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At least 1,207 records · Page 67

A well-posed numerical method to track isolated conformal map singularities in Hele-Shaw flow

We present a new numerical method for calculating an evolving 2D Hele-Shaw interface when surface tension effects are neglected. In the case where the flow is directed from the less viscous fluid into the more viscous fluid, the motion of the interface is ill-posed; small deviations in the initial condition will produce significant changes in the ensuing motion. This situation is disastrous for numerical computation, as small round-off errors can quickly lead to large inaccuracies in the computed solution. Our method of computation is most easily formulated using a conformal map from the fluid domain into a unit disk. The method relies on analytically continuing the initial data and equations of motion into the region exterior to the disk, where the evolution problem becomes well-posed. The equations are then numerically solved in the extended domain. The presence of singularities in the conformal map outside of the disk introduces specific structures along the fluid interface. Our method can explicitly track the location of isolated pole and branch point singularities, allowing us to draw connections between the development of interfacial patterns and the motion of singularities as they approach the unit disk. In particular, we are able to relate physical features such as finger shape, side-branch formation, and competition between fingers to the nature and location of the singularities. The usefulness of this method in studying the formation of topological singularities (self-intersections of the interface) is also pointed out.

Baker, Gregory↗

Chemical and structural characterization of EUV photoresists as a function of depth by standing-wave x-ray photoelectron spectroscopy

The success in the miniaturization of the electronic device constituents depends mostly on the photolithographic techniques. Recently, to achieve patterning at the sub-10-nm node, extreme ultraviolet (EUV) lithography has been introduced into high volume production. Continued scaling of EUV via increased numerical aperture to achieve nodes at 3-nm and below requires the development of fundamentally new patterning materials and new characterization methods. Current EUV-resist film thicknesses are in the 20- to 40-nm range, and further thickness reduction is required for the next generation. Therefore, interfaces become exceedingly important, and the properties of the resist film would be dominated by top and bottom interfacial effects. X-ray photoelectron spectroscopy (XPS) combined with standing-wave excitation (SW-XPS), a fairly new method in the EUV lithography field, previously had been largely applied in multilayers and superlattices for characterizing the composition and electronic structure of buried layers and interfaces as a function of depth. We applied the SW-XPS method to organic/inorganic photoresists to provide depth-selective information on their structural and chemical conditions of as a function of temperature, EUV exposure, different underlayers, and other fundamental parameters. As a first attempt, we perform an SW-XPS feasibility study on self-assembled monolayer (SAM) films after exposure to an electron beam. By SW-XPS, we determined that the interface between the Al 2 O 3 underlayer and the SAMs is smooth, with a mean roughness of about 0.2 nm. Moreover, we determined that the SAM chains are, on average, tilted by 1/430 deg off the sample normal. The SW-XPS results also suggest that the SAM is not a perfectly aligned and uniform monolayer, with some areas having thickness higher than a single monolayer. We demonstrated that SW-XPS can provide useful information on ultrathin materials with high potential for being used as a characterization method of organic/inorganic photoresists.

36 MATERIALS SCIENCE↗

Phase Stability and Electrochemical Performance of La-Site-Doped Li6La3Zr0.5Nb0.5Ta0.5Hf0.5O12 High-Entropy Garnets

We investigate La-site substitution in the high-entropy garnet Li6La3Zr0.5Nb0.5Ta0.5Hf0.5O12 (LLZNTH) using Ba2+, Sr2+, and Sm3+ to elucidate how dopant governs phase stability, Li-site distribution, and electrochemical behavior. X-ray diffraction shows that Sr2+ is incorporated homogeneously into the garnet lattice, whereas the larger Ba2+ and smaller Sm3+ ions partially exceed the structural tolerance, generating secondary phases. Nevertheless, the Sm-doped composition (x = 0.05) exhibits the highest room-temperature ionic conductivity (2.7 × 10–4 S cm–1). Neutron powder diffraction reveals that Sm substitution drives a redistribution of Li+ from the tetrahedral 24 d sites into the higher-mobility 96 h positions, enhancing the connectivity of the three-dimensional Li-ion migration network. A Sm-doping series (x = 0.01–0.05) further shows that only sufficiently high Sm levels induce this redistribution, whereas lower concentrations retain Li arrangements similar to the undoped garnet. Critical current density measurements demonstrate that La-site dopants also influence interfacial stability against Li metal, underscoring a trade-off between bulk transport enhancement and mechanical robustness. Collectively, these findings reveal that in high-entropy garnets improved ionic conductivity can originate not only from phase-pure structures but also from targeted modification of the Li sublattice, even when accompanied by secondary phases, offering a compositional design principle for garnet electrolytes.

Li, Chang [Mechanical Engineering, School of Scien↗

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding—perhaps most importantly the temporal dynamic changes occurring therein—serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO 2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt 0 -O vacancy -Ce 3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Antiferromagnetic Fe Te 2 1 T - phase formation at the Sb 2 Te 3 / Ni 80 Fe 20 interface

Bilayer topological insulator/ferromagnet (TI/FM) heterostructures are promising for spintronic applications due to their low switching energy and therefore power efficiency. Until recently, the reactivity of TI with FM films was overlooked in the spin orbit-torque literature, even though there are reports that it is energetically favorable for TIs to react with transition metals and form interfacial layers. Here, in this study we fabricated a TI/FM heterostructure comprised of molecular beam epitaxy grown Sb 2 Te 3 and DC sputtered Ni 80 Fe 20 . Broadband ferromagnetic resonance revealed spin-pumping evident by the significant enhancement in Gilbert damping, which is likely a signature of the topological surface states or the presence of large spin-orbit-coupling in the adjacent Sb 2 Te 3 . With low-temperature magnetometry, an exchange bias is observed which indicates an exchange interaction between an antiferromagnet (AFM) and an adjacent FM. Cross-section high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) characterization of the Sb 2 Te 3 - Ni 80 Fe 20 bilayer revealed a complex interface showing diffusion of Fe and Ni into the Sb 2 Te 3 film yielding the formation of a FeTe 2 1T-type structural phase. Furthermore, density functional theory calculations revealed that the FeTe 2 1T-phase has an AFM ground state. Due to experimental limitations in the electron energy loss spectroscopy measurements precise chemistry of the interfacial phase could not be determined, therefore it is possible that the FeTe 2 1T and/or an intermixed (Fe 1-x Ni x )Te 2 1T is the AFM interfacial phase contributing to exchange bias in the system. This work emphasizes the chemical complexity of TI/FM interfaces that host novel, metastable magnetic topological phases and require more in-depth studies of other similar interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The role of confined collagen geometry in decreasing nucleation energy barriers to intrafibrillar mineralization

Mineralization of collagen is critical for the mechanical functions of bones and teeth. Calcium phosphate nucleation in collagenous structures follows distinctly different patterns in highly confined gap regions (nanoscale confinement) than in less confined extrafibrillar spaces (microscale confinement). Although the mechanism(s) driving these differences are still largely unknown, differences in the free energy for nucleation may explain these two mineralization behaviors. Here, we report on experimentally obtained nucleation energy barriers to intra- and extrafibrillar mineralization, using in situ X-ray scattering observations and classical nucleation theory. Polyaspartic acid, an extrafibrillar nucleation inhibitor, increases interfacial energies between nuclei and mineralization fluids. In contrast, the confined gap spaces inside collagen fibrils lower the energy barrier by reducing the reactive surface area of nuclei, decreasing the surface energy penalty. The confined gap geometry, therefore, guides the two-dimensional morphology and structure of bioapatite and changes the nucleation pathway by reducing the total energy barrier.

59 BASIC BIOLOGICAL SCIENCES↗

Mechanical Properties of Solidifying Assemblies of Nanoparticle Surfactants at the Oil–Water Interface

The effect of polymer surfactant structure and concentration on the self-assembly, mechanical properties, and solidification of nanoparticle surfactants (NPSs) at the oil-water interface was studied. The surface tension of the oil-water interface was found to depend strongly on the choice of the polymer surfactant used to assemble the NPSs, with polymer surfactants bearing multiple polar groups being the most effective at reducing interfacial tension and driving the NPS assembly. By contrast, only small variations in the shear modulus of the system were observed, suggesting that it is determined largely by particle density. In the presence of polymer surfactants bearing multiple functional groups, NPS assemblies on pendant drop surfaces were observed to spontaneously solidify above a critical polymer surfactant concentration. Interfacial solidification accelerated rapidly as polymer surfactant concentration was increased. On long timescales after solidification, pendant drop interfaces were observed to spontaneously wrinkle at sufficiently low surface tensions (approximately 5 mN m -1 ). Interfacial shear rheology of the NPS assemblies was elastic-dominated, with the shear modulus ranging from 0.1 to 1 N m -1 , comparable to values obtained for nanoparticle monolayers elsewhere. Finally, our work paves the way for the development of designer, multicomponent oil-water interfaces with well-defined mechanical, structural, and functional properties.

36 MATERIALS SCIENCE↗

Quantifying the Correlation between Coordination Chemistry, Interfacial Formation, and Electrochemical Performances for Mg Battery Electrolytes

Here, the rise of magnesium batteries as promising post-Li-ion energy storage technologies has sparked considerable attention toward understanding the fundamental aspects of coordination chemistry concerning Mg cations in multivalent electrolytes. This exploration includes investigating how coordination influences crucial electrolyte properties like solubility, electroreduction stability, and the formation of the interphase, all of which are pivotal for practical battery applications. Despite recent progress in developing a few functional electrolytes, a comprehensive understanding of the solvation structure that can facilitate efficient Mg deposition performance and the formulation of general design rules based on the solvation structure is still lacking. In our study, we endeavor to establish a connection between solvent and anion interactions with Mg 2+ , interface formation, and cycling performance through a series of organic ether solvents (tetrahydrofuran, glyme, diglyme, and triglyme) and amine solvents (dimethylamine, 3-methoxypropylamine, and dimethoxyethylamine). Our findings reveal a distinct coordination trend for solvent/Mg 2+ and (Mg-TFSI):solvent across various solvents, which dictates the extent of ion pairing for TFSI salts with increasing solvent molecule size and denticity. The solvated species in the bulk electrolyte across different solvents lead to diverse interfacial chemistries with varying decomposition components. We also explore the cycling efficiency as well as Mg deposition overpotentials for different solvents. A correlation analysis was conducted to assess the interplay between the structure and performance. Lastly, we apply the insights gained from these results to tailor the relative anion/Mg 2+ coordination structures using cosolvent systems, aiming for improved cell performance.

25 ENERGY STORAGE↗

Competing Magnetic Interactions and Field-Induced Metamagnetic Transition in Highly Crystalline Phase-Tunable Iron Oxide Nanorods

The inherent existence of multi phases in iron oxide nanostructures highlights the significance of them being investigated deliberately to understand and possibly control the phases. Here, the effects of annealing at 250 °C with a variable duration on the bulk magnetic and structural properties of high aspect ratio biphase iron oxide nanorods with ferrimagnetic Fe3O4 and antiferromagnetic α-Fe2O3 are explored. Increasing annealing time under a free flow of oxygen enhanced the α-Fe2O3 volume fraction and improved the crystallinity of the Fe3O4 phase, identified in changes in the magnetization as a function of annealing time. A critical annealing time of approximately 3 h maximized the presence of both phases, as observed via an enhancement in the magnetization and an interfacial pinning effect. This is attributed to disordered spins separating the magnetically distinct phases which tend to align with the application of a magnetic field at high temperatures. The increased antiferromagnetic phase can be distinguished due to the field-induced metamagnetic transitions observed in structures annealed for more than 3 h and was especially prominent in the 9 h annealed sample. Our controlled study in determining the changes in volume fractions with annealing time will enable precise control over phase tunability in iron oxide nanorods, allowing custom-made phase volume fractions in different applications ranging from spintronics to biomedical applications.

36 MATERIALS SCIENCE↗

Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

A novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.

36 MATERIALS SCIENCE↗

Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe 2 O 3 /NiO heterojunction

NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe 2 O 3 /NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni 3+ within 10 ps following selective photoexcitation of the underlying Fe 2 O 3 substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe 2 O 3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this model system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aerobijels: Ultralight Carbon Monoliths from Cocontinuous Emulsions

In this work, bijels are used to develop a new class of ultralight hierarchically porous aerogels exhibiting multimodal porosity across multiple length scales. Through in situ functionalization of a particle-laden liquid interface wherein binary liquid pairs are kinetically trapped out of equilibrium through interfacial jamming, monolithic and freestanding carbon electrodes are produced with prescribed bulk densities down to ≈2 mg cm -3 . Exemplary electrokinetic experiments indicate that the bicontinuity of the pore structure is essential for enhancing transport to and from the active electrode surfaces, demonstrating that these materials possess a superior ability to accumulate and transport charge when compared to analogous systems with restricted pore connectivity and fluid throughput. This approach offers a new synthetic route to bicontinuous and hierarchical aerogel materials with nested multimodal porosities. Furthermore, the flexibility of this scheme can address critical issues related to transport-limited behaviors that arise in many technological fields, ranging from energy and catalysis research to remediation and sensing applications.

36 MATERIALS SCIENCE↗

Structure/Interface Coupling Effect for High-Voltage LiCoO 2 Cathodes

LiCoO 2 (LCO) is widely applied in today's rechargeable battery markets for consumer electronic devices. However, LCO operations at high voltage are hindered by accelerated structure degradation and electrode/electrolyte interface decomposition. To overcome these challenges, co-modified LCO (defined as CB-Mg-LCO) that couples pillar structures with interface shielding are successfully synthesized for achieving high-energy-density and structurally stable cathode material. Benefitting from the "Mg-pillar" effect, irreversible phase transitions are significantly suppressed and highly reversible Li + shuttling is enabled. Interestingly, bonding effects between the interfacial lattice oxygen of CB-Mg-LCO and amorphous Co x B y coating layer are found to elevate the formation energy of oxygen vacancies, thereby considerably mitigating lattice oxygen loss and inhibiting irreversible phase transformation. Meanwhile, interface shielding effects are also beneficial for mitigating parasitic electrode/electrolyte reactions, subsequent Co dissolution, and ultimately enable a robust electrode/electrolyte interface. As a result, the as-designed CB-Mg-LCO cathode achieves a high capacity and excellent cycle stability with 94.6% capacity retention at an extremely high cut-off voltage of 4.6 V. We report these findings provide new insights for cathode material modification methods, which serves to guide future cathode material design.

25 ENERGY STORAGE↗

Interfacial Strong Coupling and Negative Dispersion of Propagating Polaritons in Freestanding Oxide Membranes

Membranes of complex oxides like perovskite SrTiO3 extend the multi-functional promise of oxide electronics into the nanoscale regime of 2D materials. Here, it is demonstrated that freestanding oxide membranes supply a reconfigurable platform for nano-photonics based on propagating surface phonon polaritons. Infrared near-field imaging and spectroscopy enabled by a tunable ultrafast laser are applied to study pristine nano-thick SrTiO3 membranes prepared by hybrid molecular beam epitaxy. As predicted by coupled mode theory, it is found that strong coupling of interfacial polaritons realizes symmetric and antisymmetric hybridized modes with simultaneously tunable negative and positive group velocities. By resolving reflection of these propagating modes from membrane edges, defects, and substrate structures, their dispersion is quantified with position-resolved nano-spectroscopy. Remarkably, polariton negative dispersion is found to be both robust and tunable through choice of membrane dielectric environment and thickness, and proposes a novel design for in-plane Veselago lensing harnessing this control. This work lays the foundation for tunable transformation optics at the nanoscale using polaritons in a wide range of freestanding complex oxide membranes.

freestanding oxide membranes↗

Engineering of Grain Boundaries in CeO 2 Enabling Tailorable Resistive Switching Properties

Abstract Defect engineering in valence change memories aimed at tuning the concentration and transport of oxygen vacancies are studied extensively, however mostly focusing on contribution from individual extended defects such as single dislocations and grain boundaries. In this work, the impact of engineering large numbers of grain boundaries on resistive switching mechanisms and performances is investigated. Three different grain morphologies, that is, “random network,” “columnar scaffold,” and “island‐like,” are realized in CeO 2 thin films. The devices with the three grain morphologies demonstrate vastly different resistive switching behaviors. The best overall resistive switching performance is shown in the devices with “columnar scaffold” morphology, where the vertical grain boundaries extending through the film facilitate the generation of oxygen vacancies as well as their migration under external bias. The observation of both interfacial and filamentary switching modes only in the devices with a “columnar scaffold” morphology further confirms the contribution from grain boundaries. In contrast, the “random network” or “island‐like” structures result in excessive or insufficient oxygen vacancy concentration migration paths. The research provides design guidelines for grain boundary engineering of oxide‐based resistive switching materials to tune the resistive switching performances for memory and neuromorphic computing applications.

36 MATERIALS SCIENCE↗

High modulus biocomposites via additive manufacturing: Cellulose nanofibril networks as “microsponges”

For the successful transition of additive manufacturing (AM) from prototyping to manufacturing of structural load bearing parts, feedstock systems with improved mechanical properties are needed. In terms of sustainability and environmental impact, selection of biobased renewable alternatives instead of petroleum-based options is important. Nanocellulose, which gives plants and trees their structural integrity, can offer significant improvements in the mechanical properties of AM polymers, provided that the right fibril morphology, dispersion and adhesion are achieved. In this study, although the interfacial adhesion between the hydrophilic cellulose nanofibrils (CNFs) and the hydrophobic polylactate matrix was not strong, and the optimal dispersion in individual fibril level was not attained, dramatic improvements in mechanical properties of neat polymer were achieved (up to 80% tensile strength increase, up to 200% elastic modulus increase). An interlocking reinforcing mechanism in which CNF bundles act as “microsponges” was proposed and supported by high resolution electron microscopy images, x-ray computed chromatography scans and thermal and dynamic mechanical behavior. Additively manufactured samples showed significantly higher elastic modulus (7.12 GPa vs. 6.57 GPa at 30 wt % CNF content) and dramatically improved storage modulus (1.72 GPa vs. 0.9 GPa at 30 wt % CNF content) in the printing direction compared to compression molded samples. Finally, in conclusion, preparation and 3D-printing of a 100% biobased renewable feedstock material with substantial mechanical property improvements were successfully demonstrated, which can open up new window of opportunities in the AM industry.

42 ENGINEERING↗

A solid-state extrusion pathway extensible to upcycling aluminum scrap and end-of-life permanent magnets into ductile Al-6061/SmCo 5 structural magnetic composites

Permanent magnets offer strong potential for multifunctional structural components, but their inherent brittleness limits direct integration. Here, SolidStir® Extrusion (SSE) is used to embed SmCo5 powder into AA6061 in the solid state, and the resulting microstructure, interfacial chemistry, mechanical properties, and magnetic response are systematically characterized. SSE fragments the initial SmCo 5 powder into predominantly fine particles dispersed within an ultrafine Al matrix, with a volume fraction of ∼ 4–6 % in this proof-of-concept study. Interfacial reactions form a continuous Al–Co reaction layer, with local atomic-resolution indexing consistent with Al 13 Co 4 , together with Sm–Si-rich reaction products, while the matrix contains Sm–Co–Si-rich precipitates and Mg 2 Si, producing features from nanometers to micrometers. Compared with an Al extrudate, this architecture increases yield strength by ∼ 42 % and tensile strength by ∼ 31 %, while preserving uniform elongation, and it sustains work hardening in compression from 150 to 400 °C. The composite retained hard-magnetic behavior, with axial magnetization of 12.7 A·m 2 kg −1 at 6 T and intrinsic coercivity of 9.6 kOe. These findings demonstrate that SSE can produce Al-based load-bearing magnetic composites while preserving useful SmCo5 functionality.

36 MATERIALS SCIENCE↗