Bifunctional nanoprecipitates strengthen and ductilize a medium-entropy alloy.

Single-phase high- and medium-entropy alloys with face-centred cubic (fcc) structure can exhibit high tensile ductility1,2 and excellent toughness2,3, but their room-temperature strengths are low1-3. Dislocation obstacles such as grain boundaries4, twin boundaries5, solute atoms6 and precipitates7-9 can increase strength. However, with few exceptions8-11, such obstacles tend to decrease ductility. Interestingly, precipitates can also hinder phase transformations12,13. Here, using a model, precipitate-strengthened, Fe-Ni-Al-Ti medium-entropy alloy, we demonstrate a strategy that combines these dual functions in a single alloy. The nanoprecipitates in our alloy, in addition to providing conventional strengthening of the matrix, also modulate its transformation from fcc-austenite to body-centred cubic (bcc) martensite, constraining it to remain as metastable fcc after quenching through the transformation temperature. During subsequent tensile testing, the matrix progressively transforms to bcc-martensite, enabling substantial increases in strength, work hardening and ductility. This use of nanoprecipitates exploits synergies between precipitation strengthening and transformation-induced plasticity, resulting in simultaneous enhancement of tensile strength and uniform elongation. Our findings demonstrate how synergistic deformation mechanisms can be deliberately activated, exactly when needed, by altering precipitate characteristics (such as size, spacing, and so on), along with the chemical driving force for phase transformation, to optimize strength and ductility.

Armoring of MgO by a Passivation Layer Impedes Direct Air Capture of CO2.

It has been proposed to use magnesium oxide (MgO) to separate carbon dioxide directly from the atmosphere at the gigaton level. We show experimental results on MgO single crystals reacting with the atmosphere for longer (decades) and shorter (days to months) periods with the goal of gauging reaction rates. Here, we find a substantial slowdown of an initially fast reaction as a result of mineral armoring by reaction products (surface passivation). In short-term experiments, we observe fast hydroxylation, carbonation, and formation of amorphous hydrated magnesium carbonate at early stages, leading to the formation of crystalline hydrated Mg carbonates. The preferential location of Mg carbonates along the atomic steps on the crystal surface of MgO indicates the importance of the reactive site density for carbonation kinetics. The analysis of 27-year-old single-crystal MgO samples demonstrates that the thickness of the reacted layer is limited to ∼1.5 µm on average, which is thinner than expected and indicates surface passivation. Thus, if MgO is to be employed for direct air capture of CO2, surface passivation must be circumvented.

Direct atomic fabrication and dopant positioning in Si using electron beams with active real-time image-based feedback.

Semiconductor fabrication is a mainstay of modern civilization, enabling the myriad applications and technologies that underpin everyday life. However, while sub-10 nanometer devices are already entering the mainstream, the end of the Moore's law roadmap still lacks tools capable of bulk semiconductor fabrication on sub-nanometer and atomic levels, with probe-based manipulation being explored as the only known pathway. Here we demonstrate that the atomic-sized focused beam of a scanning transmission electron microscope can be used to manipulate semiconductors such as Si on the atomic level, inducing growth of crystalline Si from the amorphous phase, reentrant amorphization, milling, and dopant front motion. These phenomena are visualized in real-time with atomic resolution. We further implement active feedback control based on real-time image analytics to automatically control the e-beam motion, enabling shape control and providing a pathway for atom-by-atom correction of fabricated structures in the near future. These observations open a new epoch for atom-by-atom manufacturing in bulk, the long-held dream of nanotechnology.

Interface Engineering of Domain Structures in BiFeO3 Thin Films.

A wealth of fascinating phenomena have been discovered at the BiFeO3 domain walls, examples such as domain wall conductivity, photovoltaic effects, and magnetoelectric coupling. Thus, the ability to precisely control the domain structures and accurately study their switching behaviors is critical to realize the next generation of novel devices based on domain wall functionalities. In this work, the introduction of a dielectric layer leads to the tunability of the depolarization field both in the multilayers and superlattices, which provides a novel approach to control the domain patterns of BiFeO3 films. Moreover, we are able to study the switching behavior of the first time obtained periodic 109° stripe domains with a thick bottom electrode. Besides, the precise controlling of pure 71° and 109° periodic stripe domain walls enable us to make a clear demonstration that the exchange bias in the ferromagnet/BiFeO3 system originates from 109° domain walls. Our findings provide future directions to study the room temperature electric field control of exchange bias and open a new pathway to explore the room temperature multiferroic vortices in the BiFeO3 system.

Engineering an Insulating Ferroelectric Superlattice with a Tunable Band Gap from Metallic Components.

The recent discovery of "polar metals" with ferroelectriclike displacements offers the promise of designing ferroelectrics with tunable energy gaps by inducing controlled metal-insulator transitions. Here we employ first-principles calculations to design a metallic polar superlattice from nonpolar metal components and show that controlled intermixing can lead to a true insulating ferroelectric with a tunable band gap. We consider a 2/2 superlattice made of two centrosymmetric metallic oxides, La_{0.75}Sr_{0.25}MnO_{3} and LaNiO_{3}, and show that ferroelectriclike displacements are induced. The ferroelectriclike distortion is found to be strongly dependent on the carrier concentration (Sr content). Further, we show that a metal-to-insulator (MI) transition is feasible in this system via disproportionation of the Ni sites. Such a disproportionation and, hence, a MI transition can be driven by intermixing of transition metal ions between Mn and Ni layers. As a result, the energy gap of the resulting ferroelectric can be tuned by varying the degree of intermixing in the experimental fabrication method.

The Effect of Polar Fluctuation and Lattice Mismatch on Carrier Mobility at Oxide Interfaces.

Since the discovery of two-dimensional electron gas (2DEG) at the oxide interface of LaAlO3/SrTiO3 (LAO/STO), improving carrier mobility has become an important issue for device applications. In this paper, by using an alternate polar perovskite insulator (La0.3Sr0.7) (Al0.65Ta0.35)O3 (LSAT) for reducing lattice mismatch from 3.0% to 1.0%, the low-temperature carrier mobility has been increased 30 fold to 35,000 cm(2) V(-1) s(-1). Moreover, two critical thicknesses for the LSAT/STO (001) interface are found, one at 5 unit cells for appearance of the 2DEG and the other at 12 unit cells for a peak in the carrier mobility. By contrast, the conducting (110) and (111) LSAT/STO interfaces only show a single critical thickness of 8 unit cells. This can be explained in terms of polar fluctuation arising from LSAT chemical composition. In addition to lattice mismatch and crystal symmetry at the interface, polar fluctuation arising from composition has been identified as an important variable to be tailored at the oxide interfaces to optimize the 2DEG transport.

A Sacrificial Coating Strategy Toward Enhancement of Metal-Support Interaction for Ultrastable Au Nanocatalysts.

Supported gold (Au) nanocatalysts hold great promise for heterogeneous catalysis; however, their practical application is greatly hampered by poor thermodynamic stability. Herein, a general synthetic strategy is reported where discrete metal nanoparticles are made resistant to sintering, preserving their catalytic activities in high-temperature oxidation processes. Taking advantage of the unique coating chemistry of dopamine, sacrificial carbon layers are constructed on the material surface, stabilizing the supported catalyst. Upon annealing at high temperature under an inert atmosphere, the interactions between support and metal nanoparticle are dramatically enhanced, while the sacrificial carbon layers can be subsequently removed through oxidative calcination in air. Owing to the improved metal-support contact and strengthened electronic interactions, the resulting Au nanocatalysts are resistant to sintering and exhibit excellent durability for catalytic combustion of propylene at elevated temperatures. Moreover, the facile synthetic strategy can be extended to the stabilization of other supported catalysts on a broad range of supports, providing a general approach to enhancing the thermal stability and sintering resistance of supported nanocatalysts.

Dimensionality Controlled Octahedral Symmetry-Mismatch and Functionalities in Epitaxial LaCoO3/SrTiO3 Heterostructures.

Epitaxial strain provides a powerful approach to manipulate physical properties of materials through rigid compression or extension of their chemical bonds via lattice-mismatch. Although symmetry-mismatch can lead to new physics by stabilizing novel interfacial structures, challenges in obtaining atomic-level structural information as well as lack of a suitable approach to separate it from the parasitical lattice-mismatch have limited the development of this field. Here, we present unambiguous experimental evidence that the symmetry-mismatch can be strongly controlled by dimensionality and significantly impact the collective electronic and magnetic functionalities in ultrathin perovskite LaCoO3/SrTiO3 heterojunctions. State-of-art diffraction and microscopy reveal that symmetry breaking dramatically modifies the interfacial structure of CoO6 octahedral building-blocks, resulting in expanded octahedron volume, reduced covalent screening, and stronger electron correlations. Such phenomena fundamentally alter the electronic and magnetic behaviors of LaCoO3 thin-films. We conclude that for epitaxial systems, correlation strength can be tuned by changing orbital hybridization, thus affecting the Coulomb repulsion, U, instead of by changing the band structure as the common paradigm in bulks. These results clarify the origin of magnetic ordering for epitaxial LaCoO3 and provide a route to manipulate electron correlation and magnetic functionality by orbital engineering at oxide heterojunctions.

Atomic-Level Sculpting of Crystalline Oxides: Toward Bulk Nanofabrication with Single Atomic Plane Precision.

The atomic-level sculpting of 3D crystalline oxide nanostructures from metastable amorphous films in a scanning transmission electron microscope (STEM) is demonstrated. Strontium titanate nanostructures grow epitaxially from the crystalline substrate following the beam path. This method can be used for fabricating crystalline structures as small as 1-2 nm and the process can be observed in situ with atomic resolution. The fabrication of arbitrary shape structures via control of the position and scan speed of the electron beam is further demonstrated. Combined with broad availability of the atomic resolved electron microscopy platforms, these observations suggest the feasibility of large scale implementation of bulk atomic-level fabrication as a new enabling tool of nanoscience and technology, providing a bottom-up, atomic-level complement to 3D printing.

Direct observation of ferroelectric field effect and vacancy-controlled screening at the BiFeO3/LaxSr1-xMnO3 interface.

The development of interface-based magnetoelectric devices necessitates an understanding of polarization-mediated electronic phenomena and atomistic polarization screening mechanisms. In this work, the LSMO/BFO interface is studied on a single unit-cell level through a combination of direct order parameter mapping by scanning transmission electron microscopy and electron energy-loss spectroscopy. We demonstrate an unexpected ~5% lattice expansion for regions with negative polarization charge, with a concurrent anomalous decrease of the Mn valence and change in oxygen K-edge intensity. We interpret this behaviour as direct evidence for screening by oxygen vacancies. The vacancies are predominantly accumulated at the second atomic layer of BFO, reflecting the difference of ionic conductivity between the components. This vacancy exclusion from the interface leads to the formation of a tail-to-tail domain wall. At the same time, purely electronic screening is realized for positive polarization charge, with insignificant changes in lattice and electronic properties. These results underline the non-trivial role of electrochemical phenomena in determining the functional properties of oxide interfaces. Furthermore, these behaviours suggest that vacancy dynamics and exclusion play major roles in determining interface functionality in oxide multilayers, providing clear implications for novel functionalities in potential electronic devices.

Oxygen-vacancy-induced polar behavior in (LaFeO3)2/(SrFeO3) superlattices.

Complex oxides displaying ferroelectric and/or multiferroic behavior are of high fundamental and applied interest. In this work, we show that it is possible to achieve polar order in a superlattice made up of two nonpolar oxides by means of oxygen vacancy ordering. Using scanning transmission electron microscopy imaging, we show the polar displacement of magnetic Fe ions in a superlattice of (LaFeO3)2/(SrFeO3) grown on a SrTiO3 substrate. Using density functional theory calculations, we systematically study the effect of epitaxial strain, octahedral rotations, and surface terminations in the superlattice and find them to have a negligible effect on the antipolar displacements of the Fe ions lying in between SrO and LaO layers of the superlattice (i.e., within La0.5Sr0.5FeO3 unit cells). The introduction of oxygen vacancies, on the other hand, triggers a polar displacement of the Fe ions. We confirm this important result using electron energy loss spectroscopy, which shows partial oxygen vacancy ordering in the region where polar displacements are observed and an absence of vacancy ordering outside of that area.

Room Temperature Ferrimagnetism and Ferroelectricity in Strained, Thin Films of BiFe0.5Mn0.5O3.

Highly strained films of BiFe0.5Mn0.5O3 (BFMO) grown at very low rates by pulsed laser deposition were demonstrated to exhibit both ferrimagnetism and ferroelectricity at room temperature and above. Magnetisation measurements demonstrated ferrimagnetism (TC ∼ 600K), with a room temperature saturation moment (MS ) of up to 90 emu/cc (∼ 0.58 µB /f.u) on high quality (001) SrTiO3. X-ray magnetic circular dichroism showed that the ferrimagnetism arose from antiferromagnetically coupled Fe3+ and Mn3+. While scanning transmission electron microscope studies showed there was no long range ordering of Fe and Mn, the magnetic properties were found to be strongly dependent on the strain state in the films. The magnetism is explained to arise from one of three possible mechanisms with Bi polarization playing a key role. A signature of room temperature ferroelectricity in the films was measured by piezoresponse force microscopy and was confirmed using angular dark field scanning transmission electron microscopy. The demonstration of strain induced, high temperature multiferroism is a promising development for future spintronic and memory applications at room temperature and above.

Water-mediated electrochemical nano-writing on thin ceria films.

Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing.

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products.

Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N2, reaching a current density of 20 mA cmgeo -2 at 1.04 V - 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu(2-x)+-OO-• active sites in CuCo, which initiates nucleophilic substitution of NH2 from the amide, leading to N-N coupling between *NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni3+ and Ni4+, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH- ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO2 - as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level.

Oxygen vacancy distributions and dynamics directly control the operation of solid-oxide fuel cells and are intrinsically coupled with magnetic, electronic and transport properties of oxides. For understanding the atomistic mechanisms involved during operation of the cell it is highly desirable to know the distribution of vacancies on the unit-cell scale. Here, we develop an approach for direct mapping of oxygen vacancy concentrations based on local lattice parameter measurements by scanning transmission electron microscopy. The concept of chemical expansivity is demonstrated to be applicable on the subunit-cell level: local stoichiometry variations produce local lattice expansion that can be quantified. This approach was successfully applied to lanthanum strontium cobaltite thin films epitaxially grown on substrates of different symmetry, where polarized neutron reflectometry revealed a strong difference in magnetic properties. The different vacancy content found in the two films suggests the change in oxygen chemical potential as a source of distinct magnetic properties, opening pathways for structural tuning of the vacancy concentrations and their gradients.

Local probing of electrochemically induced negative differential resistance in TiO2 memristive materials.

The early stages of electroforming in TiO(2) were explored using a combination of electrochemical strain microscopy and local I-V curve measurements. Negative differential resistance and corresponding surface deformation were observed below the electroforming voltages. Electrochemical strain microscopy allowed probing of the changes in local electrochemical activity during the pre-forming and forming stages. The associated structural changes were visualized by transmission electron microscopy. The results allowed an understanding of the electrochemical processes in the early stages of electroforming, and provide a comprehensive approach for exploring irreversible and partially reversible bias-induced transformations in solids.

Entropy stabilized cubic Li7La3Zr2O12 with reduced lithium diffusion activation energy: studied using solid-state NMR spectroscopy.

Stabilizing cubic polymorph of Li7La3Zr2O12 at low temperatures is challenging and currently limited to mono- or dual-ion doping with aliovalent ions. Herein, a high-entropy strategy at the Zr sites was deployed to stabilize the cubic phase and lower the lithium diffusion activation energy, evident from the static 7Li and MAS 6Li NMR spectra.

Oxygen Vacancy Injection as a Pathway to Enhancing Electromechanical Response in Ferroelectrics.

Since their discovery in late 1940s, perovskite ferroelectric materials have become one of the central objects of condensed matter physics and materials science due to the broad spectrum of functional behaviors they exhibit, including electro-optical phenomena and strong electromechanical coupling. In such disordered materials, the static properties of defects such as oxygen vacancies are well explored but the dynamic effects are less understood. In this work, the first observation of enhanced electromechanical response in BaTiO3 thin films is reported driven via dynamic local oxygen vacancy control in piezoresponse force microscopy (PFM). A persistence in peizoelectricity past the bulk Curie temperature and an enhanced electromechanical response due to a created internal electric field that further enhances the intrinsic electrostriction are explicitly demonstrated. The findings are supported by a series of temperature dependent band excitation PFM in ultrahigh vacuum and a combination of modeling techniques including finite element modeling, reactive force field, and density functional theory. This study shows the pivotal role that dynamics of vacancies in complex oxides can play in determining functional properties and thus provides a new route toward- achieving enhanced ferroic response with higher functional temperature windows in ferroelectrics and other ferroic materials.