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At least 127 records · Page 7

Hard x-ray standing-wave photoemission study of the interfaces in a BiFeO$_3$/La$_{0.7}$Sr$_{0.3}$MnO$_3$ superlattice

Hybrid multiferroics such as BiFeO$_3$ (BFO) and La$_{0.7}$Sr$_{0.3}$MnO$_3$ (LSMO) heterostructures are highly interesting functional systems due to their complex electronic and magnetic properties. One of the key parameters influencing the emergent properties is the quality of interfaces, where varying interdiffusion lengths can give rise to different chemistry and distinctive electronic states. Here we report high-resolution depth resolved chemical and electronic investigation of BFO/LSMO superlattice using standing-wave hard X-ray photoemission spectroscopy in the first-order Bragg as well as near-total-reflection geometry. Our results show that the interfaces of BFO on top of LSMO are atomically abrupt, while the LSMO on top of BFO interfaces show an interdiffusion length of around 1.2 unit cells. The two interfaces also exhibit different chemical gradients, with the BFO/LSMO interface being Sr-terminated by a spectroscopically distinctive high binding energy component in Sr 2p core-level spectra, which is spatially contained within 1 unit cell from the interface. From the electronic point of view, unique valence band features were observed for bulk-BFO, bulk-LSMO and their interfaces. Our X-ray optical analysis revealed a unique electronic signature at the BFO/LSMO interface, which we attribute to the coupling between those respective layers. Valence band decomposition based on the Bragg-reflection standing-wave measurement also revealed the band alignment between BFO and LSMO layers. Our work demonstrates that standing-wave hard x-ray photoemission is a reliable non-destructive technique for probing depth-resolved electronic structure of buried layers and interfaces with sub-unit-cell resolution. Equivalent investigations can be successfully applied to a broad class of material such as perovskite complex oxides with emergent interfacial phenomena.

Martins, HP↗

Understanding LIB Battery Electrodes Through Classical Electrochemical Interface Theory

Classical models of the electrochemical interface can be applied to complex and dynamic electrodes to understand important mechanisms that are relevant to device-level phenomena like calendar aging or cycle life. Here, we show that negative alloy electrodes with wide electrochemical windows cannot be assumed to have static interfaces throughout all states of charge. Under high states of charge, the interface -including the solid electrolyte interphase - has characteristics that resemble a highly polarized electrode far from the point of zero charge. Under these conditions, the interface can be understood through the Helmholtz model. At lower states of charge, the interface capacitance decreases and the space charge layer length increases. This transformation resembles a metal electrode approaching the point of zero charge which is understood through the Gouy-Chapman-Stern-Grahame model of the electrochemical interface. This transformation happens at both silicon and carbon-coated silicon interfaces. From voltage-limited cycling experiments, in the limit of the diffuse double layer, the silicon electrode impedance rises significantly in the first few cycles. This rise is related to the continuous electrochemical reduction of electrolyte components from an interface that is not electronically screened from the electrolyte. In other words, an electrode interface for batteries should resemble a 'Helmholtz-like' structure.

anode↗

3D interface size effects on slip transfer in Ti/Nb nanolaminates

Two-phase nanolaminates are well-renowned for achieving extraordinarily high strengths but at the sacrifice of reduced toughness and strain to failure. Recently ”thick” interfaces, or so called 3D interfaces, in Cu/Nb nanolaminates were experimentally shown to improve both of these mechanical properties. Here, in this work, we study the effect of 3D interfaces in the hexagonal close packed (HCP)/body centered cubic (BCC) Ti/Nb nanolaminate system. Nanoindentation hardness testing suggests increased strength with the introduction of a 3D Ti–Nb interface and a positive size effect with increases in 3D interface thickness from 5 nm to 20 nm. To understand this effect from a single dislocation perspective, we present a phase-field dislocation dynamics (PFDD) model for multi-phase HCP/BCC systems. We employ the model to simulate stress-driven transfer of single dislocations across 3D Ti/Nb interfaces of various thicknesses. Our results show that the critical stress for slip transfer increases with the thickness of the interface. This positive size effect is stronger for transfer from basal or prismatic dislocations in the Ti layer to 110$\langle$111$\rangle$ dislocations in the Nb layer than the reverse. For this Ti/Nb system, a critical thickness of 2 nm is identified at which the asymmetry in slip transfer is minimized. This work showcases 3D interfaces as a beneficial microstructure modification to strengthen as well as reduce anisotropy in nanocrystalline materials containing HCP phases.

Dislocations↗

Structure prediction of epitaxial inorganic interfaces by lattice and surface matching with Ogre

We present a new version of the Ogre open source Python package with the capability to perform structure prediction of epitaxial inorganic interfaces by lattice and surface matching. In the lattice matching step, a scan over combinations of substrate and film Miller indices is performed to identify the domain-matched interfaces with the lowest mismatch. Subsequently, surface matching is conducted by Bayesian optimization to find the optimal interfacial distance and in-plane registry between the substrate and the film. For the objective function, a geometric score function is proposed based on the overlap and empty space between atomic spheres at the interface. The score function reproduces the results of density functional theory (DFT) at a fraction of the computational cost. The optimized interfaces are pre-ranked using a score function based on the similarity of the atomic environment at the interface to the bulk environment. Final ranking of the top candidate structures is performed with DFT. Ogre streamlines DFT calculations of interface energies and electronic properties by automating the construction of interface models. The application of Ogre is demonstrated for two interfaces of interest for quantum computing and spintronics, Al/InAs and Fe/InSb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine-learning interatomic potentials for interfaces in all-solid-state batteries: Perspectives on training data, model selection, and validation

Interfaces play a pivotal role in dictating the performance and reliability of all-solid-state batteries (ASSBs), where complex electro-chemo-mechanical phenomena at grain boundaries (GBs) and interfaces can lead to degradation and failure. Traditional atomistic simulation methods, such as first-principles calculations and classical molecular dynamics, face limitations in modeling these interfaces due to either high computational cost or insufficient transferability to the diverse atomic environments evolving at interfaces. Machine-learning interatomic potentials (MLIPs) have emerged as a transformative approach, enabling large-scale, high-accuracy simulations of disordered and chemically complex systems by leveraging the predictability of machine learning models trained on first-principles data. Recent applications of MLIPs have demonstrated their ability to capture intricate behaviors at ASSB interfaces, including ion transport, interfacial evolution, and degradation mechanisms, with accuracy and efficiency unattainable by conventional methods. This prospective paper presents comprehensive analysis and practical guidance for MLIP development for GBs and interfaces in ASSBs, with a focus on three key pillars: data generation, model selection, and validation. Here, we review the current state of MLIP applications for GBs and interfaces in both general and ASSB-specific materials, highlighting best practices and challenges in constructing diverse and representative datasets, choosing appropriate machine learning architectures, and rigorously validating model performance. We also discuss emerging strategies and opportunities for improved reliability and efficiency of MLIPs to simulate realistic interfaces in ASSBs.

Energy - Storage↗

Finite Element Modeling of the Fiber-Matrix Interface in Polymer Composites

Polymer composites are used in numerous industries due to their high specific strength and high specific stiffness. Composites have markedly different properties than both the reinforcement and the matrix. Of the several factors that govern the final properties of the composite, the interface is an important factor that influences the stress transfer between the fiber and matrix. The present study is an effort to characterize and model the fiber-matrix interface in polymer matrix composites. Finite element models were developed to study the interfacial behavior during pull-out of a single fiber in continuous fiber-reinforced polymer composites. A three-dimensional (3D) unit-cell cohesive damage model (CDM) for the fiber/matrix interface debonding was employed to investigate the effect of interface/sizing coverage on the fiber. Furthermore, a two-dimensional (2D) axisymmetric model was used to (a) analyze the sensitivity of interface stiffness, interface strength, friction coefficient, and fiber length via a parametric study; and (b) study the shear stress distribution across the fiber-interface-matrix zone. It was determined that the force required to debond a single fiber from the matrix is three times higher if there is adequate distribution of the sizing on the fiber. The parametric study indicated that cohesive strength was the most influential factor in debonding. Moreover, the stress distribution model showed the debonding mechanism of the interface. It was observed that the interface debonded first from the matrix and remained in contact with the fiber even when the fiber was completely pulled out.

36 MATERIALS SCIENCE↗

Prediction of Solute Segregation at Metal/Oxide Interfaces Using Machine Learning Approaches

The atomic structure and chemistry at metal/oxide interfaces play a crucial role in determining their properties. However, studying semi-coherent metal/oxide interfaces that include misfit dislocations through density functional theory (DFT) is often computationally expensive due to the large number of atoms involved, ranging from hundreds to thousands. In this study, we explore solute segregation behavior at the Fe/Y 2 O 3 interface—an important model interface for cladding applications in nuclear fission reactors—by combining DFT calculations with a machine learning (ML) approach. ML models are trained using DFT-calculated segregation energies (𝐸 𝑆𝑒𝑔 ) to identify the key chemical and geometric factors influencing solute segregation at metal/oxide interfaces, revealing the competition between these features in determining 𝐸 𝑆𝑒𝑔 . Moreover, the segregation behavior at a specific Fe/Y 2 O 3 interface is predicted with high accuracy using ML models trained on data from this interface. Furthermore, it is found that the ML models could also predict solute segregation at a different Fe/Y 2 O 3 interface with a new orientation relationship (OR), at a computational cost of less than 1/45 of that required for similar DFT calculations.

36 - MATERIALS SCIENCE↗

Avoiding CO 2 Improves Thermal Stability at the Interface of Li 7 La 3 Zr 2 O 12 Electrolyte with Layered Oxide Cathodes

Abstract Solid‐state batteries promise higher energy densities and better safety than Li‐ion batteries with liquid electrolytes. However, the interface between solid electrolyte and cathode is unstable at the elevated temperatures that are needed while sintering to achieve good bonding between ceramic components. Here, the hypothesis is that, the gas environment, especially the presence of CO 2, is critical in determining the stability of the solid electrolyte–cathode interface. The effect of gas species on the interface is systematically probed, by a using Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte with a thin film LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode as a model system to enable interface sensitivity. Detrimental phases formed at the interface and their onset conditions are identified by X‐ray absorption spectroscopy, X‐ray diffraction, and Gibbs free energy analysis. As a result, removing CO 2 and minimizing H 2 O(g) during sintering is necessary to obtain good contact at the LLZO|cathode interface without forming secondary phases. Sintering in O 2 is ideal, yielding excellent chemical stability and low interfacial resistance. Secondary phases also do not form in N 2, but oxygen loss occurs at elevated temperatures. The interfacial resistance obtained upon sintering in pure O 2 is comparable to the lowest values at LLZO interfaces with protective coatings, but here without the need for interface coatings.

25 ENERGY STORAGE↗

Toughening of interface networks through the introduction of weak links

The resistance of polycrystalline materials to intergranular fracture depends on the toughness of the interfaces between neighboring grains. Using finite element simulations on model, two-dimensional microstructures, we demonstrate that the steady-state crack growth resistance of a polycrystal that contains exclusively high toughness interfaces is suboptimal: its crack growth resistance may be increased by introducing a minority fraction of weak interfaces at random locations within the interface network. Furthermore, the weaker are these interfaces, the greater is their toughening effect. These weak interfaces toughen the material through crack deflection and branching, nucleation of secondary cracks, and inelastic dissipation within intact interfaces. Furthermore, our findings suggest that fracture resistance-oriented material development should not aim to eliminate all weak interfaces, but rather judiciously incorporate a low fraction of them.

36 MATERIALS SCIENCE↗

Probing degradation at solid-state battery interfaces using machine-learning interatomic potential

Solid-state batteries featuring fast ion-conducting solid electrolytes are promising next-generation energy storage technologies, yet challenges remain for practical deployment due to electro-chemo-mechanical instabilities at solid-solid interfaces. These interfaces, which include homogeneous/internal interfaces such as grain boundaries (GBs) and heterogeneous/external interfaces between solid-electrolyte and electrode materials, can impede Li-ion transport, deteriorate performance, and eventually lead to cell failure. Here, in this study, we leverage large-scale molecular simulations, enabled by validated machine-learning interatomic potentials, to directly probe the onset of interfacial degradation at the garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid-electrolyte/LiCoO 2 (LCO) cathode interface. By surveying different interfacial geometries and compositions, it is found that Li-deficient interfaces can lead to severe interfacial disordering with cation mixing and Co interdiffusion from LCO into LLZO. By contrast, Li-sufficient interfaces are less disordered, although elemental segregation with local ordering is observed. As a consequence of Co interdiffusion, Co-rich regions are formed at the GBs of LLZO due to cation segregation and trapping effects. This behavior is independent of the GB tilting axis, degree of disorder at the GBs, and Co concentration, which implies Co clustering at GBs is a general phenomenon in polycrystalline LLZO and can dictate its overall transport and mechanical properties. Our findings elucidate the underlying fundamental mechanisms that give rise to experimentally observed physicochemical properties and provide guidelines for interface design that can mitigate interfacial degradation and improve cycling performance.

25 ENERGY STORAGE↗

Dynamics of oil–water interface at the beginning of the ultrasonic emulsification process

A lot of effort has been dedicated in recent years towards understanding the basics of cavitation induced emulsification, mainly in the form of single cavitation bubbles. Regarding bulk acoustic emulsification, a lot less research has been done. In our here presented work we utilize advanced high-speed observation techniques in visible light and X-Rays to build upon that knowledge and advance the understanding of bulk emulsion preparation. During research we discovered that emulsion formation has an acute impact on the behavior of the interface and more importantly on its position relative to the horn, hence their interdependence must be carefully studied. We did this by observing bulk emulsification with 2 cameras simultaneously and corroborating these measurements with observation under X-Rays. Since the ultrasonic horns location also influences interface behavior, we shifted its initial position to different locations nearer to and further away from the oil–water interface in both phases. We found that a few millimeters distance between the horn and interface is not enough for fine emulsion formation, but that they must be completely adjacent to each other, with the horn being located inside the oil–water interface. We also observed some previously undiscovered phenomena, such as the splitting of the interface to preserve continuous emulsion formation, climbing of the interface up the horn and circular interface protrusions towards the horn forming vertical emulsion streams. Interestingly, no visible W/O emulsion was ever formed during our experiments, only O/W regardless of initial horn position.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interface models for three-dimensional Rayleigh–Taylor instability

We derive interface models for three-dimensional Rayleigh–Taylor instability (RTI), making use of a novel asymptotic expansion in the non-locality of the fluid flow. These interface models are derived for the purpose of studying universal features associated with RTI such as the Froude number in single-mode RTI, the predicted quadratic growth of the interface amplitude under multi-mode random perturbations, the optimal (viscous) mixing rates induced by the RTI and the self-similarity of horizontally averaged density profiles and the remarkable stabilization of the mixing layer growth rate which arises for the three-fluid two-interface heavy–light–heavy configuration, in which the addition of a third fluid bulk slows the growth of the mixing layer to a linear rate. Our interface models can capture the formation of small-scale structures induced by severe interface roll-up, reproduce experimental data in a number of different regimes and study the effects of multiple interface interactions even as the interface separation distance becomes exceedingly small. Compared with traditional numerical schemes used to study such phenomena, our models provide a computational speed-up of at least two orders of magnitude.

Mechanics↗

Enhancing Sensitivity in Targeted Single-Cell Proteomics by Coupling a Dual Ion Funnel Interface with Triple Quadrupole Mass Spectrometer

Single-cell proteomics (SCP) has emerged as a powerful approach for understanding cellular heterogeneity and biological processes at unprecedented resolution. However, the extremely limited protein content of individual cells (femtogram to picogram levels) pushes current mass spectrometry instrumentation to its sensitivity limits, creating a critical analytical bottleneck. While selected reaction monitoring (SRM) using triple quadrupole (QqQ) instruments 1 offers advantages in sensitivity and reproducibility for targeted proteomics quantification, SRM still struggles with sensitivity for quantification of moderate- or low-abundance proteins from single-cell sample amounts. Here, we report the development and systematic evaluation of a dual ion funnel interface designed to address the sensitivity limitation by significantly enhancing ion transmission efficiency in commercial QqQ mass spectrometers. The dual ion funnel interface, composed of a curved S-funnel followed by a conventional ion funnel, improves ion transmission efficiency while reducing chemical noise through selective ion focusing. The performance of the dual ion funnel interface was systematically compared to standard interface on a TSQ Vantage platform across samples with different levels of complexity. The dual funnel interface demonstrated to provide up to 25-fold improvement in sensitivity across a wide range of protein concentrations in different biological matrices (low complex mouse macrophage and high complex human cells). Critically, enhanced sensitivity was accompanied by increased analytical reproducibility with lower coefficient of variations. Most importantly, the dual funnel interface enabled reliable quantification of low-abundance proteins that were barely detectable or not detected by the standard interface, extending analysis to single-cell equivalent amounts while maintaining excellent reproducibility. These results demonstrate that the dual funnel interface addresses the critical bottleneck in quantitative targeted proteomics, providing a technological foundation for ultrasensitive targeted SCP that requires both high sensitivity and robust quantitative performance.

Min, Sehong↗

Water structure and electric fields at the interface of oil droplets

Interfacial water exhibits rich and complex behaviour, playing an important part in chemistry, biology, geology and engineering. However, there is still much debate on the fundamental properties of water at hydrophobic interfaces, such as orientational ordering, the concentration of hydronium and hydroxide, improper hydrogen bonds and the presence of large electric fields. This controversy arises from the challenges in measuring interfacial systems, even with the most advanced experimental techniques and theoretical approaches available. Here we report on an in-solution, interface-selective Raman spectroscopy method using multivariate curve resolution to probe hexadecane-in-water emulsions, aided by a monomer-field theoretical model for Raman spectroscopy. Our results indicate that oil-water emulsion interfaces can exhibit reduced tetrahedral order and weaker hydrogen bonding, along with a substantial population of free hydroxyl groups that experience about 95 cm -1 redshift in their stretching mode compared with planar oil-water interfaces. Given the known electrostatic zeta potential characteristic of oil droplets, we propose the existence of a strong electric field (about 50-90 MV cm -1 ) emanating from the oil phase. This field is inferred indirectly but supported by control experiments and theoretical estimates. These observations are either absent or opposite in the molecular hydrophobic interface formed by small solutes or at planar oil-water interfaces. Instead, water structural disorder and enhanced electric fields emerge as unique features of the mesoscale interface in oil-water emulsions, potentially contributing to the accelerated chemical reactivity observed at hydrophobic-water interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Surfactants on Noble Metal Liquid-Gas Interface Mass Transfer in Molten Salt Reactors

Noble metals, a group of insoluble fission products (FPs), can accumulate in molten salt reactors (MSRs) and influence system performance and safety through deposition. Upon generation in fission, noble metals are transported by circulating salt and may either deposit on structural surfaces or enter the circulating gas bubble interfaces. While sparging was primarily designed for xenon and krypton removal, the mass transfer of noble metals into bubble interfaces highlights a potential pathway for their transport and partial extraction. The properties of the liquid-gas interface therefore play an important role in noble metal deposition and removal behaviors. Observations from earlier studies suggest that noble metals accumulated at the bubble interface can act as surfactants, making the bubble interface partially immobile. This behavior reduces the mass transfer capacity of circulating bubbles and affects both the overall distribution of noble metals in the loop and their removal efficiency. To investigate the influence of surfactants on noble metal transport, deposition, and extraction behaviors in MSRs, a previously developed and validated species transport model incorporating noble metal interphase mass transfer was used to simulate these behaviors. Two designed cases were studied to predict the distribution of 132Te along the Molten Salt Reactor Experiment (MSRE) loop under different bubble interface conditions. The results show that the mass transfer coefficients at the liquid-gas interface, determined by bubble interface characteristics, significantly influence noble metal distribution within the reactor loop. These findings emphasize the importance of continuously introducing fresh circulating bubbles into the molten salt to improve the removal efficiency of insoluble FPs from the MSR primary loop.

MSR↗

Best practices for first-principles simulations of epitaxial inorganic interfaces

Abstract At an interface between two materials physical properties and functionalities may be achieved, which would not exist in either material alone. Epitaxial inorganic interfaces are at the heart of semiconductor, spintronic, and quantum devices. First principles simulations based on density functional theory (DFT) can help elucidate the electronic and magnetic properties of interfaces and relate them to the structure and composition at the atomistic scale. Furthermore, DFT simulations can predict the structure and properties of candidate interfaces and guide experimental efforts in promising directions. However, DFT simulations of interfaces can be technically elaborate and computationally expensive. To help researchers embarking on such simulations, this review covers best practices for first principles simulations of epitaxial inorganic interfaces, including DFT methods, interface model construction, interface structure prediction, and analysis and visualization tools.

Physics↗

Interface-independent sound speed and thermal conductivity of atomic-layer-deposition-grown amorphous AlN / Al 2 O 3 multilayers with varying oxygen composition

Dielectric amorphous multilayers (AMLs) play a critical role in a wide array of technologies such as optical coatings, nanoelectronics, energy harvesting, and recovery devices. However, despite their wide applications, a robust understanding of the effect of the interplay between chemical and structural disorder on the thermal properties of AMLs is still lacking. Therefore, in this paper, we experimentally and numerically investigate the effects of composition and interface density on the sound speed and thermal conductivity of a series of amorphous aluminum nitride and aluminum oxide multilayers grown via plasma-enhanced atomic layer deposition. To systematically change the composition, the oxygen content of the AMLs is proportionally varied with interface density during growth. We find that the longitudinal sound speed of these AMLs is dictated by the oxygen content instead of the number of interfaces. The thermal conductivity, in contrast, is dictated by both interface density and oxygen content. The interfaces act to decrease the thermal conductivity, whereas the oxygen content increases the thermal conductivity. Due to the competing influence of the interfaces and oxygen content, the thermal conductivity of the AMLs remains nearly constant as a function of interface density. Furthermore, our study provides crucial insights into the effect of the interplay of composition and interfaces on the sound speed and thermal conductivity of AMLs.

36 MATERIALS SCIENCE↗

Phase-field model of alloy solidification far from chemical equilibrium at the solid-liquid interface

We further develop a recently introduced phase-field model of far-from-equilibrium alloy solidification under additive manufacturing conditions [K. Ji et al., Phys. Rev. Lett. 130, 026203 (2023)]. This model utilizes enhanced solute diffusivity within the spatially diffuse interface region to quantitatively capture solute trapping with a larger interface width, thereby making simulations on experimentally relevant length and timescales computationally feasible. The main developments presented here include testing the robustness of different variational formulations, extending the model to concentrated alloys by incorporating solid and liquid free energies from thermodynamic databases, as illustrated for hypoeutectic Al-Ag alloys with CALPHAD, extending convergence tests as a function of interface width to 3D, and carrying out simulations in both 2D and 3D to examine existing theories of microstructure development. Our results indicate that the simplest variational formulation that interpolates the bulk free-energy density between its solid and liquid forms is the most robust. Remarkably, for hypoeutectic Al-Ag alloys, this formulation yields a high-velocity nonequilibrium phase diagram that is independent of interface width, thereby demonstrating that the framework of enhanced solute diffusivity can be nontrivially extended to concentrated alloys. Other variational formulations have restricted ranges of materials or processing parameters that can be reliably modeled. We use 2D simulations to construct high-velocity microstructure selection maps for dilute Al-Cu alloys. The results validate the important role of latent heat rejection at the interface and extend the limited predictions of linear stability analysis [A. Karma and A. Sarkissian, Phys. Rev. E 47, 513 (1993)] and sharp-interface 1D simulations to fully nonlinear regimes. Furthermore, 3D simulations, carried out using a computationally tractable axisymmetric cellular/dendritic interface shape, demonstrate a good convergence similar to that observed in 2D as a function of interface width. Full 3D simulations, in turn, reveal that the standard theory of absolute stability is a good predictor of the upper critical velocity beyond which steady-state growth becomes unstable, despite the different morphological manifestations of this instability in 2D and 3D.

36 MATERIALS SCIENCE↗