Showing papers by "Makina Yabashi published in 2023"

Probing lithium mobility at a solid electrolyte surface

Abstract: Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.

Transonic Dislocation Propagation in Diamond

Abstract: The motion of line defects (dislocations), the primary driver of plasticity, has been studied for almost a century but one of the most fundamental questions remains unsolved: what defines the maximum speed at which dislocations can propagate? Early interpretations based on elasticity theory suggest that dislocation motion should not exceed the transverse wave speed, but recent models and atomistic simulations predict that transverse wave speed is a forbidden speed but not the upper limit. We use femtosecond x-ray radiography to observe how dislocations in shock-compressed single-crystalline diamond travel with the plastic shock wavefront. The observed dislocation motions in the diamond show that dislocations can move faster than the transverse wave speed. As the ultrafast motion of dislocations causes unique behavior by which solids strengthen or fail, understanding the upper limit of dislocation mobility is critical to accurately model, predict, and control the mechanical properties of materials under extreme conditions.

Atomic-scale observation of solvent reorganization influencing photoinduced structural dynamics in a copper complex photosensitizer

Abstract: Photochemical reactions in solution are governed by a complex interplay between transient intramolecular electronic and nuclear structural changes and accompanying solvent rearrangements. State-of-the-art time-resolved X-ray solution scattering has emerged in the last decade as a powerful technique to observe solute and solvent motions in real time. However, disentangling solute and solvent dynamics and how they mutually influence each other remains challenging. Here, we simultaneously measure femtosecond X-ray emission and scattering to track both the intramolecular and solvation structural dynamics following photoexcitation of a solvated copper photosensitizer. Quantitative analysis assisted by molecular dynamics simulations reveals a two-step ligand flattening strongly coupled to the solvent reorganization, which conventional optical methods could not discern. First, a ballistic flattening triggers coherent motions of surrounding acetonitrile molecules. In turn, the approach of acetonitrile molecules to the copper atom mediates the decay of intramolecular coherent vibrations and induces a further ligand flattening. These direct structural insights reveal that photoinduced solute and solvent motions can be intimately intertwined, explaining how the key initial steps of light harvesting are affected by the solvent on the atomic time and length scale. Ultimately, this work takes a step forward in understanding the microscopic mechanisms of the bidirectional influence between transient solvent reorganization and photoinduced solute structural dynamics.

Indirect evidence for elemental hydrogen in laser-compressed hydrocarbons

Abstract: We demonstrate a significantly simplified experimental approach for investigating liquid metallic hydrogen, which is crucial to understand the internal structure and evolution of giant planets. Plastic samples were shockcompressed and then probed by short pulses of X-rays generated by free electron lasers. By comparison with ab initio simulations, we provide indirect evidence for the creation of elemental hydrogen in shock-compressed plastics at ∼150GPa and ∼5,000K and thus in a regime where hydrogen is predicted to be metallic. Being the most common form of condensed matter in our solar system, and ostensibly the simplest of all elements, hydrogen is the model case for many theoretical studies and we provide a new possibility to benchmark models for conditions with extreme pressures and temperatures. Moreover, this approach will also allow to probe the chemical behavior of metallic hydrogen in mixture with other elements, which, besides its importance for planetary physics, may open up promising pathways for the synthesis of new materials.Received 25 April 2022Accepted 10 April 2023DOI:https://doi.org/10.1103/PhysRevResearch.5.L022023Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasHigh-energy-density plasmasHigh-pressure studiesLaboratory studies of space & astrophysical plasmasMaterialsShock wavesTechniquesDFT+DMFTX-ray diffractionPlasma Physics

Seeded Stimulated X-ray Emission at 5.9 keV

Abstract: X-ray free-electron lasers (XFELs) provide intense pulses that can generate stimulated X-ray emission, a phenomenon that has been observed and studied in materials ranging from neon to copper. Two schemes have been employed: amplified spontaneous emission (ASE) and seeded stimulated emission (SSE), where a second color XFEL pulse provides the seed. Both phenomena are currently explored for coherent X-ray laser sources and spectroscopy. Here, we report measurements of ASE and SSE of the 5.9 keV Mn K α 1 fluorescence line from a 3.9 molar NaMnO 4 solution, pumped with 7 femtosecond FWHM XFEL pulses at 6.6 keV. We observed ASE at a pump pulse intensity of 1.7×10 19 W/cm 2 , consistent with earlier findings. We observed SSE at dramatically reduced pump pulse intensities down to 1.1×10 17 W/cm 2 . These intensities are well within the range of many existing XFEL instruments, which supports the experimental feasibility of SSE as a tool to generate coherent X-ray pulses, spectroscopic studies of transition metal complexes, and other applications.

Application of soft X-ray microspectroscopic analyses to architectural structures – a case study on ceramic-tile/adhesive/mortar-structured composite materials

Abstract: Abstract Synchrotron radiation (SR)-based soft X-ray (SX) microspectroscopy has been applied as a promising analytical method to investigate architectural structures that comprise ceramic-tile/adhesive/mortar-structured composite materials. Microprobe X-ray fluorescence (µXRF) spectra, elemental distribution maps and microprobe near-edge X-ray absorption fine structure (µNEXAFS) spectra were observed near each interface in the composite materials using an SX-beam with a beam size of 1–2 µm full-width at half-maximum (FWHM). Elemental distribution maps for O, Na, Mg, Al, and Si were obtained to clearly visualize the interfaces of the composite materials with pixel sizes of 10 and 1 µm with the aid of line profile analyses. When the photon flux of the focused SX-beam reached approximately 8 × 108 ph/s, the critical dose time ( ) for the adhesive was estimated to be 30 min ( is the time at which the peak intensity of a specific chemical state in the µNEXAFS spectrum decreases to 1/e of the initial undamaged state due to radiation damage). We demonstrated the capability of the proposed method to survey local information regarding element-specific chemical states at the ceramic-tile/adhesive and adhesive/mortar interfaces before the adhesive is severely damaged due to the intense SX-beam.

Thermus thermophilus polyploid cells directly imaged by X-ray laser diffraction.

Abstract: Thermus thermophilus is reportedly polyploid and carries four to five identical genome copies per cell, based on molecular biological experiments. To directly detect polyploidy in this bacterium, we performed live cell imaging by X-ray free-electron laser (XFEL) diffraction and observed its internal structures. The use of femtosecond XFEL pulses enables snapshots of live, undamaged cells. For successful XFEL imaging, we developed a bacterial culture method using a starch- and casein-rich medium that produces a predominance of rod-shaped cells shorter than the focused XFEL beam size, which is slightly smaller than 2 µm. When cultured in the developed medium, the length of T. thermophilus cells, which is typically ~4 µm, was less than half its usual length. We placed living cells in a micro-liquid enclosure array and successively exposed each enclosure to a single XFEL pulse. A cell image was successfully obtained by the coherent diffractive imaging technique with iterative phase retrieval calculations. The reconstructed cell image revealed five peaks, which are most likely to be nucleoids, arranged in a row in the polyploid cell without gaps. This study demonstrates that XFELs offer a novel approach for visualizing the internal nanostructures of living, micrometer-sized, polyploid bacterial cells.

Capturing transient core-to-core resonances in Kr in intense extreme-ultraviolet laser fields by electron-ion coincidence spectroscopy

Abstract: Resonances between core-hole states have been long hypothesized to understand dynamics of atoms and molecules exposed to intense XFEL pulses, but evaded clear identification due to their transient nature. The authors report clear evidence of core-to-core resonances by electron-ion coincidence spectroscopy on Kr atoms and elucidate the importance in nonlinear electronic responses of matter to high-frequency laser fields.

Femtosecond reduction of atomic scattering factors triggered by intense x-ray pulse

Abstract: X-ray diffraction of silicon irradiated with tightly focused femtosecond x-ray pulses (photon energy: 11.5 keV, pulse duration: 6 fs) was measured at various x-ray intensities up to $4.6\times10^{19}$ W/cm$^2$. The measurement reveals that the diffraction intensity is highly suppressed when the x-ray intensity reaches of the order of $10^{19}$ W/cm$^2$. With a dedicated simulation, we confirm the observed reduction of the diffraction intensity is attributed to the femtosecond change in individual atomic scattering factors due to the ultrafast creation of highly ionized atoms through photoionization, Auger decay, and subsequent collisional ionization. We anticipate that this ultrafast reduction of atomic scattering factor will be a basis for new x-ray nonlinear techniques, such as pulse shortening and contrast variation x-ray scattering.

Ultrafast Control of Crystal Structure in a Topological Charge-Density-Wave Material

Abstract: Optical control of crystal structures is a promising route to change physical properties including topological nature of a targeting material. Time-resolved X-ray diffraction measurements using the X-ray free-electron laser are performed to study the ultrafast lattice dynamics of VTe$_2$, which shows a unique charge-density-wave (CDW) ordering coupled to the topological surface states as a first-order phase transition. A significant oscillation of the CDW amplitude mode is observed at a superlattice reflection as well as Bragg reflections. The frequency of the oscillation is independent of the fluence of the pumping laser, which is prominent to the CDW ordering of the first-order phase transition. Furthermore, the timescale of the photoinduced 1$T^{\prime\prime}$ to 1$T$ phase transition is independent of the period of the CDW amplitude mode.

Detecting driving potentials at the buried SiO2 nanolayers in solar cells by chemical-selective nonlinear x-ray spectroscopy

Abstract: We present an approach to selectively examine an asymmetric potential in the buried layer of solar cell devices by means of nonlinear x-ray spectroscopy. Detecting second harmonic generation signals while resonant to the SiO2 core level, we directly observe existence of the band bending effect in the SiO2 nanolayer, buried in the heterostructures of Al/LiF/SiO2/Si, TiO2/SiO2/Si, and Al2O3/SiO2/Si. The results demonstrate high sensitivity of the method to the asymmetric potential that determines performance of functional materials for photovoltaics or other optoelectronic devices.

Ionization of Xenon Clusters by a Hard X-ray Laser Pulse

Abstract: Ultrashort pulse X-ray free electron lasers (XFFLs) provided us with an unprecedented regime of X-ray intensities, revolutionizing ultrafast structure determination and paving the way to the novel field of non-linear X-ray optics. While pioneering studies revealed the formation of a nanoplasma following the interaction of an XFEL pulse with nanometer-scale matter, nanoplasma formation and disintegration processes are not completely understood, and the behavior of trapped electrons in the electrostatic potential of highly charged species is yet to be decrypted. Here we report the behavior of the nanoplasma created by a hard X-ray pulse interacting with xenon clusters by using electron and ion spectroscopy. To obtain a deep insight into the formation and disintegration of XFEL-ignited nanoplasma, we studied the XFEL-intensity and cluster-size dependencies of the ionization dynamics. We also present the time-resolved data obtained by a near-infrared (NIR) probe pulse in order to experimentally track the time evolution of plasma electrons distributed in the XFEL-ignited nanoplasma. We observed an unexpected time delay dependence of the ion yield enhancement due to the NIR pulse heating, which demonstrates that the plasma electrons within the XFEL-ignited nanoplasma are inhomogeneously distributed in space.

Figure correction of a Wolter mirror master mandrel by organic abrasive machining.

Abstract: In this study, figure correction of a master mandrel of a Wolter mirror by organic abrasive machining (OAM) was demonstrated. In OAM, a flow of slurry, dispersed with organic particles, locally removes the surface of a workpiece in contact with a rotating machining tool. A computer-controlled machining system was used to perform the selective removal of a fused silica surface at a spatial resolution of 200 µm. A master mandrel of a Wolter mirror for soft x-ray microscopes was fabricated with a figure accuracy of <1 nm root mean square, which is sufficient for diffraction-limited imaging at a wavelength of 10 nm.

Fabrication of atomically precise, super smooth, and damage-free x-ray optics

Abstract: An atomically precise, super smooth, and damage-free surface is highly demanded for x-ray mirrors, multilayer optics, channel-cut crystal monochromators (CCM), and gratings. An ultra-precision optic with a figure error of several nm is crucial for single-nanometer spatial resolution, signal strength, and contrast. Moreover, sub-angstrom root-mean-square surface roughness is beneficial for high reflectivity and the lowest unwanted scattering. Additionally, a damage-free surface with no alter layer is greatly desired for CCM and grating substrates because it is essential for the high reflectivity of the CCM and the uniform etching rate of the grating’s ruling. In the manufacturing of x-ray mirrors, to obtain the desired figure error, a non-contact figuring method, such as ion beam figuring (IBF), plasma chemical vaporization machining (PCVM), or Elastic Emission Machining (EEM), is usually employed thanks to its high controllability and stability. EEM has proved the best performance in terms of achieving a low figure error and maintaining a good surface roughness. After shaping/figuring, a finishing method is usually applied to improve its surface roughness without distorting its figure error. Recently, Catalyst-Referred Etching (CARE) has realized its potential and applicability to x-ray mirror manufacturing as a finishing method. Thanks to its removal mechanism, a highly ordered surface with a root-mean-square of 0.03 nm RMS is attained. In the polishing of a CCM, because a mechanical method is usually used to polish its surface at the narrow gap, the residual mechanical damage induced a low reflectivity and low spatial resolution. PCVM with a wire electrode has recently been proposed and demonstrated its excellent performance. The damage-free surface of a CCM with a gap of less than 100µm has been successfully realized by PCVM. In this paper, recent achievements in figuring (EEM), surface finishing (CARE), and damage removal (PCVM) are presented and discussed.

Bulk superconductivity in Pb-substituted BiS$_{\bf 2}$-based compounds studied by hard-x-ray spectroscopy

Abstract: In this study, we investigate the bulk electronic structure of Pb-substituted LaO$_{0.5}$F$_{0.5}$BiS$_2$ single crystals, using two types of hard-x-ray spectroscopy. High-energy-resolution fluorescence-detected x-ray absorption spectroscopy revealed a spectral change at low temperatures. Using density functional theory (DFT) simulations, we find that the temperature-induced change originates from a structural phase transition, similar to the pressure-induced transition in LaO$_{0.5}$F$_{0.5}$BiS$_2$. This finding suggests that the mechanism of bulk superconductivity induced by Pb substitution is the same as that under high pressure. Furthermore, a novel low-valence state with a mixture of divalent and trivalent Bi ions is discovered using hard x-ray photoemission spectroscopy with the aid of DFT calculations.

Ultrafast Subpicosecond Magnetisation Of a Two-Dimensional Ferromagnet.

Abstract: Strong spin-charge interactions in several ferromagnets are expected to lead to subpicosecond (sub-ps) magnetisation of the magnetic materials through control of the carrier characteristics via electrical means, which is essential for ultrafast spin-based electronic devices. Thus far, ultrafast control of magnetisation has been realized by optically pumping a large number of carriers into the d or f orbitals of a ferromagnet; however, it is extremely challenging to be implemented by electrical gating. This work demonstrates a new method for sub-ps magnetisation manipulation, called wavefunction engineering, in which w e control only the spatial distribution (wavefunction) of s (or p) electrons and require no change in the total carrier density. Using a ferromagnetic semiconductor (FMS) (In,Fe)As quantum well (QW), w e observe instant enhancement, as fast as 600 fs, of the magnetisation upon irradiating a femtosecond (fs) laser pulse. O ur analysis shows that the instant enhancement of the magnetisation is induced when the two-dimensional (2D) electron wavefunctions (WFs) in the FMS QW are rapidly moved by a photo-Dember electric field formed by an asymmetric distribution of the photocarriers. Because this WF engineering method can be equivalently implemented by applying a gate electric field, o ur results open a new way to realise ultrafast magnetic storage and spin-based information processing in present electronic systems. This article is protected by copyright. All rights reserved.

Nonisotropic atomic motion in a nonthermal phase transition of diamond (Conference Presentation)

Abstract: X-ray Free Electron Laser (XFEL) radiation may transform diamond into graphite. Two X-ray pulses were used; the first as pump to trigger the phase transition and the second as probe performing X-ray diffraction. The experiment was performed at the SACLA XFEL facility at the beamline 3 experimental hutch 5. The samples were polycrystalline diamond. The pump and probe photon energies were 7 and 10.5 keV, respectively, and the delay between the X-ray pulses was varied from 0 to 286 fs. To provide a range of energy densities, the X-ray focus was adjusted between 150 nm and 1 um. The (111), (220) and (311) diffraction peaks were observed. The intensity of each diffraction peak decreased with time indicating a disordering of the crystal lattice. From a Debye-Waller analysis, the root-mean-square (rms) atomic displacement perpendicular to particular lattice planes are calculated. At higher fluences, the rms atomic displacement perpendicular to the (111) planes is significantly larger than that perpendicular to the (220) or (311) planes. By accepting two successive XFEL pulses at a time delay of 33 ms, graphite (002) diffraction was observed beginning at a threshold dose of 1.7 eV/atom. The experimental results will be compared with calculations using a hybrid model based on tight-binding molecular dynamics.

Ambient temperature structure of phosphoketolase from Bifidobacterium longum determined by serial femtosecond X-ray crystallography.

Abstract: Phosphoketolase and transketolase are thiamine diphosphate-dependent enzymes and play a central role in the primary metabolism of bifidobacteria: the bifid shunt. The enzymes both catalyze phosphorolytic cleavage of xylulose 5-phosphate or fructose 6-phosphate in the first reaction step, but possess different substrate specificity in the second reaction step, where phosphoketolase and transketolase utilize inorganic phosphate (Pi) and D-ribose 5-phosphate, respectively, as the acceptor substrate. Structures of Bifidobacterium longum phosphoketolase holoenzyme and its complex with a putative inhibitor, phosphoenolpyruvate, were determined at 2.5 Å resolution by serial femtosecond crystallography using an X-ray free-electron laser. In the complex structure, phosphoenolpyruvate was present at the entrance to the active-site pocket and plugged the channel to thiamine diphosphate. The phosphate-group position of phosphoenolpyruvate coincided well with those of xylulose 5-phosphate and fructose 6-phosphate in the structures of their complexes with transketolase. The most striking structural change was observed in a loop consisting of Gln546-Asp547-His548-Asn549 (the QN-loop) at the entrance to the active-site pocket. Contrary to the conformation of the QN-loop that partially covers the entrance to the active-site pocket (`closed form') in the known crystal structures, including the phosphoketolase holoenzyme and its complexes with reaction intermediates, the QN-loop in the current ambient structures showed a more compact conformation with a widened entrance to the active-site pocket (`open form'). In the phosphoketolase reaction, the `open form' QN-loop may play a role in providing the binding site for xylulose 5-phosphate or fructose 6-phosphate in the first step, and the `closed form' QN-loop may help confer specificity for Pi in the second step.

Forensic Discrimination of Drug Powder Based on Drug Mixing Condition Determined Using Micro Fourier Transform Infrared Spectroscopy

Abstract: The quantitative evaluation of the drug mixing condition was conducted for application in the forensic discrimination of drug powders using micro Fourier transform infrared (FT-IR) spectroscopy. Bromhexine hydrochloride (BHCl) and p-hydroxybenzoic acid (PHBA) were used as the simulated drug and additive, respectively. Equal masses of two chemicals were (1) simply mixed, (2) homogenized using agate mortar, or (3) dissolved in methanol and dried, and then (4) homogenized using agate mortar. The mixed powders dispersed on BaF2 plates were subjected to mapping analysis of micro FT-IR spectroscopy using synchrotron radiation (SR) or globar light in transmission mode with aperture sizes of 2.5 x 2.5 and 10 x 10μm2, and x–y scanning steps of 2.5 and 10 μm, respectively. The areas of the vibration bands specific to BHCl (C–N bending) and PHBA (C=O stretching) were converted to the molar contents (CBHCl, CPHBA), and the relative content ratio (RCR: CPHBA/[CBHCl + CPHBA]) was used as one mixing parameter. The resulting two-dimensional distribution map provided the relative spatial localizations of the two species, and frequency histograms with a horizontal axis of RCR were plotted to evaluate the RCR distribution. The percentage frequency of the extreme value in which RCR was 0 or 1 (%EV) was used as one mixing index. After excluding the extreme values, the coefficient of variation (CV) of the RCR distribution was used as another mixing index. The differentiation among four mixing modes could be evaluated from the standpoint of %EV and CV, and the discrimination capacity by SR instrument was superior to that by globe light instrument.

Observing soft x-ray magnetization-induced second harmonic generation at a heterojunction interface

Abstract: Second harmonic generation (SHG) spectroscopy in the visible and infrared regions has been a useful tool to selectively probe electronic properties at surfaces and interfaces. By examining variation of SHG under a magnetic field, one can also evaluate magnetic properties at the surfaces/interfaces. When multiple elements are involved in SHG, however, it is difficult to separate their contributions. In order to meet the demand of studying increasingly complex magnetic multilayer materials, element selectivity is desired. Here, using an Fe-based multilayer sample with broken inversion symmetry, we present observation of magnetization-induced SHG in the soft x-ray regime around the Fe M-shell absorption edge. Significant variation of SHG signal was captured depending on the direction of the magnetic moment, assuring sensitivity of the measurement likely enhanced by the Fe M-edge inner-shell resonance. The present methodology paves the way for element specific studies of magnetic properties at buried interfaces.