developed for electron bunch or photon pulse synchronous read‐out with frame rates of up to 2.7 MHz. At the FLASH facility at DESY, a current version of KALYPSO with 256 pixels has been installed at a grating spectrometer as online diagnostics to monitor the pulse‐resolved spectra of the high‐repetition‐rate FEL pulses. Application‐specific front‐end electronics based on MicroTCA standard have been developed for data acquisition and processing. Continuous data read‐out with low latency in the microsecond range enables the integration into fast feedback applications. In this paper, pulse‐resolved FEL spectra recorded at 1.0 MHz repetition rate for various operation conditions at FLASH are presented, and the first application of an adaptive feedback for accelerator control based on photon beam diagnostics is demonstrated. [ABSTRACT FROM AUTHOR]

We report on the first experimental results obtained with a newly designed instrument for high-resolution soft X-ray spectroscopy, using reflection zone plates (RZPs) on a spherical substrate. The spectrometer was tested with a fluorescence source. High-resolution flat field spectra within ±50% around the design energies were measured at an interval of 150–750 eV, using only two RZPs: the first RZP, with its design energy of 277 eV, covered the band of 150–370 eV, and the second RZP, with a design energy of 459 eV, covered the band of 350–750 eV, where the upper boundary of this energy range was defined by the Ni coating of the RZPs. The absolute quantum efficiency of the spectrometer, including the optical element and the detector, was, on average, above 10%, and reached 20% at the designed energies of the RZPs. The resolving power E/∆E exceeded 600 for energies E inside the core range of 200–550 eV.

We have investigated the photoionization and photofragmentation yields of gas-phase multiply protonated melittin cations for photon energies at the K-shell absorption edges of carbon, nitrogen, and oxygen. Two similar experimental approaches were employed. In both experiments, mass selected [melittin+qH]q+ (q=2-4) ions were accumulated in radiofrequency ion traps. The trap content was exposed to intense beams of monochromatic soft X-ray photons from synchrotron beamlines and photoproducts were analyzed by means of time-of-flight mass spectrometry. Mass spectra were recorded for fixed photon energies, and partial ion yield spectra were recorded as a function of photon energy. The combination of mass spectrometry and soft X-ray spectroscopy allows for a direct correlation of protein electronic structure with various photoionization channels. Non-dissociative single and double ionization are used as a reference. The contribution of both channels to various backbone scission channels is quantified and related to activation energies and protonation sites. Soft X-ray absorption mass spectrometry combines fast energy deposition with single and double ionization and could complement established activation techniques.ᅟ [ABSTRACT FROM AUTHOR]

Abstract: Preservation of protein conformation upon transfer into the gas phase is key for structure determination of free single molecules, for example using X‐ray free‐electron lasers. In the gas phase, the helicity of melittin decreases strongly as the protein's protonation state increases. We demonstrate the sensitivity of soft X‐ray spectroscopy to the gas‐phase structure of melittin cations ([melittin+qH]q+, q=2–4) in a cryogenic linear radiofrequency ion trap. With increasing helicity, we observe a decrease of the dominating carbon 1 s–π* transition in the amide C=O bonds for non‐dissociative single ionization and an increase for non‐dissociative double ionization. As the underlying mechanism we identify inelastic electron scattering. Using an independent atom model, we show that the more compact nature of the helical protein conformation substantially increases the probability for off‐site intramolecular ionization by inelastic Auger electron scattering. [ABSTRACT FROM AUTHOR]

Metal-halide perovskites are complex materials with outstanding optoelectronic properties. Thus it is of interest to analyze these materials by using every available research tool. Synchrotron tools have played an important role in fundamental and applied research for decades. Many synchrotron-based hard X-ray tools are already providing effective feedback to the perovskite solar cell (PSC) research community. With several fourth-generation light sources up and running or under development, this contribution will continue to impact every aspect of scientific advancement including PSC research. Arguably, the contribution of soft X-rays in PSC research is relatively limited. In view of the developments in the synchrotron world and the fact that a multimethod approach, combining laboratory-based techniques as well as synchrotron-based techniques, is necessary to provide constructive feedback to the PSC community we present here a collection of arguments and procedures with the aim of highlighting the use of soft X-ray scanning transmission X-ray microscopy (STXM). Some aspects of these arguments are elaborated with STXM investigation of perovskite material formamidinium-methylammonium lead iodide (FA 1−x MA x PbI 3). • Soft X-ray absorption edges of hybrid perovskite materials makes soft x-ray STXM valuable tool for studying these materials. • Spatially resolved bulk as well as interface sensitive chemical and morphological mapping can be obtained using this techique. • Various considerations related to sample preparation, sample transportation and data acquisition have been presented. • Several XAS features in the C, N, O K-edge and I M-edge have been identified for some model perovskite materials. [ABSTRACT FROM AUTHOR]

Soft X-ray spectra from high Z rare-earth (lanthanide) elements have been systematically observed in optically thin, high-temperature plasmas produced in the Large Helical Device (LHD), a facility for magnetically confined fusion research. It has been demonstrated that the discrete and quasicontinuum (UTA) spectral features from highly charged lanthanide ions are observed depending on the plasma temperature. The analyses of the measured spectra are ongoing by comparisons with theoretical calculations and/or previous experimental data available. The discrete spectra recorded in high-temperature conditions are dominated by individual lines of Ge- to Ni-like ions, while prominent peaks in the narrowed UTA spectra observed in low-temperature conditions are well explained by the transitions of Ag- to Rh-like ions.

A gas cell for in-situ measurements of Volatile Organic Compounds (VOCs) and their adsorption behaviour on different surfaces by means of X-ray Fluorescence (XRF) and X-ray Absorption Fine-Structure (XAFS) spectroscopy has been developed. The cell is especially designed to allow for the efficient excitation and detection of low-Z elements such as carbon, oxygen or nitrogen as main components of VOCs. Two measurement modes are available. In the surface mode, adsorption on a surface can be studied using XAFS by fluorescence detection under shallow angles of incidence. The transmission mode enables the simultaneous investigation of gaseous samples via XAFS in transmittance and fluorescence detection modes. Proof-of-principle experiments were performed at the PTB plane grating monochromator beamline for soft X-ray radiation at the synchrotron radiation facility BESSY II. The flexible design and high versatility of the cell are demonstrated with the investigation of ethanol (EtOH) as one of the most abundant VOCs. The comparison of Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectra under transmission and fluorescence detection in the gas phase with measurements of adsorbed molecules on a Si-wafer surface both at the C and O-K absorption edges proves the applicability of the cell for the monitoring of adsorption processes. [Display omitted] • X-ray spectroscopy of gaseous samples • Specially in the spectral range of soft X-ray radiation (C, N, O) • Transmission and fluorescence simultaneously. • Sample cell for X-ray Fluorescence (XRF) and X-ray Absorption Fine-Structure (XAFS) • Grazing incidence excitation allows for quantitative XRF investigations • Investigations of Volatile Organic Compounds (VOCs) on exchangeable surfaces. • Proof-of-principle experiment shows adsorption of ethanol on Si wafer surface. [ABSTRACT FROM AUTHOR]

The role of the nitrogen incorporation into titanium, its chemical nature, the location in the titanium lattice and its electrochemical performance were investigated by a combination of several spectroscopy and microscopy techniques using samples prepared by CVD of NH 3 at different temperatures and successive electrochemically tested in 1 M of HClO 4 . We found that nitrogen is incorporated in either the interstitial or substitutional site of the lattice depending on the preparation temperature modifying strongly its corrosion resistance which was ascribed to the N 2p hybridization with the Ti 3d orbitals. It was found that at low temperature the N 2p orbitals were more likely to hybridize with Ti 3d -t 2g orbitals while higher temperature favors the hybridization with the Ti 3d -e g orbitals. This is responsible for the corrosion resistance shown by the samples prepared at higher temperature. [ABSTRACT FROM AUTHOR]

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Light elements are particularly important in biogeochemical processes. These include organic matter components and macronutrients (C, N, O, S, P), micronutrients (Na, Mg, K, Mg), mineral elements (Si, Al), and transition metals. Determining the chemical speciation of these light elements in environmental samples is important for understanding bioavailability, decomposition, contamination mobility, and nutrient cycling. Soft X-ray absorption spectroscopy is a useful tool available to probe the chemistry of atoms important in biogeochemical processes. X-ray absorption spectroscopy (XAS) probes the local bonding and coordination environment of these elements in whole samples. Bulk XAS techniques permit for high throughput, the study of whole soils, and high sampling density. These analyses are complementary to X-ray transmission microscopy techniques which are limited by low throughput, thin particles (<100 nm), and low sampling density. In many projects, these bulk XAS measurements may be essential to understanding large-scale processes in soils such as the global C cycle. Despite these important applications, bulk soft XAS has not been extensively applied to environmental samples until recently. The primary reasons for this gap is the lack of beamline endstations that are suitable for "dirty" samples and the technical challenges related to acquiring and normalizing spectra from dilute samples. Many of these technical challenges have now been overcome through the development of energy-resolving detectors, proper detector positioning, and development of liquid cell applications. Technical developments and recent applications will be presented, showing how bulk soft X-ray XAS is now positioned to contribute significantly to advancing the characterization of soils and environmental samples. [ABSTRACT FROM AUTHOR]

In this study, the stability and electronic characteristics of epitaxial silicene bilayers and multilayers on the Ag(111) surface are investigated through synchrotron-based soft X-ray emission and absorption spectroscopy and first-principles, full-potential density functional theory simulations. The calculations predict a novel tristable AA-stacked bilayer structure that can explain the (√3 × √3)R30° honeycomb topography commonly observed through scanning tunneling microscopy and noncontact atomic force microscopy. It is reported that the electronic structure of this epitaxial bilayer is similar to those of epitaxial monolayers on Ag(111), namely, metallic and showing significant interaction with the underlying substrate. However, the soft X-ray spectroscopy experiments suggest that during multilayer growth a majority of the epitaxial silicon reverts to a bulk-like state, a result that has significant implications toward the existence of large-area epitaxial silicene multilayers. [ABSTRACT FROM AUTHOR]

Growing environmental concerns have renewed the interest for light induced catalytic reactions to synthesize cleaner chemical fuels from syngas. This, however, requires a sound understanding for the dynamics taking place at molecular level as a result of light – matter interaction. We present herein the principles of soft X-ray resonant emission spectroscopy (RXES) and resonant inelastic scattering (RIXS) and the importance of these spectroscopic techniques in materials science in light of their unique ability to emanate characteristic fingerprints on the geometric structure, chemical bonding charge and spin states in addition to chemical sensitivity. The addition of in situ/operando RXES and RIXS capability offers new opportunities to project important material properties and functionalities under conditions nearly identical to the operational modes. [ABSTRACT FROM AUTHOR]

Understanding the mechanisms of catalytic and reactions calls for in situ/operando spectroscopic characterization. Here we report the developments of in situ reaction cells at the Advanced Light Source for soft X-ray spectroscopic studies of nanoparticle catalysts during the catalytic reactions. The operation of these various cells and their capabilities are illustrated with examples from the studies of Co-based nanocatalysts. [ABSTRACT FROM AUTHOR]

The charge ordering of Fe 2+ and Fe 3+ ions in LuFe 2 O 4 induces ferroelectricity below 330 K. In this study, the X-ray absorption spectra (XAS) at the Fe L 2,3 -edge are investigated to study charge ordered- and disordered-states. The polarization dependence of XAS revealed that the energy level of ( d xy , d x 2– y 2 ) is lower than that of ( d yz , d zx ). In the charge-ordered state, the Fe L 3 -XAS shows a double-peak structure, which is a characteristic of Fe 2+ and Fe 3+ ions. In the high-temperature region, the double-peak structure becomes a broad single peak, because of overlap with the thermally excited state. [ABSTRACT FROM AUTHOR]

Silicene is a two-dimensional structure composed of a buckled hexagonal honeycomb lattice of silicon atoms. Freestanding silicene is yet to be synthesized, but epitaxial silicene monolayers have been directly observed or predicted to exist on a number of supporting substrates. Herein the atomic and electronic structures of five distinct epitaxial silicene morphologies on Ag(111) are examined through the complementary techniques of density functional theory and soft X-ray spectroscopy at the Si L2,3 edge. Hybridization with the Ag(111) substrate is shown to cause these silicene monolayers to become strongly metallic, and the specific electronic interactions that are responsible for this metallic nature are determined. The results imply that epitaxial silicene on Ag(111) does not possess the Dirac cone electronic structure that is characteristic of freestanding silicene and graphene sheets. [ABSTRACT FROM AUTHOR]

Electronic band structures of two novel semiconducting nitrides of the group-IV elements of Th3P4-type crystal structure, c-M3N4, where MZr or Hf, is investigated using an element specific soft X-ray spectroscopy for the first time. From the pairs of N 1s X-ray absorption and N 2p → 1s resonant X-ray emission spectra partial densities of states (PDOS) of nitrogen, predicted to be strongly hybridized with those of the metals, are obtained for both compounds. From these data the electronic band gaps of oxygen bearing c-Zr3N4 and of c-Hf3N4, predicted before to be direct or nearly direct, are derived to be Eg = 1.6 eV and Eg = 1.8 eV, respectively. While the experimentally determined Eg for c-Hf3N4 agrees with the theoretical one obtained using the local density approximation (LDA) method, the Eg measured for oxygen bearing c-Zr3N4 is significantly higher than those calculated using both the LDA and the generalized gradient approximation method. The examined compounds, having high hardness, elastic moduli and oxidation resistance, appear to be multifunctional materials suitable also for applications as (opto)electronic materials. Band gap evolution in c-M3N4 nitrides as a function of the cation type, Zr or Hf. [ABSTRACT FROM AUTHOR]