Spatially resolved steady-state negative capacitance.

Negative capacitance is a newly discovered state of ferroelectric materials that holds promise for electronics applications by exploiting a region of thermodynamic space that is normally not accessible1-14. Although existing reports of negative capacitance substantiate the importance of this phenomenon, they have focused on its macroscale manifestation. These manifestations demonstrate possible uses of steady-state negative capacitance-for example, enhancing the capacitance of a ferroelectric-dielectric heterostructure4,7,14 or improving the subthreshold swing of a transistor8-12. Yet they constitute only indirect measurements of the local state of negative capacitance in which the ferroelectric resides. Spatial mapping of this phenomenon would help its understanding at a microscopic scale and also help to achieve optimal design of devices with potential technological applications. Here we demonstrate a direct measurement of steady-state negative capacitance in a ferroelectric-dielectric heterostructure. We use electron microscopy complemented by phase-field and first-principles-based (second-principles) simulations in SrTiO3/PbTiO3 superlattices to directly determine, with atomic resolution, the local regions in the ferroelectric material where a state of negative capacitance is stabilized. Simultaneous vector mapping of atomic displacements (related to a complex pattern in the polarization field), in conjunction with reconstruction of the local electric field, identify the negative capacitance regions as those with higher energy density and larger polarizability: the domain walls where the polarization is suppressed.

Author Correction: Spatially resolved steady-state negative capacitance.

In this Letter, the first name of author Bhagwati Prasad was misspelled Bhagawati. This error has been corrected online.

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.

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.

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.

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.

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.

Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries.

Dendrite-free electrodeposition of lithium metal is necessary for the adoption of high energy-density rechargeable lithium metal batteries. Here, we demonstrate a mechanism of using a liquid crystalline electrolyte to suppress dendrite growth with a lithium metal anode. A nematic liquid crystalline electrolyte modifies the kinetics of electrodeposition by introducing additional overpotential due to its bulk-distortion and anchoring free energy. By extending the phase-field model, we simulate the morphological evolution of the metal anode and explore the role of bulk-distortion and anchoring strengths on the electrodeposition process. We find that adsorption energy of liquid crystalline molecules on a lithium surface can be a good descriptor for the anchoring energy and obtain it using first-principles density functional theory calculations. Unlike other extrinsic mechanisms, we find that liquid crystals with high anchoring strengths can ensure smooth electrodeposition of lithium metal, thus paving the way for practical applications in rechargeable batteries based on metal anodes.

Vortex Domain Walls in Ferroelectrics.

Controlling the domain formation in ferroelectric materials at the nanoscale is a fertile ground to explore emergent phenomena and their technological prospects. For example, charged ferroelectric domain walls in BiFeO3 and ErMnO3 exhibit significantly enhanced conductivity which could serve as the foundation for next-generation circuits (Estévez and Laurson, Phys. Rev. B 2015, 91, 054407). Here, we describe a concept in which polar vortices perform the same role as a ferroelectric domain wall in classical domain structures with the key difference being that the polar vortices can accommodate charged (i.e., head-to-head and tail-to-tail) domains, for example, in ferroelectric PbTiO3/dielectric SrTiO3 superlattices. Such a vortex domain wall structure can be manipulated in a reversible fashion under an external applied field.

Observation of Strong Polarization Enhancement in Ferroelectric Tunnel Junctions.

Ferroelectric heterostructures, with capability of storing data at ultrahigh densities, could act as the platform for next-generation memories. The development of new device paradigms has been hampered by the long-standing notion of inevitable ferroelectricity suppression under reduced dimensions. Despite recent experimental observation of stable polarized states in ferroelectric ultrathin films, the out-of-plane polarization components in these films are strongly attenuated compared to thicker films, implying a degradation of device performance in electronic miniaturization processes. Here, in a model system of BiFeO3/La0.7Sr0.3MnO3, we report observation of a dramatic out-of-plane polarization enhancement that occurs with decreasing film thickness. Our electron microscopy analysis coupled with phase-field simulations reveals a polarization-enhancement mechanism that is dominated by the accumulation of oxygen vacancies at interfacial layers. The results shed light on the interplay between polarization and defects in nanoscale ferroelectrics and suggest a route to enhance functionality in oxide devices.

Light-Activated Gigahertz Ferroelectric Domain Dynamics.

Using time- and spatially resolved hard x-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO_{3} are simultaneously captured on subnanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photoinduced electric field of up to 20×10^{6} V/m is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling method is developed that reveals the microscopic origin of these dynamics, leading to gigahertz polarization and elastic waves traveling in the crystal with sonic speeds and spatially varying frequencies. The advances in spatiotemporal imaging and dynamical modeling tools open up opportunities for disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains.

Stability of Polar Vortex Lattice in Ferroelectric Superlattices.

A novel mesoscale state comprising of an ordered polar vortex lattice has been demonstrated in ferroelectric superlattices of PbTiO3/SrTiO3. Here, we employ phase-field simulations, analytical theory, and experimental observations to evaluate thermodynamic conditions and geometric length scales that are critical for the formation of such exotic vortex states. We show that the stability of these vortex lattices involves an intimate competition between long-range electrostatic, long-range elastic, and short-range polarization gradient-related interactions leading to both an upper and a lower bound to the length scale at which these states can be observed. We found that the critical length is related to the intrinsic domain wall width, which could serve as a simple intuitive design rule for the discovery of novel ultrafine topological structures in ferroic systems.

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.

A molecular ferroelectric thin film of imidazolium perchlorate on silicon.

Molecular ferroelectrics have garnered significant attention due to their structural tunability, low synthesis temperature, and high flexibility. Herein, we successfully synthesized imidazole perchlorate (ImClO4) single crystals and high-quality, highly-oriented thin films on Si substrates. These films demonstrated a high inverse piezoelectric coefficient of 55.7 pm/V. Two types of domain bands were observed: type-I bands tilted ~60° relative to the horizontal axis, and type-II bands positioned perpendicular to the horizontal axis. Under a + 20 V bias, type-I bands showed a reduction and detachment of 180° domain walls to form a needle-like domain. It extended toward the band boundary after applying -20 V bias, which grew along the boundary upon contact. In contrast, type-II bands showed straight domain wall motion and displayed a higher piezoresponse than type-I bands. The growth of  high quality molecular ferroelectric thin films on Si substrates paves the way for the development of on-chip devices.

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.

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.

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.

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.

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.