Soft X-ray Synchrotron Radiation Research Articles

Forming Bonds While Breaking Old Ones: Isomer-Dependent Formation of H3O+ from Aminobenzoic Acid During X-ray-Induced Fragmentation.

Intramolecular hydrogen transfer, a reaction where donor and acceptor sites of a hydrogen atom are part of the same molecule, is a ubiquitous reaction in biochemistry and organic synthesis. In this work, we report hydronium ion (H3O+) production from aminobenzoic acid (ABA) after core-level ionization with soft X-ray synchrotron radiation. The formation of H3O+ during the fragmentation requires that at least two hydrogen atoms migrate to one of the oxygen atoms within the molecule. The comparison of two structural isomers, ortho- and meta-ABA, revealed that the production of H3O+ depends strongly on the structure of the molecule, the ortho-isomer being much more prone to produce H3O+. The isomer-dependency suggests that the amine group acts as a donor in the hydrogen transfer process. In the case of ortho-ABA, detailed H3O+ production pathways were investigated using photoelectron-photoion-photoion coincidence (PEPIPICO) spectroscopy. It was found that H3O+ can result from a direct two-body dissociation but also from sequential fragmentation processes.

Fe2O3 for stable K-ion storage: mechanism insight into dimensional construction from stress distribution and micro-tomography.

Fe2O3 is considered a potential electrode material owing to its high theoretical capacity, low cost, and non-toxic characteristics. However, the significant volume expansion and structural degradation during charging and discharging hinder its application in potassium ion batteries. The electrochemical properties of the electrode material are primarily influenced by the diffusion efficiency of ions and the mechanics of the object. From the construction of a one dimensional structure, a three-dimensional flower-like Fe2O3 with a high specific surface and low-dimensional spherical Fe2O3 were prepared. Considering the convenience and visualization of the research, micron-scale Fe2O3 was prepared, although the larger particle size will lose part of the capacity. Notably, compared with the spherical structure, the specific capacity of the flower structure was increased by about 100%. The von Mises stress distribution on the two structures was simulated by the finite element method, revealing the mechanism of electrode failure induced by volume expansion and confirming the vital role of the multidimensional system in relieving stress concentration and improving electrochemical performance. Furthermore, synchrotron radiation soft X-ray absorption spectrum and X-ray micro-tomography revealed the phase transformation process and reaction mechanism of Fe2O3 in potassium ion batteries. The dimensional structure construction strategy reported here can provide theoretical support for modifying transition metal oxides.

Monitoring Electron Flow in Nickel Single-Atom Catalysts during Nitrogen Photofixation.

An efficient catalytic system for nitrogen (N2) photofixation generally consists of light-harvesting units, active sites, and an electron-transfer bridge. In order to track photogenerated electron flow between different functional units, it is highly desired to develop in situ characterization techniques with element-specific capability, surface sensitivity, and detection of unoccupied states. In this work, we developed in situ synchrotron radiation soft X-ray absorption spectroscopy (in situ sXAS) to probe the variation of electronic structure for a reaction system during N2 photoreduction. Nickel single-atom and ceria nanoparticle comodified reduced graphene oxide (CeO2/Ni-G) was designed as a model catalyst. In situ sXAS directly reveals the dynamic interfacial charge transfer of photogenerated electrons under illumination and the consequent charge accumulation at the catalytic active sites for N2 activation. This work provides a powerful tool to monitor the electronic structure evolution of active sites under reaction conditions for photocatalysis and beyond.

Elemental changes in heart and coronaries after breast cancer radiotherapy assessed by synchrotron radiation soft X-ray spectromicroscopy

Radiotherapy (RT) plays a pivotal role in the treatment of breast cancer (BC) and various thoracic malignancies. Radiation induced heart disease (RIHD) is one such long term toxicity which can offset the improvement in cancer specific mortality. Long term normal tissue toxicity is becoming a bigger concern, as early diagnosis and the improvement in the treatment of these cancers has led to patients surviving longer. Our research group on Physics applied to biomedical sciences has been investigating the side effects of BC treatment (RT and chemotherapy) for more than ten years. The cardiac regeneration has been studied to better understand the damage that occurs following radiation procedures in the heart tissue after many thoracic cancer treatments. One possible complication is coronary artery disease induced by irradiation after radiotherapy in thoracic area. Studies on the structures of cardiac tissue and the distribution of low atomic weight element can help to understand mechanisms associated with damage to healthy tissue, as these are of fundamental importance to metabolism in biological systems. The present study aimed to elucidate how radiotherapy in the thoracic area causes damage in the coronary artery, and to verify the potential use of losartan in reducing, or even preventing, the side effects of irradiation in this artery. To assess elemental and morphological differences in aortic and coronary samples, the Low Energy X-Ray Fluorescence (LEXRF) technique using Synchrotron Radiation was employed. SR- LEXRF and scanning transmission X-ray microscopy measurements were carried out at the beamline TwinMic at Elettra Sincrotrone Triste, Italy.

Magnetoelastic anisotropy in Heusler-type Mn2−δCoGa1+δ films

Perpendicular magnetization is essential for high-density memory application using magnetic materials. High-spin polarization of conduction electrons is also required for realizing large electric signals from spin-dependent transport phenomena. Heusler alloy is a well-known material class showing the half-metallic electronic structure. However, its cubic lattice nature favors in-plane magnetization and thus minimizes the perpendicular magnetic anisotropy (PMA), in general. This study focuses on an inverse-type Heusler alloy, Mn$_{2-\delta}$CoGa$_{1+\delta}$ (MCG) with a small off-stoichiometry ($\delta$) , which is expected to be a half-metallic material. We observed relatively large uniaxial magnetocrystalline anisotropy constant ($K_\mathrm{u}$) of the order of 10$^5$ J/m$^3$ at room temperature in MCG films with a small tetragonal distortion of a few percent. A positive correlation was confirmed between the $c/a$ ratio of lattice constants and $K_\mathrm{u}$. Imaging of magnetic domains using Kerr microscopy clearly demonstrated a change in the domain patterns along with $K_\mathrm{u}$. X-ray magnetic circular dichroism (XMCD) was employed using synchrotron radiation soft x-ray beam to get insight into the origin for PMA. Negligible angular variation of orbital magnetic moment ($\Delta m_\mathrm{orb}$) evaluated using the XMCD spectra suggested a minor role of the so-called Bruno's term to $K_\mathrm{u}$. Our first principles calculation reasonably explained the small $\Delta m_\mathrm{orb}$ and the positive correlation between the $c/a$ ratio and $K_\mathrm{u}$. The origin of the magnetocrystalline anisotropy was discussed based on the second-order perturbation theory in terms of the spin--orbit coupling, claiming that the mixing of the occupied $\uparrow$- and the unoccupied $\downarrow$-spin states is responsible for the PMA of the MCG films.

Synchrotron radiation transmission by two coupled flat microchannel plates: new opportunities to control the focal spot characteristics.

An improved theoretical model to calculate the focal spot properties of coherent synchrotron radiation (SR) soft X-ray beams by combining and aligning two microchannel plates (MCPs) is presented. The diffraction patterns of the radiation behind the MCP system are simulated in the framework of the electrodynamical model of the radiation emission from two-dimensional finite antenna arrays. Simulations show that this particular optical device focuses the soft X-ray radiation in a circular central spot with a radius of ∼4 µm. The study points out that such MCP-based devices may achieve micrometre and sub-micrometre spot sizes as required by many applications in the soft X-ray range. Finally, based on experimental and theoretical results of the radiation transmission by this MCP-based device, a new method to characterize the spatial properties of brilliant SR sources is discussed.

Three-dimensional bulk Fermi surfaces and Weyl crossings of Co2MnGa thin films underneath a protection layer

Angle-resolved photoelectron spectroscopy utilizing soft x-ray synchrotron radiation was applied to Heusler-type ${\mathrm{Co}}_{2}\mathrm{MnGa}$ thin films that have a 1-nm Al capping layer. The bulk Fermi surfaces and band structures varied along the out-of-plane momentum, stemming from the three-dimensional crystal structure, in the absence of any in situ surface treatment. In addition, there were characteristic intersecting bands (Weyl cones), with crossing points near the Fermi level, which were consistent with computed results. The Weyl cones are of bulk origin and are responsible for the high anomalous Nernst and the anomalous Hall coefficients. A close comparison of the experimental band structures in ${\mathrm{Co}}_{2}\mathrm{MnGe}$ and ${\mathrm{Co}}_{2}\mathrm{MnGa}$ indicated that the rigid band picture is valid in both alloys and that fine carrier tuning is possible by replacing Ga with Ge to improve the anomalous conductivity.

Investigation of the dielectric relaxation mechanisms for Pb(Fe1/2Nb1/2)O3 single crystal based on the universal relaxation law

Large-sized multiferroics Pb(Fe1/2Nb1/2)O3 (PFN) single crystal was grown by Bridgeman method in order to understand the giant dielectric response by investigating the electrical conductivity and dielectric properties. The synchrotron radiation soft x-ray absorption spectrum revealed the valence states of Fe in PFN crystal. PFN exhibits semiconductor behaviors in the thermal active electrical conductivity investigation. Besides, the frequency-dependent dielectric constants were measured in the frequency range from 100 Hz to 1 MHz to study the dielectric relaxation behaviors. Two relaxation processes were found and described by Havriliak-Negami equation. The origin of dielectric relaxation in PFN with semiconductor characters was discussed based on the universal relaxation law for a dipolar system.

X-ray induced luminescence spectroscopy for DNA damaging intermediates aided by a monochromatic synchrotron radiation

Purpose To identify the bonding sites of initial radiation interaction with DNA and to trace the following chemical reaction sequences on the pathway of damage induction, we carry out a spectroscopy XIL (X-ray induced luminescence) using soft X-ray synchrotron radiation. This is a nondestructive analysis of the excited intermediate species produced in a molecular mechanism on the damage induction pathway. Materials and Methods We introduce aqueous samples of UMP (uridine-5’-monophosphate) in the vacuum by the use of a liquid micro-jet technique. The luminescence in the region of UV-VIS (from visible to ultraviolet) radiation induced after the absorption of monochromatic soft X-ray by aqueous UMP is measured with sweeping the soft X-ray energy in the region of 370–560 eV. Results The enhanced XIL intensities for aqueous UMP in the region of soft X-ray of 410–530 eV (in “water window” region) are obtained. The enhancement of XIL intensities in the UV-VIS region, relative to the water control, is explained by the excitation and ionization of a K-shell electron of nitrogen atoms in the uracil moiety. The enhanced XIL intensities do not match the structure of XANES (X-ray absorption near-edge structure) of the aqueous UMP. This suggests that the XIL intensities reflect the quantum yields of luminescence, or the quantum yields for conversion by UMP of an absorbed X-ray into UV-VIS radiation. In this paper, spectra of luminescence are shown to be resolved by combining low pass filters. The filtered luminescence spectra are obtained at the center of gravity (λc) of the band pass wavelength regions at λc = 270nm, 295 nm, 340 nm, 385 nm, 450 nm, and 525 nm., which show a trend similar to the fluorescence of nucleobases induced by ultraviolet radiation. Conclusion It is concluded that the origin of the observed XIL is the hydrated uracil moiety in aqueous UMP, decomposition of which is suppressed by the migration of excess charge and internal energy after the double ionization due to Auger decay.

Fabrication of high aspect ratio and tilted nanostructures using extreme ultraviolet and soft x-ray interference lithography

We demonstrate the fabrication of metal and dielectric nanostructures using interference lithography with extreme ultraviolet (EUV) and soft x-ray synchrotron radiation down to a 2.5 nm wavelength. These specific wavelengths are chosen because of the industrial relevance for EUV lithography and because they are in the vicinity of the oxygen absorption edge of the high-resolution hydrogen silsesquioxane photoresist, allowing for the exposure of thick layers. We investigate the requirements to fabricate such structures and demonstrate that tall metal nanostructures with aspect ratios up to 7 could be achieved by EUV interference lithography and subsequent electroplating. We use the unique depth-of-focus-free property of interference and achromatic Talbot lithography to fabricate uniformly tilted dielectric nanostructures.

光電子運動量顕微鏡：UVSORでの拠点構築と展開

Three-dimensional momentum-resolved photoelectron spectroscopy with a µm-order field of view was achieved by combining Photoelectron Momentum Microscope with a soft X-ray synchrotron radiation source. We built a new experimental station dedicated for momentum-resolved photoelectron spectroscopy and microscopy at BL6U, an undulator-based soft X-ray beamline of the UVSOR synchrotron facility. This experimental station provides a means to characterize the electronic structures of surface atomic sites, thin films, molecular adsorbates, and bulk crystals.

3D Imaging and Quantification of the Integrin at a Single-Cell Base on a Multisignal Nanoprobe and Synchrotron Radiation Soft X-ray Tomography Microscopy.

The development of three-dimensional (3D) single-cell imaging and protein quantitative methods can provide more comprehensive information for diagnoses. We report the design and synthesis of a multisignal nanoprobe (AuGdNC@BSA-CV) for single-cell 3D imaging and quantifying the integrin αIIbβ3 using correlated synchrotron radiation soft X-ray tomography microscopy and an iterative tomographic algorithm termed equally sloped tomography for the first time. Moreover, on the basis of the Au or Gd content of our nanoprobe, the number of integrin αIIbβ3 on a single cell also can be accurately quantified (1.5 × 107 per cell) via inductively coupled plasma mass spectrometry.

Visualizing Half-Metallic Bulk Band Structure with Multiple Weyl Cones of the Heusler Ferromagnet.

Using a well-focused soft x-ray synchrotron radiation beam, angle-resolved photoelectron spectroscopy was applied to a full-Heusler-type Co_{2}MnGe alloy to elucidate its bulk band structure. A large parabolic band at the Brillouin zone center and several bands that cross the Fermi level near the Brillouin zone boundary were identified in line with the results from first-principles calculations. These Fermi-level crossings are ascribed to majority spin bands that are responsible for electron transport with extremely high spin polarization especially along the direction perpendicular to the interface of magnetoresistive devices. The spectroscopy confirms there is no contribution of the minority spin bands to the Fermi surface, signifying half-metallicity for the alloy. Furthermore, two topological Weyl cones with band crossing points were identified around the X point, yielding the conclusion that Co_{2}MnGe could exhibit topologically meaningful behavior such as large anomalous Hall and Nernst effects driven by the Berry flux in its half-metallic band structure.

Aerosol Synthesis and Gas-Phase Photoelectron Spectroscopy of Ag-Bi-I Nanosystems

We report on the aerosol generation of ligand-free silver iodobismuthate (Ag-Bi-I) nanoparticles (NPs) and on in situ investigation of their electronic structure using synchrotron radiation soft X-ray aerosol photoelectron spectroscopy (XAPS). The structural and morphological characterizations revealed the aerosol to be composed of spherical rudorffite Ag3BiI6 particles, approximately 100 nm in size. The XAPS showed well-resolved signals from all expected elements (Ag, Bi, and I) and allowed estimation of the NP work function to be about 4.5 eV. The ionization energy of Ag3BiI6 NPs was determined to be 6.1 eV that is in good agreement with our calculations based on a hybrid functional approach. The presented method of production of Ag3BiI6 aerosol can prove beneficial for the future development of Ag-Bi-I-based photovoltaic materials, since it allows the deposition of Ag-Bi-I particles on large surface areas of arbitrary shape and roughness.

Development of a high-precision XYZ translator and estimation of beam profile of the vacuum ultraviolet and soft X-ray undulator beamline BL-13B at the Photon Factory.

A high-precision XYZ translator was developed for the microanalysis of electronic structures and chemical compositions on material surfaces by electron spectroscopy techniques, such as photoelectron spectroscopy and absorption spectroscopy, utilizing the vacuum ultraviolet and soft X-ray synchrotron radiation at an undulator beamline BL-13B at the Photon Factory. Using the high-precision translator, the profile and size of the undulator beam were estimated. They were found to strongly depend on the photon energy but were less affected by the polarization direction. To demonstrate the microscopic measurement capability of an experimental apparatus incorporating a high-precision XYZ translator, the homogeneities of an SnO film and a naturally grown anatase TiO2 single crystal were investigated using X-ray absorption and photoemission spectroscopies. The upgraded system can be used for elemental analyses and electronic structure studies at a spatial resolution in the order of the beam size.

Photoelectron Momentum Microscope at BL6U of UVSOR-III synchrotron

Photoelectron spectroscopy resolved in three-dimensional momentum space with a microscopic field of view is realized by combining a so-called Momentum Microscope with a soft X-ray synchrotron radiation source. A new experimental station for momentum-resolved photoelectron micro-spectroscopy and spectro-microscopy has been built at BL6U, an undulator-based soft X-ray beamline of the UVSOR synchrotron facility. This experimental station specializes in characterizing the electronic structure of surface atomic sites, thin films, molecular adsorbates, and bulk crystals. The instrument details are described along with possible measurement techniques.

Single-order soft x-ray spectra with spectroscopic photon sieve**Project supported by the National Natural Science Foundation for Young Scientists of China (Grant No. 11805179).

A single-order diffraction transmission grating named spectroscopic photon sieve (SPS) for soft x-ray region is proposed and demonstrated in this paper. The SPS consists of many circular pinholes located randomly, and can realize both free-standing diffractions and the suppression of higher-order differations. In this paper, the basic concept, numerical simulations, and calibration results of a 1000-lines/mm SPS for soft x-ray synchrotron radiation are presented. As predicted by theoretical calculations, the calibration results of a 1000-lines/mm SPS verify that the higher-order diffractions can be significantly suppressed along the symmetry axis. With the current nanofabrication technique, the SPS can potentially have a higher line density, and can be widely used in synchrotron radiation, laser-induced plasma diagnostics, and astrophysics.

Hydration of Nucleobase as Probed by Electron Emission of Uridine-5′-Mono-Phosphate (UMP) in Aqueous Solution Induced by Nitrogen K-Shell Ionization

To identify the precise early radiation processes of DNA lesions, we measure electron kinetic energy spectra emitted from uridine-5′ monophosphate (UMP) in aqueous solution for the photoionization of the N 1s orbital electron and for the following Auger effect using a monochromatic soft X-ray synchrotron radiation at energies above the nitrogen K-shell ionization threshold. The change of photoelectron spectra for UMP in aqueous solutions at different proton concentrations (pH = 7.5 and 11.3) is ascribed to the chemical shift of the N3 nitrogen atom in uracil moiety of canonical and deprotonated forms. The lowest double ionization potentials for aqueous UMP at different pH obtained from the Auger electron spectra following the N 1s photoionization values show the electrostatic aqueous interaction of uracil moiety of canonical (neutral) and deprotonated (negatively charged) forms with hydrated water molecules.

Synchrotron radiation soft X-ray microscopy and low energy X-ray fluorescence to reveal elemental changes in spermatozoa treated with photobiomodulation therapy.

Male infertility is a worldwide clinical issue that increases the number of couples resorting to assisted reproductive technologies (ARTs) to achieve pregnancy. Photobiomodulation therapy (PBMT) is a promising technique that can biostimulate cells and tissues and it is currently successfully employed to enhance the sperm motility in vitro. Nevertheless, its use has been so far restricted to the research field. In the present work, we exploited two PBMT protocols at an 800 nm wavelength on sperm derived from infertile individuals, detecting an increase in sperm motility 1 hour after irradiation. Moreover, in order to add new information about the molecular effect of PBMT, the content of some light elements was evaluated using high resolution X-ray fluorescence imaging. Interestingly, an increase in Na content was detected in the irradiated samples, possibly suggesting a role of this element in sperm motility; indeed, a low Na content was previously correlated with a poor sperm quality, low semen volume, and modest fertilization rate. Amplifying the knowledge of PBMT in the ART field will expedite the translational potentiality of the PBMT use in clinical settings.

Pristine and oxidised Ag-nanoparticles on free-standing graphene as explored by X-ray photoelectron and Auger spectroscopy

Silver nanoparticles with a mean diameter of 15 nm have been grown on free-standing graphene and explored by soft X-ray synchrotron radiation using the ESCAmicroscopy beamline at Elettra. In particular, the 3d core orbitals and valence band (4d/5 s) of pristine and plasma-oxidised Ag-nanoparticles have been investigated by X-ray photoelectron spectroscopy (XPS), X-ray induced valence band photoemission, and MNN Auger spectroscopy. The X-ray spectra of the pristine Ag-nanoparticles, i.e. XPS, Auger and UPS spectra, are very similar to these of the metallic Ag-bulk film while the spectra of the oxidised Ag-nanoparticles exhibit distinct differences with respect to the oxidised Ag-bulk film. This is inferred from a larger valence band width, an extended valence band photoemission intensity nearly up to the Fermi level of the bulk metal, a smaller two-hole Coulomb correlation energy and a rather bulk-like Auger spectrum. We interpret this as to result from a shell-like composition of the Ag-nanoparticles with a thin passivating oxide layer and an inner metallic core. Moreover, the 3d photoemission peak of the oxidised nanoparticles is shifted to higher binding energy with respect to the bulk oxide peak. This is attributed not only to an XPS chemical shift but also to an additional final state Coulomb charging according to the electrostatic liquid drop model. Comparing the core binding energy shift of Ag-nanoparticles with the electrostatic potential of a spherical compact particle and a flat nanoislands a morphology transformation of the oxidised nanoparticles from 3D to 2D is obvious in the size range 5–15 nm.