Theoretical Understanding of Electromigration-Related Surface Diffusion and Current-Induced Force in Ag-Pd Systems.

Electromigration, as a common reason for interconnect failure, is becoming increasingly important in the ongoing decrease in the integrated circuit manufacturing process. A study is being carried out utilizing the ab initio calculational method to gain a deeper understanding of electromigration, with a focus on the atom diffusion process in the Ag-Pd alloy system, a commonly used interconnect material. We begin by establishing that the primary mechanism of diffusion is step-edge diffusion on the (111) surface. Following this, we examine the current-induced force exerted on the migrating Ag atom. The Pd substitutional defect reveals an effect that increases the energy barrier of diffusion and decreases the current-induced force that powers the directional migration.

Air Corrosion of Layered Cathode Materials for Sodium-Ion Batteries: Cation Mixing and a Practical Suppression Strategy.

Layered oxide cathodes of sodium-ion batteries (SIBs) are considered promising candidates due to their fascinating high capacity, good cyclability, and environmental friendliness. However, the air sensitivity of layered SIB cathodes causes high electrode manufacturing costs and performance deterioration, hampering their practical application. Herein, a commercial O3-type layered Na(Ni1/3Fe1/3Mn1/3)O2 (NNFM) material is adopted to investigate the air corrosive problem and the suppression strategy. We reveal that once the layered material comes in contact with ambient air, cations migrate from transition metal (TM) layers to sodium layers at the near surface, although Na+ and TM ions show quite different ion radii. Experimental results and theoretical calculations show that more Ni/Na disorder occurs in the air-exposed O3-NNFM materials, owing to a lower Ni migration energy barrier. The cation mixing results in detrimental structural distortion, along with the formation of residual alkali species on the surface, leading to high impedance for Na+ diffusion during charge/discharge. To tackle this problem, an ultrathin and uniform hydrophobic molecular layer of perfluorodecyl trimethoxysilane is assembled on the O3-NNFM surface, which significantly suppresses unfavorable chemistry and structure degradation during air storage. The in-depth understanding of the structural degradation mechanism and suppression strategy presented in this work can facilitate high-energy cathode manufacturing from the perspective of future practical implementation and commercialization.

Lithium Borohydride Nanorods: Self-Assembling Growth and Remarkable Hydrogen Cycling Properties.

Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.

Ordered planar plating/stripping enables deep cycling zinc metal batteries.

Metal anodes are emerging as culminating solutions for the development of energy-dense batteries in either aprotic, aqueous, or solid battery configurations. However, unlike traditional intercalation electrodes, the low utilization of "hostless" metal anodes due to the intrinsically disordered plating/stripping impedes their practical applications. Herein, we report ordered planar plating/stripping in a bulk zinc (Zn) anode to achieve an extremely high depth of discharge exceeding 90% with negligible thickness fluctuation and long-term stable cycling. The Zn can be plated/stripped with (0001)Zn preferential orientation throughout the consecutive charge/discharge process, assisted by a self-assembled supramolecular bilayer at the Zn anode-electrolyte interface. Through real-time tracking of the Zn atoms migration, we reveal that the ordered planar plating/stripping is driven by the construction of in-plane Zn─N bindings and the gradient energy landscape at the reaction fronts. The breakthrough results provide alternative insights into the ordered plating/stripping of metal anodes toward rechargeable energy-dense batteries.

Giant electric field-induced second harmonic generation in polar skyrmions.

Electric field-induced second harmonic generation allows electrically controlling nonlinear light-matter interactions crucial for emerging integrated photonics applications. Despite its wide presence in materials, the figures-of-merit of electric field-induced second harmonic generation are yet to be elevated to enable novel device functionalities. Here, we show that the polar skyrmions, a topological phase spontaneously formed in PbTiO3/SrTiO3 ferroelectric superlattices, exhibit a high comprehensive electric field-induced second harmonic generation performance. The second-order nonlinear susceptibility and modulation depth, measured under non-resonant 800 nm excitation, reach ~54.2 pm V-1 and ~664% V-1, respectively, and high response bandwidth (higher than 10 MHz), wide operating temperature range (up to ~400 K) and good fatigue resistance (>1010 cycles) are also demonstrated. Through combined in-situ experiments and phase-field simulations, we establish the microscopic links between the exotic polarization configuration and field-induced transition paths of the skyrmions and their electric field-induced second harmonic generation response. Our study not only presents a highly competitive thin-film material ready for constructing on-chip devices, but opens up new avenues of utilizing topological polar structures in the fields of photonics and optoelectronics.

Novel Sandwich-Structured Flexible Composite Films with Enhanced Piezoelectric Performance.

Piezoelectric poly(vinylidene fluoride) (PVDF) and its copolymers have been widely investigated for applications in wearable electric devices and sensing systems, owing to their intrinsic piezoelectricity and superior flexibility. However, their weak piezoelectricity poses major challenges for practical applications. To overcome these challenges, we propose a two-step synthesis approach to fabricate sandwich-structured piezoelectric films (BaTiO3@PDA/PVDF/BaTiO3@PDA) with significantly enhanced ferroelectric and piezoelectric properties. As compared to pristine PVDF films or conventional 0-3 composite films, a maximum polarization (Pmax) of 11.24 µC/cm2, a remanent polarization (Pr) of 5.83 µC/cm2, and an enhanced piezoelectric coefficient (d33 ∼ 14.6 pC/N) were achieved. Simulation and experimental results have demonstrated that the sandwich structure enhances the ability of composite films to withstand higher poling electric fields in comparison with 0-3 composites. The sandwich-structured piezoelectric films are further integrated into a wireless sensor system with a high force sensitivity of 288 mV/N, demonstrating great potential for movement monitoring applications. This facile approach shows great promise for the large-scale production of composite films with remarkable flexibility, ferroelectricity, and piezoelectricity for wearable sensing devices.

Dynamic Motion of Polar Skyrmions in Oxide Heterostructures.

Polar skyrmions have been widely investigated in oxide heterostructures due to their exotic properties and intriguing physical insights. However, the field-driven motion of polar skyrmions, akin to that of the magnetic counterpart, remains elusive. Herein, using phase-field simulations, we demonstrate the dynamic motion of polar skyrmions with integrated external thermal, electrical, and mechanical stimuli. External heating reduced the spontaneous polarization, while an applied electric field decreased the skyrmion size and weakened the interactions between the skyrmions. Together, the skyrmion motion barrier is significantly reduced from 40 to 2 eV under 9 V at 500 K. An applied mechanical force transformed the skyrmions into a c-domain region near the indenter center under the electric field, providing the space and driving force needed for the motion of the skyrmions. This study confirms that polar skyrmions can move like particles and provides concrete design principles for polar skyrmion-based electronic devices.

Enhanced Ultrasound Transmission through Skull Using Flexible Matching Layer with Gradual Acoustic Impedance.

Transcranial ultrasound imaging and therapy have gained significant attention due to their noninvasive nature, absence of ionizing radiation, and portability. However, the presence of the skull, which has a high acoustic impedance, presents a challenge for the penetration of ultrasound into intracranial tissue. This leads to a low transmission of ultrasound through the skull, hindering energy focusing and imaging quality. To address this challenge, we propose a novel approach that utilizes a flexible matching layer with gradual acoustic impedance to enhance ultrasound transmission through the skull. This matching layer is constructed using Poly(dimethylsiloxane) (PDMS)/tungsten powders as the structural component responsible for the gradual impedance, while agarose serves as the flexible matrix. Our simulation and experimental results demonstrate that the matching layer with an exponential gradual acoustic impedance significantly improves the ultrasound transmission coefficient across a wide frequency range compared to traditional quarter wavelength matching layers. Specifically, at 2 MHz, the maximum transmission coefficient reaches 49.5%, more than four times higher than that of the skull without a matching layer (only 11.7%). Additionally, the good flexibility of our matching layer ensures excellent adhesion to the curved surface of the skull, further enhancing its application potential in transcranial ultrasound imaging and therapy. The improved transmission performance allows for a lower ultrasound transmission power, effectively addressing overheating and safety issues.

Customizing CO2 Electroreduction by Pulse-Induced Anion Enrichment.

Electrochemically converting CO2 into specified high-value products is critical for carbon neutral economics. However, governing the product distribution of the CO2 electroreduction on Cu-based catalysts remains challenging. Herein, we put forward an anion enrichment strategy to efficiently dictate the route of *CO reduction by a pulsed electrolysis strategy. Upon periodically applying a positive potential on the cathode, the anion concentration in the vicinity of the electrode increases apparently. By adopting KF, KCl, and KHCO3 as electrolytes, the dominant CO2 electroreduction product on commercial Cu foil can be tuned into CO (53% ± 2.5), C2+ (76.6 ± 2.1%), and CH4 (42.6 ± 2.1%) under pulsed electrolysis. Notably, one can delicately tailor the ratios of CO/CH4, CH4/C2+, and C2+/CO by simply changing the composition of the electrolyte. Density functional theory calculations demonstrate that locally enriched anions can affect the key CO2RR intermediates in different ways owing to their specific electronegativity and volume, which leads to the distinct selectivity. The present study highlights the importance of tuning ionic species at the electrode-electrolyte interface for customizing the CO2 electroreduction products.

Pure Chiral Polar Vortex Phase in PbTiO3/SrTiO3 Superlattices with Tunable Circular Dichroism.

Nontrivial polarization textures have been demonstrated in ferroelectric/dielectric superlattices, where the electrostatic, elastic, and different gradient energies compete in a delicate balance. When PbTiO3/SrTiO3 superlattices are grown on DyScO3, the coexistence of ferroelectric domains and vortex structure is observed for n = 12-20 unit cells. Here, we report an approach to achieve single-phase vortex structures in superlattices by controlling the epitaxial strain using Sr1.04Al0.12Ga0.35Ta0.50O3 substrates. The domain width follows Kittel's law with the thickness of the ferroelectric PbTiO3 layers. A phase transition from vortex to a disordered phase with temperature is characterized by the correlation length. Resonant soft X-ray diffraction circular dichroism at the titanium L-edge reveals enhanced chirality with the thickness of the ferroelectric layer. These results are supported by second-principles simulations, which demonstrate that the integrated helicity increases with n. The stabilization of chiral single-phase polar vortices in ferroelectric/dielectric superlattices can enable novel optoelectronic devices with enhanced ferroelectric-light interaction.

Ferroelectric solitons crafted in epitaxial bismuth ferrite superlattices.

In ferroelectrics, complex interactions among various degrees of freedom enable the condensation of topologically protected polarization textures. Known as ferroelectric solitons, these particle-like structures represent a new class of materials with promise for beyond-CMOS technologies due to their ultrafine size and sensitivity to external stimuli. Such polarization textures have scarcely been demonstrated in multiferroics. Here, we present evidence for ferroelectric solitons in (BiFeO3)/(SrTiO3) superlattices. High-resolution piezoresponse force microscopy and Cs-corrected high-angle annular dark-field scanning transmission electron microscopy reveal a zoo of topologies, and polarization displacement mapping of planar specimens reveals center-convergent/divergent topological defects as small as 3 nm. Phase-field simulations verify that some of these structures can be classed as bimerons with a topological charge of ±1, and first-principles-based effective Hamiltonian computations show that the coexistence of such structures can lead to non-integer topological charges, a first observation in a BiFeO3-based system. Our results open new opportunities in multiferroic topotronics.

Emergent Ferroelectric Switching Behavior from Polar Vortex Lattice.

Topologically protected polar textures have provided a rich playground for the exploration of novel, emergent phenomena. Recent discoveries indicate that ferroelectric vortices and skyrmions not only host properties markedly different from traditional ferroelectrics, but also that these properties can be harnessed for unique memory devices. Using a combination of capacitor-based capacitance measurements and computational models, it is demonstrated that polar vortices in dielectric-ferroelectric-dielectric trilayers exhibit classical ferroelectric bi-stability together with the existence of low-field metastable polarization states. This behavior is directly tied to the in-plane vortex ordering, and it is shown that it can be used as a new method of non-destructive readout-out of the poled state.

Emergent chirality in a polar meron to skyrmion phase transition.

Polar skyrmions are predicted to emerge from the interplay of elastic, electrostatic and gradient energies, in contrast to the key role of the anti-symmetric Dzyalozhinskii-Moriya interaction in magnetic skyrmions. Here, we explore the reversible transition from a skyrmion state (topological charge of -1) to a two-dimensional, tetratic lattice of merons (with topological charge of -1/2) upon varying the temperature and elastic boundary conditions in [(PbTiO3)16/(SrTiO3)16]8 membranes. This topological phase transition is accompanied by a change in chirality, from zero-net chirality (in meronic phase) to net-handedness (in skyrmionic phase). We show how scanning electron diffraction provides a robust measure of the local polarization simultaneously with the strain state at sub-nm resolution, while also directly mapping the chirality of each skyrmion. Using this, we demonstrate strain as a crucial order parameter to drive isotropic-to-anisotropic structural transitions of chiral polar skyrmions to non-chiral merons, validated with X-ray reciprocal space mapping and phase-field simulations.

Surface Engineering for Ultrathin Metal Anodes Enabling High-Performance Zn-Ion Batteries.

Zn-ion batteries with low cost and high safety have been regarded as a promising energy storage technology for grid storage. It is well-known that the metal anode surface orientation is vital to its reversibility. Herein, we demonstrate a facile route to control the Zn metal anode surface orientation through electrodeposition with electrolyte additives. An ultrathin (101)-inclined Zn metal anode (down to 2 µm) is obtained by adding a small amount of dimethyl sulfoxide (DMSO) in the ZnSO4 aqueous electrolyte. Scanning electron microscopy indicates the formation of flat terrace-like surfaces, while in situ optical observations demonstrate the reversible plating and stripping. DFT calculations reveal that the large reconstruction of the Zn-(101) surface with DMSO and H2O adsorption to lower the interface energy is the main driving force for surface preference. Raman, XPS, and ToF-SIMS characterizations are performed to unveil the surface SEI components. Exceptional electrochemical performance is demonstrated for the (101)-inclined Zn metal anode in a half cell, which could cycle for 200 h with a low overpotential (<50 mV). The Zn||V2O full cells are assembled, showing much better cycle performance for the 5 µm (101)-inclined Zn metal anode as compared to the commercialized 10 µm Zn metal foil, with a maximum specific capacity of 359 mAh/g and >170 mAh/g after over 300 cycles. We hope this study will spur further interest in the control of surface crystallographic orientation for a stable ultrathin Zn metal anode.

Localized Recrystallization of a Lithium-Metal Anode during Fast Stripping in High-Activity Liquid Electrolytes.

The lithium-metal anode is one of the most promising candidates for "beyond-lithium-ion" batteries thanks to its high specific capacity and low negative electrochemical potential. However, the electrode-electrolyte interface instability hinders its commercialization in rechargeable batteries. During cycles of charging and discharging, the lithium-metal anode is electrochemically plated and stripped along with the morphological evolution, which determines the cycling performance. In this work, with a phase-field model, we computationally characterize the morphological evolution dynamics during the plating and stripping steps at the lithium-metal-electrolyte interface. Our model is valid in a wide range of lithium concentrations in liquid electrolytes by incorporating nonidealities of electrolyte solutions into the interfacial reaction kinetics. Intriguingly, at fast stripping, i.e., high discharging overpotential, we observe an unexpected localized recrystallization phenomenon in high-lithium-ion-concentration valley regions. This recrystallization phenomenon mitigates the overall reaction rate heterogeneity and provides a potential approach to improving the morphological stability. Furthermore, we systematically investigate the correlation between the recrystallization phenomenon and lithium-ion activity and draw a simplified phase diagram for the overpotential-dependent recrystallization.

Non-volatile electric-field control of inversion symmetry.

Competition between ground states at phase boundaries can lead to significant changes in properties under stimuli, particularly when these ground states have different crystal symmetries. A key challenge is to stabilize and control the coexistence of symmetry-distinct phases. Using BiFeO3 layers confined between layers of dielectric TbScO3 as a model system, we stabilize the mixed-phase coexistence of centrosymmetric and non-centrosymmetric BiFeO3 phases at room temperature with antipolar, insulating and polar semiconducting behaviour, respectively. Application of orthogonal in-plane electric (polar) fields results in reversible non-volatile interconversion between the two phases, hence removing and introducing centrosymmetry. Counterintuitively, we find that an electric field 'erases' polarization, resulting from the anisotropy in octahedral tilts introduced by the interweaving TbScO3 layers. Consequently, this interconversion between centrosymmetric and non-centrosymmetric phases generates changes in the non-linear optical response of over three orders of magnitude, resistivity of over five orders of magnitude and control of microscopic polar order. Our work establishes a platform for cross-functional devices that take advantage of changes in optical, electrical and ferroic responses, and demonstrates octahedral tilts as an important order parameter in materials interface design.

Integrated Numerical Simulations and Experimental Measurements for the Sintering Process of Injection-Molded Ti-6Al-4V Alloy.

Metal injection molding (MIM) is an advanced manufacturing technology that enables the mass production of high-performance and complex materials, such as the Ti-6Al-4V alloy. The determination of the size change and deformation of the Ti-6Al-4V alloy after the sintering process is challenging and critical for quality control. The numerical simulation could be a fast and cost-effective way to predict size change and deformation, given the large degrees of freedom for the sintering process. Herein, a finite element method based on the thermal-elastic-viscoplastic macroscopic model is developed to predict the shrinkage, deformation, relative density, and crack of injection-molded Ti-6Al-4V after sintering, using the Simufact software. Excellent agreements between experimental measurements and numerical simulations of the size and deformation are demonstrated (within a 3% error), confirming the accuracy of the numerical model. This approach can serve as a guideline for the mold design and sintering optimization of the MIM process.

Protocol for phase-field simulations of lithium dendrite growth with MOOSE framework.

Phase-field simulation is a powerful tool for understanding lithium metal electrodeposition. This protocol outlines the process of numerically solving the phase-field equations using the MOOSE framework. Here, we describe steps to obtain the spatiotemporal distribution of major physical characteristics such as phase-field, ion concentration, overpotential, and driving force. Such an approach may help to reveal the underlying physics and kinetics of dendrite growth, while also providing design principles for suppressing lithium dendrites. For complete details on the use and execution of this protocol, please refer to Hong and Viswanathan (2018).

Surface Coating of NCM-811 Cathode Materials with g-C3N4 for Enhanced Electrochemical Performance.

Li(Ni0.8, Co0.1, Mn0.1)O2 (NCM-811) cathode materials have been commercialized recently, aiming to increase the specific capacity and specific energy of the lithium-ion battery for practical applications in electric vehicles. The surface coating has been proved to be an effective approach for the stabilization of NCM-based cathodes, which could reduce the structural instability and prevent surface reactions between the cathode materials and electrolytes. Herein, we demonstrate the facile synthesis of graphitic carbon nitride (g-C3N4)-coated NCM cathodes with both the sonication-assisted liquid exfoliation method (g-C3N4NS@NCM-811) and chemical vapor-assisted coating method (g-C3N4@NCM-811). It is discovered that coating with a thin g-C3N4 layer could reduce the impedance of the NCM-811 cathode material, as well as increase the cycle stability of the cathode material, leading to increased capacity retention from 130 mA h/g (for the pristine sample) to 140 mA h/g after 225 cycles. While the coating of thick g-C3N4 nanosheets could hinder the lithium intercalation, resulting in significant loss of specific capacity. This study paves the way toward practical applications of the g-C3N4-coated NCM-811 cathode materials.

Theoretical Understanding of Polar Topological Phase Transitions in Functional Oxide Heterostructures: A Review.

The exotic topological phase is attracting considerable attention in condensed matter physics and materials science over the past few decades due to intriguing physical insights. As a combination of "topology" and "ferroelectricity," the ferroelectric (polar) topological structures are a fertile playground for emergent phenomena and functionalities with various potential applications. Herein, the review starts with the universal concept of the polar topological phase and goes on to briefly discuss the important role of computational tools such as phase-field simulations in designing polar topological phases in oxide heterostructures. In particular, the history of the development of phase-field simulations for ferroelectric oxide heterostructures is highlighted. Then, the current research progress of polar topological phases and their emergent phenomena in ferroelectric functional oxide heterostructures is reviewed from a theoretical perspective, including the topological polar structures, the establishment of phase diagrams, their switching kinetics and interconnections, phonon dynamics, and various macroscopic properties. Finally, this review offers a perspective on the future directions for the discovery of novel topological phases in other ferroelectric systems and device design for next-generation electronic device applications.