Scanning Transmission X-ray Microscopy Research Articles

Analysis of X-ray images and spectra (aXis2000): A toolkit for the analysis of X-ray spectromicroscopy data

Spectromicroscopy refers to analytical methods that combine imaging and spectroscopy to provide detailed, spatially resolved analytical information about a sample, such as the type and quantitative spatial distributions of chemical components, geometric or magnetic alignment information, crystal structure, etc. The analysis of X-ray images and spectra (aXis2000) software described in this work provides a set of routines within a single, integrated, graphical-oriented package to read, display, manipulate and analyze spectromicroscopy data, with particular focus on soft X-ray spectromicroscopy methods such as scanning transmission X-ray microscopy (STXM), X-ray photoemission electron microscopy (XPEEM), scanning photoelectron X-ray microscopy (SPEM) and transmission X-ray microscopy (TXM). Here, this free software is described and compared to other software that can provide similar or complementary capabilities. Examples of spectromicroscopic analyses using advanced features of aXis2000 are provided.

Cellulose nanocrystal/polymer nanocomposite latex via surfactant-free emulsion polymerization

Polar cellulose nanocrystals (CNCs) are difficult to disperse well in hydrophobic polymer matrices, and usually surfactants or expensive and time-consuming functionalization of the reinforcement or matrix have been attempted to improve dispersion. Here, we report a new, facile method to prepare CNC/polymer nanocomposite latices directly via surfactant-free emulsion polymerization of vinyl monomers and CNCs initiated by a cationic, water-soluble, free-radical initiator. The distribution of CNCs in the latex particles can be tailored through controlling the reaction procedures, namely, whether the monomers are added before or after preheating the CNCs with the initiator and has been confirmed by scanning electron microscopy (SEM) and scanning transmission X-ray microscopy (STXM) studies. CNCs distribute inside the latex particles if the monomers are added after the preheating step, and owing to the more even distribution of CNCs, such nanocomposite latices exhibit better mechanical properties than those prepared without preheating or via physically mixing CNCs with emulsions polymerized using conventional surfactant system. A latex particle formation mechanism is proposed based on these phenomena and polymerization kinetics studied in this work. Unlike typical CNC-based Pickering emulsion polymerization, our process can be operated without the need for intense mechanical shearing and provide an industrially scalable approach to prepare stable CNC/polymer nanocomposite latices that can be melt processed or used directly in a variety of applications, such as paints and coatings, adhesives, or cosmetics.

A library of calcium mineral reference spectra recorded by parallel imaging using NEXAFS spectromicroscopy

Calcium minerals are ubiquitous in geology and life chemistry. Understanding the phase and chemical state of calcium minerals is important for numerous processes including materials chemistry, hard tissue biogenesis and geological processes. Photoemission spectroscopies such as near edge X-ray absorption fine structure (NEXAFS) and scanning transmission X-ray microscopy have been instrumental in identifying and characterizing calcium minerals in all these areas. In this work, we have recorded reference spectra for a range of different calcium minerals including a series of calcium carbonates, calcium oxalates and calcium phosphates. While collections of reference spectra for several calcium minerals can be found in the literature, these spectra have been reported in different contexts using a variety of instruments. We, here, report a comprehensive list of references recorded in parallel in a single experiment by imaging an array of calcium minerals using a NEXAFS microscope. We present reference NEXAFS spectra at the calcium L-, carbon K- and oxygen K-edges.

Illuminating the brain: Revealing brain biochemistry with synchrotron X-ray spectromicroscopy

The synchrotron x-ray spectromicroscopy technique Scanning Transmission X-ray Microscopy (STXM) offers a powerful means to examine the underlying biochemistry of biological systems, owing to its combined chemical sensitivity and nanoscale spatial resolution. Here we introduce and demonstrate methodology for the use of STXM to examine the biochemistry of the human brain. We then discuss how this approach can help us better understand the biochemical changes that occur during the development of degenerative brain disorders, potentially facilitating the development of new therapies for disease diagnosis and treatment.

On the use of soft X-ray STXM for organic-inorganic halide perovskite photovoltaic materials

Metal-halide perovskites are complex materials with outstanding optoelectronic properties. Thus it is of interest to analyze these materials by using every available research tool. Synchrotron tools have played an important role in fundamental and applied research for decades. Many synchrotron-based hard X-ray tools are already providing effective feedback to the perovskite solar cell (PSC) research community. With several fourth-generation light sources up and running or under development, this contribution will continue to impact every aspect of scientific advancement including PSC research. Arguably, the contribution of soft X-rays in PSC research is relatively limited. In view of the developments in the synchrotron world and the fact that a multimethod approach, combining laboratory-based techniques as well as synchrotron-based techniques, is necessary to provide constructive feedback to the PSC community we present here a collection of arguments and procedures with the aim of highlighting the use of soft X-ray scanning transmission X-ray microscopy (STXM). Some aspects of these arguments are elaborated with STXM investigation of perovskite material formamidinium-methylammonium lead iodide (FA1−xMAxPbI3).

Developments in sample environment for a scanning transmission X-ray microscope at UVSOR-III synchrotron

The beamline, BL4U, in UVSOR-III Synchrotron is dedicated to scanning transmission X-ray microscopy (STXM) based on 2-dimensional soft X-ray absorption and has been in operation since 2013, to enable both academic and industrial users to carry out advanced chemical analysis under various sample environments. In this paper, we have summarized our major developments for the last decade; especially, expansion of the photon energy range down to the Li K-edge (55 eV), sample cryo-cooling to reduce radiation damage, 3-dimensional computer tomography, and air-free sample transfer.

Energy material analysis via in-situ/operando scanning transmission x-ray microscopy: A review

The development of advanced energy systems is essential for replacing fossil fuel-based societies, and progress in the fundamental understanding of solid-state energy materials has revolutionized this field. In particular, investigating the inhomogeneity of reactions in energy systems requires analysis at the level of individual particles, which are the smallest units in the system. Synchrotron-based scanning transmission X-ray microscopy (STXM) is a valuable tool for exploring reaction and degradation mechanisms, and providing nanoscale site-specific information on chemical and structural changes within single particles. In-situ/operando STXM is particularly useful for observing reactions under well-controlled conditions in real time, thus providing insights into local phenomena obscured by the ensemble effect. This review highlights the research achievements of in-situ/operando STXM in the field of energy materials and provides perspectives for advanced X-ray imaging techniques that can further enhance STXM capabilities.

Visualization of air-induced oxidation in single crystalline LiFe0.6Mn0.4PO4 nanowires with carbon sheath using soft X-ray spectromicroscopy

Single crystalline LiFe0.6Mn0.4PO4 (LFMP) nanowires with carbon sheath were analyzed by scanning transmission X-ray microscopy (STXM) with a spatial resolution of around 130 nm. The pinpoint Fe L-edge X-ray absorption spectroscopy (XAS) spectra in the STXM images revealed the natural oxidation of Fe2+ to Fe3+ near the tip of the nanowire by air exposure. The pinpoint O K-edge XAS spectra simultaneously changed with the Fe L-edge XAS in the STXM mapping because of the hybridization between the O 2p and Fe 3d orbitals. On the other hand, the Mn L-edge XAS spectra showed an almost uniform Mn2+ state all over the nanowires, suggesting that the Mn2+ state is stable against the natural oxidation in contrast to the Fe2+ state. We have thus demonstrated that STXM is a useful technique to visualize oxidized areas of materials and to reveal detailed information about their electronic structure.

Soft X-ray scanning transmission microscopy as a selective probe of topical dermal drug delivery: The role of petrolatum and occlusion

Selective and label-free probing of drugs by scanning transmission X-ray microscopy (STXM) is applied along with hyperspectral imaging to probe topically applied drugs in human skin explants ex vivo. A comparison of data evaluation strategies is reported, which includes changes in optical density at selected photon energies in the O 1 s regime, linear combination modeling using reference spectra, as well as principal component and cluster analyses. It is shown that consistent results are obtained from linear combination modeling of reference spectra and changes in optical density. The dermal penetration of the anti-inflammatory drug rapamycin is investigated with high spatial resolution using a petrolatum-based formulation. For such well-known formulation the result of occlusion is investigated leading to drug uptake into corneocytes. Additional changes in drug penetration induced by weakening the skin barrier by the serine protease trypsin are also included. These results are discussed in comparison with the dermal penetration of other drug formulations. Finally, alternatives to present data acquisition strategies in STXM are discussed with respect to sub-sampling in combination with mathematical approaches, so that the full chemical and spatial information can be retrieved and radiation damage is minimized.

Applicability of Focused-ion-beam-based Thin Sectioning for STXM-NEXAFS Analysis of Carbon Species: An Examination of Kaolinite-bacteria Composite

Thin sectioning of organo-mineral nanocomposites enables the elucidation of organic chemistry in their intact structures. Yet its preparation may cause material damage. Using artificial clay-bacteria composites, we showed that thin sectioning using focused ion beam (FIB) caused no significant alternation to carbon (C) chemistry in the composites analyzed by C K-edge spectra with scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure (STXM-NEXAFS), suggesting positive applicability of this approach. Thin sectioning of organo-mineral nanocomposites enables the elucidation of organic chemistry in their intact structures. Yet its preparation may cause material damage. Using artificial clay-bacteria composites, we showed that thin sectioning using FIB caused no significant alternation to carbon (C) chemistry in the composites analyzed by C K-edge spectra with STXM-NEXAFS, suggesting positive applicability of this approach.

High-Resolution X-ray Spectromicroscopy Reveals Process-Structure Correlations in sub-5-μm Diameter Carbon Nanotube-Polymer Composite Dry-Spun Yarns.

A persistent lack of detailed and quantitative structural analysis of these hierarchical carbon nanotube (CNT) ensembles precludes establishing processing-structure-property relationships that are essential to enhance macroscale performance (e.g., in mechanical, electrical, thermal applications). Here, we use scanning transmission X-ray microscopy (STXM) to analyze the hierarchical, twisted morphology of dry-spun CNT yarns and their composites, quantifying key structural characteristics such as density, porosity, alignment, and polymer loading. As the yarn twist density increases (15,000 to 150,000 turns per meter), the yarn diameter decreased (4.4-1.4 μm) and density increased (0.55-1.26 g·cm-3), as intuitively expected. Yarn density, ρ, ubiquitously scaled with diameter d according to ρ ∼ d-2 for all parameters studied here. Spectromicroscopy probes with 30 nm resolution and elemental specificity were employed to analyze the radial and longitudinal distribution of the oxygen-containing polymer content (∼30% weight fraction), demonstrating nearly perfect filling of the voids between CNTs with a vapor-phase polymer coating and cross-linking process. These quantitative correlations highlight the intimate connections between processing conditions and yarn structure with important implications for translating the nanoscale properties of CNTs to the macroscale.

Imaging of short-wavelength spin waves in a nanometer-thick YIG/Co bilayer

We report the imaging of short-wavelength spin waves in a continuous nanometer-thick YIG film with a Co stripe patterned on top. Dynamic dipolar coupling between the YIG film and the Co stripe lowers the spin-wave wavelength when spin waves enter the YIG/Co bilayer region from the bare YIG film, causing partial reflection at the YIG/Co edge. We use time-resolved scanning transmission x-ray microscopy to image the mode conversion process down to a wavelength of 280 nm and extract the spin-wave dispersion, decay length, and magnetic damping in the YIG/Co bilayer. We also analyze spin-wave reflection from the YIG/Co edge and its dependence on the wavelength of incoming and transmitted spin waves.

Microbial traces found in microdolomite associated with seep-related shallow gas hydrate

Recently, microdolomite grains with a diameter of about 30–150 μm were discovered within seep-related shallow gas hydrate in the eastern margin of the Japan Sea, and the preliminary assumption has been that their formation is mediated by microbially secreted extracellular polymeric substances (EPS). To verify this interpretation, the present study investigates the characteristics of minerals and organic matter inside the microdolomite grains. Observation by polarizing microscopy reveals that the microdolomite grains generally consist of combinations of distinct cores and external cements. The cores are mostly dark or cloudy and their abundance does not show clear depth dependence, while the external cements are generally isopachous in the shallow part and polygonal in the deeper portions. To further clarify the characteristics of these cores and external cements, thin-foil sections were prepared from two major types of microdolomite, one with a dark core and polygonal external cement, and one with a cloudy core and isopachous external cement. These thin-foil sections were then analyzed by scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM). In the dark core, fibriform pores of about 100 nm diameter were observed to be closely related with amorphous calcium carbonate (ACC) and carboxy groups, likely created by heterogeneous nucleation on microbial EPS surfaces. The polygonal external cement is composed of monocrystalline dolomite, representing slow crystal growth in the deeper part where hydrate formation is less active. On the other hand, the observed cloudy core and the isopachous external cement are, respectively, composed of scattered and accumulated rhombohedral dolomite crystals, presumably resulting from homogeneous nucleation in saline pockets of rapidly growing hydrate and subsequent crystal accumulation on the surface of spherical oil films.

Soft X-ray spectro-ptychography of boron nitride nanobamboos, carbon nanotubes and permalloy nanorods.

Spectro-ptychography offers improved spatial resolution and additional phase spectral information relative to that provided by scanning transmission X-ray microscopes. However, carrying out ptychography at the lower range of soft X-ray energies (e.g. below 200 eV to 600 eV) on samples with weakly scattering signals can be challenging. Here, results of soft X-ray spectro-ptychography at energies as low as 180 eV are presented, and its capabilities are illustrated with results from permalloy nanorods (Fe 2p), carbon nanotubes (C 1s) and boron nitride bamboo nanostructures (B 1s, N 1s). The optimization of low-energy X-ray spectro-ptychography is described and important challenges associated with measurement approaches, reconstruction algorithms and their effects on the reconstructed images are discussed. A method for evaluating the increase in radiation dose when using overlapping sampling is presented.

Apochromatic X-ray focusing

Achromatic doublets are combinations of two individual lenses designed to focus different wavelengths of light in the same position. Apochromatic optics are improved versions of the achromatic schemes which extend the wavelength range significantly. Both achromatic and apochromatic optics are well-established for visible light. However, X-ray achromatic lenses did not exist until very recently, and X-ray apochromatic lenses have never been experimentally demonstrated. Here, we create an X-ray apochromatic lens system using an appropriate combination of a Fresnel zone plate and a diverging compound refractive lens with a tuned separation distance. The energy-dependent performance of this apochromat was characterized at photon energies between 6.5 and 13.0 keV by ptychographic reconstruction of the focal spot and scanning transmission X-ray microscopy of a resolution test sample. The apochromat delivered a reconstructed focal spot size of 940 × 740 nm2. The apochromatic combination shows a four-fold improvement in the chromatic aberration correction range compared to an achromatic doublet configuration. Thus, apochromatic X-ray optics have the potential to increase the focal spot intensity for a wide variety of X-ray applications.

Scanning transmission X-ray microscopy of hydrogen evolution electrocatalysts on reduction graphene oxide membranes

Cobalt is one of the promising metal catalysts for hydrogen evolution reaction, and its catalytic performance can be further improved by supporting on graphene oxide and reduced graphene oxide as an active interface to the substrate. Scanning transmission X-ray microscopy (STXM) identifies the position-dependent functional groups on the membranes and chemical structure evolution of the CoxOy. The in-situ mass spectrometer analysis shows the reduction current and H2 generation of the electrocatalyst enhanced by the addition of graphene oxide and reduced graphene oxide to CoxOy, as compared to the CoxOy on the bare substrate. The best hydrogen evolution reaction performance of CoxOy at − 2.5 V is correlated with the high Co3+ concentration existed on the reduced graphene oxide, as evidenced by the nano- and element-resolved capability of STXM. With the economical electro-reduction synthesis, this study provides brand-new insights into the critical role of substrate rGO and electrocatalyst CoxOy toward the design of high efficiency electrocatalyst.

Imaging the complex interactions in CuAg-PEO nanoparticles ensemble for enhanced CO2 reduction

CO2 electrochemical reduction (CO2ER) is a promising technology that can convert CO2 into useful chemicals and fuels with simultaneously reducing greenhouse gas emissions. Cu nanoparticles-based catalysts are an optimal choice of CO2ER due to its excellent conductivity and catalytic activity. In this study, we combined scanning transmission X-ray microscopy (STXM) and spectro-ptychography to investigate the chemical and electronic structural changes of the CuAg nanocatalysts before and after CO2ER. We observed that Cu species with the same valence state self-aggregate into separated phases. For the spent CuAg nanocatalysts after CO2ER, most Cu(I) and Cu(0) species are oxidized to Cu(II) together with CuO transforming into undetermined Cu(II) species. We believe these mechanisms are the key reason why the CuAg nanocatalysts lost catalytic activity. Such information will be highly valuable for understanding Cu nanoparticles catalyzed CO2ER.

Scanning transmission X-ray spectromicroscopy: A nanotool to probe hematite nanorods for solar water splitting

We report a scanning transmission X-ray microscopy (STXM) study of hematite nanorods, prototypical photoanode used in solar water splitting. Hematite nanorods were obtained by hydrothermal growth from aqueous solutions using FeCl3 as precursor. Potentials for onset of water splitting are smaller using this synthesis method, compared to values reported for hematite photoanodes obtained by epitaxial growth. STXM revealed the presence of a hexahydrate iron chloride phase at the surface of the nanorods, which is linked to the low onset potential values. We detail the quantification approach that revealed the specific microstructure of individual hematite nanorods.

Development of a red persistent luminescent composite: Electrospun nanofiber polymer coating prevents emission quenching by water

Sulfide persistent luminescent materials are known for their efficient luminescence, although a limitation in application of these materials is their susceptibility to hydrolysis. In this work, the electrospinning technique was used to encapsulate polycrystalline SrS:Eu2+,Sm3+ within PVDF-co-HFP nanofibers, after which thermostimulated luminescence could be observed with the naked eye following treatment with boiling water, confirming that the storage capacity of the powder was maintained after encapsulation. The composite material presented high levels of flexibility, hydrophobicity, and thermal and chemical stability. The structural characteristics of the synthesized SrS:Eu2+,Sm3+ were elucidated using X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The morphologies of the SrS:Eu2+,Sm3+ grains and the electrospun nanofibers were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray fluorescence (XRF) mapping, and scanning transmission X-ray microscopy (STXM). Mechanical properties including elastic modulus and deformation degree were evaluated by PeakForce quantitative nanomechanical mapping (PF-QNM). The luminescent properties were investigated using photoluminescence spectroscopy (PLS), diffuse reflectance spectroscopy (DRS), and X-ray excited optical luminescence (XEOL), which showed that the photonic functionality of the material in the nanofibers was preserved, even after severe treatment with boiling water.

Uncoordinated chemistry enables highly conductive and stable electrolyte/filler interfaces for solid-state lithium–sulfur batteries

Composite-polymer-electrolytes (CPEs) embedded with advanced filler materials offer great promise for fast and preferential Li+ conduction. The filler surface chemistry determines the interaction with electrolyte molecules and thus critically regulates the Li+ behaviors at the interfaces. Herein, we probe into the role of electrolyte/filler interfaces (EFI) in CPEs and promote Li+ conduction by introducing an unsaturated coordination Prussian blue analog (UCPBA) filler. Combining scanning transmission X-ray microscope stack imaging studies and first-principle calculations, fast Li+ conduction is revealed only achievable at a chemically stable EFI, which can be established by the unsaturated Co-O coordination in UCPBA to circumvent the side reactions. Moreover, the as-exposed Lewis-acid metal centers in UCPBA efficiently attract the Lewis-base anions of Li salts, which facilitates the Li+ disassociation and enhances its transference number (tLi+). Attributed to these superiorities, the obtained CPEs realize high room-temperature ionic conductivity up to 0.36 mS cm-1 and tLi+ of 0.6, enabling an excellent cyclability of lithium metal electrodes over 4,000 h as well as remarkable capacity retention of 97.6% over 180 cycles at 0.5 C for solid-state lithium-sulfur batteries. This work highlights the crucial role of EFI chemistry in developing highly conductive CPEs and high-performance solid-state batteries.