Multimodal X-ray Research Articles

Multimodal X-ray microanalysis of a UFeO4: evidence for the environmental stability of ternary U(v) oxides from depleted uranium munitions testing.

An environmentally aged radioactive particle of UFeO4 recovered from soil contaminated with munitions depleted uranium (DU) was characterised by microbeam synchrotron X-ray analysis. Imaging of uranium speciation by spatially resolved X-ray diffraction (μ-XRD) and X-ray absorption spectroscopy (μ-XAS) was used to localise UFeO4 in the particle, which was coincident with a distribution of U(v). The U oxidation state was confirmed using X-ray Absorption Near Edge Structure (μ-XANES) spectroscopy as +4.9 ± 0.15. Le-Bail fitting of the particle powder XRD pattern confirmed the presence of UFeO4 and a minor alteration product identified as chernikovite (H3O)(UO2)(PO4)·3H2O. Refined unit cell parameters for UFeO4 were in good agreement with previously published values. Uranium-oxygen interatomic distances in the first co-ordination sphere were determined by fitting of Extended X-ray Absorption Fine Structure (μ-EXAFS) spectroscopy. The average first shell U-O distance was 2.148 ± 0.012 Å, corresponding to a U valence of +4.96 ± 0.13 using bond valence sum analysis. Using bond distances from the published structure of UFeO4, U and Fe bond valence sums were calculated as +5.00 and +2.83 respectively, supporting the spectroscopic analysis and confirming the presence of a U(v)/Fe(iii) pair. Overall this investigation provides important evidence for the stability of U(v) ternary oxides, in oxic, variably moist surface environment conditions for at least 25 years.

Strain Mapping of CdTe Grains in Photovoltaic Devices

Strain within grains and at grain boundaries (GBs) in polycrystalline thin-film absorber layers limits the overall performance because of higher defect concentrations and band fluctuations. However, the nanoscale strain distribution in operational devices is not easily accessible using standard methods. X-ray nanodiffraction offers the unique possibility to evaluate the strain or lattice spacing at nanoscale resolution. Furthermore, the combination of nanodiffraction with additional techniques in the framework of multimodal scanning X-ray microscopy enables the direct correlation of the strain with material and device parameters such as the elemental distribution or local performance. This approach is applied for the investigation of the strain distribution in CdTe grains in fully operational photovoltaic solar cells. It is found that the lattice spacing in the (111) direction remains fairly constant in the grain cores but systematically decreases at the GBs. The lower strain at GBs is accompanied by an increase of the total tilt. These observations are both compatible with the inhomogeneous incorporation of smaller atoms into the lattice, and local stress induced by neighboring grains.

Multimodal x-ray and electron microscopy of the Allende meteorite.

Multimodal microscopy that combines complementary nanoscale imaging techniques is critical for extracting comprehensive chemical, structural, and functional information, particularly for heterogeneous samples. X-ray microscopy can achieve high-resolution imaging of bulk materials with chemical, magnetic, electronic, and bond orientation contrast, while electron microscopy provides atomic-scale spatial resolution with quantitative elemental composition. Here, we combine x-ray ptychography and scanning transmission x-ray spectromicroscopy with three-dimensional energy-dispersive spectroscopy and electron tomography to perform structural and chemical mapping of an Allende meteorite particle with 15-nm spatial resolution. We use textural and quantitative elemental information to infer the mineral composition and discuss potential processes that occurred before or after accretion. We anticipate that correlative x-ray and electron microscopy overcome the limitations of individual imaging modalities and open up a route to future multiscale nondestructive microscopies of complex functional materials and biological systems.

X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells

X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells

X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells.

X-ray beam induced current (XBIC) measurements allow mapping ofthe nanoscale performance of electronic devices such as solar cells. Ideally, XBIC is employed simultaneously with other techniques within a multi-modal X-ray microscopy approach. An example is given herein combining XBIC with X-ray fluorescence to enable point-by-point correlations of the electrical performance with chemical composition. For the highest signal-to-noise ratio in XBIC measurements, lock-in amplification plays a crucial role. By this approach, the X-ray beam is modulated by an optical chopper upstream of the sample. The modulated X-ray beam induced electrical signal is amplified and demodulated to the chopper frequency using a lock-in amplifier. By optimizing low-pass filter settings, modulation frequency, and amplification amplitudes, noise can efficiently be suppressed for the extraction of a clear XBIC signal. A similar setup can be used to measure the X-ray beam induced voltage (XBIV). Beyond standard XBIC/XBIV measurements, XBIC can be measured with bias light or bias voltage applied such that outdoor working conditions of solar cells can be reproduced during in-situ and operando measurements. Ultimately, the multi-modal and multi-dimensional evaluation of electronic devices at the nanoscale enables new insights into the complex dependencies between composition, structure, and performance, which is an important step towards solving the materials' paradigm.

The Dynamics of Abnormal Grain Growth in a Particle Containing System: New Insights from Multimodal Three-Dimensional X-Ray Imaging

The Dynamics of Abnormal Grain Growth in a Particle Containing System: New Insights from Multimodal Three-Dimensional X-Ray Imaging

Multimodal X-ray imaging of grain-level properties and performance in a polycrystalline solar cell.

The factors limiting the performance of alternative polycrystalline solar cells as compared with their single-crystal counterparts are not fully understood, but are thought to originate from structural and chemical heterogeneities at various length scales. Here, it is demonstrated that multimodal focused nanobeam X-ray microscopy can be used to reveal multiple aspects of the problem in a single measurement by mapping chemical makeup, lattice structure and charge collection efficiency simultaneously in a working solar cell. This approach was applied to micrometre-sized individual grains in a Cu(In,Ga)Se2 polycrystalline film packaged in a working device. It was found that, near grain boundaries, collection efficiency is increased, and that in these regions the lattice parameter of the material is expanded. These observations are discussed in terms of possible physical models and future experiments.

In-Situ/Operando X-ray Characterization of Metal Hydrides.

In this article, the capabilities of soft and hard X-ray techniques, including X-ray absorption (XAS), soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), and their application to solid-state hydrogen storage materials are presented. These characterization tools are indispensable for interrogating hydrogen storage materials at the relevant length scales of fundamental interest, which range from the micron scale to nanometer dimensions. Since nanostructuring is now well established as an avenue to improve the thermodynamics and kinetics of hydrogen release and uptake, due to properties such as reduced mean free paths of transport and increased surface-to-volume ratio, it becomes of critical importance to explicitly identify structure-property relationships on the nanometer scale. X-ray diffraction and spectroscopy are effective tools for probing size-, shape-, and structure-dependent material properties at the nanoscale. This article also discusses the recent development of in-situ soft X-ray spectroscopy cells, which enable investigation of critical solid/liquid or solid/gas interfaces under more practical conditions. These unique tools are providing a window into the thermodynamics and kinetics of hydrogenation and dehydrogenation reactions and informing a quantitative understanding of the fundamental energetics of hydrogen storage processes at the microscopic level. In particular, in-situ soft X-ray spectroscopies can be utilized to probe the formation of intermediate species, byproducts, as well as the changes in morphology and effect of additives, which all can greatly affect the hydrogen storage capacity, kinetics, thermodynamics, and reversibility. A few examples using soft X-ray spectroscopies to study these materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the hydrogen storage systems.

Environmentally Friendly Zr-Based Conversion Nanocoatings for Corrosion Inhibition of Metal Surfaces Evaluated by Multimodal X-ray Analysis

Chemical conversion coating as an effective corrosion inhibition has wide range of applications in industries and is of great expectation to be environmentally friendly and cost-effective. Zirconiu...

Grain boundary wetting correlated to the grain boundary properties: A laboratory-based multimodal X-ray tomography investigation

The penetration behavior of liquid gallium in aluminum is characterized using laboratory X-ray attenuation tomography and related to grain boundary properties obtained from the 3D grain map reconstructed by laboratory diffraction contrast tomography (LabDCT). The data is unique because more than 100 grain boundaries are analyzed. It is suggested that it is the grain boundary energy which determines if a boundary is wetted or not: low energy boundaries are much more resistant to liquid gallium than higher energy ones. The potentials of using laboratory diffraction contract tomography for statistical studies of grain boundaries are thereby demonstrated.

Single-shot X-ray dark-field imaging with omnidirectional sensitivity using random-pattern wavefront modulator

With the development of multi-modal x-ray imaging techniques, dark-field signals have drawn increasing interest due to the complementary information to the conventional attenuation-contrast signal. The directional sensitivity of the dark-field signal can reveal the orientation of the microstructure of the imaged object. We propose to use single-shot dark-field imaging with a random-pattern wavefront modulator to achieve omni-directional sensitivity, which will be valuable for the study of strongly ordered systems. Compared to previous studies, the proposed method shows significant advance by requiring neither dedicated fabrication of x-ray optics nor prolonged scanning. The treatment has been demonstrated on images acquired both at synchrotron facilities and with a laboratory source. The flexibility and the accessibility ensure the potential for easy implementation of the method to benefit a wide range of fields.

Understanding Chemomechanical Li-ion Cathode Degradation through Multi-Scale, Multi-Modal X-ray Spectromicroscopy

Understanding Chemomechanical Li-ion Cathode Degradation through Multi-Scale, Multi-Modal X-ray Spectromicroscopy

Tunable X-ray speckle-based phase-contrast and dark-field imaging using the unified modulated pattern analysis approach

X-ray phase-contrast and dark-field imaging provides valuable, complementary information about the specimen under study. Among the multimodal X-ray imaging methods, X-ray grating interferometry and speckle-based imaging have drawn particular attention, which, however, in their common implementations incur certain limitations that can restrict their range of applications. Recently, the unified modulated pattern analysis (UMPA) approach was proposed to overcome these limitations and combine grating- and speckle-based imaging in a single approach. Here, we demonstrate the multimodal imaging capabilities of UMPA and highlight its tunable character regarding spatial resolution, signal sensitivity and scan time by using different reconstruction parameters.

Quantitative Observation of Threshold Defect Behavior in Memristive Devices with Operando X-ray Microscopy

Memristive devices are an emerging technology that enables both rich interdisciplinary science and novel device functionalities, such as nonvolatile memories and nanoionics-based synaptic electronics. Recent work has shown that the reproducibility and variability of the devices depend sensitively on the defect structures created during electroforming as well as their continued evolution under dynamic electric fields. However, a fundamental principle guiding the material design of defect structures is still lacking due to the difficulty in understanding dynamic defect behavior under different resistance states. Here, we unravel the existence of threshold behavior by studying model, single-crystal devices: resistive switching requires that the pristine oxygen vacancy concentration reside near a critical value. Theoretical calculations show that the threshold oxygen vacancy concentration lies at the boundary for both electronic and atomic phase transitions. Through operando, multimodal X-ray imaging, we show that field tuning of the local oxygen vacancy concentration below or above the threshold value is responsible for switching between different electrical states. These results provide a general strategy for designing functional defect structures around threshold concentrations to create dynamic, field-controlled phases for memristive devices.

3D nanopetrography and chemical imaging of datable zircons by synchrotron multimodal X-ray tomography

Zircon is the most widely used mineral in petrochronology and provides key information about magmatic and crustal differentiation history of plutonic rocks, transport paths of clastic material ‘from source to sink’ and significantly contributes in the reconstruction of enigmatic planetary-scale tectonic episodes since the Archaean. However, detailed textural analysis of this accessory mineral has always been hampered by two-dimensional (2D) analytical limitations. With the advancements in X-ray nanotomography technology, it is now possible to non-destructively, yet digitally, cut, visualize, compare and quantify internal textures within zircons, their growth and zoning patterns and chemical distribution of trace elements in three dimensions (3D). We present a novel multimodal approach of using a synchrotron radiation nanobeam to perform 3D nanopetrography of < 100 µm zircons at ~100 nm resolution, demonstrating the capabilities of the technique by analysis of Paleoproterozoic zircons from the Central Finland Granitoid Complex. The integrated X-ray absorption, diffraction and fluorescence tomography revealed sector and oscillatory zoning patterns in 3D as well as differences in zoning pattern between trace elements, in addition to lattice parameters and inclusion composition within zircons. The multimodal synchrotron nanotomography elucidates the 3D nanopetrography and trace element composition of submillimeter-sized zircons in unprecedented detail.

Multimodal hard x-ray imaging with resolution approaching 10 nm for studies in material science

We report multimodal scanning hard x-ray imaging with spatial resolution approaching 10 nm and its application to contemporary studies in the field of material science. The high spatial resolution is achieved by focusing hard x-rays with two crossed multilayer Laue lenses and raster-scanning a sample with respect to the nanofocusing optics. Various techniques are used to characterize and verify the achieved focus size and imaging resolution. The multimodal imaging is realized by utilizing simultaneously absorption-, phase-, and fluorescence-contrast mechanisms. The combination of high spatial resolution and multimodal imaging enables a comprehensive study of a sample on a very fine length scale. In this work, the unique multimodal imaging capability was used to investigate a mixed ionic-electronic conducting ceramic-based membrane material employed in solid oxide fuel cells and membrane separations (compound of Ce0.8Gd0.2O2−x and CoFe2O4) which revealed the existence of an emergent material phase and quantified the chemical complexity at the nanoscale.

Effect of insufficient temporal coherence on visibility contrast in X-ray grating interferometry.

X-ray grating interferometry, which has been spotlighted in the last decade as a multi-modal X-ray imaging technique, can provide three independent images, i.e., absorption, differential-phase, and visibility-contrast images. We report on a cause of the visibility contrast, an effect of insufficient temporal coherence, that can be observed when continuous-spectrum X-rays are used. This effect occurs even for a sample without unresolvable random structures, which are known as the main causes of visibility contrast. We performed an experiment using an acrylic cylinder and quantitatively explained the visibility contrast due to this effect.

Radiation-responsive scintillating nanotheranostics for reduced hypoxic radioresistance under ROS/NO-mediated tumor microenvironment regulation.

: Hypoxia-induced radioresistance is the primary reason for failure of tumor radiotherapy (RT). Changes within the irradiated tumor microenvironment (TME) including oxygen, reactive oxygen species (ROS) and nitric oxide (NO) are closely related to radioresistance. Therefore, there is an urgent need to develop new approaches for overcoming hypoxic radioresistance by incorporating TME regulation into current radiotherapeutic strategies.Methods: Herein, we explored a radiation-responsive nanotheranostic system to enhance RT effects on hypoxic tumors by multi-way therapeutic effects. This system was developed by loading S-nitrosothiol groups (SNO, a NO donor) and indocyanine green (ICG, a photosensitizer) onto mesoporous silica shells of Eu3+-doped NaGdF4 scintillating nanocrystals (NSC).Results: Under X-ray radiation, this system can increase the local dosage by high-Z elements, promote ROS generation by X-ray-induced photodynamic therapy, and produce high levels of NO to enhance tumor-killing effects and improve hypoxia via NO-induced vasodilation. In vitro and in vivo studies revealed that this combined strategy can greatly reinforce DNA damage and apoptosis of hypoxic tumor cells, while significantly suppressing tumor growth, improving tumor hypoxia and promoting p53 up-regulation and HIF1α down-regulation. In addition, this system showed pronounced tumor contrast performance in T1-weighted magnetic resonance imaging and computed tomography.Conclusion: This work demonstrates the great potential of scintillating nanotheranostics for multimodal imaging-guided X-ray radiation-triggered tumor combined therapy to overcome radioresistance.

Multimodal Phase-Based X-Ray Microtomography with Nonmicrofocal Laboratory Sources

We present an alternative laboratory implementation of x-ray phase-contrast tomography through a beam-tracking approach. A nonmicrofocal rotating anode source is combined with a high-resolution detector and an absorbing mask to obtain attenuation, phase, and ultra-small-angle scattering tomograms of different specimens. A theoretical model is also presented which justifies the implementation of beam tracking with polychromatic sources and provides quantitative values of attenuation and phase, under the assumption of low sample attenuation. The method is tested on a variety of samples featuring both large and small x-ray attenuation, phase, and scattering signals. The complementarity of the contrast channels can enable subtle distinctions between materials and tissue types, which appear indistinguishable to conventional tomography scanners.

Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS2, can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description of the reaction mechanism.