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Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO2- species, which cap the MXene surface with an O-B-O configuration. In contrast to conventional chlorine/oxygen-terminated Nb2C with localized charge transport, OBO-terminated Nb2C features band transport described by the Drude model, exhibiting a 15-fold increase in electrical conductivity and a 10-fold improvement in charge mobility at the d.c. limit. This transition is attributed to surface ordering that effectively mitigates charge carrier backscattering and trapping. Additionally, OBO terminations provide Ti3C2 MXene with substantially enriched Li+-hosting sites and thereby a large charge-storage capacity of 420 mAh g-1. Our findings illustrate the potential of intricate termination configurations in MXenes and their applications for (opto)electronics and energy storage.
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High-quality patterning determines the properties of patterned emerging two-dimensional (2D) conjugated polymers which is essential for potential applications in future electronic nanodevices. However, the suitable patterning method for 2D polymers is yet concluded because it's still challenging to gain comprehensive understanding of their damage mechanisms by visualizing the structural modification during patterning process. Here, the damage mechanisms during patterning of 2D polymers, induced by various patterning methods, are unveiled based on a systematic study of structural damage and edge morphology on an imine-based 2D polymer (polyimine). Patterning using focused electron beam, focused ion beam (FIB) and mechanical carving is evaluated. Focused electron beam successively introduces sputtering effect, knock-on displacement damage and massive radiolysis effect as increasing the electron dose from 9.46×107 e-/nm2 to 1.14×1010 e-/nm2. The successful pattering is enabled by knock-on damage while impeded by carbon contamination when beyond a critical sample thickness. FIB creates current-dependent edge morphologies and extensive damage from the ion implantation caused by the tail of unfocused beam. A precisely controlled tip can tear the polyimine film through grain boundaries and in hence create the patterning edge with suitable edge roughness for certain application senarios when the beam damage is avoided. Taking structural damage and the resulting quantitative edge roughness into consideration, this study provides a detailed instruction on the proper patterning techniques for 2D crystalline polymers and paves the way for tailored intrinsic properties and device fabrication using these novel materials. .
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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.
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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.
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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.
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Silicene, a monolayer of silicon atoms arranged in a honeycomb lattice, is excellently compatible with the materials used in today's semiconductor manufacturing. In this paper, silicene-terminated CaSi2 is cleaved inside a transmission electron microscope using an in situ manipulator. HRTEM studies on a standard lift-out lamella performed from several crystallographic orientations confirm the cell parameters of a = 3.7 Å and c = 30.60 Å, and allow to determine its exact orientation in the SEM/FIB system. A FIB procedure with corrected tilting and rotating angles has been developed to ensure that the tensile force applied by the manipulator is perpendicular to the (0 0 1) plane, and that the [1 0 0] pole axis could be used for HRTEM imaging. A sharp and flat cleavage interface with a length of more than 1 µm was observed in one in situ experiment. HRTEM images from multiple regions confirm that the flat cleavage follows the (0 0 3) plane of the CaSi2 crystal. The current in situ study demonstrates that a surface sheet with silicene-like atomic arrangement can be mechanically exfoliated from silicide compounds.
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Despite the recent progress in the synthesis of crystalline boronate ester covalent organic frameworks (BECOFs) in powder and thin-film through solvothermal method and on-solid-surface synthesis, respectively, their applications in electronics, remain less explored due to the challenges in thin-film processability and device integration associated with the control of film thickness, layer orientation, stability and crystallinity. Moreover, although the crystalline domain sizes of the powder samples can reach micrometer scale (up to ≈1.5â µm), the reported thin-film samples have so far rather small crystalline domains up to 100â nm. Here we demonstrate a general and efficient synthesis of crystalline two-dimensional (2D) BECOF films composed of porphyrin macrocycles and phenyl or naphthyl linkers (named as 2D BECOF-PP or 2D BECOF-PN) by employing a surfactant-monolayer-assisted interfacial synthesis (SMAIS) on the water surface. The achieved 2D BECOF-PP is featured as free-standing thin film with large single-crystalline domains up to ≈60â µm2 and tunable thickness from 6 to 16â nm. A hybrid memory device composed of 2D BECOF-PP film on silicon nanowire-based field-effect transistor is demonstrated as a bio-inspired system to mimic neuronal synapses, displaying a learning-erasing-forgetting memory process.
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Direct covalent functionalization of large-area single-layer hexagonal boron nitride (hBN) with various polymer brushes under mild conditions is presented. The photopolymerization of vinyl monomers results in the formation of thick and homogeneous (micropatterned, gradient) polymer brushes covalently bound to hBN. The brush layer mechanically and chemically stabilizes the material and allows facile handling as well as long-term use in water splitting hydrogen evolution reactions.
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Conjugated polymers featuring tunable band gaps/positions and tailored active centers, are attractive photoelectrode materials for water splitting. However, their exploration falls far behind their inorganic counterparts. Herein, we demonstrate a molecular engineering strategy for the tailoring aromatic units of conjugated acetylenic polymers from benzene- to thiophene-based. The polarized thiophene-based monomers of conjugated acetylenic polymers can largely extend the light absorption and promote charge separation/transport. The C≡C bonds are activated for catalyzing water reduction. Using on-surface Glaser polycondensation, as-fabricated poly(2,5-diethynylthieno[3,2-b]thiophene) on commercial Cu foam exhibits a record H2 -evolution photocurrent density of 370â µA cm-2 at 0.3â V vs. reversible hydrogen electrode among current cocatalyst-free organic photocathodes (1-100â µA cm-2 ). This approach to modulate the optical, charge transfer, and catalytic properties of conjugated polymers paves a critical way toward high-activity organic photoelectrodes.
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Owing to their high theoretical energy density, environmental benign character, and low cost, rechargeable Zn-air batteries have emerged as an attractive energy technology. Unfortunately, their energy efficiency is seriously plagued by sluggish oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) that alternately occurs on air electrodes. Herein, we demonstrate Co-based metal-organic framework (Co(bpdc)(H2 O)4 (bpdc=biphenyl -4, 4'-dicarboxylic acid), Co-MOF) arrays as novel bifunctional oxygen electrocatalysts. The Co-MOF is in situ constructed on a three-dimensional graphite foam (GF) through a hydrothermal reaction. In a 1 m KOH aqueous solution, the resultant Co-MOF/GF exhibits an OER overpotential of only ≈220â mV at 10â mA cm-2 , which is much lower than those for Ir/C and previously reported noble metal-free electrocatalysts. In conjunction with its ORR half-wave potential of 0.7â V (vs. RHE), the Co-MOF/GF manifests a greatly decreased potential gap of ≈0.75â V in comparison with Pt/C-Ir/C couple and previously reported bifunctional oxygen electrocatalysts. Furthermore, an assembled rechargeable zinc-air battery using Co-MOF electrocatalyst in an air electrode delivers a maximum power density of 86.2â mW cm-2 and superior charge-discharge performance. Microscopic, spectroscopic and electrochemical analyses prove that the initial Co-MOF is transformed into Co-oxyhydroxides during the OER and ORR process, which essentially serve as bifunctional active centers.
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Extraordinary electronic and photonic features render black phosphorus (BP) an important material for the development of novel electronics and optoelectronics. Despite recent progress in the preparation of thinly layered BP flakes, scalable synthesis of large-size, pristine BP flakes remains a major challenge. An electrochemical delamination strategy is demonstrated that involves intercalation of diverse cations in non-aqueous electrolytes, thereby peeling off bulk BP crystals into defect-free flakes comprising only a few layers. The interplay between tetra-n-butylammonium cations and bisulfate anions promotes a high exfoliation yield up to 78 % and large BP flakes up to 20.6â µm. Bottom-gate and bottom-contact field-effect transistors, comprising single BP flakes only a few layers thick, exhibit a high hole mobility of 252±18â cm2 V-1 s-1 and a remarkable on/off ratio of (1.2±0.15)×105 at 143â K under vacuum. This efficient and scalable delamination method holds great promise for development of BP-based composites and optoelectronic devices.
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In this work, we show the doping of graphene most likely from heteroatoms induced by the substrate using Raman spectra, x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy and ab initio molecular dynamics (MD) simulations. The doping of graphene on a highly boron-doped silicon substrate was achieved by an annealing at 400 K for about 3 h in an oven with air flow. With the same annealing, only the Raman features similar to that from the pristine graphene were observed in the freestanding graphene and the graphene on a typical Si/SiO2 wafer. Ab initio MD simulations were performed for defected graphene on boron-doped silicon substrate at several temperatures. All vacancy sites in the graphene are occupied either with B atoms or Si atoms resulting in the mixed boron-silicon doping of the graphene. The MD simulations validated the experimetal finding of graphene doped behavior observed by Raman spectrum. The electronic structure analysis indicated the p-type nature of doped graphene. The observed doping by the possible incorporation of heteroatoms into the graphene, simply only using 400 K annealing the boron-doped Si substrate, could provide a new approach to synthesize doped graphene in a more economic way.
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Area selectivity is an emerging sub-topic in the field of atomic layer deposition (ALD), which employs opposite nucleation phenomena to distinct heterogeneous starting materials on a surface. In this paper, we intend to grow Ru exclusively on locally pre-defined Pt patterns, while keeping a SiO2 substratum free from any deposition. In a first step, we study in detail the Ru ALD nucleation on SiO2 and clarify the impact of the set-point temperature. An initial incubation period with actually no growth was revealed before a formation of minor, isolated RuO x islands; clearly no continuous Ru layer formed on SiO2. A lower temperature was beneficial in facilitating a longer incubation and consequently a wider window for (inherent) selectivity. In a second step, we write C-rich Pt micro-patterns on SiO2 by focused electron-beam-induced deposition (FEBID), varying the number of FEBID scans at two electron beam acceleration voltages. Subsequently, the localized Pt(C) deposits are pre-cleaned in O2 and overgrown by Ru ALD. Already sub-nanometer-thin Pt(C) patterns, which were supposedly purified into some form of Pt(O x ), acted as very effective activation for the locally restricted, thus area-selective ALD growth of a pure, continuous Ru covering, whereas the SiO2 substratum sufficiently inhibited towards no growth. FEBID at lower electron energy reduced unwanted stray deposition and achieved well-resolved pattern features. We access the nucleation phenomena by utilizing a hybrid metrology approach, which uniquely combines in-situ real-time spectroscopic ellipsometry, in-vacuo x-ray photoelectron spectroscopy, ex-situ high-resolution scanning electron microscopy, and mapping energy-dispersive x-ray spectroscopy.
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A laboratory-based X-ray microscope is used to investigate the 3D structure of unstained whole pollen grains. For the first time, high-resolution laboratory-based hard X-ray microscopy is applied to study pollen grains. Based on the efficient acquisition of statistically relevant information-rich images using Zernike phase contrast, both surface- and internal structures of pine pollen - including exine, intine and cellular structures - are clearly visualized. The specific volumes of these structures are calculated from the tomographic data. The systematic three-dimensional study of pollen grains provides morphological and structural information about taxonomic characters that are essential in palynology. Such studies have a direct impact on disciplines such as forestry, agriculture, horticulture, plant breeding and biodiversity.
Assuntos
Pólen/ultraestrutura , Tomografia Computadorizada por Raios X , Processamento de Imagem Assistida por Computador , Imageamento Tridimensional , Microscopia Eletrônica de Varredura , Microscopia de Contraste de Fase , PinusRESUMO
We demonstrate full-field X-ray microscopy using crossed multilayer Laue lenses (MLL). Two partial MLLs are prepared out of a 48 µm high multilayer stack consisting of 2451 alternating zones of WSi2 and Si. They are assembled perpendicularly in series to obtain two-dimensional imaging. Experiments are done in a laboratory X-ray microscope using Cu-Kα radiation (E = 8.05 keV, focal length f = 8.0 mm). Sub-100 nm resolution is demonstrated without mixed-order imaging at an appropriate position of the image plane. Although existing deviations from design parameters still cause aberrations, MLLs are a promising approach to realize hard X-ray microscopy at high efficiencies with resolutions down to the sub-10 nm range in future.
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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.
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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.
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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:â¢The design and testing of customized micro-tools to precisely apply mechanical load to individual Cu-pillars.â¢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.â¢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.
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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.
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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.