X-ray Nanoprobe Research Articles

Preparation and enhanced supercapacitive performance of Ni-Zn-Co-S/3D Ni porous substrate using electrochemical and synchrotron X-ray spectroscopic techniques

The Ni-Zn-Co-S/3D Ni porous substrate was successfully synthesized and used as electrode material in supercapacitors. The morphology, structural characterization and supercapacitive performance of Ni-Zn-Co-S/3D Ni porous substrate can be controlled by adjusting the deposition time of 3D Ni porous substrate and the concentration of Zn-Co precursor solution. The Ni-Zn-Co-S/3D Ni porous substrate was characterized and investigated by SEM, TEM, XRD, XPS, and electrochemical analysis to expound their advantages and the mechanisms of energy storage/conversion processes. The results evidenced that Ni-Zn-Co-S/3D Ni porous substrate provided an effective strategy to significantly enhance the supercapacitive performance through the synergistic effect of unique interconnected architecture and redox characteristics of multiple metal oxides, which could create more electrochemically active sites for the fast redox reaction. These results also combined with X-ray spectroscopic technique (hard X-ray nanoprobe) gave us a better understanding to establish the optimization of the synthesis parameters for the preparation of electrode materials and could further provides useful insights for the future development and optimization of next-generation advanced energy storage/conversion technologies.

In-Operando Nanoscale X-ray Analysis Revealing the Local Electrical Properties of Rubidium-Enriched Grain Boundaries in Cu(In,Ga)Se2 Solar Cells.

Chalcogenide Cu(In,Ga)Se2 solar cells yield one of the highest efficiencies among all thin-film photovoltaics. However, the variability of the absorber compositions and incorporated alkali elements strongly affect the conversion efficiency. Thus, effective strategies for spatially resolved tracking of the alkali concentration and composition during operation are needed to alleviate this limitation. Here, using a hard X-ray nanoprobe, we apply a synergistic approach of X-ray fluorescence analysis and X-ray beam-induced current techniques under operando conditions. The simultaneous monitoring of both compositional and functional properties in complete solar cells illustrates the exceptional capabilities of this combination of techniques in top-view geometry, where high spatial resolution resulted even underneath the electrical contacts. Our observations reveal Rb agglomerations in selected areas and compositional variations between different grains and their boundaries. The concurrent detection of the functionality exhibits negligible effects on the collection efficiency for Rb-enriched grain boundaries in comparison to their neighboring grains, which indicates the passivation of detrimental defects.

Halide Perovskites – Optoelectronic and Structural Characterization Methods

Halide Perovskites – Optoelectronic and Structural Characterization Methods

A helium mini-cryostat for the nanoprobe beamline ID16B at ESRF: characteristics and performance.

A helium mini-cryostat has been developed for the hard X-ray nanoprobe ID16B of the European Synchrotron to collect X-ray excited optical luminescence and X-ray fluorescence at low temperature (<10 K). The mini-cryostat has been specifically designed to fit within the strong space restrictions and high-demanding mechanical constraints imposed by the beamline to provide vibration-free operation and maximal thermal stability. This paper reports the detailed design, architecture and technical requirements of the mini-cryostat, and presents the first experimental data measured using the cryogenic equipment. The resulting cryo-system features ultimate thermal stability, fast cool-down and ultra-low vibrations. The simultaneous X-ray fluorescence and X-ray excited optical luminescence data acquired from bulk GaN and core/shell InGaN/GaN multi-quantum wells validated the excellent performance of the cryostat with ultimate resolution, stability and sensitivity.

Emerging Experimental Strategies for Studies on Inhomogeneous Nanomaterials. Exploring Electronics, Atomic Structure and Properties by Synchrotron X-Ray-Based Techniques

Through representative examples, we illustrate the strategic value of synchrotron X-ray-based techniques for nanomaterial characterization, especially for inhomogeneous nanomaterials. These examples are used to describe opportunities, motivations for new questions and possible reexamination of older topics, not only due to the proven success of the scientific instrumentation, but also because the extraordinary specific advantages offered by the new X-ray micro and nanoprobes techniques.

Magnetic Field Optimization of an In-Vacuum Undulator at NSLS-II Transactions on Applied Superconductivity

A 3.0 m long In-Vacuum Undulator (IVU) is employed at the National Synchrotron Light Source II (NSLS-II) for the Hard X-ray Nanoprobe (HXN) beamline providing structural and X-ray fluorescence imaging with world-leading spatial resolution. On July 1 st 2018 a gearbox shaft in the gap drive train assembly sheared due to corrosion fatigue caused by stress due to mechanical misalignment. The device was extracted from the storage ring and measured. The magnetic field measurements detected a degradation of the magnetic performance as well as a localized demagnetization of the magnetic modules of the first 3 upstream periods. This paper describes the mechanical repairs and the magnetic phase shimming optimization implemented to restore the spectral performance of the device.

Indentation response of a superlattice thin film revealed by in-situ scanning X-ray nanodiffraction

Nanocrystalline materials such as thin films, and in particular, multilayers with a periodicity in the nanometer range, i.e. superlattice films, possess properties that cannot be found in their coarse-grained bulk counterparts. Mechanical characterization of such structures is therefore of high interest, but also very challenging, due to the small length scales involved and has therefore most often been performed ex-situ using electron microscopy. In this work, however, we report on the first in-situ micromechanical analysis of a CrN-AlN superlattice thin film cross-section. The sample was deposited using reactive magnetron sputtering and sublayer thicknesses were chosen so as to stabilize AlN in its cubic crystal structure. Using a synchrotron X-ray nanoprobe, maps of internal stresses and morphological changes were tracked by means of wide-angle X-ray diffraction and simultaneous small-angle X-ray scattering, while the sample was loaded to various degrees with a wedged diamond tip. The results reveal a high compressive strength of about 13 GPa, while through-thickness cracks form, following tensile stresses >1.4 GPa and thereby provide a relaxation mechanism. Layer rotation up to several degrees and significant layer compression up to 7% were also found, but along with the internal stress response, their nature is mostly elastic, meaning that in the post-loading state only a fraction of the effects observed under load remains.

Use of Multi-Modal Synchrotron Analytical Techniques to Understand Anomalous Localized and General Corrosion Behavior of Additively Manufactured 316L Stainless Steel

Additive manufacturing (AM) of alloys such as stainless steels has the potential to be a disruptive technology for design of complex structures which eliminates the potentially damaging effects of mechanical failure and localized corrosion associated with interfaces between separate parts (which can now be printed as part of a single assembly). In addition, increasingly complex geometries can be manufactured with nearly as much ease as simple ones, and new mechanisms for optimization and generative design can allow manufacturers to achieve significant material and weight savings. However, challenges remain, in particular due to the potential for material variabilities both between parts made with the same nominal build parameters and even within a single build, as the consistency in properties inherent in the commercial-scale forging of alloys to be machined into components is exchanged for the considerable advantages of on-site, distributed custom parts production. Our studies and related work by other groups indicates that this is clearly true in the case of corrosion susceptibility in AM alloys. By studying the relationship between build parameters and electrochemical properties, we propose that it will be possible to tailor alloys for enhanced corrosion properties.AM processes produce materials with hierarchical microstructures containing fusion boundaries at the macroscale, irregular grains and grain boundaries at the microscale, and subgrain dislocation structures at the nanoscale. In laser powder bed fusion (LPBF) formed 316L stainless steel structures, corrosion performance has been discussed in the context of chemical heterogeneities formed in the presence of these hierarchical microstructures. However, the large variability in reported measurements underscores the need for statistically significant microstructural data, which is often difficult to access via electron microscopy alone. In this presentation, we explore multi-modal synchrotron X-ray techniques for quantifying hierarchical microstructures and their connection to the underlying chemical distribution in 316L stainless steel. Our results show that the dislocation density depends on the printing conditions with implications for the chemical distribution at the nanoscale, which in turn may play a key role in inconsistent corrosion behavior.LPDF 316L samples formed at varying speeds using pulsed and continuous laser deposition are compared via cyclic polarization in 3.5% NaCl and 0.1M HCl solutions, as well as using standard methods for characterizing sensitization. Surface corrosion layers are characterized using laboratory-based X-ray photoelectron spectroscopy to determine the impact on passivity of the aforementioned microsegregation associated with process-induced microstructures. Corrosion rates and pit densities are then discussed to build a connection between printing conditions and corrosion performance vis-à-vis microstructural and chemical information from synchrotron measurements performed at Brookhaven National Laboratory (BNL), including high energy X-ray diffraction using the X-ray Powder Diffraction (XPD) beamline at the National Synchrotron Light Source-II (NSLS-II) which provided data on minor precipitate population(s), atomic structure and dislocation microstructures critical to corrosion behavior. In addition, heterogeneities in elemental composition data is provided by 2D X-ray fluorescence (XRF) and 2D X-ray Absorption Spectroscopy (XAS) nanometer resolution-mapping obtained at the Hard X-ray Nanoprobe (HXN) beamline at the NSLS-II and correlated with process-induced hierarchal structures via use of the microscopy facilities at the Center for Functional Nanomaterials (CFN).By employing a combination of multi-modal synchrotron characterization techniques, electron microscopy, and baseline testing protocol combined with electrochemical polarization experiments, we are able to study the the role of microstructure across multiple length scales on electrochemical properties and corrosion performance. Understanding the impact of microstructure and chemical heterogeneities on the susceptibility to pitting and intergranular attack will enable microstructurally-informed process optimization and materials design for enhancing the corrosion resistance of LPBF 316L stainless steel, with implications for AM and subsequent durability of alloys in general.

Metals Coprecipitation with Barite: Nano-XRF Observation of Enhanced Strontium Incorporation.

Coprecipitation can be an effective treatment method for the removal of environmentally relevant metals from industrial wastewaters such as produced waters from the oil and gas industry. The precipitation of barite, BaSO4, through the addition of sulfate removes barium while coprecipitating strontium and other alkaline earth metals even when these are present at concentrations below their solubility limit. Among other analytical methods, X-ray fluorescence (XRF) nanospectroscopy at the Hard X-ray Nanoprobe (HXN) beamline at the National Synchrotron Light Source II (NSLS-II) was used to quantify Sr incorporation into barite. Thermodynamic modeling of (Ba,Sr)SO4 solid solutions was done using solid solution—aqueous solution (SS-AS) theory. The quantitative, high-resolution nano-XRF data show clearly that the Sr content in (Ba,Sr)SO4 solid solutions varies widely among particles and even within a single particle. We observed substantial Sr incorporation that is far larger than thermodynamic models predict, likely indicating the formation of metastable solid solutions. We also observed that increasing barite supersaturation of the aqueous phase led to increased Sr incorporation, as predicted by available kinetic models. These results suggest that coprecipitation offers significant potential for designing treatment systems for aqueous metals' removal in desired metastable compositions. Solution conditions may be optimized to enhance the incorporation of Sr by increasing sulfate addition such that the barite saturation index remains above ∼3 or by increasing the aqueous Sr to Ba ratio.

Ptychographic characterization of a coherent nanofocused X-ray beam.

The NanoMAX hard X-ray nanoprobe is the first beamline to take full advantage of the diffraction-limited storage ring at the MAX IV synchrotron and delivers a high coherent photon flux for applications in diffraction and imaging. Here, we characterize its coherent and focused beam using ptychographic analysis. We derive beam profiles in the energy range 6-22 keV and estimate the coherent flux based on a probe mode decomposition approach.

Capabilities of time-resolved X-ray excited optical luminescence of the Taiwan Photon Source 23A X-ray nanoprobe beamline.

Time-resolved X-ray excited optical luminescence (TR-XEOL) was developed successfully for the 23A X-ray nanoprobe beamline located at the Taiwan Photon Source (TPS). The advantages of the TR-XEOL facility include (i) a nano-focused X-ray beam (<60 nm) with excellent spatial resolution and (ii) a streak camera that can simultaneously record the XEOL spectrum and decay time. Three time spans, including normal (30 ps to 2 ns), hybrid (30 ps to 310 ns) and single (30 ps to 1.72 µs) bunch modes, are available at the TPS, which can fulfil different experimental conditions involving samples with various lifetimes. It is anticipated that TR-XEOL at the TPS X-ray nanoprobe could provide great characterization capabilities for investigating the dynamics of photonic materials.

Hard X-ray nanoprobe and time-resolved XEOL to observe increasing luminescence of ZnO and GaN epitaxial structures

Hard X-ray excited optical luminescence (XEOL) with a nanofocused beam provides both excellent spatial resolution and high enough peak power density, which makes XEOL mapping and luminescence dynamics study achievable. We present here the time and X-ray intensity dependence of the near-band-edge (NBE) luminescence from the nonpolar a-plane MgZnO/ZnO multiple quantum wells (MQWs): the emission intensity increases more than 10 times after high X-ray irradiation. Different from the well-known NBE emission lifetime of ZnO (less than 1 ns), the long decay time gradually decreases from 130 ns to 35 ns with the increasing X-ray irradiation time. We attribute the observed changes in NBE luminescence to the excitation of the Mg-related energy state by the high energy X-ray nanobeam. This suggestion was further confirmed in the XEOL spectra of the Mg-doped and Si-doped c-plane GaN epi-films.

(Invited) Synchrotron-Based Hard X-Ray Microscopy: Instruments for 3-D Spectroscopic Imaging at the Nanoscale

Advances in materials increasingly rely on the 3-D characteristics of its microstructure and chemistry at the nanoscale. This presentation will review 3-D spectroscopic imaging techniques that measure microstructural and chemical properties, and discuss its influence on material function and performance. The presentation will then focus on two synchrotron-based 3-D spectroscopic imaging instruments: the Transmission X-ray Microscope (TXM) and the Hard X-ray Nanoprobe (HXN) to characterize the 3-D structural and chemical distribution of fuel cell, gas separation membrane and nuclear waste form materials. Challenges and opportunities for future work will then be discussed. The goal of this research will be to obtain a scientific and engineering understanding into how microstructure-induced transport mechanisms govern performance, with a long-term goal to improve current materials and create new materials that will enable improved device performance and increased long-term reliability for advanced engineering applications.

(Invited) Defects and Development of High Power Vertical GaN Based Structures

This presentation highlights the use of x-ray scattering and electron microscopy to characterize selectively doped GaN layers for high power vertical diodes. Examples from these techniques will include assessment of residual impurities and crystalline damage in selectively doped regions resulting from dry etching or ion implantation processes and if such defects are removed by subsequent etching and / or annealing steps. X-ray reflectivity (XRR) combined with high angle reciprocal space mapping and dynamical diffraction simulations are effective means by which to assess the strain and defect distribution in the wafers. Advanced synchrotron techniques, through the use of hard x-ray nanoprobes and diffraction imaging, offer further insight into the development of these technologies. Transmission Electron Microscopy measurements, including electron energy loss spectroscopy, energy dispersive x-ray analysis, and selected area diffraction patterns, determine whether impurities were introduced by the selective doping process and whether the damage removal processes were able to remove growth and implantation-induced defects. A better understanding of the roles of defects on device performance is based on these techniques.

A versatile nanoreactor for complementary in situ X-ray and electron microscopy studies in catalysis and materials science.

Two in situ `nanoreactors' for high-resolution imaging of catalysts have been designed and applied at the hard X-ray nanoprobe endstation at beamline P06 of the PETRA III synchrotron radiation source. The reactors house samples supported on commercial MEMS chips, and were applied for complementary hard X-ray ptychography (23 nm spatial resolution) and transmission electron microscopy, with additional X-ray fluorescence measurements. The reactors allow pressures of 100 kPa and temperatures of up to 1573 K, offering a wide range of conditions relevant for catalysis. Ptychographic tomography was demonstrated at limited tilting angles of at least ±35° within the reactors and ±65° on the naked sample holders. Two case studies were selected to demonstrate the functionality of the reactors: (i) annealing of hierarchical nanoporous gold up to 923 K under inert He environment and (ii) acquisition ofa ptychographic projection series at ±35° of a hierarchically structured macroporous zeolite sample under ambient conditions. The reactors are shown to be a flexible and modular platform for in situ studies in catalysis and materials science which may be adapted for a range of sample and experiment types, opening new characterization pathways in correlative multimodal in situ analysis of functional materials at work. The cells will presently be made available for all interested users of beamline P06 at PETRA III.

Coherent Bragg imaging of 60 nm Au nanoparticles under electrochemical control at the NanoMAX beamline.

Nanoparticles are essential electrocatalysts in chemical production, water treatment and energy conversion, but engineering efficient and specific catalysts requires understanding complex structure-reactivity relations. Recent experiments have shown that Bragg coherent diffraction imaging might be a powerful tool in this regard. The technique provides three-dimensional lattice strain fields from which surface reactivity maps can be inferred. However, all experiments published so far have investigated particles an order of magnitude larger than those used in practical applications. Studying smaller particles quickly becomes demanding as the diffracted intensity falls. Here, in situ nanodiffraction data from 60 nm Au nanoparticles under electrochemical control collected at the hard X-ray nanoprobe beamline of MAX IV, NanoMAX, are presented. Two-dimensional image reconstructions of these particles are produced, and it is estimated that NanoMAX, which is now open for general users, has the requisites for three-dimensional imaging of particles of a size relevant for catalytic applications. This represents the first demonstration of coherent X-ray diffraction experiments performed at a diffraction-limited storage ring, and illustrates the importance of these new sources for experiments where coherence properties become crucial.

The Velociprobe: An ultrafast hard X-ray nanoprobe for high-resolution ptychographic imaging.

Motivated by the advanced photon source upgrade, a new hard X-ray microscope called "Velociprobe" has been recently designed and built for fast ptychographic imaging with high spatial resolution. We are addressing the challenges of high-resolution and fast scanning with novel hardware designs, advanced motion controls, and new data acquisition strategies, including the use of high-bandwidth interferometric measurements. The use of granite, air-bearing-supported stages provides the necessary long travel ranges for coarse motion to accommodate real samples and variable energy operation while remaining highly stable during fine scanning. Scanning the low-mass zone plate enables high-speed and high-precision motion of the probe over the sample. With an advanced control algorithm implemented in a closed-loop feedback system, the setup achieves a position resolution (3σ) of 2 nm. The instrument performance is evaluated by 2D fly-scan ptychography with our developed data acquisition strategies. A spatial resolution of 8.8 nm has been demonstrated on a Au test sample with a detector continuous frame rate of 200 Hz. Using a higher flux X-ray source provided by double-multilayer monochromator, we achieve 10 nm resolution for an integrated circuit sample in an ultrafast scan with a detector's full continuous frame rate of 3000 Hz (0.33 ms per exposure), resulting in an outstanding imaging rate of 9 × 104 resolution elements per second.

Three-Dimensional Correlative Imaging of a Malaria-Infected Cell with a Hard X-ray Nanoprobe.

Benefiting from the recent advances of synchrotron X-ray nanoprobes, we demonstrate three-dimensional (3D) correlative nanoimaging on malaria-infected human red blood cells. By combining X-ray fluorescence tomography and phase contrast nanotomography on the same cell with sub-100 nm pixel size, we establish a routine workflow from the data acquisition, data processing, to tomographic reconstruction. We quantitatively compare the elemental volumes obtained with different reconstruction methods, with the total variation minimization giving the most satisfactory results. We reveal elemental correlations in different cell compartments more reliably on reconstructions as opposed to 2D projections. Finally, we determine for the first time the 3D mass fraction maps of multiple elements at the subcellular level. The estimated total number of Fe atoms and the total mass of red blood cells show very good agreement with previously reported values.

A piezoelectric deformable X-ray mirror for phase compensation based on global optimization.

As a strong tool for the study of nanoscience, the synchrotron hard X-ray nanoprobe technique enables researchers to investigate complex samples with many advantages, such as in situ setup, high sensitivity and the integration of various experimental methods. In recent years, an important goal has been to push the focusing spot size to the diffraction limit of ∼10 nm. The multilayer-based Kirkpatrick-Baez (KB) mirror system is one of the most important methods used to achieve this goal. This method was chosen by the nanoprobe beamline of the Phase-II project at the Shanghai Synchrotron Radiation Facility. To overcome the limitations of current polishing technologies, the use of an additional phase compensator was necessary to decrease the wavefront distortions. In this experiment, a prototype phase compensator has been created to show how to obtain precise wavefront compensation. With the use of finite-element analysis and Fizeau interferometer measurements, some important factors such as the piezoresponse, different actuator distributions, stability and hysteresis were investigated. A global optimization method based on the measured piezoresponse has also been developed. This method overcame the limitations of the previous local algorithm related to the adjustment of every single actuator for compact piezoelectric layouts. The mirror figure can approach a target figure after several iterations. The figure difference can be reduced to several nanometres, which is far better than the mirror figure errors. The prototype was also used to successfully compensate for the real wavefront errors from upstream and for its own figure errors, measured using the speckle scanning technique. The residual figure error was reduced to a root-mean-square value of 0.7 nm.

M-BLANK: a program for the fitting of X-ray fluorescence spectra.

The X-ray fluorescence data from X-ray microprobe and nanoprobe measurements must be fitted to obtain reliable elemental maps. The most common approach in many fitting programs is to initially remove a per-pixel baseline. Using X-ray fluorescence data of yeast and glial cells, it is shown that per-pixel baselines can result in significant, systematic errors in quantitation and that significantly improved data can be obtained by calculating an average blank spectrum and subtracting this from each pixel.