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The formation of Al 3 Sc, in 100 nm Al 0.8 Sc 0.2 films, is found to be driven by exposure to high temperature through higher deposition temperature or annealing. High film resistivity was observed in films with lower deposition temperature that exhibited a lack of crystallinity, which is anticipated to cause more electron scattering. An increase in deposition temperature allows for the nucleation and growth of crystalline Al 3 Sc regions that were verified by electron diffraction. The increase in crystallinity reduces electron scattering, which results in lower film resistivity. Annealing Al 0.8 Sc 0.2 films at 600 °C in an Ar vacuum environment also allows for the formation and recrystallization of Al 3 Sc and Al and yields saturated resistivity values between 9.58 and 10.5 μΩ-cm regardless of sputter conditions. Al 3 Sc was found to nucleate and grow in a random orientation when deposited on SiO 2 , and highly {111} textured when deposited on 100 nm Ti and AlN films that were used as template layers. The rocking curve of the Al 3 Sc 111 reflection for the as-deposited films on Ti and AlN at 450 °C was 1.79° and 1.68°, respectively. Annealing the film deposited on the AlN template reduced the rocking curve substantially to 1.01° due to recrystallization of Al 3 Sc and Al within the film. [Display omitted] • The formation of Al 3 Sc is found to be driven by exposure to high temperatures. • Low deposition temperatures lead to low crystallinity films with high resistivity. • {111} textured Al 3 Sc achieved by leveraging temperature and a template layer. • Annealing Al 0.8 Sc 0.2 films reduces resistivity regardless of sputter conditions. • Strong recrystallization effect seen in annealed films with {111} textured Al 3 Sc. [ABSTRACT FROM AUTHOR]

One-dimensional (1D) nanostructures, often referred to as nanowires, have attracted considerable attention due to their unique mechanical, chemical, and electrical properties. Although numerous novel technological applications are being proposed for these structures, many of the processes used to synthesize these materials involve a vapor phase and require high temperatures and long growth times. Potentially faster methods requiring templates, such as anodized aluminum oxide, involve multiple fabrication steps, which would add significantly to the cost of the final material and may preclude their widespread use. In the present study, it is shown that template-free electrodeposition from an alkaline solution can produce arrays of Sn nanoneedles directly onto Cu foil substrates. This electrodeposition process occurs at 55 °C; it is proposed that the nanoneedles grow via a catalyst-mediated mechanism. In such a process, the growth is controlled at the substrate/nanostructure interface rather than resulting from random plating-induced defects such as dendrites or aging defects such as tin whiskers. There are multiple potential applications for 1D Sn nanostructures—these include anodes in lithium-ion and magnesium-ion batteries and as thermal interface materials. To test this potential, type 2032 lithium-ion battery button cells were fabricated using the electrodeposited Sn. These cells showed initial capacities as high as 850 mAh/g and cycling stability for over 200 cycles. [ABSTRACT FROM AUTHOR]

Abstract: We demonstrate an ex situ method for analyzing the chemistry of battery electrode particles after electrochemical cycling using the transmission electron microscope (TEM). The arrangement of particles during our analysis is the same as when the particles are being cycled. We start by sectioning LiFePO4 battery electrodes using an ultramicrotome. We then show that mapping of the Fe2+ and Fe3+ oxidation state using energy-filtered TEM (EFTEM) and multivariate statistical analysis techniques can be used to determine the spatial distribution of Li in the particles. This approach is validated by comparison with scanning transmission X-ray microscopy (STXM) analysis of the same samples [Chueh et al. Nanoletters, 13 (3) (2013) 866–72]. EFTEM uses a parallel electron beam and reduces the electron-beam dose (and potential beam-induced damage) to the sample when compared to alternate techniques that use a focused probe (e.g. STEM–EELS). Our analysis confirms that under the charging conditions of the analyzed battery, mixed phase particles are rare and thus Li intercalation is limited by the nucleation of new phases. [Copyright &y& Elsevier]

Abstract: A simple solution-based method has been developed to vary the composition of redox active ruthenium oxide with highly proton-conducting niobium hydroxide to create stable, high capacitance electrodes at elevated temperatures. This method presents a dramatic departure from most other ruthenium oxide systems, which are prepared through annealing of hydrous ruthenium oxide. Typically RuO2 processed at high temperature only exhibits high electrical conductivity and suffers from poor proton conduction, giving low overall capacitances. Here, the optimized Ru/Nb oxide composition can be used to achieve high power densities, high capacitances, and stabilized electrodes while significantly reducing ruthenium content. Extensive materials characterization including high-resolution cross-sectional TEM, elemental mapping, XRD, electrochemical impedance spectroscopy, and proton NMR were used to evaluate the structure of the material system. The electrochemically inert niobium oxide serves as a network former enhancing accessibility to redox active ruthenium oxide. The dispersion of RuO2 in the NbO(OH) x matrix results in reduced RuO2 particle size, as observed via TEM and XRD, while also increasing the proton concentration in the material. Interconnected RuO2 particles provide electrically conducting pathways, even at low Ru contents, where percolation networks remain intact. Ruthenium is more efficiently utilized in the Ru/Nb composites and ruthenium content can be significantly reduced without decreasing capacitive performance. In addition, the composite electrodes, with the fine mixing of Ru and Nb, give higher power performance than for RuO2 alone. [Copyright &y& Elsevier]

Abstract: We have determined metallographic cooling rates of 9 IVB irons by measuring Ni gradients 3μm or less in length at kamacite–taenite boundaries with the analytical transmission electron microscope and by comparing these Ni gradients with those derived by modeling kamacite growth. Cooling rates at 600–400°C vary from 475K/Myr at the low-Ni end of group IVB to 5000K/Myr at the high-Ni end. Sizes of high-Ni particles in the cloudy zone microstructure in taenite and the widths of the tetrataenite rims, which both increase with decreasing cooling rate, are inversely correlated with the bulk Ni concentrations of the IVB irons confirming the correlation between cooling rate and bulk Ni. Since samples of a core that cooled inside a thermally insulating silicate mantle should have uniform cooling rates, the IVB core must have cooled through 500°C without a silicate mantle. The correlation between cooling rate and bulk Ni suggests that the core crystallized concentrically outwards. Our thermal and fractional crystallization models suggest that in this case the radius of the core was 65±15km when it cooled without a mantle. The mantle was probably removed when the IVB body was torn apart in a glancing impact with a larger body. Clean separation of the mantle from the solid core during this impact could have been aided by a thin layer of residual metallic melt at the core-mantle boundary. Thus the IVB irons may have crystallized in a well-mantled core that was 70±15km in radius while it was inside a body of radius 140±30km. [Copyright &y& Elsevier]

Abstract: Obtaining particulate compositional maps from scanned PIXE (proton-induced X-ray emission) measurements is extremely difficult due to the complexity of analyzing spectroscopic data collected with low signal-to-noise at each scan point (pixel). Multivariate spectral analysis has the potential to analyze such data sets by reducing the PIXE data to a limited number of physically realizable and easily interpretable components (that include both spectral and image information). We have adapted the AXSIA (automated expert spectral image analysis) program, originally developed by Sandia National Laboratories to quantify electron-excited X-ray spectroscopy data, for this purpose. Samples consisting of particulates with known compositions and sizes were loaded onto Mylar and paper filter substrates and analyzed by scanned micro-PIXE. The data sets were processed by AXSIA and the associated principal component spectral data were quantified by converting the weighting images into concentration maps. The results indicate automated, nonbiased, multivariate statistical analysis is useful for converting very large amounts of data into a smaller, more manageable number of compositional components needed for locating individual particles-of-interest on large area collection media. [Copyright &y& Elsevier]

Abstract: Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits. [Copyright &y& Elsevier]

High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO 2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO 2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications., (© 2024 Wiley‐VCH GmbH.)

We report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.

Understanding and controlling nanoscale interface phenomena, such as band bending and secondary phase formation, is crucial for electronic device optimization. In granular metal (GM) studies, where metal nanoparticles are embedded in an insulating matrix, the importance of interface phenomena is frequently neglected. We demonstrate that GMs can serve as an exemplar system for evaluating the role of secondary phases at interfaces through a combination of x-ray photoemission spectroscopy (XPS) and electrical transport studies. We investigated SiN x as an alternative to more commonly used oxide-insulators, as SiN x -based GMs may enable high temperature applications when paired with refractory metals. Comparing Co-SiN x and Mo-SiN x GMs, we found that, in the tunneling-dominated insulating regime, Mo-SiN x had reduced metal-silicide formation and orders-of-magnitude lower conductivity. XPS measurements indicate that metal-silicide and metal-nitride formation are mitigatable concerns in Mo-SiN x . Given the metal-oxide formation seen in other GMs, SiN x is an appealing alternative for metals that readily oxidize. Furthermore, SiN x provides a path to metal-nitride nanostructures, potentially useful for various applications in plasmonics, optics, and sensing., (© 2023 IOP Publishing Ltd.)

Heat-treated FeCo-based magnetic alloys were characterized using a suite of electron microscopy techniques to gain insight into their structural properties. Electron channeling contrast imaging (ECCI) in the scanning electron microscope (SEM) found unique grains towards the outer edge of a FeCo sample with nonuniform background contrast. High-magnification ECCI imaging of these nonuniform grains revealed a weblike network of defects that were not observed in standard uniform background contrast grains. High-resolution electron backscattered diffraction (HR-EBSD) confirmed these defect structures to be dislocation networks and additionally found subgrain boundaries within the nonuniform contrast grains. The defect content within these grains suggests that they are unrecrystallized grains, and ECCI can be used as a rapid method to quantify unrecrystallized grains. To demonstrate the insight that can be garnered via ECCI on these unique grains, the sample was imaged before and after micro indentation. This experiment showed that slip bands propagate throughout the material until interacting with the dislocation networks, suggesting that these specific defects provide a barrier to plastic deformation. Taken together, these results show how ECCI can be used to better understand failure mechanisms in alloys and provides further evidence that dislocation networks play a critical role in the brittle failure of FeCo alloys., Competing Interests: Conflict of Interest The authors declare that they have no competing interest., (Published by Oxford University Press on behalf of the Microscopy Society of America 2023.)

We present an in-depth study of metal-insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions ( φ ) from 0.2-0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7-2.6 nm average diameters and percolation thresholds between φ = 0.4-0.5. The room temperature conductivities for the φ = 0.2 samples are several orders of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal-insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal-insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs., (© 2022 IOP Publishing Ltd.)

Owing to their facile synthesis, tailorable porosity, diverse compositions, and low toxicity, zeolitic imidazolate framework (ZIF) nanoparticles (NPs) have emerged as attractive platforms for a variety of biologically relevant applications. To date, a small subset of ZIFs representing only two topologies and very few linker chemistries have been studied in this realm. We seek to expand the bio-design space for ZIF NPs through the targeted synthesis of a hierarchically complex ZIF based on two types of cages, ZIF-20, with lta topology. This study demonstrates the rapid synthesis and size tunability of ZIF-20 particles across the micro and nanoregimes via microwave heating and the use of a modulating agent. To evaluate the utility of ZIF particles for biological applications, we examine their stability in biologically relevant media and demonstrate biocompatibility with A549 human epithelial cells. Further, the ability to encapsulate and release methylene blue, a therapeutic and bioimaging agent, is validated. Importantly, ZIF-20 NPs display a unique behavior relative to previously studied ZIFs based on their specific structural and chemical features. This finding highlights the need to expand the design space across the broader ZIFs family, to exploit a wider range of relevant properties for biological applications and beyond.

The mechanochemical reaction kinetics of sulfur with copper to form a metastable copper sulfide phase at room temperature is investigated in ultrahigh vacuum by modifying the properties of the copper during cleaning in vacuum. The measured kinetics is in agreement with a theory first proposed by Karthikeyan and Rigney that predicts that the rate depends linearly both on the contact time and on the strain-rate sensitivity of the substrate. The mechanism for this process was investigated using thin samples of copper fabricated using a focused-ion-beam and by measuring the crystal structure and elemental composition of the copper subsurface region by electron microscopy after reaction. The measured sulfur depth distributions produced by shear-induced surface-to-bulk transport were in good agreement with values calculated using rate constants that also model the reaction kinetics. Sulfur was found both in crystalline regions and also concentrated along grain boundaries, implying that formation of metastable phases is facilitated by both the presence of dislocations and by grain boundaries.

Tin-germanium alloys are increasingly of interest as optoelectronic and thermoelectric materials as well as materials for Li/Na ion battery electrodes. However, the lattice incompatibility of bulk Sn and Ge makes creating such alloys challenging. By exploiting the unique strain tolerance of nanosized crystals, we have developed a facile synthetic method for homogeneous SnxGe1-x alloy nanocrystals with composition varying from essentially pure Ge to 95% Sn while still maintaining the cubic structure.

Ligand binding to membrane receptors initiates cascades of biochemical events leading to physiological responses. Hundreds of proteins and lipids are implicated in signaling networks and programs in genomics and proteomics are continuously adding new components to the signaling "parts lists". Here, we generate high resolution maps of signaling networks using cytoplasmic face-up membrane sheets that can be labeled with immunogold probes (3-10 nm) and imaged in the transmission electron microscope. Our model system is the mast cell and we focus on mapping the topography of the high affinity IgE receptor, Fc(epsilon)RI, its associated tyrosine kinases, Lyn and Syk, and the signaling proteins that propagate signals from these kinases. Crosslinked receptors and their signaling partners segregate during signaling to multiple, dynamic membrane domains, including a transient Fc(epsilon)RI-Lyn domain and at least two other distinct domains, one characterized by the presence of receptor, Syk and multiple signaling proteins, but not Lyn (primary signaling domains), and one characterized by the presence of LAT and PLCgamma1 but not receptor (secondary signaling domains). PI 3-kinase associates with both primary and secondary signaling domains and may help to recruit specific signaling proteins through the local remodeling of inositol phospholipids. The lipid raft markers, GM1 and Thy-1, fail to localize in native membrane sheets either with each other or with signaling domains. We introduce new probes to localize multiple signaling molecules on the same membrane sheet and new computational tools to capture and analyze their topographical relationships. In the future, we expect that high resolution maps of signaling networks will be integrated with chemical kinetic analyses, with cell fractionation data and with a range of real-time fluorescence measurements, into mathematical models with power to predict mechanisms that regulate the efficiency, specificity, amplitude and duration of signaling pathways.