Presence of Delocalized Ti 3d Electrons in Ultrathin Single-Crystal SrTiO3.

Strontium titanate (STO), with a wide spectrum of emergent properties such as ferroelectricity and superconductivity, has received significant attention in the community of strongly correlated materials. In the strain-free STO film grown on the SrRuO3 buffer layer, the existing polar nanoregions can facilitate room-temperature ferroelectricity when the STO film thickness approaches 10 nm. Here we show that around this thickness scale, the freestanding STO films without the influence of a substrate show the tetragonal structure at room temperature, contrasting with the cubic structure seen in bulk form. The spectroscopic measurements reveal the modified Ti-O orbital hybridization that causes the Ti ion to deviate from its nominal 4+ valency (3d0 configuration) with excess delocalized 3d electrons. Additionally, the Ti ion in TiO6 octahedron exhibits an off-center displacement. The inherent symmetry lowering in ultrathin freestanding films offers an alternative way to achieve tunable electronic structures that are of paramount importance for future technological applications.

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites.

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO2 ), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C2 compounds with a high CO2 conversion rate remains challenging for current AP technologies. We performed CO2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C2 H5 OH) selectivity of>99 % and a CO2 conversion rate of up to 17.1 mmol gcat -1 h-1 with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO2 to C2 H5 OH conversion pathway.

Realization of Electron Antidoping by Modulating the Breathing Distortion in BaBiO3.

The recent proposal of antidoping scheme breaks new ground in conceiving conversely functional materials and devices; yet, the few available examples belong to the correlated electron systems. Here, we demonstrate both theoretically and experimentally that the main group oxide BaBiO3 is a model system for antidoping using oxygen vacancies. The first-principles calculations show that the band gap systematically increases due to the strongly enhanced Bi-O breathing distortions away from the vacancies and the annihilation of Bi 6s/O 2p hybridized conduction bands near the vacancies. Our further spectroscopic experiments confirm that the band gap increases systematically with electron doping, with a maximal gap enhancement of ∼75% when the film's stoichiometry is reduced to BaBiO2.75. These results unambiguously demonstrate the remarkable antidoping effect in a material without strong electron correlations and underscores the importance of bond disproportionation in realizing such an effect.

Photon-counting MCP/Timepix detectors for soft X-ray imaging and spectroscopic applications.

Detectors with microchannel plates (MCPs) provide unique capabilities to detect single photons with high spatial (<10 µm) and timing (<25 ps) resolution. Although this detection technology was originally developed for applications with low event rates, recent progress in readout electronics has enabled their operation at substantially higher rates by simultaneous detection of multiple particles. In this study, the potential use of MCP detectors with Timepix readout for soft X-ray imaging and spectroscopic applications where the position and time of each photon needs to be recorded is investigated. The proof-of-principle experiments conducted at the Advanced Light Source demonstrate the capabilities of MCP/Timepix detectors to operate at relatively high input counting rates, paving the way for the application of these detectors in resonance inelastic X-ray scattering and X-ray photon correlation spectroscopy (XPCS) applications. Local count rate saturation was investigated for the MCP/Timepix detector, which requires optimization of acquisition parameters for a specific scattering pattern. A single photon cluster analysis algorithm was developed to eliminate the charge spreading effects in the detector and increase the spatial resolution to subpixel values. Results of these experiments will guide the ongoing development of future MCP devices optimized for soft X-ray photon-counting applications, which should enable XPCS dynamics measurements down to sub-microsecond timescales.

Robust Surface States and Coherence Phenomena in Magnetically Alloyed SmB_{6}.

Samarium hexaboride is a candidate for the topological Kondo insulator state, in which Kondo coherence is predicted to give rise to an insulating gap spanned by topological surface states. Here we investigate the surface and bulk electronic properties of magnetically alloyed Sm_{1-x}M_{x}B_{6} (M=Ce, Eu), using angle-resolved photoemission spectroscopy and complementary characterization techniques. Remarkably, topologically nontrivial bulk and surface band structures are found to persist in highly modified samples with up to 30% Sm substitution and with an antiferromagnetic ground state in the case of Eu doping. The results are interpreted in terms of a hierarchy of energy scales, in which surface state emergence is linked to the formation of a direct Kondo gap, while low-temperature transport trends depend on the indirect gap.

A design of resonant inelastic X-ray scattering (RIXS) spectrometer for spatial- and time-resolved spectroscopy.

The optical design of a Hettrick-Underwood-style soft X-ray spectrometer with Wolter type 1 mirrors is presented. The spectrometer with a nominal length of 3.1 m can achieve a high resolving power (resolving power higher than 10000) in the soft X-ray regime when a small source beam (<3 µm in the grating dispersion direction) and small pixel detector (5 µm effective pixel size) are used. Adding Wolter mirrors to the spectrometer before its dispersive elements can realize the spatial imaging capability, which finds applications in the spectroscopic studies of spatially dependent electronic structures in tandem catalysts, heterostructures, etc. In the pump-probe experiments where the pump beam perturbs the materials followed by the time-delayed probe beam to reveal the transient evolution of electronic structures, the imaging capability of the Wolter mirrors can offer the pixel-equivalent femtosecond time delay between the pump and probe beams when their wavefronts are not collinear. In combination with some special sample handing systems, such as liquid jets and droplets, the imaging capability can also be used to study the time-dependent electronic structure of chemical transformation spanning multiple time domains from microseconds to nanoseconds. The proposed Wolter mirrors can also be adopted to the existing soft X-ray spectrometers that use the Hettrick-Underwood optical scheme, expanding their capabilities in materials research.

Disparate Exciton-Phonon Couplings for Zone-Center and Boundary Phonons in Solid-State Graphite.

The exciton-phonon coupling in highly oriented pyrolytic graphite is studied using resonant inelastic x-ray scattering (RIXS) spectroscopy. With ∼70 meV energy resolution, multiple low energy excitations associated with coupling to phonons can be clearly resolved in the RIXS spectra. Using resonance dependence and the closed form for RIXS cross section without considering the intermediate state mixing of phonon modes, the dimensionless coupling constant g is determined to be 5 and 0.35, corresponding to the coupling strength of 0.42 eV+/-20 meV and 0.20 eV+/-20 meV, for zone center and boundary phonons, respectively. The reduced g value for the zone-boundary phonon may be related to its double resonance nature.

Rhombohedral prussian white as cathode for rechargeable sodium-ion batteries.

A novel air-stable sodium iron hexacyanoferrate (R-Na1.92Fe[Fe(CN)6]) with rhombohedral structure is demonstrated to be a scalable, low-cost cathode material for sodium-ion batteries exhibiting high capacity, long cycle life, and good rate capability. The cycling mechanism of the iron redox is clarified and understood through synchrotron-based soft X-ray absorption spectroscopy, which also reveals the correlation between the physical properties and the cell performance of this novel material. More importantly, successful preparation of a dehydrated iron hexacyanoferrate with high sodium-ion concentration enables the fabrication of a discharged sodium-ion battery with a non-sodium metal anode, and the manufacturing feasibility of low cost sodium-ion batteries with existing lithium-ion battery infrastructures has been tested.

Spectroscopic Determination of the Atomic f-Electron Symmetry Underlying Hidden Order in URu2Si2.

The low-temperature hidden-order state of URu2Si2 has long been a subject of intense speculation, and is thought to represent an as-yet-undetermined many-body quantum state not realized by other known materials. Here, x-ray absorption spectroscopy and high-resolution resonant inelastic x-ray scattering are used to observe electronic excitation spectra of URu2Si2, as a means to identify the degrees of freedom available to constitute the hidden-order wave function. Excitations are shown to have symmetries that derive from a correlated 5f(2) atomic multiplet basis that is modified by itinerancy. The features, amplitude, and temperature dependence of linear dichroism are in agreement with ground states that closely resemble the doublet Γ5 crystal field state of uranium.

Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes.

A multiplexed high-resolution imaging spectrometer for resonant inelastic soft X-ray scattering spectroscopy.

The optical design of a two-dimensional imaging soft X-ray spectrometer is described. A monochromator will produce a dispersed spectrum in a narrow vertical illuminated stripe (∼2 µm wide by ∼2 mm tall) on a sample. The spectrometer will use inelastically scattered X-rays to image the extended field on the sample in the incident photon energy direction (vertical), resolving the incident photon energy. At the same time it will image and disperse the scattered photons in the orthogonal (horizontal) direction, resolving the scattered photon energy. The principal challenge is to design a system that images from the flat-field illumination of the sample to the flat field of the detector and to achieve sufficiently high spectral resolution. This spectrometer provides a completely parallel resonant inelastic X-ray scattering measurement at high spectral resolution (∼30,000) over the energy bandwidth (∼5 eV) of a soft X-ray absorption resonance.

Low-energy quasi-circular electron correlations with charge order wavelength in Bi2Sr2CaCu2O8+δ.

Most resonant inelastic x-ray scattering (RIXS) studies of dynamic charge order correlations in the cuprates have focused on the high-symmetry directions of the copper oxide plane. However, scattering along other in-plane directions should not be ignored as it may help understand, for example, the origin of charge order correlations or the isotropic scattering resulting in strange metal behavior. Our RIXS experiments reveal dynamic charge correlations over the qx-qy scattering plane in underdoped Bi2Sr2CaCu2O8+δ. Tracking the softening of the RIXS-measured bond-stretching phonon, we show that these dynamic correlations exist at energies below approximately 70 meV and are centered around a quasi-circular manifold in the qx-qy scattering plane with radius equal to the magnitude of the charge order wave vector, qCO. This phonon-tracking procedure also allows us to rule out fluctuations of short-range directional charge order (i.e., centered around [qx = ±qCO, qy = 0] and [qx = 0, qy = ±qCO]) as the origin of the observed correlations.

Phase transformation and lithiation effect on electronic structure of Li(x)FePO4: an in-depth study by soft X-ray and simulations.

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in Li(x)FePO(4) nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of Li(x)FePO(4) nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high-resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first-principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO(4) single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the Li(x)FePO(4) system.

Could Irradiation Introduce Oxidized Oxygen Signals in Resonant Inelastic X-ray Scattering of Battery Electrodes?

The characterization of oxidized oxygen states through high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) has become a crucial approach for studying the oxygen redox activities in high-energy battery cathodes. However, this approach has been recently challenged due to the concern of irradiation damage. Here we revisited a typical Li-rich electrode, Li1.144Ni0.136Mn0.544Co0.136O2, in both lithiated and delithiated states and evaluated the X-ray irradiation effect in the lengthy mRIXS experiments. Our results show that irradiation cannot introduce any oxidized oxygen feature, and the features of oxidized oxygen are weakened with a high X-ray dose. The results confirm again that mRIXS detects the intrinsic oxidized oxygen state in battery electrodes. However, the distinct irradiation effects in different systems imply that irradiation could selectively target the least stable elemental or chemical states, which should be analyzed with caution in the study of active chemical states.

Controlled Experiments and Optimized Theory of Absorption Spectra of Li Metal and Salts.

Investigation of Li metal and ionic compounds through experimental and theoretical spectroscopy has been of tremendous interest due to their prospective applications in Li-metal and Li-ion batteries. Li K-edge soft X-ray absorption spectroscopy (sXAS) provides the most direct spectroscopic characterization; unfortunately, due to the low core-level energy and the highly reactive surface, Li-K sXAS of Li metal has been extremely challenging, as evidenced by many controversial reports. Here, through controlled and ultra-high energy resolution experiments of two kinds of in situ prepared samples, we report the intrinsic Li-K sXAS of Li-metal that displays a prominent leading peak that has not been revealed before. Furthermore, theoretical simulations show that, due to the low number of valence electrons in Li, the Li-K sXAS is strongly affected by the response of the valence electrons to the core hole. We successfully reproduce the Li-K sXAS by state-of-the-art calculations with considerations of a number of relevant parameters such as temperature, energy resolution, and, especially, contributions from transitions which are forbidden in the single-particle treatment. Such a comparative experimental and theoretical investigation is further extended to a series of Li ionic compounds, which highlight the importance of considering the total and single-particle energies for obtaining an accurate alignment of the spectra. Our work provides the first reliable Li-K sXAS of the Li metal surface with advanced theoretical calculations. The experimental and theoretical results provide a critical benchmark for studying Li chemistry in both metallic and ionic states.

Spectroscopic characterization of electronic structures of ultra-thin single crystal La0.7Sr0.3MnO3.

We have successfully fabricated high quality single crystalline La0.7Sr0.3MnO3 (LSMO) film in the freestanding form that can be transferred onto silicon wafer and copper mesh support. Using soft x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopy in transmission and reflection geometries, we demonstrate that the x-ray emission from Mn 3s-2p core-to-core transition (3sPFY) seen in the RIXS maps can represent the bulk-like absorption signal with minimal self-absorption effect around the Mn L3-edge. Similar measurements were also performed on a reference LSMO film grown on the SrTiO3 substrate and the agreement between measurements substantiates the claim that the bulk electronic structures can be preserved even after the freestanding treatment process. The 3sPFY spectrum obtained from analyzing the RIXS maps offers a powerful way to probe the bulk electronic structures in thin films and heterostructures when recording the XAS spectra in the transmission mode is not available.

Full Energy Range Resonant Inelastic X-ray Scattering of O2 and CO2: Direct Comparison with Oxygen Redox State in Batteries.

The evolving oxygen state plays key roles in the performance and stability of high-energy batteries involving oxygen redox reactions. Here, high-efficiency full energy range O-K mapping of resonant inelastic X-ray scattering (mRIXS) was collected from O2 (O0) and CO2 (O2- with strong covalency) molecules and compared directly with Li2O2 (O-) and the oxidized oxygen state in representative Na/Li-ion battery electrodes. Our results confirm again that the critical mRIXS feature around the 523.7 eV emission energy is from intrinsically oxidized oxygen, but not from the highly covalent oxygen state (CO2). The comparison of the mRIXS profile of the four different oxygen states, i.e., O2-, O-, On- (0 < n < 2), and O0, reveals that oxygen redox states in batteries have distinct widths and positions along the excitation energy compared with Li2O2 and O2. The nature of the oxidized oxygen state in oxide electrodes is thus beyond a simple molecular configuration of either peroxide or O2.

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

A setup for extreme-ultraviolet ultrafast angle-resolved photoelectron spectroscopy at 50-kHz repetition rate.

Time- and angle-resolved photoelectron spectroscopy (trARPES) is a powerful method to track the ultrafast dynamics of quasiparticles and electronic bands in energy and momentum space. We present a setup for trARPES with 22.3 eV extreme-ultraviolet (XUV) femtosecond pulses at 50-kHz repetition rate, which enables fast data acquisition and access to dynamics across momentum space with high sensitivity. The design and operation of the XUV beamline, pump-probe setup, and ultra-high vacuum endstation are described in detail. By characterizing the effect of space-charge broadening, we determine an ultimate source-limited energy resolution of 60 meV, with typically 80-100 meV obtained at 1-2 × 1010 photons/s probe flux on the sample. The instrument capabilities are demonstrated via both equilibrium and time-resolved ARPES studies of transition-metal dichalcogenides. The 50-kHz repetition rate enables sensitive measurements of quasiparticles at low excitation fluences in semiconducting MoSe2, with an instrumental time resolution of 65 fs. Moreover, photo-induced phase transitions can be driven with the available pump fluence, as shown by charge density wave melting in 1T-TiSe2. The high repetition-rate setup thus provides a versatile platform for sensitive XUV trARPES, from quenching of electronic phases down to the perturbative limit.

High temperature singlet-based magnetism from Hund's rule correlations.

Uranium compounds can manifest a wide range of fascinating many-body phenomena, and are often thought to be poised at a crossover between localized and itinerant regimes for 5f electrons. The antiferromagnetic dipnictide USb2 has been of recent interest due to the discovery of rich proximate phase diagrams and unusual quantum coherence phenomena. Here, linear-dichroic X-ray absorption and elastic neutron scattering are used to characterize electronic symmetries on uranium in USb2 and isostructural UBi2. Of these two materials, only USb2 is found to enable strong Hund's rule alignment of local magnetic degrees of freedom, and to undergo distinctive changes in local atomic multiplet symmetry across the magnetic phase transition. Theoretical analysis reveals that these and other anomalous properties of the material may be understood by attributing it as the first known high temperature realization of a singlet ground state magnet, in which magnetism occurs through a process that resembles exciton condensation.