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A 1D imaging soft X‐ray spectrometer installed on the small quantum systems (SQS) scientific instrument of the European XFEL is described. It uses movable cylindrical constant‐line‐spacing gratings in the Rowland configuration for energy dispersion in the vertical plane, and Wolter optics for simultaneous 1D imaging of the source in the horizontal plane. The soft X‐ray fluorescence spectro‐imaging capability will be exploited in pump–probe measurements and in investigations of propagation effects and other nonlinear phenomena. [ABSTRACT FROM AUTHOR]

A 1D imaging soft X-ray spectrometer installed on the small quantum systems (SQS) scientific instrument of the European XFEL is described. It uses movable cylindrical constant-line-spacing gratings in the Rowland configuration for energy dispersion in the vertical plane, and Wolter optics for simultaneous 1D imaging of the source in the horizontal plane. The soft X-ray fluorescence spectro-imaging capability will be exploited in pump–probe measurements and in investigations of propagation effects and other nonlinear phenomena.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed. [ABSTRACT FROM AUTHOR]

The detection of inelastically scattered soft x-rays with high energy resolution usually requires large grating spectrometers. Recently, photoelectron spectrometry for analysis of x-rays (PAX) has been rediscovered for modern spectroscopy experiments at synchrotron light sources. By converting scattered photons to electrons and using an electron energy analyser, the energy resolution for resonant inelastic x-ray scattering (RIXS) becomes decoupled from the x-ray spot size and instrument length. In this work, we develop PAX towards high energy resolution using a modern photoemission spectroscopy setup studying Ba2Cu3O4Cl2 at the Cu L 3-edge. We measure a momentum transfer range of 24% of the first Brillouin zone simultaneously. Our results hint at the observation of a magnon excitation below 100 meV energy transfer and show intensity variations related to the dispersion of dd -excitations. With dedicated setups, PAX can complement the best and largest RIXS instruments, while at the same time opening new opportunities to acquire RIXS at a range of momentum transfers simultaneously and combine it with angle-resolved photoemission spectroscopy in a single instrument. [ABSTRACT FROM AUTHOR]

Resonant inelastic X-ray scattering (RIXS) has played a pivotal role in advancing our understanding of spin-orbit physics in 5d transition metal materials. The progress in RIXS techniques has closely paralleled improvements in energy resolution, which have enabled the study of very low-lying excitations and led to the discovery of numerous new phenomena with significant scientific and technological implications. The multi-bend achromat (MBA) lattice upgrade of third-generation synchrotron sources, such as the Advanced Photon Source (APS), heralds a transformative era by introducing enhancements in brilliance and emittance. These advancements provide an opportunity to push the boundaries of RIXS techniques, meeting the challenges at the research frontiers of material science. This article aims to highlight key instrumental and technical advancements that enable the achievement of meV resolution in RIXS and discuss the impact of such high-resolution RIXS on exploring spin-orbit physics in 5d transition metal materials.

The X-ray emission spectrometer at SPring-8 BL07LSU has recently been upgraded with advanced modifications that enable the rotation of the spectrometer with respect to the scattering angle. This major upgrade allows the scattering angle to be flexibly changed within the range of 45–135°, which considerably simplifies the measurement of angle-resolved X-ray emission spectroscopy. To accomplish the rotation system, a sophisticated sample chamber and a highly precise spectrometer rotation mechanism have been developed. The sample chamber has a specially designed combination of three rotary stages that can smoothly move the connection flange along the wide scattering angle without breaking the vacuum. In addition, the spectrometer is rotated by sliding on a flat metal surface, ensuring exceptionally high accuracy in rotation and eliminating the need for any further adjustments during rotation. A control system that integrates the sample chamber and rotation mechanism to automate the measurement of angle-resolved X-ray emission spectroscopy has also been developed. This automation substantially streamlines the process of measuring angle-resolved spectra, making it far easier than ever before. Furthermore, the upgraded X-ray emission spectrometer can now also be utilized in diffraction experiments, providing even greater versatility to our research capabilities.

A prevalent class of challenges in modern physics are inverse problems, where physical quantities must be extracted from experimental measurements. End-to-end machine learning approaches to inverse problems typically require constructing sophisticated estimators to achieve the desired accuracy, largely because they need to learn the complex underlying physical model. Here, we discuss an alternative paradigm: by making the physical model auto-differentiable we can construct a neural surrogate to represent the unknown physical quantity sought, while avoiding having to relearn the known physics entirely. We dub this process surrogate training embedded in physics (STEP) and illustrate that it generalizes well and is robust against overfitting and significant noise in the data. We demonstrate how STEP can be applied to perform dynamic kernel deconvolution to analyse resonant inelastic X-ray scattering spectra and show that surprisingly simple estimator architectures suffice to extract the relevant physical information.

A momentum resolved resonant inelastic X-ray scattering (qRIXS) experimental station with continuously rotatable spectrometers and parallel detection is designed to operate at different beamlines at synchrotron and free electron laser (FEL) facilities. This endstation, currently located at the Advanced Light Source (ALS), has five emission ports on the experimental chamber for mounting the high-throughput modular soft X-ray spectrometers (MXS) [24]. Coupled to the rotation from the supporting hexapod, the scattered X-rays from 27.5° (forward scattering) to 152.5° (backward scattering) relative to the incident photon beam can be recorded, enabling the momentum-resolved RIXS spectroscopy. The components of this endstation are described in details, and the preliminary RIXS measurements on highly oriented pyrolytic graphite (HOPG) reveal the low energy vibronic excitations from the strong electron-phonon coupling at C K edge around σ* band. The grating upgrade option to enhance the performance at low photon energies is presented and the potential of this spectroscopy is discussed in summary.

Abstract The sustained interest in investigating magnetism in the 2D limit of insulating antiferromagnets is driven by the possibilities of discovering, or engineering, novel magnetic phases through layer stacking. However, due to the difficulty of directly measuring magnetic interactions in 2D antiferromagnets, it is not yet understood how intralayer magnetic interactions in insulating, strongly correlated, materials can be modified through layer proximity. Herein, the impact of reduced dimensionality in the model van der Waals antiferromagnet NiPS3 is explored by measuring electronic excitations in exfoliated samples using Resonant Inelastic X‐ray Scattering (RIXS). The resulting spectra shows systematic broadening of NiS6 multiplet excitations with decreasing layer count from bulk down to three atomic layers (3L). It is shown that these trends originate from a decrease in transition metal‐ligand and ligand–ligand hopping integrals, and by charge‐transfer energy evolving from Δ = 0.83 eV in the bulk to 0.37 eV in 3L NiPS3. Relevant intralayer magnetic exchange integrals computed from the electronic parameters exhibit a decrease in the average interaction strength with thickness. This study underscores the influence of interlayer electronic interactions on intralayer ones in insulating magnets, indicating that magnetic Hamiltonians in few‐layer insulating magnets can greatly deviate from their bulk counterparts.

An endstation for resonant inelastic X-ray scattering (RIXS), dedicated to operations in the hard X-ray regime, has been constructed at the 1C beamline of Pohang Light Source II. At the Ir L3-edge, a total energy resolution of 34.2 meV was achieved, close to the theoretical estimation of 34.0 meV, which considers factors such as the incident energy bandpass, intrinsic analyzer resolution, geometrical broadening of the spectrometer, finite beam-size effect and Johann aberration. The performance of the RIXS instrument is demonstrated by measuring the RIXS spectra of Sr2IrO4. The endstation can be easily reconfigured to measure energy-integrated intensities with very low background for diffuse scattering and diffraction experiments.

Fast charging and high-power delivering batteries are highly demanded in mobile electronics, electric vehicles and grid energy storage, but there are full of challenges. The star-material Li3V2(PO4)3 is demonstrated as a promising high-rate cathode material meeting the above requirements. Herein, we report the carbon decorated Li3V2(PO4)3 (LVP/C) cathode prepared via a facile method, which displays a remarkable high-rate capability and long-term cycling performance. Briefly, the prepared LVP/C delivers a high discharge capacity of 122 mAh g−1 (~93% of the theoretical capacity) at a high rate up to 20 C and a superior capacity retention of 87.1% after 1000 cycles. Importantly, by applying a combination of X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering, we clearly elucidate the structural and chemical evolutions of LVP upon various potentials and cycle numbers. We show unambiguous spectroscopic evidences that the evolution of the hybridization strength between V and O in LVP/C as a consequence of lithiation/delithiation is highly reversible both in the bulk and on the surface during the discharge-charge processes even over extended cycles, which should be responsible for the remarkable electrochemical performance of LVP/C. Our present study provides not only an effective synthesis strategy but also deeper insights into the surface and bulk electrochemical reaction mechanism of LVP, which should be beneficial for the further design of high-performance LVP electrode materials.

Redox reactions of oxygen have been considered critical in controlling the electrochemical properties of lithium-excessive layered-oxide electrodes. However, conventional electrode materials without overlithiation remain the most practical. Typically, cationic redox reactions are believed to dominate the electrochemical processes in conventional electrodes. Herein, we show unambiguous evidence of reversible anionic redox reactions in LiNi1/3 Co1/3 Mn1/3 O2 . The typical involvement of oxygen through hybridization with transition metals is discussed, as well as the intrinsic oxygen redox process at high potentials, which is 75 % reversible during initial cycling and 63 % retained after 10 cycles. Our results clarify the reaction mechanism at high potentials in conventional layered electrodes involving both cationic and anionic reactions and indicate the potential of utilizing reversible oxygen redox reactions in conventional layered oxides for high-capacity lithium-ion batteries.

Redox reactions of oxygen have been considered critical in controlling the electrochemical properties of lithium-excessive layered-oxide electrodes. However, conventional electrode materials without overlithiation remain the most practical. Typically, cationic redox reactions are believed to dominate the electrochemical processes in conventional electrodes. Herein, we show unambiguous evidence of reversible anionic redox reactions in LiNi1/3 Co1/3 Mn1/3 O2 . The typical involvement of oxygen through hybridization with transition metals is discussed, as well as the intrinsic oxygen redox process at high potentials, which is 75 % reversible during initial cycling and 63 % retained after 10 cycles. Our results clarify the reaction mechanism at high potentials in conventional layered electrodes involving both cationic and anionic reactions and indicate the potential of utilizing reversible oxygen redox reactions in conventional layered oxides for high-capacity lithium-ion batteries.

As a parent compound of Li-rich electrodes, Li2MnO3 exhibits high capacity during the initial charge; however, it suffers notoriously low Coulombic efficiency due to oxygen and surface activities. Here, we successfully optimize the oxygen activities toward reversible oxygen redox reactions by intentionally introducing protons into lithium octahedral vacancies in the Li2MnO3 system with its original structural integrity maintained. Combining structural probes, theoretical calculations, and resonant inelastic X-ray scattering results, a moderate coupling between the introduced protons and lattice oxygen at the oxidized state is revealed, which stabilizes the oxygen activities during charging. Such a coupling leads to an unprecedented initial Coulombic efficiency (99.2%) with a greatly improved discharge capacity of 302 mAh g-1 in the protonated Li2MnO3 electrodes. These findings directly demonstrate an effective concept for controlling oxygen activities in Li-rich systems, which is critical for developing high-energy cathodes in batteries.

Harnessing anionic redox reactions is of prime importance for boosting the capacity of sodium-ion batteries (NIBs). However, quantifying the cyclability of anionic redox reactions is still challenging. Herein, we conduct a qualitative and quantitative investigation of the cationic and anionic redox reactions of a prototype Na-rich layered oxide, namely, Na3RuO4, by a combination of bulk-sensitive X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering. We unequivocally reveal that both Ru cations and oxygen anions are involved in the charge compensation process of Na3RuO4. Ru redox is highly reversible over extended electrochemical cycles, while the cyclability of lattice oxygen redox gradually decreases with the retention of only 36% after 30 cycles, which is mainly responsible for the capacity fading of Na3RuO4. Our findings provide deeper insights into the complex oxygen redox mechanism, which plays a decisive role for designing high-energy Na-rich electrode materials for NIBs.

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.

This study investigates the evolution of superconductivity in K2-xFe4+ySe5 using temperature-dependent X-ray absorption and resonant inelastic X-ray scattering techniques. Magnetization measurements show that polycrystalline superconducting (SC) K1.9Fe4.2Se5 has a critical temperature (T c) of ∼31 K with a varying superconducting volume fraction, which strongly depends on its synthesis temperature. An increase in Fe-structural/vacancy disorder in SC samples with more Fe atoms occupying vacant 4d sites is found to be closely related to the decrease in the spin magnetic moment of Fe. Moreover, the nearest-neighbor Fe-Se bond length in SC samples exceeds that in the non-SC (NS) sample, K2Fe4Se5, which indicates a weaker hybridization between the Fe 3d and Se 4p states in SC samples. These results clearly demonstrate the correlations among the local electronic and atomic structures and the magnetic properties of K2-xFe4+ySe5 superconductors, providing deeper insight into the electron pairing mechanisms of superconductivity.

This study investigates the evolution of superconductivity in K2-xFe4+ySe5 using temperature-dependent X-ray absorption and resonant inelastic X-ray scattering techniques. Magnetization measurements show that polycrystalline superconducting (SC) K1.9Fe4.2Se5 has a critical temperature (T c) of ∼31 K with a varying superconducting volume fraction, which strongly depends on its synthesis temperature. An increase in Fe-structural/vacancy disorder in SC samples with more Fe atoms occupying vacant 4d sites is found to be closely related to the decrease in the spin magnetic moment of Fe. Moreover, the nearest-neighbor Fe-Se bond length in SC samples exceeds that in the non-SC (NS) sample, K2Fe4Se5, which indicates a weaker hybridization between the Fe 3d and Se 4p states in SC samples. These results clearly demonstrate the correlations among the local electronic and atomic structures and the magnetic properties of K2-xFe4+ySe5 superconductors, providing deeper insight into the electron pairing mechanisms of superconductivity.

The detection of inelastically scattered soft x-rays with high energy resolution usually requires large grating spectrometers. Recently, photoelectron spectrometry for analysis of x-rays (PAX) has been rediscovered for modern spectroscopy experiments at synchrotron light sources. By converting scattered photons to electrons and using an electron energy analyser, the energy resolution for resonant inelastic x-ray scattering (RIXS) becomes decoupled from the x-ray spot size and instrument length. In this work, we develop PAX towards high energy resolution using a modern photoemission spectroscopy setup studying Ba _2 Cu _3 O _4 Cl _2 at the Cu L _3 -edge. We measure a momentum transfer range of 24% of the first Brillouin zone simultaneously. Our results hint at the observation of a magnon excitation below 100 meV energy transfer and show intensity variations related to the dispersion of dd -excitations. With dedicated setups, PAX can complement the best and largest RIXS instruments, while at the same time opening new opportunities to acquire RIXS at a range of momentum transfers simultaneously and combine it with angle-resolved photoemission spectroscopy in a single instrument.

Realizing reversible reduction-oxidation (redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes at different electrochemical states and its comparison with peroxides, we provide a comprehensive analysis of five components observed in the mRIXS results. While all the five components evolve upon electrochemical cycling, only two of them correspond to the critical states associated with oxygen redox reactions. One is a specific feature at 531.0 eV excitation and 523.7 eV emission energy, the other is a low-energy loss feature. We show that both features evolve with electrochemical cycling of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes, and could be used for characterizing oxidized oxygen states in the lattice of battery electrodes. This work provides an important benchmark for a complete assignment of all mRIXS features collected from battery materials, which sets a general foundation for future studies in characterization, analysis, and theoretical calculation for probing and understanding oxygen redox reactions.

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.

Recently, 2D layered transition metal dichalcogenides (TMDs) have attracted great scientific interest in electrochemical energy storage research. Vanadium disulfide (VS2) as an important family member of TMDs, is a promising electrode material for lithium-ion cells because of its remarkable electrical conductivity and high Li+ diffusion rate, but its electrochemical reaction mechanism is still poorly understood. Herein, we have prepared VS2 nanosheets as the electrode and systematically investigated its structural and chemical evolution during the electrochemical processes by employing both in situ and ex situ x-ray spectroscopy. The VS2 undergoes intercalation and conversion reactions in sequence during discharge and this process is found to be partially reversible during the subsequent charge. The decreased reversibility of the conversion reaction over extended cycles could be mainly responsible for the capacity fading of the VS2 electrode. In addition, the hybridization strength between S and V shows a strong dependence on the states of charge, as directly illustrated by the intensity change of the V-S hybridized states and pure V states. We have also found that the solid electrolyte interphase on the electrode surface is dynamically evolved during cycling, which may be a universal phenomenon for the conversion-based electrodes. This study is expected to be beneficial for the further development of high-performance VS2-based electrodes.

The I21 beamline at Diamond Light Source is dedicated to advanced resonant inelastic X-ray scattering (RIXS) for probing charge, orbital, spin and lattice excitations in materials across condensed matter physics, applied sciences and chemistry. Both the beamline and the RIXS spectrometer employ divergent variable-line-spacing gratings covering a broad energy range of 280–3000 eV. A combined energy resolution of ∼35 meV (16 meV) is readily achieved at 930 eV (530 eV) owing to the optimized optics and the mechanics. Considerable efforts have been paid to the design of the entire beamline, particularly the implementation of the collection mirrors, to maximize the X-ray photon throughput. The continuous rotation of the spectrometer over 150° under ultra high vacuum and a cryogenic manipulator with six degrees of freedom allow accurate mappings of low-energy excitations from solid state materials in momentum space. Most importantly, the facility features a unique combination of the high energy resolution and the high photon throughput vital for advanced RIXS applications. Together with its stability and user friendliness, I21 has become one of the most sought after RIXS beamlines in the world.

Resonant inelastic X-ray scattering (RIXS) has become an important scientific tool. Nonetheless, conventional high-resolution (few hundred meV or less) RIXS measurements, especially in the soft X-ray range, require low-throughput grating spectrometers, which limits measurement accuracy. Here, the performance of a different method for measuring RIXS, i.e. photoelectron spectrometry for analysis of X-rays (PAX), is computationally investigated. This method transforms the X-ray measurement problem of RIXS to an electron measurement problem, enabling use of high-throughput, compact electron spectrometers. X-rays to be measured are incident on a converter material and the energy distribution of the resultant photoelectrons, the PAX spectrum, is measured with an electron spectrometer. A deconvolution algorithm for analysis of such PAX data is proposed. It is shown that the deconvolution algorithm works well on data recorded with ∼0.5 eV resolution. Additional simulations show the potential of PAX for estimation of RIXS features with smaller widths. For simulations using the 3d levels of Ag as a converter material, and with 105 simulated detected electrons, it is estimated that features with a few hundred meV width can be accurately estimated in a model RIXS spectrum. For simulations using a sharp Fermi edge to encode RIXS spectra, it is estimated that one can accurately distinguish 100 meV FWHM peaks separated by 45 meV with 105 simulated detected electrons that were photoemitted from within 0.4 eV of the Fermi level.

With the increasing interest in transition metal chalcogenides, sulfide minerals containing the disulfide unit (S22-) have gained intensive attention for potential applications in energy storage devices, such as lithium-ion batteries (LIBs). Vanadium tetrasulfide (VS4) possesses a unique linear-chain structure with a Peierls distortion and shows great promise for application in LIBs. However, its electrochemical reaction mechanism is still controversial, mainly due to the amorphous nature of the intermediates and final products. Here, by applying multiple X-ray spectroscopies, we reveal that VS4 undergoes lithium intercalation and conversion reactions sequentially during the first discharge process, which are partially reversible in the subsequent charge process. However, an anomalous intercalation/conversion mixed reaction mechanism is dominant for the second cycle, mainly owing to the amorphization of the VS4 electrode during the first cycle. In addition, the sulfur atoms are also involved in the redox reaction during cycling, with the anionic contribution of S22- ↔ 2S2- transformation. Furthermore, we find that the formation process of the solid electrolyte interphase is highly dynamic during the discharge and charge processes. The present study provides deeper insights into the complex reaction mechanism of VS4. This knowledge can accelerate the development of high-performance VS4-based electrode materials for LIBs.

With the increasing interest in transition metal chalcogenides, sulfide minerals containing the disulfide unit (S22-) have gained intensive attention for potential applications in energy storage devices, such as lithium-ion batteries (LIBs). Vanadium tetrasulfide (VS4) possesses a unique linear-chain structure with a Peierls distortion and shows great promise for application in LIBs. However, its electrochemical reaction mechanism is still controversial, mainly due to the amorphous nature of the intermediates and final products. Here, by applying multiple X-ray spectroscopies, we reveal that VS4 undergoes lithium intercalation and conversion reactions sequentially during the first discharge process, which are partially reversible in the subsequent charge process. However, an anomalous intercalation/conversion mixed reaction mechanism is dominant for the second cycle, mainly owing to the amorphization of the VS4 electrode during the first cycle. In addition, the sulfur atoms are also involved in the redox reaction during cycling, with the anionic contribution of S22- ↔ 2S2- transformation. Furthermore, we find that the formation process of the solid electrolyte interphase is highly dynamic during the discharge and charge processes. The present study provides deeper insights into the complex reaction mechanism of VS4. This knowledge can accelerate the development of high-performance VS4-based electrode materials for LIBs.

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.

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

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.

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]

The I21 beamline at Diamond Light Source is dedicated to advanced resonant inelastic X‐ray scattering (RIXS) for probing charge, orbital, spin and lattice excitations in materials across condensed matter physics, applied sciences and chemistry. Both the beamline and the RIXS spectrometer employ divergent variable‐line‐spacing gratings covering a broad energy range of 280–3000 eV. A combined energy resolution of ∼35 meV (16 meV) is readily achieved at 930 eV (530 eV) owing to the optimized optics and the mechanics. Considerable efforts have been paid to the design of the entire beamline, particularly the implementation of the collection mirrors, to maximize the X‐ray photon throughput. The continuous rotation of the spectrometer over 150° under ultra high vacuum and a cryogenic manipulator with six degrees of freedom allow accurate mappings of low‐energy excitations from solid state materials in momentum space. Most importantly, the facility features a unique combination of the high energy resolution and the high photon throughput vital for advanced RIXS applications. Together with its stability and user friendliness, I21 has become one of the most sought after RIXS beamlines in the world. [ABSTRACT FROM AUTHOR]

Resonant inelastic X‐ray scattering (RIXS) has become an important scientific tool. Nonetheless, conventional high‐resolution (few hundred meV or less) RIXS measurements, especially in the soft X‐ray range, require low‐throughput grating spectrometers, which limits measurement accuracy. Here, the performance of a different method for measuring RIXS, i.e. photoelectron spectrometry for analysis of X‐rays (PAX), is computationally investigated. This method transforms the X‐ray measurement problem of RIXS to an electron measurement problem, enabling use of high‐throughput, compact electron spectrometers. X‐rays to be measured are incident on a converter material and the energy distribution of the resultant photoelectrons, the PAX spectrum, is measured with an electron spectrometer. A deconvolution algorithm for analysis of such PAX data is proposed. It is shown that the deconvolution algorithm works well on data recorded with ∼0.5 eV resolution. Additional simulations show the potential of PAX for estimation of RIXS features with smaller widths. For simulations using the 3d levels of Ag as a converter material, and with 105 simulated detected electrons, it is estimated that features with a few hundred meV width can be accurately estimated in a model RIXS spectrum. For simulations using a sharp Fermi edge to encode RIXS spectra, it is estimated that one can accurately distinguish 100 meV FWHM peaks separated by 45 meV with 105 simulated detected electrons that were photoemitted from within 0.4 eV of the Fermi level. [ABSTRACT FROM AUTHOR]

A prevalent class of challenges in modern physics are inverse problems, where physical quantities must be extracted from experimental measurements. End-to-end machine learning approaches to inverse problems typically require constructing sophisticated estimators to achieve the desired accuracy, largely because they need to learn the complex underlying physical model. Here, we discuss an alternative paradigm: by making the physical model auto-differentiable we can construct a neural surrogate to represent the unknown physical quantity sought, while avoiding having to relearn the known physics entirely. We dub this process surrogate training embedded in physics (STEP) and illustrate that it generalizes well and is robust against overfitting and significant noise in the data. We demonstrate how STEP can be applied to perform dynamic kernel deconvolution to analyse resonant inelastic X-ray scattering spectra and show that surprisingly simple estimator architectures suffice to extract the relevant physical information., Competing Interests: We declare we have no competing interests., (© 2024 The Authors.)

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 , and both have found to positively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na 0.67 Mg x Ni 0.33- x Mn 0.67 O 2 (x < 0 < 0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO 4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed., (open access.)

The electronic structure and the electron‐phonon couplings in a novel mass‐production‐compatible Al2O3/TiO2 2D electron system (2DES) are investigated using resonant inelastic soft X‐ray scattering. The experimental data from the samples of various TiO2 thicknesses unequivocally show that the Ti3+ state indeed exists at the deep interface to serve as an n‐type dopant for the 2DES. The electronic structure of Ti3+ species is scrutinized as entirely separated from that of the Ti4+ host lattice. Furthermore, features of sub‐eV energy loss phonon modes are clearly observed, indicating substantial electron‐phonon coupling effects. Such low energy loss features are enhanced in thinner TiO2 samples, implying that polaronic local lattice deformation is enhanced due to the presence of Ti3+. These findings suggest that the 2DES properties can be controlled via well‐established TiO2 engineering, thereby enthroning the binary oxide heterostructure as a promising candidate for 2DES device applications. [ABSTRACT FROM AUTHOR]

In resonant inelastic X-ray scattering (RIXS), core hole resonance modes are used to enhance coupling between photons and low energy electronic degrees of freedom. Resonating with shallow core holes accessed in the extreme ultraviolet (EUV) can provide greatly improved energy resolution at standard resolving power, but has been found to often yield qualitatively different spectra than similar measurements performed with higher energy X-rays. This paper uses experimental data and multiplet-based numerical simulations for the M-edges of Co-, Ni-, and Cu-based Mott insulators to review the properties that distinguish EUV RIXS from more commonly performed higher energy measurements. Key factors such as the origin of the strong EUV elastic line and advantages of EUV spectral functions over soft X-ray RIXS for identifying intrinsic excitation line shapes are discussed.

We report on the development of a high‐resolution and highly efficient beamline for soft X‐ray resonant inelastic X‐ray scattering (RIXS) located at the Taiwan Photon Source. This beamline adopts an optical design that uses an active grating monochromator (AGM) and an active grating spectrometer (AGS) to implement the energy compensation principle of grating dispersion. Active gratings are utilized to diminish defocus, coma and higher‐order aberrations, as well as to decrease the slope errors caused by thermal deformation and optical polishing. The AGS is mounted on a rotatable granite platform to enable momentum‐resolved RIXS measurements with scattering angles over a wide range. Several high‐precision instruments developed in‐house for this beamline are described briefly. The best energy resolution obtained from this AGM–AGS beamline was 12.4 meV at 530 eV, achieving a resolving power of 4.2 × 104, while the bandwidth of the incident soft X‐rays was kept at 0.5 eV. To demonstrate the scientific impact of high‐resolution RIXS, we present an example of momentum‐resolved RIXS measurements on a high‐temperature superconducting cuprate, i.e. La2–xSrxCuO4. The measurements reveal the A1g buckling phonons in superconducting cuprates, opening a new opportunity to investigate the coupling between these phonons and charge‐density waves. [ABSTRACT FROM AUTHOR]

Polymeric carbon nitride (PCN) is a promising class of materials for solar‐to‐chemical energy conversion. The increase of the photocatalytic activity of PCN is often achieved by the incorporation of heteroatoms, whose impact on the electronic structure of PCN remains poorly explored. This work reveals that the local electronic structure of PCN is strongly altered by doping with sulfur and iron using X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS). From XAS at the carbon and nitrogen K‐edges, sulfur atoms are found to mostly affect carbon atoms, in contrast to iron doping mostly altering nitrogen sites. In RIXS at the nitrogen K‐edge, a vibrational progression, affected by iron doping, is evidenced, which is attributed to a vibronic coupling between excited electrons in nitrogen atoms and C–N stretching modes in PCN heterocycling rings. This work opens new perspectives for the characterization of vibronic coupling in polymeric photocatalysts. [ABSTRACT FROM AUTHOR]