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At least 1,081 records · Page 60

Deterministic Fabrication of Large-Area, High-Crystallinity Oxide Moiré Superlattices

Oxide twistronics extends moiré engineering beyond van der Waals materials, offering a promising platform for accessing emergent interfacial phenomena arising from the strong coupling of lattice, charge, and orbital degrees of freedom in complex oxides. However, deterministic fabrication of high-crystallinity oxide moiré superlattices over large lateral dimensions remains challenging due to the three-dimensional bonding network of oxides. Here, we demonstrate a scalable, generalized fabrication strategy that enables the formation of high-crystallinity oxide moiré superlattices with clean, chemically bonded interfaces and precisely controlled twist angles down to nominal values of 0.1°, achieving subdegree twist-angle accuracy across large contiguous lateral dimensions approaching the millimeter scale. Using NaNbO3 as a model system, we show that the resulting interlayer coupling drives pronounced structural reconstruction that modifies both the phase structure and ferroelectric domain configuration. Synchrotron-based X-ray 3D reciprocal space mapping reveals the emergence of a single-phase state in twisted bilayers, in contrast to the mixed-phase structure observed in single-layer membranes prior to twist assembly. The structural signatures are further consistent with gradual lattice rotation distributed along the thickness direction that may accommodate interfacial shear strain, distinct from reconstruction observed in van der Waals moiré systems which primarily occurs through in-plane stacking rearrangement. This collective lattice response is correlated with twist-dependent nanoscale electromechanical modulations observed by piezoresponse force microscopy. These results establish a scalable materials platform for oxide twistronics and support the implementation of twist-engineered functionalities in practical, macroscale device architectures.

Ghanbari, Reza [North Carolina State University (N↗

Ionic-liquid-Assisted Fabrication of Lignocellulosic Thin Films with Tunable Hydrophobicity

Thin films with enhanced water repellency and mechanical strength can be fabricated from renewable lignocellulosic feedstock as a replacement for petrochemical-derived synthetic polymers, such that it minimizes life cycle impact on the environment and human health. In this work, hybrid poplar wood, either untreated (control) or pretreated with hot water at 160 °C for 20 min (HWE-20), 60 min (HWE-60), and 90 min (HWE-90), was dissolved in 1-ethyl-3-methylimidazolium acetate and regenerated to fabricate thin films. The HWE-90 films were enriched in lignin by 74%, specifically on the surface, which along with hemicellulose depletion imparted hydrophobicity (108° water contact angle) when compared to the control (56°), HWE-20 (77°), and HWE-60 (84°) films. They also exhibited 86% reduced water vapor sorption hysteresis and 75% improved storage modulus compared to the control. Thus, we demonstrate how to tune the lignocellulosic film properties via a combination of hot water pretreatment and ionic liquid dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (Ru x Ni 1–x –OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophase before pyrolysis and silica removal. The resulting Ru x Ni 1–x –OMC materials are in-depth characterized with X-ray diffraction, N 2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru 0.9 Ni 0.1 –OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h –1 ) was obtained, and the Ru 0.9 Ni 0.1 –OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.

Yang, Ying↗

On-Demand and Location Selective Particle Assembly via Electrophoretic Deposition for Fabricating Structures with Particle-to-Particle Precision

Here, programmable positioning of 2 μm polystyrene (PS) beads with single particle precision and location selective, “on-demand”, particle deposition was demonstrated by utilizing patterned electrodes and electrophoretic deposition (EPD). An electrode with differently sized hole patterns, from 0.5 to 5 μm, was used to illustrate the discriminatory particle deposition events based on the voltage and particle-to-hole size ratio. With decreasing patterned hole size, a larger electric field was required for a particle deposition event to occur in that hole. For the 5 μm hole, particle deposition began to occur at 10 V/cm where as an electric field of 15 V/cm was required for particles to begin depositing in the 2 μm holes. The likelihood of particle depositions continued to increase for smaller sized holes as the electric field increased. Eventually, a monolayer of particles began to form at approximately 20 V/cm. In essence, a voltage threshold was found for each hole pattern of different sizes, allowing fine adjustments in pattern hole size and voltage to control when a particle deposition event took place, even with the patterns on the same electrode. This phenomenon opens a route toward controlled, multimaterial deposition and assembly onto substrates without repatterning of the electrode or complicated surface modification of the particles. An analytical approach using the theories for electrophoresis and dielectrophoresis found the former to be the dominating force for depositing a particle into a patterned hole. Ebeam lithography was used to pattern spherical holes in precise configurations onto electrode surfaces, where each hole accompanied a polystyrene (PS) particle placement and attachment during EPD. The versatility of e-beam lithography was utilized to create arbitrary pattern configurations to fabricate particle assemblies of limitless configurations, enabling fabrication of unique materials assemblies and interfaces.

36 MATERIALS SCIENCE↗

Fabrication and application of flexible, multimodal light-emitting devices for wireless optogenetics

The rise of optogenetics provides unique opportunities to advance materials and biomedical engineering, as well as fundamental understanding in neuroscience. This protocol describes the fabrication of optoelectronic devices for studying intact neural systems. Unlike optogenetic approaches that rely on rigid fiber optics tethered to external light sources, these novel devices carry wirelessly powered microscale, inorganic light-emitting diodes (μ-ILEDs) and multimodal sensors inside the brain. Here, we describe the technical procedures for construction of these devices, their corresponding radiofrequency power scavengers and their implementation in vivo for experimental application. In total, the timeline of the procedure, including device fabrication, implantation and preparation to begin in vivo experimentation, can be completed in ~3–8 weeks. Implementation of these devices allows for chronic (tested for up to 6 months) wireless optogenetic manipulation of neural circuitry in animals navigating complex natural or home-cage environments, interacting socially, and experiencing other freely moving behaviors.

60 APPLIED LIFE SCIENCES↗

High-Performance Screen-Printed Thermoelectric Films on Fabrics

Printing techniques could offer a scalable approach to fabricate thermoelectric (TE) devices on flexible substrates for power generation used in wearable devices and personalized thermo-regulation. However, typical printing processes need a large concentration of binder additives, which often render a detrimental effect on electrical transport of the printed TE layers. Here, we report scalable screenprinting of TE layers on flexible fiber glass fabrics, by rationally optimizing the printing inks consisting of TE particles (p-type Bi 0.5 Sb 1.5 Te 3 or n-type Bi 2 Te 2.7 Se 0.3 ), binders, and organic solvents. We identified a suitable binder additive, methyl cellulose, which offers suitable viscosity for printability at a very small concentration (0.45–0.60 wt.%), thus minimizing its negative impact on electrical transport. Following printing, the binders were subsequently burnt off via sintering and hot pressing. We found that the nanoscale defects left behind after the binder burnt off became effective phonon scattering centers, leading to low lattice thermal conductivity in the printed n-type material. With the high electrical conductivity and low thermal conductivity, the screen-printed TE layers showed high room-temperature ZT values of 0.65 and 0.81 for p-type and n-type, respectively.

36 MATERIALS SCIENCE↗

Mineral Fabric as a Hidden Variable in Fracture Formation in Layered Media

Two longstanding goals in subsurface science are to induce fractures with a desired geometry and to adaptively control the interstitial geometry of existing fractures in response to changing subsurface conditions. Here, we demonstrate that microscopic mineral fabric and structure interact with macroscopic strain fields to generate emergent meso-scale geometries of induced fractures. These geometries define preferential directions of flow. Using additively manufactured rock, we demonstrate that highly conductive flow paths can be formed in tensile fractures by creating corrugated surfaces. Generation, suppression and enhancement of corrugations depend on the relative orientation between mineral fabric and layering. These insights into the role of micro-scale structure on macro-scale flow provide a new method for designing subsurface strategies to maximize potential production or to inhibit flow.

36 MATERIALS SCIENCE↗

All-atmospheric fabrication of Ag–Cu core–shell nanowire transparent electrodes with Haacke figure of merit >600 × 10–3 Ω−1

Abstract Transparent conducting electrodes (TCEs) are essential components in devices such as touch screens, smart windows, and photovoltaics. Metal nanowire networks are promising next-generation TCEs, but best-performing examples rely on expensive metal catalysts (palladium or platinum), vacuum processing, or transfer processes that cannot be scaled. This work demonstrates a metal nanowire TCE fabrication process that focuses on high performance and simple fabrication. Here we combined direct and plating metallization processes on electrospun nanowires. We first directly metallize silver nanowires using reactive silver ink. The silver catalyzes subsequent copper plating to produce Ag–Cu core–shell nanowires and eliminates nanowire junction resistances. The process allows for tunable transmission and sheet resistance properties by adjusting electrospinning and plating time. We demonstrate state-of-the-art, low-haze TCEs using an all-atmospheric process with sheet resistances of 0.33 Ω sq −1 and visible light transmittances of 86% (including the substrate), leading to a Haacke figure of merit of 652 × 10 –3 Ω −1 . The core–shell nanowire electrode also demonstrates high chemical and bending durability.

36 MATERIALS SCIENCE↗

Fabrication of THz corrugated wakefield structure and its high power test

We present overall process for developing terahertz (THz) corrugated structure and its beam-based measurement results. 0.2-THz corrugated structures were fabricated by die stamping method as the first step demonstration towards GW THz radiation source and GV/m THz wakefield accelerator. 150-μm thick disks were produced from an OFHC (C10100) foil by stamping. Two types of disks were stacked alternately to form 46 mm structure with ~ 170 corrugations. Custom assembly was designed to provide diffusion bonding with a high precision alignment of disks. The compliance of the fabricated structure have been verified through beam-based wakefield measurement at Argonne Wakefield Accelerator Facility. Both measured longitudinal and transverse wakefield showed good agreement with simulated wakefields. Measured peak gradients, 9.4 MV/m/nC for a long single bunch and 35.4 MV/m/nC for a four bunch trains, showed good agreement with the simulation.

43 PARTICLE ACCELERATORS↗

Low-loss superconducting resonators fabricated from tantalum films grown at room temperature

The use of α-tantalum in superconducting circuits has enabled a considerable improvement in the coherence time of transmon qubits. The standard approach to grow α-tantalum thin films on silicon involves heating the substrate, which takes several hours per deposition and prevents the integration of this material with wafers containing temperature-sensitive components. We report a detailed experimental study of an alternative growth method of α-tantalum on silicon, which is achieved at room temperature through the use of a niobium seed layer. Despite a substantially higher density of oxygen-rich grain boundaries in the films sputtered at room temperature, resonators made from these films are found to have state-of-the-art quality factors, comparable to resonators fabricated from tantalum grown at high temperature. This finding challenges previous assumptions about correlations between material properties and microwave loss of superconducting thin films, and opens a new avenue for the integration of tantalum into fabrication flows with limited thermal budget.

36 MATERIALS SCIENCE↗

A smart strategy to fabricate Ru nanoparticle inserted porous carbon nanofibers as highly efficient levulinic acid hydrogenation catalysts

Herein, we first put forward a smart strategy to in situ fabricate Ru nanoparticle (NP) inserted porous carbon nanofibers by one-pot conversion of Ru-functionalized metal organic framework fibers. Such fiber precursors are skillfully constructed by cooperative assembly of different proportional RuCl3 and Zn(Ac)2·2H2O along with trimesic acid (H3BTC) in the presence of N,N-dimethylformamide. The following high-temperature pyrolysis affords uniform and evenly dispersed Ru NPs (ca. 12-16 nm), which are firmly inserted into the hierarchically porous carbon nanofibers formed simultaneously. The resulting Ru-carbon nanofiber (Ru-CNF) catalysts prove to be active towards the liquid-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL), a biomass-derived platform molecule with wide applications in the preparation of renewable chemicals and liquid transportation fuels. The optimal GVL yield of 96.0% is obtained, corresponding to a high activity of 9.23 molLAh–1gRu–1, 17 times of that using the commercial Ru/C catalyst. Moreover, the Ru-CNF catalyst is extremely stable, and can be cycled up to 7 times without significant loss of reactivity. Our strategy demonstrated here reveals new possibilities to make proficient metal catalysts, and provides a general way to fabricate metal-carbon nanofiber composites available for other applications.

36 MATERIALS SCIENCE↗

IR-Live: fabrication of a low-cost plastic microfluidic device for infrared spectromicroscopy of living cells

Water is a strong mid-infrared absorber, which has hindered the full exploitation of label-free and non-invasive infrared (IR) spectromicroscopy techniques for the study of living biological samples. To overcome this barrier, many researchers have built sophisticated fluidic chambers or microfluidic chips wherein the depth of the liquid medium in the sample compartment is limited to 10 μm or less. We report an innovative and simple way to fabricate plastic devices with infrared transparent view-ports enabling infrared spectromicroscopy of living biological samples; therefore the device is named “IR-Live”. Advantages of this approach include lower production costs, a minimal need to access a micro-fabrication facility, and unlimited mass or waste exchange for the living samples surrounding the view-port area. We demonstrate that the low-cost IR-Live in combination with microfluidic perfusion techniques enables long term (>60 h) cell culture, which broadens the capability of IR spectromicroscopy for studying living biological samples. To illustrate this, we first applied the device to study protein and lipid polarity in migrating REF52 fibroblasts by collecting 2-dimensional spectral chemical maps at a micrometer spatial resolution. Then, we demonstrated the suitability of our approach to study dynamic cellular events by collecting a time series of spectral maps of U937 monocytes during the early stage of cell attachment to a bio-compatible surface.

47 OTHER INSTRUMENTATION↗

Rapid prototyping of microchannels with surface patterns for fabrication of polymer fibers

Microfluidic technology has provided innovative solutions to numerous problems, but the cost of designing and fabricating microfluidic channels is impeding its expansion. In this study, Shrinky-Dink thermoplastic sheets are used to create multilayered complex templates for microfluidic channels. We also used inkjet and laserjet printers to raise a predetermined microchannel geometry by depositing several layers of ink for each feature consecutively. We achieved feature heights over 100 μm, which were measured and compared with surface profilometry. Templates closest to the target geometry were then used to create microfluidic devices from soft-lithography with the molds as a template. These microfluidic devices were, futhermore used to fabricate polymer microfibers using the microfluidic focusing approach to demonstrate the potential that this process has for microfluidic applications. Finally, an economic analysis was conducted to compare the price of common microfluidic template manufacturing methods. We showed that multilayer microchannels can be created significantly quicker and cheaper than current methods for design prototyping and point-of-care applications in the biomedical area.

42 ENGINEERING↗

Methacrylated gelatin-embedded fabrication of 3D graphene-supported Co 3 O 4 nanoparticles for water splitting

In this work, we developed a general platform for the fabrication of transition metal oxide nanoparticles supported by a graphene foam (GF) by first coating it with a methacrylated gelatin (GelMA) hydrogel, which served as a 3D matrix for nanoparticle dispersion. The engineered GelMA/GF matrix was hydrophilic with good mechanical strength and high conductivity, therefore providing a good platform for the dispersion of a variety of metal/oxide precursors. Due to this platform, well-dispersed Co 3 O 4 nanoparticles with the smallest size of 3 nm assembled on the nitrogen-doped graphene foam (Co 3 O 4 /NGF). The crystalline transformation from a CoCl 2 [H 2 O] 2 precursor to Co 3 O 4 was revealed by in operando X-ray diffraction and absorption techniques. After applying Co 3 O 4 /NGF as a free-standing electrocatalyst for water splitting, the nanoparticles of size 3 nm exhibited optimal catalytic activity in alkaline media; the corresponding cell could promote water splitting at a current density of 10 mA cm -2 with only 1.63 V and exhibited excellent stability in a 25 h long-term operation. Our results demonstrate that the GelMA hydrogel-coated 3D graphene foam can be a promising platform for the design and fabrication of graphene-based multifunctional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication and 3D tomographic characterization of nanowire arrays and meshes with tunable dimensions from shear-aligned block copolymers

We demonstrate a scalable method to create metallic nanowire arrays and meshes over square-centimeter-areas with tunable sub-100 nm dimensions and geometries using the shear alignment of block copolymers. We use the block copolymer poly(styrene)- b -poly(2-vinyl pyridine) (PS–P2VP) since the P2VP block complexes with metal salts like Na 2 PtCl 4 , thereby enabling us to directly pattern nanoscale platinum features. We investigate what shear alignment processing parameters are necessary to attain high quality and well-ordered nanowire arrays and quantify how the block copolymer's molecular weight affects the resulting Pt nanowires’ dimensions and defect densities. Through systematic studies of processing parameters and scanning transmission electron microscopy (STEM) tomography, we determine that the equivalent of 2–3 monolayers of PS–P2VP are required to produce a single layer of well-aligned nanowires. The resulting nanowires’ widths and heights can be tuned between 11–27 nm and 9–50 nm, respectively, and have periodicites varying between 37 and 63 nm, depending on the choice of block copolymer molecular weight. We observe that the height-to-width ratio of the nanowires also increases with molecular weight, reaching a value of almost 2 with the largest dimensions fabricated. As a result, we demonstrate that an additional layer of Pt nanowires can be orthogonally aligned on top of and without disturbing an underlying layer, thereby enabling the fabrication of Pt nanowire meshes with tunable sub-100 nm dimensions and geometries over a cm 2 -area.

36 MATERIALS SCIENCE↗

De novo fabrication of multi-heteroatom-doped carbonaceous materials via an in situ doping strategy

Finding a succinct strategy to fabricate multi-heteroatom-doped nanoporous carbonaceous materials is a long-term challenge and highly desired research topic. The key to success is the rational design of easy to obtain and functionalized precursors. Herein, de novo fabrication of carbonaceous materials doped with multiple heteroatoms namely boron, nitrogen, oxygen, fluorine, and sulfur was achieved via a one-step in situ doping procedure using task-specific ionic liquids (TSILs) as precursors. Our strategy hinges on the adoption of particularly designed TSILs with structures functionalized with (1) boron source-containing anions, (2) imidazolium functionalities as the carbon and nitrogen source, (3) nitrile groups capable of trimerization during the heating process, and (4) bis(trifluoromethanesulphonyl)imide and related anions performing as the source of heteroatoms (i.e., fluorine, nitrogen, sulfur, and oxygen) and porogens. The unique structures of the as-prepared TSILs make them qualified precursors for the production of multi-heteroatom-doped carbonaceous materials through simple thermal treatment, with surface areas up to 1021 m 2 g -1 . The introduction of multiple heteroatoms provides the carbonaceous materials with efficient adsorption performance for the capture of hazardous anionic pollutants, dyes, and neutral organic molecules. This finding expands the versatility of TSILs with multi-functionalized architectures, delivering nanoporous materials with wide applications.

36 MATERIALS SCIENCE↗

Diazirine-based photo-crosslinkers for defect free fabrication of solution processed organic light-emitting diodes

The fabrication of solution deposited OLEDs is fraught with difficulties, largely due to the interlayer mixing and surface erosion during sequential deposition of the layers. We demonstrate that these problems can be circumvented by using photopolymerizable diazirine-based cross-linker capable of converting soluble organic materials into highly cross-linked insoluble networks. 3-Trifluoromethyl(aryl)diazirines photolyze readily upon the 10–15 min exposure of 365 nm UV irradiation to generate carbenes, which react with polymers or small molecules via C–H bond insertion producing highly cross-linked materials. This photo-generated cross-linking does not require any catalyst, initiator or short-wavelength UV light and is performed at room temperature, releasing molecular nitrogen as the only byproduct. To show the cross-linked polymer layers do not display inter-layer mixing, we deposited red-emitting regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) over cross-linked (10% cross-linker) blue emitting dioctyl polyfluorene (PFO) layer. The overlaid layers showed clear and well-defined boundary with no interlayer mixing. The surface morphology of the solution deposited layers was investigated by AFM to show that the cross-linked layers exhibited significant decrease in surface roughness. This is also shown on the example of the hole transporting material 4,4'-bis[N-(1-naphthyl)-N-phenylamino]-biphenyl (NPB) which displayed roughness average to decrease from 6.4 nm to 1.0 nm. The effect of decreased surface roughness on the performance of phosphorescent OLEDs was investigated by fabricating devices with configuration of ITO/PEDOT:PSS/NPB:(0%/5%/10%) cross-linker/MCP:6% Ir(mppy) 3 /TPBI/CsF/Al. Furthermore, following the diazirine-mediated cross-linking, the OLEDs displayed a decrease in turn-on voltage from 3.8 V to 3.0 V along with a six-fold enhancement of external quantum efficiency (EQE max ) from 1.1% to 6.8% and maximum luminous efficiency increase from 3.8 cd A -1 to 22.9 cd A -1 . These results demonstrate that the simple diazirine mediated photo-cross-linking using mild conditions compatible with organic layers is a promising strategy for improving the performance of the solution-processed OLEDs.

36 MATERIALS SCIENCE↗

One-step fabrication of robust lithium ion battery separators by polymerization-induced phase separation

Conventional lithium ion battery separators are microporous polyolefin membranes that play a passive role in the electrochemical cell. Next generation separators should offer significant performance enhancements, while being fabricated through facile, low cost approaches with the ability to readily tune physicochemical properties. This study presents a single-step manufacturing technique based on UV-initiated polymerization-induced phase separation (PIPS), wherein microporous separators are fabricated from multifunctional monomers and ethylene carbonate (EC), which functions as both the pore-forming agent (porogen) and electrolyte component in the electrochemical cell. By controlling the ratio of the 1,4-butanediol diacrylate (BDDA) monomer to ethylene carbonate, monolithic microporous membranes are readily prepared with 25 μm thickness and pore sizes and porosities ranging from 6.8 to 22 nm and 15.4% to 38.5%, respectively. With 38.5% apparent porosity and an average pore size of 22 nm, the poly(1,4-butanediol diacrylate) (pBDDA) separator takes up 127% liquid electrolyte, resulting in an ionic conductivity of 1.98 mS cm –1 , which is greater than in conventional Celgard 2500. Lithium ion battery half cells consisting of LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathodes and pBDDA separators were shown to undergo reversible charge/discharge cycling with an average discharge capacity of 142 mA h g –1 and a capacity retention of 98.4% over 100 cycles – comparable to cells using state-of-the-art separators. Moreover, similar discharge capacities were achieved in rate performance tests due to the high ionic conductivity and electrolyte uptake of the film. Finally, the pBDDA separators were shown to be thermally stable to 374 °C, lack low temperature thermal transitions that can compromise cell safety, and exhibit no thermal shrinkage up to 150 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗