Local strain inhomogeneities during electrical triggering of a metal-insulator transition revealed by X-ray microscopy.

Electrical triggering of a metal-insulator transition (MIT) often results in the formation of characteristic spatial patterns such as a metallic filament percolating through an insulating matrix or an insulating barrier splitting a conducting matrix. When MIT triggering is driven by electrothermal effects, the temperature of the filament or barrier can be substantially higher than the rest of the material. Using X-ray microdiffraction and dark-field X-ray microscopy, we show that electrothermal MIT triggering leads to the development of an inhomogeneous strain profile across the switching device, even when the material does not undergo a pronounced, discontinuous structural transition coinciding with the MIT. Diffraction measurements further reveal evidence of unique features associated with MIT triggering including lattice distortions, tilting, and twinning, which indicate structural nonuniformity of both low- and high-resistance regions inside the switching device. Such lattice deformations do not occur under equilibrium, zero-voltage conditions, highlighting the qualitative difference between states achieved through increasing temperature and applying voltage in nonlinear electrothermal materials. Electrically induced strain, lattice distortions, and twinning could have important contributions in the MIT triggering process and drive the material into nonequilibrium states, providing an unconventional pathway to explore the phase space in strongly correlated electronic systems.

3D surface reconstruction of cellular cryo-soft X-ray microscopy tomograms using semisupervised deep learning.

Cryo-soft X-ray tomography (cryo-SXT) is a powerful method to investigate the ultrastructure of cells, offering resolution in the tens of nanometer range and strong contrast for membranous structures without requiring labeling or chemical fixation. The short acquisition time and the relatively large field of view leads to fast acquisition of large amounts of tomographic image data. Segmentation of these data into accessible features is a necessary step in gaining biologically relevant information from cryo-soft X-ray tomograms. However, manual image segmentation still requires several orders of magnitude more time than data acquisition. To address this challenge, we have here developed an end-to-end automated 3D segmentation pipeline based on semisupervised deep learning. Our approach is suitable for high-throughput analysis of large amounts of tomographic data, while being robust when faced with limited manual annotations and variations in the tomographic conditions. We validate our approach by extracting three-dimensional information on cellular ultrastructure and by quantifying nanoscopic morphological parameters of filopodia in mammalian cells.

Real-time imaging of acoustic waves in bulk materials with X-ray microscopy.

The dynamics of lattice vibrations govern many material processes, such as acoustic wave propagation, displacive phase transitions, and ballistic thermal transport. The maximum velocity of these processes and their effects is determined by the speed of sound, which therefore defines the temporal resolution (picoseconds) needed to resolve these phenomena on their characteristic length scales (nanometers). Here, we present an X-ray microscope capable of imaging acoustic waves with subpicosecond resolution within mm-sized crystals. We directly visualize the generation, propagation, branching, and energy dissipation of longitudinal and transverse acoustic waves in diamond, demonstrating how mechanical energy thermalizes from picosecond to microsecond timescales. Bulk characterization techniques capable of resolving this level of structural detail have previously been available on millisecond time scales-orders of magnitude too slow to capture these fundamental phenomena in solid-state physics and geoscience. As such, the reported results provide broad insights into the interaction of acoustic waves with the structure of materials, and the availability of ultrafast time-resolved dark-field X-ray microscopy opens a vista of new opportunities for 3D imaging of materials dynamics on their intrinsic submicrosecond time scales.

Nanoscale chemical imaging with structured X-ray illumination.

High-resolution imaging with compositional and chemical sensitivity is crucial for a wide range of scientific and engineering disciplines. Although synchrotron X-ray imaging through spectromicroscopy has been tremendously successful and broadly applied, it encounters challenges in achieving enhanced detection sensitivity, satisfactory spatial resolution, and high experimental throughput simultaneously. In this work, based on structured illumination, we develop a single-pixel X-ray imaging approach coupled with a generative image reconstruction model for mapping the compositional heterogeneity with nanoscale resolvability. This method integrates a full-field transmission X-ray microscope with an X-ray fluorescence detector and eliminates the need for nanoscale X-ray focusing and raster scanning. We experimentally demonstrate the effectiveness of our approach by imaging a battery sample composed of mixed cathode materials and successfully retrieving the compositional variations of the imaged cathode particles. Bridging the gap between structural and chemical characterizations using X-rays, this technique opens up vast opportunities in the fields of biology, environmental, and materials science, especially for radiation-sensitive samples.

Cation reordering instead of phase transitions: Origins and implications of contrasting lithiation mechanisms in 1D ζ- and 2D α-V2O5.

Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (V2O5) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-V2O5 that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-V2O5 crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, operando synchrotron X-ray diffraction measurements, and phase-field modeling. We find the operation of sharply divergent mechanisms to accommodate increasing concentrations of Li-ions: a series of distortive phase transformations that result in puckering and expansion of interlayer spacing in layered α-V2O5, as compared with cation reordering along interstitial sites in tunnel-structured ζ-V2O5 By alleviating distortive phase transformations, the ζ-V2O5 cathode shows reduced voltage hysteresis, increased Li-ion diffusivity, alleviation of stress gradients, and improved capacity retention. The findings demonstrate that alternative lithiation mechanisms can be accessed in metastable compounds by dint of their reconfigured atomic connectivity and can unlock substantially improved electrochemical performance not accessible in the thermodynamically stable phase.

Elucidating Heterogeneous Li Insertion Using Single-Crystalline and Freestanding Layered Oxide Thin Film.

The kinetics of interfacial ion insertion govern the uniformity of electrochemical reactions, playing a crucial role in lithium-ion battery performance. In two-dimensional lithium-conducting layered-oxide battery particles, variation in insertion rates across insertion channels remains unclear due to poorly defined crystal orientation at the solid-liquid interface and solid-state-lithium-diffusion length. This ambiguity complicates understanding inhomogeneous lithium-insertion channels activation. A systematic study requires crystallographically predefined interfaces and in situ lithium-concentration mapping. Here, we fabricated a freestanding, (104)-oriented-LiNi1/3Mn1/3Co1/3O2 single-crystal thin film using dissolution-induced release and performed in situ scanning-transmission-X-ray-microscopy to spatially resolve lithium-insertion at well-defined-interfaces. We observed heterogeneous lithium-concentration evolution due to channel-by-channel insertion rate variation, despite the potential for homogeneous lithium distribution via a solid-solution-phase at equilibrium in NMC111. Increasing current density exacerbates this heterogeneity, highlighting channel-by-channel variation. Our findings provide critical insights into battery electrode utilization and lifetime management, potentially guiding the design of more efficient and durable lithium-ion batteries.

Interrogation of 3d Transition Bimetallic Nanocrystal Nucleation and Growth Using In Situ Electron Microscope and Synchrotron X-ray Techniques.

Understanding the nucleation and growth mechanism of 3d transition bimetallic nanocrystals (NCs) is crucial to developing NCs with tailored nanostructures and properties. However, it remains a significant challenge due to the complexity of 3d bimetallic NCs formation and their sensitivity to oxygen. Here, by combining in situ electron microscopy and synchrotron X-ray techniques, we elucidate the nucleation and growth pathways of Fe-Ni NCs. Interestingly, the formation of Fe-Ni NCs emerges from the assimilation of Fe into Ni clusters together with the reduction of Fe-Ni oxides. Subsequently, these NCs undergo solid-state phase transitions, resulting in two distinct solid solutions, ultimately dominated by γ-Fe3Ni2. Furthermore, we deconvolve the interplays between local coordination and electronic state concerning the growth temperature. We directly visualize the oxidation-state distributions of Fe and Ni at the nanoscale and investigate their changes. This work may reshape and enhance the understanding of nucleation and growth in atomic crystallization.

Image registration for in situ X-ray nano-imaging of a composite battery cathode with deformation.

The structural and chemical evolution of battery electrodes at the nanoscale plays an important role in affecting the cell performance. Nano-resolution X-ray microscopy has been demonstrated as a powerful technique for characterizing the evolution of battery electrodes under operating conditions with sensitivity to their morphology, compositional distribution and redox heterogeneity. In real-world batteries, the electrode could deform upon battery operation, causing challenges for the image registration which is necessary for several experimental modalities, e.g. XANES imaging. To address this challenge, this work develops a deep-learning-based method for automatic particle identification and tracking. This approach was not only able to facilitate image registration with good robustness but also allowed quantification of the degree of sample deformation. The effectiveness of the method was first demonstrated using synthetic datasets with known ground truth. The method was then applied to an experimental dataset collected on an operating lithium battery cell, revealing a high degree of intra- and interparticle chemical complexity in operating batteries.

3D imaging of magnetic domains in Nd2Fe14B using scanning hard X-ray nanotomography.

Nanoscale structural and electronic heterogeneities are prevalent in condensed matter physics. Investigating these heterogeneities in 3D has become an important task for understanding material properties. To provide a tool to unravel the connection between nanoscale heterogeneity and macroscopic emergent properties in magnetic materials, scanning transmission X-ray microscopy (STXM) is combined with X-ray magnetic circular dichroism. A vector tomography algorithm has been developed to reconstruct the full 3D magnetic vector field without any prior noise assumptions or knowledge about the sample. Two tomographic scans around the vertical axis are acquired on single-crystalline Nd2Fe14B pillars tilted at two different angles, with 2D STXM projections recorded using a focused 120 nm X-ray beam with left and right circular polarization. Image alignment and iterative registration have been implemented based on the 2D STXM projections for the two tilts. Dichroic projections obtained from difference images are used for the tomographic reconstruction to obtain the 3D magnetization distribution at the nanoscale.

Visualization of Nanocarriers and Drugs in Cells and Tissue.

In this chapter, the visualization of nanocarriers and drugs in cells and tissue is reviewed. This topic is tightly connected to modern drug delivery, which relies on nanoscopic drug formulation approaches and the ability to probe nanoparticulate systems selectively in cells and tissue using advanced spectroscopic and microscopic techniques. We first give an overview of the breadth of this research field. Then, we mainly focus on topical drug delivery to the skin and discuss selected visualization techniques from spectromicroscopy, such as scanning transmission X-ray microscopy and fluorescence lifetime imaging. These techniques rely on the sensitive and quantitative detection of the topically applied drug delivery systems and active substances, either by exploiting their molecular properties or by introducing environmentally sensitive probes that facilitate their detection.

A Novel 3D High Resolution Imaging Method Using Correlative X-Ray and Electron Microscopy to Study Neodymium-Doped Yttrium Aluminum Garnet Laser-Induced Defects in Intraocular Lenses.

INTRODUCTION: Cataract extraction is the most frequently performed ophthalmological procedure worldwide. Posterior capsule opacification remains the most common consequence after cataract surgery and can lead to deterioration of the visual performance with cloudy, blurred vision and halo, glare effects. Neodymium-doped yttrium aluminum garnet (Nd:YAG) laser capsulotomy is the gold standard treatment and a very effective, safe and fast procedure in removing the cloudy posterior capsule. Damaging the intraocular lens (IOL) during the treatment may occur due to wrong focus of the laser beam. These YAG-pits may lead to a permanent impairment of the visual quality. METHODS: In an experimental study, we intentionally induced YAG pits in hydrophilic and hydrophobic acrylic IOLs using a photodisruption laser with 2.6 mJ. This experimental study established a novel 3D imaging method using correlative X-ray and scanning electron microscopy (SEM) to characterize these damages. By integrating the information obtained from both X-ray microscopy and SEM, a comprehensive picture of the materials structure and performance could be established. RESULTS: It could be revealed that although the exact same energies were used to all samples, the observed defects in the tested lenses showed severe differences in shape and depth. While YAG pits in hydrophilic samples range from 100 to 180 µm depth with a round shape tip, very sharp tipped defects up to 250 µm in depth were found in hydrophobic samples. In all samples, particles/fragments of the IOL material were found on the surface that were blasted out as a result of the laser shelling. CONCLUSION: Defects in hydrophilic and hydrophobic acrylic materials differ. Material particles can detach from the IOL and were found on the surface of the samples. The results of the laboratory study illustrate the importance of a precise and careful approach to Nd:YAG capsulotomy in order to avoid permanent damage to the IOL. The use of an appropriate contact glass and posterior offset setting to increase safety should be carried out routinely.

Live Iterative Ptychography.

We demonstrate live-updating ptychographic reconstruction with the extended ptychographical iterative engine, an iterative ptychography method, during ongoing data acquisition. The reconstruction starts with a small subset of the total data, and as the acquisition proceeds the data used for reconstruction are extended. This creates a live-updating view of object and illumination that allows monitoring the ongoing experiment and adjusting parameters with quick turn around. This is particularly advantageous for long-running acquisitions. We show that such a gradual reconstruction yields interpretable results already with a small subset of the data. We show simulated live processing with various scan patterns, parallelized reconstruction, and real-world live processing at the hard X-ray ptychographic nanoanalytical microscope PtyNAMi at the PETRA III beamline.

Direct Observation of Propagating Spin Waves in the 2D van der Waals Ferromagnet Fe5GeTe2.

Magnetism in reduced dimensionalities is of great fundamental interest while also providing perspectives for applications of materials with novel functionalities. In particular, spin dynamics in two dimensions (2D) have become a focus of recent research. Here, we report the observation of coherent propagating spin-wave dynamics in a ∼30 nm thick flake of 2D van der Waals ferromagnet Fe5GeTe2 using X-ray microscopy. Both phase and amplitude information were obtained by direct imaging below TC for frequencies from 2.77 to 3.84 GHz, and the corresponding spin-wave wavelengths were measured to be between 1.5 and 0.5 µm. Thus, parts of the magnonic dispersion relation were determined despite a relatively high magnetic damping of the material. Numerically solving an analytic multilayer model allowed us to corroborate the experimental dispersion relation and predict the influence of changes in the saturation magnetization or interlayer coupling, which could be exploited in future applications by temperature control or stacking of 2D-heterostructures.

Laboratory Liquid-Jet X-ray Microscopy and X-ray Fluorescence Imaging for Biomedical Applications.

Diffraction-limited resolution and low penetration depth are fundamental constraints in optical microscopy and in vivo imaging. Recently, liquid-jet X-ray technology has enabled the generation of X-rays with high-power intensities in laboratory settings. By allowing the observation of cellular processes in their natural state, liquid-jet soft X-ray microscopy (SXM) can provide morphological information on living cells without staining. Furthermore, X-ray fluorescence imaging (XFI) permits the tracking of contrast agents in vivo with high elemental specificity, going beyond attenuation contrast. In this study, we established a methodology to investigate nanoparticle (NP) interactions in vitro and in vivo, solely based on X-ray imaging. We employed soft (0.5 keV) and hard (24 keV) X-rays for cellular studies and preclinical evaluations, respectively. Our results demonstrated the possibility of localizing NPs in the intracellular environment via SXM and evaluating their biodistribution with in vivo multiplexed XFI. We envisage that laboratory liquid-jet X-ray technology will significantly contribute to advancing our understanding of biological systems in the field of nanomedical research.

Microscopic and spectroscopic analysis of atmospheric iron-containing single particles in Lhasa, Tibet.

The Tibetan Plateau, known as the "Third Pole", is currently in a state of perturbation caused by intensified human activity. In this study, 56 samples were obtained at the five sampling sites in typical area of Lhasa city and their physical and chemical properties were investigated by TEM/EDS, STXM, and NEXAFS spectroscopy. After careful examination of 3387 single particles, the results showed that Fe should be one of the most frequent metal elements. The Fe-containing single particles in irregular shape and micrometer size was about 7.8% and might be mainly from local sources. Meanwhile, the Fe was located on the subsurface of single particles and might be existed in the form of iron oxide. Interestingly, the core-shell structure of iron-containing particles were about 38.8% and might be present as single-, dual- or triple-core shell structure and multi-core shell structure with the Fe/Si ratios of 17.5, 10.5, 2.9 and 1.2, respectively. Meanwhile, iron and manganese were found to coexist with identical distributions in the single particles, which might induce a synergistic effect between iron and manganese in catalytic oxidation. Finally, the solid spherical structure of Fe-containing particles without an external layer were about 53.4%. The elements of Fe and Mn were co-existed, and might be presented as iron oxide-manganese oxide-silica composite. Moreover, the ferrous and ferric forms of iron might be co-existed. Such information can be valuable in expanding our understanding of Fe-containing particles in the Tibetan Plateau atmosphere.

Realizing the Full Potential of Advanced Microscopy Approaches for Interrogating Plant-Microbe Interactions.

Microscopy has served as a fundamental tool for insight and discovery in plant-microbe interactions for centuries. From classical light and electron microscopy to corresponding specialized methods for sample preparation and cellular contrasting agents, these approaches have become routine components in the toolkit of plant and microbiology scientists alike to visualize, probe and understand the nature of host-microbe relationships. Over the last three decades, three-dimensional perspectives led by the development of electron tomography, and especially, confocal techniques continue to provide remarkable clarity and spatial detail of tissue and cellular phenomena. Confocal and electron microscopy provide novel revelations that are now commonplace in medium and large institutions. However, many other cutting-edge technologies and sample preparation workflows are relatively unexploited yet offer tremendous potential for unprecedented advancement in our understanding of the inner workings of pathogenic, beneficial, and symbiotic plant-microbe interactions. Here, we highlight key applications, benefits, and challenges of contemporary advanced imaging platforms for plant-microbe systems with special emphasis on several recently developed approaches, such as light-sheet, single molecule, super-resolution, and adaptive optics microscopy, as well as ambient and cryo-volume electron microscopy, X-ray microscopy, and cryo-electron tomography. Furthermore, the potential for complementary sample preparation methodologies, such as optical clearing, expansion microscopy, and multiplex imaging, will be reviewed. Our ultimate goal is to stimulate awareness of these powerful cutting-edge technologies and facilitate their appropriate application and adoption to solve important and unresolved biological questions in the field. [Formula: see text] Copyright © 2023 The Author(s). This is an open access article distributed under the CC BY 4.0 International license.

Online dynamic flat-field correction for MHz microscopy data at European XFEL.

The high pulse intensity and repetition rate of the European X-ray Free-Electron Laser (EuXFEL) provide superior temporal resolution compared with other X-ray sources. In combination with MHz X-ray microscopy techniques, it offers a unique opportunity to achieve superior contrast and spatial resolution in applications demanding high temporal resolution. In both live visualization and offline data analysis for microscopy experiments, baseline normalization is essential for further processing steps such as phase retrieval and modal decomposition. In addition, access to normalized projections during data acquisition can play an important role in decision-making and improve the quality of the data. However, the stochastic nature of X-ray free-electron laser sources hinders the use of standard flat-field normalization methods during MHz X-ray microscopy experiments. Here, an online (i.e. near real-time) dynamic flat-field correction method based on principal component analysis of dynamically evolving flat-field images is presented. The method is used for the normalization of individual X-ray projections and has been implemented as a near real-time analysis tool at the Single Particles, Clusters, and Biomolecules and Serial Femtosecond Crystallography (SPB/SFX) instrument of EuXFEL.

Automatic synchrotron tomographic alignment schemes based on genetic algorithms and human-in-the-loop software.

Tomography imaging methods at synchrotron light sources keep evolving, pushing multi-modal characterization capabilities at high spatial and temporal resolutions. To achieve this goal, small probe size and multi-dimensional scanning schemes are utilized more often in the beamlines, leading to rising complexities and challenges in the experimental setup process. To avoid spending a significant amount of human effort and beam time on aligning the X-ray probe, sample and detector for data acquisition, most attention has been drawn to realigning the systems at the data processing stages. However, post-processing cannot correct everything, and is not time efficient. Here we present automatic alignment schemes of the rotational axis and sample pre- and during the data acquisition process using a software approach which combines the advantages of genetic algorithms and human intelligence. Our approach shows excellent sub-pixel alignment efficiency for both tasks in a short time, and therefore holds great potential for application in the data acquisition systems of future scanning tomography experiments.

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.

Hard X-ray full-field nanoimaging using a direct photon-counting detector.

Full-field X-ray nanoimaging is a widely used tool in a broad range of scientific areas. In particular, for low-absorbing biological or medical samples, phase contrast methods have to be considered. Three well established phase contrast methods at the nanoscale are transmission X-ray microscopy with Zernike phase contrast, near-field holography and near-field ptychography. The high spatial resolution, however, often comes with the drawback of a lower signal-to-noise ratio and significantly longer scan times, compared with microimaging. In order to tackle these challenges a single-photon-counting detector has been implemented at the nanoimaging endstation of the beamline P05 at PETRA III (DESY, Hamburg) operated by Helmholtz-Zentrum Hereon. Thanks to the long sample-to-detector distance available, spatial resolutions of below 100 nm were reached in all three presented nanoimaging techniques. This work shows that a single-photon-counting detector in combination with a long sample-to-detector distance allows one to increase the time resolution for in situ nanoimaging, while keeping a high signal-to-noise level.