Laboratory High-Contrast X-ray Microscopy of Copper Nanostructures Enabled by a Liquid-Metal-Jet X-ray Source.

High-resolution imaging of Cu/low-k on-chip interconnect stacks in advanced microelectronic products is demonstrated using full-field transmission X-ray microscopy (TXM). The comparison of two lens-based laboratory X-ray microscopes that are operated at two different photon energies, 8.0 keV and 9.2 keV, shows a contrast enhancement for imaging of copper nanostructures embedded in insulating organosilicate glass of a factor of 5 if 9.2 keV photons are used. Photons with this energy (Ga-Kα radiation) are generated from a Ga-containing target of a laboratory X-ray source applying the liquid-metal-jet technology. The 5 times higher contrast compared to the use of Cu-Kα radiation (8.0 keV photon energy) from a rotating anode X-ray source is caused by the fact that the energy of the Ga-Kα emission line is slightly higher than that of the Cu-K absorption edge (9.0 keV photon energy). The use of Ga-Kα radiation is of particular advantage for imaging of copper interconnects with dimensions from several 100 nm down to several 10 nm in a Cu/SiO2 or Cu/low-k backend-of-line stack. Physical failure analysis and reliability engineering in the semiconductor industry will benefit from high-contrast X-ray images of sub-µm copper structures in microchips.

Laboratory X-ray Microscopy of 3D Nanostructures in the Hard X-ray Regime Enabled by a Combination of Multilayer X-ray Optics.

High-resolution imaging of buried metal interconnect structures in advanced microelectronic products with full-field X-ray microscopy is demonstrated in the hard X-ray regime, i.e., at photon energies > 10 keV. The combination of two multilayer optics-a side-by-side Montel (or nested Kirkpatrick-Baez) condenser optic and a high aspect-ratio multilayer Laue lens-results in an asymmetric optical path in the transmission X-ray microscope. This optics arrangement allows the imaging of 3D nanostructures in opaque objects at a photon energy of 24.2 keV (In-Kα X-ray line). Using a Siemens star test pattern with a minimal feature size of 150 nm, it was proven that features < 150 nm can be resolved. In-Kα radiation is generated from a Ga-In alloy target using a laboratory X-ray source that employs the liquid-metal-jet technology. Since the penetration depth of X-rays into the samples is significantly larger compared to 8 keV photons used in state-of-the-art laboratory X-ray microscopes (Cu-Kα radiation), 3D-nanopattered materials and structures can be imaged nondestructively in mm to cm thick samples. This means that destructive de-processing, thinning or cross-sectioning of the samples are not needed for the visualization of interconnect structures in microelectronic products manufactured using advanced packaging technologies. The application of laboratory transmission X-ray microscopy in the hard X-ray regime is demonstrated for Cu/Cu6Sn5/Cu microbump interconnects fabricated using solid-liquid interdiffusion (SLID) bonding.

3D Multi-Ion Corrosion Model in Hierarchically Structured Cementitious Materials Obtained from Nano-XCT Data.

Corrosion of steel reinforcements in concrete constructions is a worldwide problem. To assess the degradation of rebars in reinforced concrete, an accurate description of electric current, potential and concentrations of various species present in the concrete matrix is necessary. Although the concrete matrix is a heterogeneous porous material with intricate microstructure, mass transport has been treated in a homogeneous material so far, modifying bulk transport coefficients by additional factors (porosity, constrictivity, tortuosity), which led to so-called effective coefficients (e.g., diffusivity). This study presents an approach where the real 3D microstructure of concrete is obtained from high-resolution X-ray computed tomography (XCT), processed to generate a mesh for finite element method (FEM) computations, and finally combined with a multi-species system of transport and electric potential equations. This methodology allows for a more realistic description of ion movements and reactions in the bulk concrete and on the rebar surface and, consequently, a better evaluation of anodic and cathodic currents, ultimately responsible for the loss of reinforcement mass and its location. The results of this study are compared with a state-of-the-art model and numerical calculations for 2D and 3D geometries.

Ultrathin positively charged electrode skin for durable anion-intercalation battery chemistries.

The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF6--intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of > 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries.

Micromechanical BEoL robustness evaluation methods enabling loading condition customization and acoustic emission damage monitoring.

For micromechanical robustness evaluation methods, it is advantageous if the mechanical loading conditions applied can be controlled as precisely as possible. For microchips, this is required to determine the robustness under specific conditions, e.g. during assembly or characteristic application/usage scenarios. In this work, three different micromechanical BEoL (Back End of Line) robustness evaluation methods are presented which should enable a more precise and flexible mechanical load induction and damage identification. They have been subsequently developed. Three main aspects characterize the customization of the developed approaches:•The design and testing of customized micro-tools to precisely apply mechanical load to individual Cu-pillars.•The implementation of an AE (Acoustic Emission) monitoring approach to detect minor damages during mechanical loading. This strategy also enabled the development of sub-critical loading experiments for which AE signals served as a damage indicator and mechanical loading was aborted upon the detection of AE events.•The development of a new measurement setup and approach to enable the solder attach of individual Cu-pillars to a mechanical testing system. The applications of these approaches should enable the induction of customized mechanical loading conditions and the identification of failure modes and damage initiation locations.

Spectromicroscopy of Nanoscale Materials in the Tender X-Ray Regime Enabled by a High Efficient Multilayer-Based Grating Monochromator.

The combination of near edge X-ray absorption spectroscopy with nanoscale X-ray imaging is a powerful analytical tool for many applications in energy technologies, catalysis, which are critical to combat climate change, as well as microelectronics and life science. Materials from these scientific areas often contain key elements, such as Si, P, S, Y, Zr, Nb, and Mo as well as lanthanides, whose X-ray absorption edges lie in the so-called tender photon energy range 1.5-5.0 keV. Neither conventional grazing incidence grating nor crystal monochromators have high transmission in this energy range, thereby yielding the tender photon energy gap. To close this gap, a monochromator setup based on a multilayer coated blazed plane grating and plane mirror is devised. The measurements show that this novel concept improves the photon flux in the tender X-ray regime by two-orders-of-magnitude enabling previously unattainable laboratory and synchrotron-based studies. This setup is applied to perform nanoscale spectromicroscopy studies. The high photon flux provides sufficient sensitivity to obtain the electronic structure of Mo in platinum-free MoNi4 nanoparticles for electrochemical energy conversion. Additionally, it is shown that the chemical bonding of nano-structures in integrated circuits can be distinguished by the electronic configuration at the Si-K edge.

Controllable Zeolite AST Crystallization: Between Classical and Reversed Crystal Growth.

Invited for the cover of this issue are Maksym Opanasenko and co-workers at Charles University in Prague, IKTS and deepXscan GmbH in Dresden. The image depicts a controllable crystallization mechanism that can be switched from classical to reversed crystal growth by manipulating the interplay between silica particles and the structure-directing agent. Read the full text of the article at 10.1002/chem.202200590.

Multi-scale microscopy study of 3D morphology and structure of MoNi4/MoO2@Ni electrocatalytic systems for fast water dissociation.

The 3D morphology of hierarchically structured electrocatalytic systems is determined based on multi-scale X-ray computed tomography (XCT), and the crystalline structure of electrocatalyst nanoparticles is characterized using transmission electron microscopy (TEM), supported by X-ray diffraction (XRD) and spatially resolved near-edge X-ray absorption fine structure (NEXAFS) studies. The high electrocatalytic efficiency for hydrogen evolution reaction (HER) of a novel transition-metal-based material system - MoNi4 electrocatalysts anchored on MoO2 cuboids aligned on Ni foam (MoNi4/MoO2@Ni) - is based on advantageous crystalline structures and chemical bonding. High-resolution TEM images and selected-area electron diffraction patterns are used to determine the crystalline structures of MoO2 and MoNi4. Multi-scale XCT provides 3D information of the hierarchical morphology of the MoNi4/MoO2@Ni material system nondestructively: Micro-XCT images clearly resolve the Ni foam and the attached needle-like MoO2 micro cuboids. Laboratory nano-XCT shows that the MoO2 micro cuboids with a rectangular cross-section of 0.5 × 1 µm2 and a length of 10-20 µm are vertically arranged on the Ni foam. MoNi4 nanoparticles with a size of 20-100 nm, positioned on single MoO2 cuboids, were imaged using synchrotron radiation nano-XCT. The application of a deep convolutional neural network (CNN) significantly improves the reconstruction quality of the acquired data.

Controllable Zeolite AST Crystallization: Between Classical and Reversed Crystal Growth.

Crystal growth mechanisms govern a wide range of properties of crystalline materials. Reversed crystal growth is one of the nonclassical mechanisms observed in many materials. However, the reversed crystallization starting from amorphous aggregates and the key factors driving this growth remain elusive. Here, we describe a characteristic model of reversed crystal growth representing the inner structure and crystallinity development of aggregates studied by microscopy and nano X-ray computed tomography. By adjusting the synthesis conditions, the fundamental function of the structure-directing agent, which determines the crystallization pathway, was revealed. As a result, the crystal growth mode can be "switched" from the classical route at a low ratio of SDA/framework elements to reversed growth at a high ratio. Our findings provide further insights into crystal growth control, which is crucial for improving synthesis protocols and designing various forms of crystalline materials.

Redox-Active Metaphosphate-Like Terminals Enable High-Capacity MXene Anodes for Ultrafast Na-Ion Storage.

2D transition metal carbides and/or nitrides, so-called MXenes, are noted as ideal fast-charging cation-intercalation electrode materials, which nevertheless suffer from limited specific capacities. Herein, it is reported that constructing redox-active phosphorus-oxygen terminals can be an attractive strategy for Nb4 C3 MXenes to remarkably boost their specific capacities for ultrafast Na+ storage. As revealed, redox-active terminals with a stoichiometric formula of PO2 - display a metaphosphate-like configuration with each P atom sustaining three PO bonds and one PO dangling bond. Compared with conventional O-terminals, metaphosphate-like terminals empower Nb4 C3 (denoted PO2 -Nb4 C3 ) with considerably enriched carrier density (fourfold), improved conductivity (12.3-fold at 300 K), additional redox-active sites, boosted Nb redox depth, nondeclined Na+ -diffusion capability, and buffered internal stress during Na+ intercalation/de-intercalation. Consequently, compared with O-terminated Nb4 C3 , PO2 -Nb4 C3 exhibits a doubled Na+ -storage capacity (221.0 mAh g-1 ), well-retained fast-charging capability (4.9 min at 80% capacity retention), significantly promoted cycle life (nondegraded capacity over 2000 cycles), and justified feasibility for assembling energy-power-balanced Na-ion capacitors. This study unveils that the molecular-level design of MXene terminals provides opportunities for developing simultaneously high-capacity and fast-charging electrodes, alleviating the energy-power tradeoff typical for energy-storage devices.

Boosting the Electrocatalytic Conversion of Nitrogen to Ammonia on Metal-Phthalocyanine-Based Two-Dimensional Conjugated Covalent Organic Frameworks.

The electrochemical N2 reduction reaction (NRR) under ambient conditions is attractive in replacing the current Haber-Bosch process toward sustainable ammonia production. Metal-heteroatom-doped carbon-rich materials have emerged as the most promising NRR electrocatalysts. However, simultaneously boosting their NRR activity and selectivity remains a grand challenge, while the principle for precisely tailoring the active sites has been elusive. Herein, we report the first case of crystalline two-dimensional conjugated covalent organic frameworks (2D c-COFs) incorporated with M-N4-C centers as novel, defined, and effective catalysts, achieving simultaneously enhanced activity and selectivity of electrocatalytic NRR to ammonia. Such 2D c-COFs are synthesized based on metal-phthalocyanine (M = Fe, Co, Ni, Mn, Zn, and Cu) and pyrene units bonded by pyrazine linkages. Significantly, the 2D c-COFs with Fe-N4-C center exhibit higher ammonia yield rate (33.6 µg h-1 mgcat-1) and Faradaic efficiency (FE, 31.9%) at -0.1 V vs reversible hydrogen electrode than those with other M-N4-C centers, making them among the best NRR electrocatalysts (yield rate >30 µg h-1 mgcat-1 and FE > 30%). In situ X-ray absorption spectroscopy, Raman spectroelectrochemistry, and theoretical calculations unveil that Fe-N4-C centers act as catalytic sites. They show a unique electronic structure with localized electronic states at Fermi level, allowing for stronger interaction with N2 and thus faster N2 activation and NRR kinetics than other M-N4-C centers. Our work opens the possibility of developing metal-nitrogen-doped carbon-rich 2D c-COFs as superior NRR electrocatalyst and provides an atomic understanding of the NRR process on M-Nx-C based electrocatalysts for designing high-performance NRR catalysts.

Monitored Tomographic Reconstruction-An Advanced Tool to Study the 3D Morphology of Nanomaterials.

Detailed and accurate three-dimensional (3D) information about the morphology of hierarchically structured materials is derived from multi-scale X-ray computed tomography (XCT) and subsequent 3D data reconstruction. High-resolution X-ray microscopy and nano-XCT are suitable techniques to nondestructively study nanomaterials, including porous or skeleton materials. However, laboratory nano-XCT studies are very time-consuming. To reduce the time-to-data by more than an order of magnitude, we propose taking advantage of a monitored tomographic reconstruction. The benefit of this new protocol for 3D imaging is that the data acquisition for each projection is interspersed by image reconstruction. We demonstrate this new approach for nano-XCT data of a novel transition-metal-based materials system: MoNi4 electrocatalysts anchored on MoO2 cuboids aligned on Ni foam (MoNi4/MoO2@Ni). Quantitative data that describe the 3D morphology of this hierarchically structured system with an advanced electrocatalytically active nanomaterial are needed to tailor performance and durability of the electrocatalyst system. We present the framework for monitored tomographic reconstruction, construct three stopping rules for various reconstruction quality metrics and provide their experimental evaluation.

Morphology and Mechanical Properties of Fossil Diatom Frustules from Genera of Ellerbeckia and Melosira.

Fossil frustules of Ellerbeckia and Melosira were studied using laboratory-based nano X-ray tomography (nano-XCT), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). Three-dimensional (3D) morphology characterization using nondestructive nano-XCT reveals the continuous connection of fultoportulae, tube processes and protrusions. The study confirms that Ellerbeckia is different from Melosira. Both genera reveal heavily silicified frustules with valve faces linking together and forming cylindrical chains. For this cylindrical architecture of both genera, valve face thickness, mantle wall thickness and copulae thickness change with the cylindrical diameter. Furthermore, EDS reveals that these fossil frustules contain Si and O only, with no other elements in the percentage concentration range. Nanopores with a diameter of approximately 15 nm were detected inside the biosilica of both genera using TEM. In situ micromechanical experiments with uniaxial loading were carried out within the nano-XCT on these fossil frustules to determine the maximal loading force under compression and to describe the fracture behavior. The fracture force of both genera is correlated to the dimension of the fossil frustules. The results from in situ mechanical tests show that the crack initiation starts either at very thin features or at linking structures of the frustules.

Interfacial Covalent Bonds Regulated Electron-Deficient 2D Black Phosphorus for Electrocatalytic Oxygen Reactions.

Developing resource-abundant and sustainable metal-free bifunctional oxygen electrocatalysts is essential for the practical application of zinc-air batteries (ZABs). 2D black phosphorus (BP) with fully exposed atoms and active lone pair electrons can be promising for oxygen electrocatalysts, which, however, suffers from low catalytic activity and poor electrochemical stability. Herein, guided by density functional theory (DFT) calculations, an efficient metal-free electrocatalyst is demonstrated via covalently bonding BP nanosheets with graphitic carbon nitride (denoted BP-CN-c). The polarized PN covalent bonds in BP-CN-c can efficiently regulate the electron transfer from BP to graphitic carbon nitride and significantly promote the OOH* adsorption on phosphorus atoms. Impressively, the oxygen evolution reaction performance of BP-CN-c (overpotential of 350 mV at 10 mA cm-2 , 90% retention after 10 h operation) represents the state-of-the-art among the reported BP-based metal-free catalysts. Additionally, BP-CN-c exhibits a small half-wave overpotential of 390 mV for oxygen reduction reaction, representing the first bifunctional BP-based metal-free oxygen catalyst. Moreover, ZABs are assembled incorporating BP-CN-c cathodes, delivering a substantially higher peak power density (168.3 mW cm-2 ) than the Pt/C+RuO2 -based ZABs (101.3 mW cm-2 ). The acquired insights into interfacial covalent bonds pave the way for the rational design of new and affordable metal-free catalysts.

Microstructure and Fracture Mechanism Investigation of Porous Silicon Nitride-Zirconia-Graphene Composite Using Multi-Scale and In-Situ Microscopy.

Silicon nitride-zirconia-graphene composites with high graphene content (5 wt.% and 30 wt.%) were sintered by gas pressure sintering (GPS). The effect of the multilayer graphene (MLG) content on microstructure and fracture mechanism is investigated by multi-scale and in-situ microscopy. Multi-scale microscopy confirms that the phases disperse evenly in the microstructure without obvious agglomeration. The MLG flakes well dispersed between ceramic matrix grains slow down the phase transformation from α to ß-Si3N4, subsequent needle-like growth of ß-Si3N4 rods and the densification due to the reduction in sintering additives particularly in the case with 30 wt.% MLG. The size distribution of Si3N4 phase shifts towards a larger size range with the increase in graphene content from 5 to 30 wt.%, while a higher graphene content (30 wt.%) hinders the growth of the ZrO2 phase. The composite with 30 wt.% MLG has a porosity of 47%, the one with 5 wt.% exhibits a porosity of approximately 30%. Both Si3N4/MLG composites show potential resistance to contact or indentation damage. Crack initiation and propagation, densification of the porous microstructure, and shift of ceramic phases are observed using in-situ transmission electron microscopy. The crack propagates through the ceramic/MLG interface and through both the ceramic and the non-ceramic components in the composite with low graphene content. However, the crack prefers to bypass ceramic phases in the composite with 30 wt.% MLG.

Numerical and Experimental Study of the Mechanical Response of Diatom Frustules.

Diatom frustules, with their hierarchical three-dimensional patterned silica structures at nano to micrometer dimensions, can be a paragon for the design of lightweight structural materials. However, the mechanical properties of frustules, especially the species with pennate symmetry, have not been studied systematically. A novel approach combining in situ micro-indentation and high-resolution X-ray computed tomography (XCT)-based finite element analysis (FEA) at the identical sample is developed and applied to Didymosphenia geminata frustule. Furthermore, scanning electron microscopy and transmission electron microscopy investigations are conducted to obtain detailed information regarding the resolvable structures and the composition. During the in situ micro-indentation studies of Didymosphenia geminata frustule, a mainly elastic deformation behavior with displacement discontinuities/non-linearities is observed. To extract material properties from obtained load-displacement curves in the elastic region, elastic finite element method (FEM) simulations are conducted. Young's modulus is determined as 31.8 GPa. The method described in this paper allows understanding of the mechanical behavior of very complex structures.

Deep Learning-based Inaccuracy Compensation in Reconstruction of High Resolution XCT Data.

While X-ray computed tomography (XCT) is pushed further into the micro- and nanoscale, the limitations of various tool components and object motion become more apparent. For high-resolution XCT, it is necessary but practically difficult to align these tool components with sub-micron precision. The aim is to develop a novel reconstruction methodology that considers unavoidable misalignment and object motion during the data acquisition in order to obtain high-quality three-dimensional images and that is applicable for data recovery from incomplete datasets. A reconstruction software empowered by sophisticated correction modules that autonomously estimates and compensates artefacts using gradient descent and deep learning algorithms has been developed and applied. For motion estimation, a novel computer vision methodology coupled with a deep convolutional neural network approach provides estimates for the object motion by tracking features throughout the adjacent projections. The model is trained using the forward projections of simulated phantoms that consist of several simple geometrical features such as sphere, triangle and rectangular. The feature maps extracted by a neural network are used to detect and to classify features done by a support vector machine. For missing data recovery, a novel deep convolutional neural network is used to infer high-quality reconstruction data from incomplete sets of projections. The forward and back projections of simulated geometric shapes from a range of angular ranges are used to train the model. The model is able to learn the angular dependency based on a limited angle coverage and to propose a new set of projections to suppress artefacts. High-quality three-dimensional images demonstrate that it is possible to effectively suppress artefacts caused by thermomechanical instability of tool components and objects resulting in motion, by center of rotation misalignment and by inaccuracy in the detector position without additional computational efforts. Data recovery from incomplete sets of projections result in directly corrected projections instead of suppressing artefacts in the final reconstructed images. The proposed methodology has been proven and is demonstrated for a ball bearing sample. The reconstruction results are compared to prior corrections and benchmarked with a commercially available reconstruction software. Compared to conventional approaches in XCT imaging and data analysis, the proposed methodology for the generation of high-quality three-dimensional X-ray images is fully autonomous. The methodology presented here has been proven for high-resolution micro-XCT and nano-XCT, however, is applicable for all length scales.

Anisotropy of Mechanical Properties of Pinctada margaritifera Mollusk Shell.

The mechanical properties such as compressive strength and nanohardness were investigated for Pinctada margaritifera mollusk shells. The compressive strength was evaluated through a uniaxial static compression test performed along the load directions parallel and perpendicular to the shell axis, respectively, while the hardness and Young modulus were measured using nanoindentation. In order to observe the crack propagation, for the first time for such material, the in-situ X-ray microscopy (nano-XCT) imaging (together with 3D reconstruction based on the acquired images) during the indentation tests was performed. The results were compared with these obtained during the micro-indentation test done with the help of conventional Vickers indenter and subsequent scanning electron microscopy observations. The results revealed that the cracks formed during the indentation start to propagate in the calcite prism until they reach a ductile organic matrix where most of them are stopped. The obtained results confirm a strong anisotropy of both crack propagation and the mechanical strength caused by the formation of the prismatic structure in the outer layer of P. margaritifera shell.

Publisher Correction: Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks.

Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s-1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis.