High-nickel LiNixMnyCo1-x-yO2 (NMC) cathodes have demonstrated superior energy density, yet their stability is compromised under high voltage conditions. To address this, we propose a strategy of heterogeneous doping with a concentration gradient, specifically through Sr–Zr co-modification. We synthesized Ni-rich NMC particles featuring several micron-sized secondary particles composed of micron-sized primary grains. This design aims to harness the structural robustness of single-crystalline grains and the favorable diffusion kinetics of polycrystalline secondary particles. Systematic characterization using a combination of electrochemical measurements and synchrotron analytics reveals an intriguing pattern of hierarchically heterogeneous Sr–Zr co-doping. It demonstrates a depth-dependent concentration gradient at the secondary particle level and competing dopant segregation over the buried grain boundaries. This unique characteristic creates opportunities for enhancing battery performance, particularly by optimizing precursors and implementing advanced modulation techniques. We also investigate the dissolution and precipitation of the cathode's transition metal cations upon high-voltage cycling. These insights suggest that a tailored compositional variation can be a viable approach to effectively design the next-generation high-Ni NMC cathode materials for high-voltage lithium batteries.

Novel focusing optics composed of twin paraboloidal capillaries coated with Pt, for laboratory X-ray sources are presented and characterized. The optics are designed to focus the X-rays, resulting in an achromatic focused beam with photon energies up to 40 keV. The performance of the optics under different operational conditions is studied by comparing the energy-photon count spectra of the direct and focused beams. Based on these analyses, the optics gain and efficiency as a function of photon energy are determined. A focal spot of 8.5 µm with a divergence angle of 0.59° is observed. The obtained characteristics are discussed and related to theoretical considerations. Moreover, the suitability and advantages of the present optics for X-ray microdiffraction is demonstrated using polycrystalline aluminium. Finally, possibilities for further developments are suggested.

Rechargeable battery research often involves improving electrodes to electrolyte materials with new chemistry with the end goals to lower cost, extend cycle life, higher energy densities and better safety. Advancements in battery and fuel cell research require the understanding of the complex interplay of several components and factors in a battery ecosystem. It calls for an integrated and multimodality approach involving several new analytical techniques which have to be capable of probing the batteries electrochemistry, structures and composition at different length and time scales, several of which have to be performed non destructively (ex-situ, in situ and in operando). Because of the need to study these in operando or at higher resolution or sensitivity, conventional lab based x-ray techniques are often inadequate. Most of this research is currently performed through synchrotron X-ray techniques. These include: X-ray Absorption Spectroscopy (XAS) to probe changes in oxidation states, bond lengths and coordination numbers of electrochemistry during charge-discharge cycles. XAS comprise XANES (X-ray absorption near edge spectroscopy) & EXAFS (Extended X-ray Absorption Fine Structure). They provide information on element-specific changes in oxidation state and local atomic structure. Such microscopic descriptors are crucial for elucidating charge transfer and structural changes associated with bonding or site mixing, two key factors in evaluating state of charge and modes of cell failure or catalytic efficiency. Another major technique is synchrotron X-ray Imaging at multiple lengthscales, from micrometers to 10s of nanometers through 3D X-ray Microscopy (XRM) to determine structural changes and degradation over time of the complex system, from the electrodes, separators, current collectors to binders. Trace level elemental composition at the ppm or sub-ppm level can be studied through high sensitivity synchrotron X-ray fluorescence spectroscopy (s-XRF)- to track the migration of metallic ions from cathode to anode during charge-discharge cycle or to investigate cross contamination during manufacturing. Unfortunately, many of these X-ray techniques such as XAS has to be performed almost exclusively at synchrotron X-ray light sources, where beamtime is infrequent and experiment time-frames are limited. As a consequence, high level battery, fuel cell or catalyst research in many research institutions have been largely curtailed. In this talk, we will discuss the advancements made in high flux, tunable lab x-ray sources and high efficiency optics for enabling novel synchrotron-equivalent XAS, XRM and XRF techniques in the laboratory. Breakthrough correlative applications through these suite of tools in the field of battery research and catalysts are now feasible in your own laboratory 24/7, without the constraint of limited access nor the research continuity challenges at synchrotron beamlines. Measurements results (including in operando) will be illustrated for conventional NMC batteries to novel solid-state lithium air batteries and next generation battery materials.

Near Infra-Red (NIR) techniques such as Laser Voltage Probing/Imaging (LVP/I), Dynamic Laser Stimulation (DLS), and Photon Emission Microscopy (PEM) are indispensable for Electrical Fault Isolation/Electrical Failure Analysis (EFI/EFA) of silicon Integrated Circuit (IC) devices. However, upcoming IC architectures based on Buried Power Rails (BPR) with Backside Power Delivery (BPD) networks will greatly reduce the usefulness of these techniques due to the presence of NIR-opaque layers that block access to the transistor active layer. Alternative techniques capable of penetrating these opaque layers are therefore of great interest. Recent developments in intense, focused X-ray microbeams for micro X-Ray Fluorescence (μXRF) microscopy open the possibility to using X-rays for targeted and intentional device alteration. In this paper, we will present results from our preliminary investigations into X-ray Device Alteration (XDA) of flip-chip packaged FinFET devices and discuss some implications of our findings for EFI/EFA.

Submitted for the MAR10 Meeting of The American Physical Society Structural signal of a dynamic glass transition1 SUDESHNA CHATTOPADHYAY (BANDYOPADHYAY), AHMET UYSAL, BENJAMIN STRIPE, GUENNADI EVMENENKO, PULAK DUTTA, Department of Physics and Astronomy, Northwestern University, STEVEN EHRLICH, Brookhaven National Laboratory, EVGUENIA A. KARAPETROVA, Argonne National Laboratory — Conventional wisdom states that there is no significant difference between the static structures of the glass and liquid states of a given material. Using x-ray reflectivity, we have studied pentaphenyl trimethyl trisiloxane, an isotropic liquid at room temperature with a dynamic glass transition at 224K. Surface density oscillations (surface layers) develop below 285K, similar to those seen in other metallic and dielectric liquids and in computer simulations [1]. Upon cooling further, there is a sharp increase in the penetration of the surface layers into the bulk material, i.e. an apparently discontinuous change in the static structure, exactly at the glass transition (224K) [2]. [1]. e.g. O. M. Magnussen et al., PRL 74, 4444 (1995); H. Mo et al. PRL 96, 096107 (2006); E. Chac’on et al., PRL 87, 166101 (2001) [2] S. Chattopadhyay et al, PRL 103, 175701 (2009) 1Supported by NSF grant no. DMR-0705137. Sudeshna Bandyopadhyay Department of Physics and Astronomy, Northwestern University Date submitted: 23 Nov 2009 Electronic form version 1.4

The manufacturing of commercial lithium-ion batteries (LIBs) involves a number of sophisticated production processes. Various cell defects can be induced, and, depending on their structural and chemical characteristics, they could lead to acute failure and/ or chronic degradation. Although tremendous efforts have been devoted to develop a robust quality control (QC) procedure, the functional role of the cell defects is not well understood. Here, we address this question through a systematic experimental study of commercial 186 50-type LIBs that have failed the QC inspection due to a self-discharging effect. We identify and recover the defective regions from the cell and conduct a comprehensive investigation from the chemical, structural, and morphological perspectives. Our results reveal how the structural defects affect the cell performance, which is highly important to industry-scale battery production.

The focusing property of an ellipsoidal monocapillary has been characterized using the ptychography method with a 405 nm laser beam. The recovered wavefront gives a 12.5×10.4μm2 focus. The reconstructed phase profile of the focused beam can be used to estimate the height error of the capillary surface. The obtained height error shows a Gaussian distribution with a standard deviation of 1.3 μm. This approach can be used as a quantitative tool for evaluating the inner functional surfaces of reflective optics, complementary to conventional metrology methods.

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We propose a novel confocal x-ray fluorescence (XRF) imaging capability at the X-ray Fluorescence Microprobe (XFM) and Submicron Resolution X-ray Spectroscopy (SRX) beamlines of the National Synchrotron Light Source II (NSLS-II). Comparing to the conventional XRF tomography, this method can image a local region of interest within tens of minutes instead of hours. We will also present the optimized design of the confocal optic and estimated imaging resolution and throughput, based on the real parameters of the beamline photon delivery systems and the proposed confocal setup.

Understanding the association between economic metals and trace elements in ore minerals is critical in mineral exploration and ore deposit research. In particular, the importance of in situ characterization of these spatial relationships to understand the geochemical relationships within a mineralogical and geological context is vital. Micro-X-ray fluorescence (μXRF) mapping is a powerful technique to create chemical images of a sample. The use of high intensity, synchrotron source μXRF (SR-μXRF) -is wellestablished in environmental sciences including remediation studies but has been limited in use for mineral exploration and production [1,2]. The combination of the 384-element Maia detector with synchrotron-source allows for very fast data collection with high count rates, making it possible to image large areas (i.e., a thin section, core, or rock slab) relatively quickly [2]. New developments in lab-based X-ray sources and optics are happening at a dizzying pace, improving the resolution, sensitivity, and speed of lab-based μXRF systems, in some cases approaching what is possible at a synchrotron facility in certain cases [3]. We have analysed a suite of gold ore samples at the CHESS synchrotron with the Maia detector and with the new Sigray AttoMap system to demonstrate their complementarity as powerful tools for studying geochemical associations in gold ore systems.

The past decade has witnessed tremendous growth in both interest and available techniques for laboratory X-ray analysis. From the progression of commercially-available micro- and nano-CT scanners to the resolution and sensitivity enhancements of x-ray fluorescence spectrometers, the scientific community is benefiting from a rapid expansion of laboratory-based x-ray techniques. In our work, we have developed a suite of advanced x-ray instrumentation providing a wide range of enhanced capabilities for specimen characterization. The key enabling technology lies in the X-ray source, which features a microstructured target capable of providing 5-10x higher brightness than conventional sealed-tube x-ray sources and offering power flux densities that rival rotating anode sources. The target array can be custom-designed to incorporate a variety of materials, facilitating fast & easy switching between characteristic emission lines and radiation spectra. This source has been subsequently integrated with state-of-the-art X-ray focusing optics, such as ellipsoidal/paraboloidal capillary lenses and finely-structured Fresnel zone plate imaging objective lenses, and sensitive scintillator-coupled CCD detection systems, opening up new opportunities for advancing laboratory x-ray inspection equipment. Here, we will describe the system geometries in detail and demonstrate how these new advancements have led us to the development of laboratory micro-XRF, nano-XRM, and XAS instrumentation. We will also briefly introduce the image-centric software workspace, which facilitates novice users to collect data quickly and reliably with minimal training overhead.

Both laboratory and synchrotron-based microanalytical techniques (e.g. microXRF, microXRD, x-ray microscopy, SAXS, etc.) have made substantial advances in the past decades, including improved algorithms and faster, higher sensitivity detectors. However, laboratory performance remains comparatively limited in performance (e.g. sensitivity and resolution), primarily due to limited laboratory x-ray source brightness and narrow selection of usable x-ray optics. Here we present our patented x-ray source concept. Coupled with our proprietary high efficiency x-ray optics, the system provides over 50X brightness over a conventional x-ray illumination beam system comprised of a microfocus source and polycapillary optic. The brightness is enabled by the design of the x-ray targets, which are comprised of microstructured x-ray emitters in thermal contact with a diamond substrate. Utilization of a diamond substrate enables highly localized and large thermal gradients that rapidly cool the metal as x-rays and heat are generated under the bombardment of electrons. In addition to brightness, the spectral output of the x-ray source, particularly the characteristic lines, is sometimes indeed more important than brightness alone. For example, fluorescence cross-sections can vary by several orders of magnitude depending on the characteristic energy employed. Throughput and contrast of x-ray imaging and microscopy are also highly dependent on x-ray energy. Because characteristic lines can be the dominant spectral output for some metals, the ability to select and change metal types within an x-ray source provides substantial performance advantages. Sigray’s x-ray source incorporates several choices of metals on its x-ray target for push-button energy selectability within the x-ray source. A turret of Sigray’s interchangeable x-ray optics that are optimized for highest efficiencies at these energies can be coupled to provide the optimal flux and spectrum for each application.

New heterogeneous 3D integration schemes and continuing miniaturization of semiconductor packaging components, such as micropillars, are driving demand for substantive changes to conventional PFA (physical failure analysis). In particular, desired performance capabilities include the ability to nondestructively determine failures within seconds to minutes. New tools should be quantitative, have sufficient resolution to determine sub-micron sized defects and voids in TSVs at the wafer or package level. It should also measure thickness and their material composition of multilayer structures above the wafer surface, such as microbumps, or those below the surface including UBM and RDL. In this paper we are introducing a novel x-ray fluorescence microscope technique capable of solving the above applications in advanced packaging for PFA and process development. The same technique can also be applied in the front end metrology of new gate materials, 3D FinFET structures within test structures in patterned wafers. Characterization of sub nanoscopic changes (sensitivity of sub-angstrom) in film and dopants deposited in 3D structures will also be shown. With its high sensitivity for trace materials, contamination analysis of post hard mask residue, post metal etch residue especially in high aspect ratio structures is also possible.

X-ray probes have grown in popularity in recent years for understanding and characterizing lithium-ion batteries. Owing to the high penetrating power of X-rays, the non-destructive nature of their interactions with matter, and the range of information they can provide, X-ray instrumentation has been demonstrated to be a powerful, flexible solution for characterization. Crystal structure and bulk composition can be analyzed through X-ray diffraction (XRD), localized composition with fluorescence (XRF), 3D microstructure with computed tomography (XCT), and oxidation states with absorption spectroscopy (XAS), all while preserving the specimen for future analysis (such as destructive and/or electrochemical testing). While X-ray techniques are undoubtedly powerful, access to them is often limited to synchrotron facilities. The instrumentation at these facilities is world-class, but the facilities tend to be significantly oversubscribed, severely limiting access for a large population of researchers. Many X-ray instruments are available in a laboratory format, but are subject to various limitations. Laboratory XRF, in particular, is often limited in spatial resolution to the 100s of micrometers, with chemical sensitivity in the parts-per-million (ppm) range. XAS and XCT techniques often are limited in throughput, requiring integration times in the tens of hours or longer. These techniques are widely used at synchrotrons, but have yet to become popular in general electrochemical characterization laboratories due to the various practical limitations encountered. In our work, we have developed a unique suite of laboratory instrumentation, capable of providing access to a variety of synchrotron X-ray techniques in stand-alone packages. We began with redesigning the conventional laboratory X-ray source in a unique way, enabling high throughput imaging with access to a variety of X-ray energies / wavelengths. This source concept was subsequently paired with an assortment of X-ray lenses, such as parabolic capillary condensers, crystal analyzers, and/or Fresnel zone plates, to enable a variety of characterization platforms. Through this design concept, we have developed a laboratory micro-XRF system capable of providing single-micron spatial resolutions with chemical sensitivity in the parts-per-billion (ppb) range, as well as a laboratory XAS configuration that provides sub-eV energy resolution, short data collection times, and spatial resolutions in the 10s of micrometers. Further, by coupling a Fresnel zone plate objective to a capillary condenser, nano-scale XCT is now possible with spatial resolutions down to 40 nm, delivering a 3D map of battery microstructure and equally applicable to studies of electrodes, separators, and other integral components of electrochemical devices. Here, we will present the design concepts of this novel characterization platform and demonstrate the application of each technique to studying Li-ion battery materials. The trace element content is mapped with microXRF, while the 3D microstructure is revealed using nano-scale XCT. Oxidation state information is mapped using XAS, thus providing a rich suite of data to aid in the understanding of battery structure, composition, and redox dynamics. We will review the types of studies that have been performed at synchrotron facilities and discuss the path forward, to increase the availability of the techniques and enhance the understanding of energy storage and conversion devices.

Focusing soft X-ray beams to small spots enables many powerful X-ray analysis techniques for small spot analysis and/or imaging. At the MAESTRO beamline [1], located at the Advanced Light Source in...

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The Fast-Track project goals are to ultimately develop an axially symmetric, achromatic paraboloidal mirror lens with a 100-nanometer focus. The optic will provide large numerical aperture, high efficiency, and high resolution, and will be a higher throughput, cost-effective alternative to conventional x-ray optics such as Kirkpatrick Baez mirrors for synchrotron beamline development and upgrades.

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