Radical-Induced Changes in Transition Metal Interfacial Magnetic Properties: A Blatter Derivative on Polycrystalline Cobalt.

In this work, we study the interface obtained by depositing a monolayer of a Blatter radical derivative on polycrystalline cobalt. By examining the occupied and unoccupied states at the interface, using soft X-ray techniques, combined with electronic structure calculations, we could simultaneously determine the electronic structure of both the molecular and ferromagnetic sides of the interface, thus obtaining a full understanding of the interfacial magnetic properties. We found that the molecule is strongly hybridized with the surface. Changes in the core level spectra reflect the modification of the molecule and the cobalt electronic structures inducing a decrease in the magnetic moment of the cobalt atoms bonded to the molecules which, in turn, lose their radical character. Our method allowed us to screen, beforehand, organic/ferromagnetic interfaces given their potential applications in spintronics.

Measuring magnetic hysteresis curves with polarized soft X-ray resonant reflectivity.

Calculations and measurements of polarization-dependent soft X-ray scattering intensity are presented during a magnetic hysteresis cycle. It is confirmed that the dependence of the intensity on the magnetic moment can be linear, quadratic or a combination of both, depending on the polarization of the incident X-ray beam and the direction of the magnetic moment. With a linearly polarized beam, the scattered intensity will have a purely quadratic dependence on the magnetic moment when the magnetic moment is parallel to the scattering plane. However, with the magnetic moment perpendicular to the scattering plane, there is also a linear component. This means that, when measuring the hysteresis with linear polarization during a hysteresis cycle, the intensity will be an even function of the applied field when the change in the magnetic moment (and field) is confined within the scattering plane but becomes more complicated when the magnetic moment is out of the scattering plane. Furthermore, with circular polarization, the dependence of the scattered intensity on the moment is a combination of linear and quadratic. With the moment parallel to the scattering plane, the linear component changes with the helicity of the incident beam. Surprisingly, in stark contrast to absorption studies, even when the magnetic moment is perpendicular to the scattering plane there is still a dependence on the moment with a linear component. This linear component is completely independent of the helicity of the beam, meaning that the hysteresis loops will not be inverted with helicity.

Assessing the Accuracy of Mass Attenuation Coefficients for Soft X-ray EPMA.

The use of soft X-rays in electron probe microanalysis (EPMA) has gained renewed interest over the past decades due to the advent of new detector technologies. Because X-ray absorption is the dominant correction for soft X-rays, a reliable set of mass attenuation coefficients (MACs) is needed for accurate composition determination. Although several MAC tabulations cover the soft X-ray range, the accuracy of such tabulations below 1 keV is not firmly established. In this study, we assess the accuracy of MAC tabulations in the soft X-ray region by comparing tabulated values for Be, B, C, N, O, and F Kα X-rays with experimental data available in the literature. We find that the 1993 semi-empirical MAC compilation of Henke et al. [(1993). Low-energy X-ray interaction coefficients: Photoabsorption, scattering, transmission and reflection at E=50-30000 eV, Z=1-92. Atom Data Nucl Data Tables54, 181-342] and the more recent theoretical MAC calculations of Sabbatucci and Salvat [(2016). Theory and calculation of the atomic photoeffect. Rad Phys Chem121, 122-140] perform slightly better than the rest of the considered tabulations. The Sabbatucci-Salvat dataset also provides the best agreement with the few existing experimental measurements for Al L2,3M X-rays.

Degradation and Self-Healing of FAPbBr3 Perovskite under Soft-X-Ray Irradiation.

The extensive use of perovskites as light absorbers calls for a deeper understanding of the interaction of these materials with light. Here, the evolution of the chemical and optoelectronic properties of formamidinium lead tri-bromide (FAPbBr3 ) films is tracked under the soft X-ray beam of a high-brilliance synchrotron source by photoemission spectroscopy and micro-photoluminescence. Two contrasting processes are at play during the irradiation. The degradation of the material manifests with the formation of Pb0 metallic clusters, loss of gaseous Br2 , decrease and shift of the photoluminescence emission. The recovery of the photoluminescence signal for prolonged beam exposure times is ascribed to self-healing of FAPbBr3 , thanks to the re-oxidation of Pb0 and migration of FA+ and Br- ions. This scenario is validated on FAPbBr3 films treated by Ar+ ion sputtering. The degradation/self-healing effect, which is previously reported for irradiation up to the ultraviolet regime, has the potential of extending the lifetime of X-ray detectors based on perovskites.

FlexPES: a versatile soft X-ray beamline at MAX†IV Laboratory.

FlexPES is a soft X-ray beamline on the 1.5 GeV storage ring at MAX IV Laboratory, Sweden, providing horizontally polarized radiation in the 40-1500 eV photon energy range and specializing in high-resolution photoelectron spectroscopy, fast X-ray absorption spectroscopy and electron-ion/ion-ion coincidence techniques. The beamline is split into two branches currently serving three endstations, with a possibility of adding a fourth station at a free port. The refocusing optics provides two focal points on each branch, and enables either focused or defocused beam on the sample. The endstation EA01 at branch A (Surface and Materials Science) is dedicated to surface- and materials-science experiments on solid samples at ultra-high vacuum. It is well suited not only to all flavours of photoelectron spectroscopy but also to fast (down to sub-minute) high-resolution X-ray absorption measurements with various detectors. Branch B (Low-Density Matter Science) has the possibility to study gas-phase/liquid samples at elevated pressures. The first endstation of this branch, EB01, is a mobile setup for various ion-ion and electron-ion coincidence techniques. It houses a versatile reaction microscope, which can be used for experiments during single-bunch or multi-bunch delivery. The second endstation, EB02, is based on a rotatable chamber with an electron spectrometer for photoelectron spectroscopy studies on primarily volatile targets, and a number of peripheral setups for sample delivery, such as molecular/cluster beams, metal/semiconductor nanoparticle beams and liquid jets. This station can also be used for non-UHV photoemission studies on solid samples. In this paper, the optical layout and the present performance of the beamline and all its endstations are reported.

High-efficiency focusing and imaging by dielectric kinoform zone plate lenses with soft X-rays.

With fast advances in enhancing the focusing/imaging resolution of Fresnel zone plate lenses toward sub-10 nm, low diffraction efficiency in connection with their rectangular zone shape still remains a big issue in both soft and hard X-ray microscopy. In hard X-ray optics, encouraging progress has recently been reported in our earlier attempts of high focusing efficiency by 3D kinoform shaped metallic zone plates, formed by greyscale electron beam lithography. This paper addresses our efforts towards high focusing/imaging efficiency by developing a novel dielectric kinoform zone plate lens for soft X-rays. The effects of the zone materials and zone shapes on the focusing/imaging quality were first theoretically investigated by a modified thin-grating-approximation method, revealing superior efficiencies of dielectric kinoform zone plates over rectangular ones in metals. Optical characterizations of replicated dielectric kinoform zone plates by greyscale electron beam lithography demonstrate a focusing efficiency of 15.5% with a resolution of 110 nm in the water window of X-rays. Apart from high efficiency, the novel kinoform zone plate lenses developed in this work exhibit significant advantages over conventional zone plates, i.e. simplified process, low cost and no need for a beamstop.

The soft X-ray and XUV split-and-delay unit at beamlines FL23/24 at FLASH2.

A split-and-delay unit for the extreme ultraviolet and soft X-ray spectral regions has been built which enables time-resolved experiments at beamlines FL23 and FL24 at the Free-electron LASer in Hamburg (FLASH). Geometric wavefront splitting at a sharp edge of a beam splitting mirror is applied to split the incoming soft X-ray pulse into two beams. Ni and Pt coatings at grazing incidence angles have been chosen in order to cover the whole spectral range of FLASH2 and beyond, up to hν = 1800 eV. In the variable beam path with a grazing incidence angle of ϑd = 1.8°, the total transmission (T) ranges are of the order of 0.48 < T < 0.84 for hν < 100 eV and T > 0.50 for 100 eV < hν < 650 eV with the Ni coating, and T > 0.06 for hν < 1800 eV for the Pt coating. For a fixed beam path with a grazing incidence angle of ϑf = 1.3°, a transmission of T > 0.61 with the Ni coating and T > 0.23 with a Pt coating is achieved. Soft X-ray pump/soft X-ray probe experiments are possible within a delay range of -5 ps < Δt < +18 ps with a nominal time resolution of tr = 66 as and a measured timing jitter of tj = 121 ± 2 as. First experiments with the split-and-delay unit determined the averaged coherence time of FLASH2 to be τc = 1.75 fs at λ = 8 nm, measured at a purposely reduced coherence of the free-electron laser.

The PERCIVAL detector: first user experiments.

The PERCIVAL detector is a CMOS imager designed for the soft X-ray regime at photon sources. Although still in its final development phase, it has recently seen its first user experiments: ptychography at a free-electron laser, holographic imaging at a storage ring and preliminary tests on X-ray photon correlation spectroscopy. The detector performed remarkably well in terms of spatial resolution achievable in the sample plane, owing to its small pixel size, large active area and very large dynamic range; but also in terms of its frame rate, which is significantly faster than traditional CCDs. In particular, it is the combination of these features which makes PERCIVAL an attractive option for soft X-ray science.

Relative biological effectiveness of low-energy X-rays (25 kV) in mutant p53 cancer cells.

Low-energy X-rays as used in radiation therapy and diagnostics such as mammography are associated with a certain risk of promoting tumour development, especially in patients with mutations in cancer-related genes like TP53. The present study therefore addressed the relative biological effectiveness (RBE) of low-energy X-rays for two human adenocarcinoma cell lines of the breast (MDA-MB-468) and pancreas (BxPC-3) with a mutation in the TP53 gene. Clonogenic survival and cytogenetic changes in terms of micronuclei (MN) formation were determined following irradiation with 25 kV X-rays and 200 kV reference irradiation in the dose range of 1-8 Gy. Except the frequency of MN-containing binucleated cells (BNC) (BNC + MN/BNC) in breast cancer cells yielding an RBE between 0.6 and 0.8, both cell lines displayed dose-dependent variations of RBE values between 1 and 2 for all biological end points (cell survival, (BNC + MN/BNC), MN/BNC, MN/(BNC + MN)) with increased effectiveness of 25 kV irradiation in pancreatic compared to breast cancer cells. The results confirm previous findings indicating increased effectiveness of low-energy X-rays and underline the necessity of careful risk estimation for cancer screening programmes.

Soft X-ray Tomography Reveals HSV-1-Induced Remodeling of Human B Cells.

Upon infection, viruses hijack the cell machinery and remodel host cell structures to utilize them for viral proliferation. Since viruses are about a thousand times smaller than their host cells, imaging virus-host interactions at high spatial resolution is like looking for a needle in a haystack. Scouting gross cellular changes with fluorescent microscopy is only possible for well-established viruses, where fluorescent tagging is developed. Soft X-ray tomography (SXT) offers 3D imaging of entire cells without the need for chemical fixation or labeling. Here, we use full-rotation SXT to visualize entire human B cells infected by the herpes simplex virus 1 (HSV-1). We have mapped the temporospatial remodeling of cells during the infection and observed changes in cellular structures, such as the presence of cytoplasmic stress granules and multivesicular structures, formation of nuclear virus-induced dense bodies, and aggregates of capsids. Our results demonstrate the power of SXT imaging for scouting virus-induced changes in infected cells and understanding the orchestration of virus-host remodeling quantitatively.

Megahertz-rate ultrafast X-ray scattering and holographic imaging at the European XFEL.

The advent of X-ray free-electron lasers (XFELs) has revolutionized fundamental science, from atomic to condensed matter physics, from chemistry to biology, giving researchers access to X-rays with unprecedented brightness, coherence and pulse duration. All XFEL facilities built until recently provided X-ray pulses at a relatively low repetition rate, with limited data statistics. Here, results from the first megahertz-repetition-rate X-ray scattering experiments at the Spectroscopy and Coherent Scattering (SCS) instrument of the European XFEL are presented. The experimental capabilities that the SCS instrument offers, resulting from the operation at megahertz repetition rates and the availability of the novel DSSC 2D imaging detector, are illustrated. Time-resolved magnetic X-ray scattering and holographic imaging experiments in solid state samples were chosen as representative, providing an ideal test-bed for operation at megahertz rates. Our results are relevant and applicable to any other non-destructive XFEL experiments in the soft X-ray range.

Characterization of biological materials with soft X-ray scattering.

The complex structure of biological assemblies is crucial for function yet challenging to discern given the chemical similarities between constituent components. Hard X-ray techniques, for example, rely on small density differences between domains that lead to modest scattering intensities. Resonant soft X-ray scattering (RSoXS) uses X-rays below 2keV to access absorption edges of low-Z elements. In this way, RSoXS can enhance scattering contrast between domains of different chemical compositions or bonding motifs, thus providing structural information about specific chemical motifs. RSoXS is emerging as a technique applicable for biological systems, having been used to characterize protein structure in solution and polysaccharide organization in plant cell walls. Sample environment instrumentation, however, is challenging in the current state of the art, particularly with liquid samples. This chapter contains a brief introduction to RSoXS and current beamline capabilities, and provides methods to prepare, store, and mount biological samples for RSoXS characterization. Furthermore, key details during RSoXS and X-ray absorption data acquisition are highlighted and some future opportunities in RSoXS instrumentation for biological systems are discussed.

Electron Probe Microanalysis of Transition Metals using L lines: The Effect of Self-absorption.

Electron microprobe-based quantitative compositional measurement of first-row transition metals using their L$\alpha$ X-ray lines is hampered by, among other effects, self-absorption. This effect, which occurs when a broad X-ray line is located close to a broad absorption edge, is not accounted for by matrix corrections. To assess the error due to neglecting self-absorption, we calculate the L$\alpha$ X-ray intensity emitted from metallic Fe, Ni, Cu, and Zn targets, assuming a Lorentzian profile for the X-ray line and taking into account the energy dependence of the mass absorption coefficient near the absorption edge. We find that calculated X-ray intensities depart increasingly, for increasing electron beam energy, from those obtained assuming a narrow X-ray line and a single fixed absorption coefficient (conventional approach), with a maximum deviation of $\sim$15% for Ni and of $\sim$10% for Fe. In contrast, X-ray intensities calculated for metallic Zn and Cu do not differ significantly from those obtained using the conventional approach. The implications of these results for the analysis of transition-metal compounds by electron probe microanalysis as well as strategies to account for self-absorption effects are discussed.

Demonstration of Near Edge X-ray Absorption Fine Structure Spectroscopy of Transition Metals Using Xe/He Double Stream Gas Puff Target Soft X-ray Source.

A near 1-keV photons from the Xe/He plasma produced by the interaction of laser beam with a double stream gas puff target were employed for studies of L absorption edges of period 4 transitional metals with atomic number Z from 26 to 30. The dual-channel, compact NEXAFS system was employed for the acquisition of the absorption spectra. L1-3 absorption edges of the samples were identified in transmission mode using broadband emission from the Xe/He plasma to show the applicability of such source and measurement system to the NEXAFS studies of the transition metals, including magnetic materials.

Combining X-ray excited optical luminescence and X-ray absorption spectroscopy for correlative imaging on the nanoscale.

X-ray absorption and optical luminescence can both provide valuable but very different information on the chemical and physical properties of materials. Although it is known that the spectral characteristics of many materials are highly heterogeneous on the micro- and/or nanoscale, no methodology has so far been shown to be capable of spatially resolving both full X-ray absorption and X-ray excited optical luminescence (XEOL) spectra on the nanoscale in a correlative manner. For this purpose, the scanning transmission X-ray microscope at the HERMES beamline of the SOLEIL synchrotron was equipped with an optical detection system capable of recording high-resolution XEOL spectra using a 40 nm soft X-ray probe. The functionality of the system was demonstrated by analyzing ZnO powder dispersions - showing simultaneously the X-ray linear dichroism and XEOL behavior of individual submicrometric ZnO crystallites.

High-efficiency diffraction gratings for EUV and soft x-rays using spin-on-carbon underlayers.

We report on the fabrication and characterization of high-resolution gratings with high efficiency in the extreme ultraviolet (EUV) and soft x-ray ranges using spin-on-carbon (SOC) underlayers. We demonstrate the fabrication of diffraction gratings down to 20 nm half-pitch (HP) on Si3N4membranes with a bilayer of hydrogen silsesquioxane (HSQ) and spin-on-carbon and show their performance as a grating mask for extreme ultraviolet interference lithography (EUV-IL). High-resolution patterning of HSQ is possible only for thin films due to pattern collapse. The combination of this high-resolution resist with SOC circumvents this problem and enables the fabrication of high aspect ratio nanostructures. Rigorous coupled-wave analysis shows that the bilayer gratings exhibit higher diffraction efficiency than what is feasible with a grating made of HSQ. We also demonstrate a simple and accurate method to experimentally measure the diffraction efficiency of high-resolution gratings by measuring the relative ratio of the dose-to-clear curves of the photoresist. The measured diffraction efficiencies are in good agreement with the theoretically predicted values. Furthermore, we verify our calculations and measurements by printing line/space patterns in chemically amplified resists down to 10 nm HP with both HSQ and bilayer grating masks using EUV-IL. The improved diffraction efficiency of the bilayers is expected to have applications not only in gratings for interference lithography, but also in Fresnel zone plates and gratings for spectroscopy in the EUV and soft x-ray ranges.

Soft X-ray nanospectroscopy for quantification of X-ray linear dichroism on powders.

X-ray linear dichroism (XLD) is a fundamental property of many ordered materials that can for instance provide information on the origin of magnetic properties and the existence of differently ordered domains. Conventionally, measurements of XLD are performed on single crystals, crystalline thin films, or highly ordered nanostructure arrays. Here, it is demonstrated how quantitative measurements of XLD can be performed on powders, relying on the random orientation of many particles instead of the controlled orientation of a single ordered structure. The technique is based on a scanning X-ray transmission microscope operated in the soft X-ray regime. The use of a Fresnel zone plate allows X-ray absorption features to be probed at ∼40 nm lateral resolution - a scale small enough to probe the individual crystallites in most powders. Quantitative XLD parameters were then retrieved by determining the intensity distributions of certain diagnostic dichroic absorption features, estimating the angle between their transition dipole moments, and fitting the distributions with four-parameter dichroic models. Analysis of several differently produced ZnO powders shows that the experimentally obtained distributions indeed follow the theoretical model for XLD. Making use of Monte Carlo simulations to estimate uncertainties in the calculated dichroic model parameters, it was established that longer X-ray exposure times lead to a decrease in the amplitude of the XLD effect of ZnO.

Buried Structure in Block Copolymer Films Revealed by Soft X-ray Reflectivity.

Interactions between polymers and surfaces can be used to influence properties including mechanical performance in nanocomposites, the glass transition temperature, and the orientation of thin film block copolymers (BCPs). In this work we investigate how specific interactions between the substrate and BCPs with varying substrate affinity impact the interfacial width between polymer components. The interface width is generally assumed to be a function of the BCP properties and independent of the surface affinity or substrate proximity. Using resonant soft X-ray reflectivity the optical constants of the film can be controlled by changing the incident energy, thereby varying the depth sensitivity of the measurement. Resonant soft X-ray reflectivity measurements were conducted on films of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) and PS-b-poly(methyl methacrylate) (PS-b-PMMA), where the thickness of the film was varied from half the periodicity (L0) of the BCP to 5.5 L0. The results of this measurement on the PS-b-P2VP films show a significant expansion of the interface width immediately adjacent to the surface. This is likely caused by the strong adsorption of P2VP to the substrate, which constrains the mobility of the junction points, preventing them from reaching their equilibrium distribution and expanding the observed interface width. The interface width decays toward equilibrium moving away from the substrate, with the decay rate being a function of film thickness below a critical limit. The PMMA block appears to be more mobile, and the BCP interfaces near the substrate match their equilibrium value.

A microfluidic dosimetry cell to irradiate solutions with poorly penetrating radiations: a step towards online dosimetry for synchrotron beamlines.

Synchrotron radiation can induce sample damage, whether intended or not. In the case of sensitive samples, such as biological ones, modifications can be significant. To understand and predict the effects due to exposure, it is necessary to know the ionizing radiation dose deposited in the sample. In the case of aqueous samples, deleterious effects are mostly induced by the production of reactive oxygen species via water radiolysis. These species are therefore good indicators of the dose. Here the application of a microfluidic cell specifically optimized for low penetrating soft X-ray radiation is reported. Sodium benzoate was used as a fluorescent dosimeter thanks to its specific detection of hydroxyl radicals, a radiolytic product of water. Measurements at 1.28 keV led to the determination of a hydroxyl production yield, G(HO.), of 0.025 ±â€…0.004 µmol J-1. This result is in agreement with the literature and confirms the high linear energy transfer behavior of soft X-rays. An analysis of the important parameters of the microfluidic dosimetry cell, as well as their influences over dosimetry, is also reported.

Calculating absorption dose when X-ray irradiation modifies material quantity and chemistry.

X-ray absorption is a sensitive and versatile tool for chemical speciation. However, when high doses are used, the absorbed energy can change the composition, amount and structure of the native material, thereby changing the aspects of the absorption process on which speciation is based. How can one calculate the dose when X-ray irradiation affects the chemistry and changes the amount of the material? This paper presents an assumption-free approach which can retrieve from the experimental data all dose-sensitive parameters - absorption coefficients, composition (elemental molecular units), material densities - which can then be used to calculate accurate doses as a function of irradiation. This approach is illustrated using X-ray damage to a solid film of a perfluorosulfonic acid fluoropolymer in a scanning transmission soft X-ray microscope. This new approach is compared against existing dose models which calculate the dose by making simplifying assumptions regarding the material quantity, density and chemistry. While the detailed measurements used in this approach go beyond typical methods to experimental analytical X-ray absorption, they provide a more accurate quantitation of radiation dose, and help to understand mechanisms of radiation damage.