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Abstract The Dzyaloshinskii-Moriya antisymmetric exchange interaction (DMI) stabilises topological spin textures with promising future spintronics applications. According to crystal symmetry, the DMI can be categorized as four different types that favour different chiral textures. Unlike the other three extensively-investigated types, out-of-plane DMI, as the last type that favours in-plane chirality, remained missing so far. Here we apply point-group-dependent DMI matrix analysis to show that out-of-plane DMI exists under reduced crystal symmetry. Through strain and structure engineering, we show how C s symmetry is realized in ultrathin magnets and observe the out-of-plane DMI stabilised in-plane chirality using spin-polarized electron microscopy. Our results show that extremely low out-of-plane DMI strengths at µeV/atom are sufficient to stabilise topological spin textures, including merons and bimerons. We also demonstrate field-induced reversible control of the in-plane chirality and merons. Our findings open up untapped paths on topological magnetic textures and their potential applications.

Abstract Grain boundaries in noble metal catalysts have been identified as critical sites for enhancing catalytic activity in electrochemical reactions such as the oxygen reduction reaction. However, conventional methods to modify grain boundary density often alter particle size, shape, and morphology, obscuring the specific role of grain boundaries in catalytic performance. This study addresses these challenges by employing gold nanoparticle assemblies to control grain boundary density through the manipulation of nanoparticle collision frequency during synthesis. We demonstrate a direct correlation between increased grain boundary density and enhanced two-electron oxygen reduction reaction activity, achieving a significant improvement in both specific and mass activity. Additionally, the gold nanoparticle assemblies with high grain boundary density exhibit remarkable electrochemical stability, attributed to boron segregation at the grain boundaries, which prevents structural degradation. This work provides a promising strategy for optimizing the activity, selectivity, and stability of noble metal catalysts through precise grain boundary engineering.

Abstract Cryo-transmission electron microscopy (cryo-EM) of frozen hydrated specimens is an efficient method for the structural analysis of purified biological molecules. However, cryo-EM and cryo-electron tomography are limited by the low signal-to-noise ratio (SNR) of recorded images, making detection of smaller particles challenging. For dose-resilient samples often studied in the physical sciences, electron ptychography – a coherent diffractive imaging technique using 4D scanning transmission electron microscopy (4D-STEM) – has recently demonstrated excellent SNR and resolution down to tens of picometers for thin specimens imaged at room temperature. Here we apply 4D-STEM and ptychographic data analysis to frozen hydrated proteins, reaching sub-nanometer resolution 3D reconstructions. We employ low-dose cryo-EM with an aberration-corrected, convergent electron beam to collect 4D-STEM data for our reconstructions. The high frame rate of the electron detector allows us to record large datasets of electron diffraction patterns with substantial overlaps between the interaction volumes of adjacent scan positions, from which the scattering potentials of the samples are iteratively reconstructed. The reconstructed micrographs show strong SNR enabling the reconstruction of the structure of apoferritin protein at up to 5.8 Å resolution. We also show structural analysis of the Phi92 capsid and sheath, tobacco mosaic virus, and bacteriorhodopsin at slightly lower resolutions.

Abstract High or medium- entropy alloys (HEAs/MEAs) are multi-principal element alloys with equal atomic elemental composition, some of which have shown record-breaking mechanical performance. However, the link between short-range order (SRO) and the exceptional mechanical properties of these alloys has remained elusive. The local destruction of SRO by dislocation glide has been predicted to lead to a rejuvenated state with increased entropy and free energy, creating softer zones within the matrix and planar fault boundaries that enhance the ductility, but this has not been verified. Here, we integrate in situ nanomechanical testing with energy-filtered four-dimensional scanning transmission electron microscopy (4D-STEM) and directly observe the rejuvenation during cyclic mechanical loading in single crystal CrCoNi at room temperature. Surprisingly, stacking faults (SFs) and twin boundaries (TBs) are reversible in initial cycles but become irreversible after a thousand cycles, indicating SF energy reduction and rejuvenation. Molecular dynamics (MD) simulation further reveals that the local breakdown of SRO in the MEA triggers these SF reversibility changes. As a result, the deformation features in HEAs/MEAs remain planar and highly localized to the rejuvenated planes, leading to the superior damage tolerance characteristic in this class of alloys.

Abstract Chemical short-range-order has been widely noticed to dictate the electrochemical properties of Li-excess cation-disordered rocksalt oxides, a class of cathode based on earth abundant elements for next-generation high-energy-density batteries. Existence of short-range-order is normally evidenced by a diffused intensity pattern in reciprocal space, however, derivation of local atomic arrangements of short-range-order in real space is hardly possible. Here, by a combination of aberration-corrected scanning transmission electron microscopy, electron diffraction, and cluster-expansion Monte Carlo simulations, we reveal the short-range-order is a convolution of three basic types: tetrahedron, octahedron, and cube. We discover that short-range-order directly correlates with Li percolation channels, which correspondingly affects Li transport behavior. We further demonstrate that short-range-order can be effectively manipulated by anion doping or post-synthesis thermal treatment, creating new avenues for tailoring the electrochemical properties. Our results provide fundamental insights for decoding the complex relationship between local chemical ordering and properties of crystalline compounds.

Abstract Transmission electron microscopy (TEM) is essential for determining atomic scale structures in structural biology and materials science. In structural biology, three-dimensional structures of proteins are routinely determined from thousands of identical particles using phase-contrast TEM. In materials science, three-dimensional atomic structures of complex nanomaterials have been determined using atomic electron tomography (AET). However, neither of these methods can determine the three-dimensional atomic structure of heterogeneous nanomaterials containing light elements. Here, we perform ptychographic electron tomography from 34.5 million diffraction patterns to reconstruct an atomic resolution tilt series of a double wall-carbon nanotube (DW-CNT) encapsulating a complex ZrTe sandwich structure. Class averaging the resulting tilt series images and subpixel localization of the atomic peaks reveals a Zr11Te50 structure containing a previously unobserved ZrTe2 phase in the core. The experimental realization of atomic resolution ptychographic electron tomography will allow for the structural determination of a wide range of beam-sensitive nanomaterials containing light elements.

Abstract High-density phase change memory (PCM) storage is proposed for materials with multiple intermediate resistance states, which have been observed in 1T-TaS2 due to charge density wave (CDW) phase transitions. However, the metastability responsible for this behavior makes the presence of multistate switching unpredictable in TaS2 devices. Here, we demonstrate the fabrication of nanothick verti-lateral H-TaS2/1T-TaS2 heterostructures in which the number of endotaxial metallic H-TaS2 monolayers dictates the number of resistance transitions in 1T-TaS2 lamellae near room temperature. Further, we also observe optically active heterochirality in the CDW superlattice structure, which is modulated in concert with the resistivity steps, and we show how strain engineering can be used to nucleate these polytype conversions. This work positions the principle of endotaxial heterostructures as a promising conceptual framework for reliable, non-volatile, and multi-level switching of structure, chirality, and resistance.

Abstract Chirality or handedness of a material can be used as an order parameter to uncover the emergent electronic properties for quantum information science. Conventionally, chirality is found in naturally occurring biomolecules and magnetic materials. Chirality can be engineered in a topological polar vortex ferroelectric/dielectric system via atomic-scale symmetry-breaking operations. We use four-dimensional scanning transmission electron microscopy (4D-STEM) to map out the topology-driven three-dimensional domain walls, where the handedness of two neighbor topological domains change or remain the same. The nature of the domain walls is governed by the interplay of the local perpendicular (lateral) and parallel (axial) polarization with respect to the tubular vortex structures. Unique symmetry-breaking operations and the finite nature of domain walls result in a triple point formation at the junction of chiral and achiral domain walls. The unconventional nature of the domain walls with triple point pairs may result in unique electrostatic and magnetic properties potentially useful for quantum sensing applications.

Abstract Grain boundaries, the two-dimensional defects between differently oriented crystals, tend to preferentially attract solutes for segregation. Solute segregation has a significant effect on the mechanical and transport properties of materials. At the atomic level, however, the interplay of structure and composition of grain boundaries remains elusive, especially with respect to light interstitial solutes like B and C. Here, we use Fe alloyed with B and C to exploit the strong interdependence of interface structure and chemistry via charge-density imaging and atom probe tomography methods. Direct imaging and quantifying of light interstitial solutes at grain boundaries provide insight into decoration tendencies governed by atomic motifs. We find that even a change in the inclination of the grain boundary plane with identical misorientation impacts grain boundary composition and atomic arrangement. Thus, it is the smallest structural hierarchical level, the atomic motifs, that controls the most important chemical properties of the grain boundaries. This insight not only closes a missing link between the structure and chemical composition of such defects but also enables the targeted design and passivation of the chemical state of grain boundaries to free them from their role as entry gates for corrosion, hydrogen embrittlement, or mechanical failure.

Abstract Lattice reconstruction and corresponding strain accumulation plays a key role in defining the electronic structure of two-dimensional moiré superlattices, including those of transition metal dichalcogenides (TMDs). Imaging of TMD moirés has so far provided a qualitative understanding of this relaxation process in terms of interlayer stacking energy, while models of the underlying deformation mechanisms have relied on simulations. Here, we use interferometric four-dimensional scanning transmission electron microscopy to quantitatively map the mechanical deformations through which reconstruction occurs in small-angle twisted bilayer MoS2 and WSe2/MoS2 heterobilayers. We provide direct evidence that local rotations govern relaxation for twisted homobilayers, while local dilations are prominent in heterobilayers possessing a sufficiently large lattice mismatch. Encapsulation of the moiré layers in hBN further localizes and enhances these in-plane reconstruction pathways by suppressing out-of-plane corrugation. We also find that extrinsic uniaxial heterostrain, which introduces a lattice constant difference in twisted homobilayers, leads to accumulation and redistribution of reconstruction strain, demonstrating another route to modify the moiré potential.

Abstract Deciphering the three-dimensional atomic structure of solid-solid interfaces in core-shell nanomaterials is the key to understand their catalytical, optical and electronic properties. Here, we probe the three-dimensional atomic structures of palladium-platinum core-shell nanoparticles at the single-atom level using atomic resolution electron tomography. We quantify the rich structural variety of core-shell nanoparticles with heteroepitaxy in 3D at atomic resolution. Instead of forming an atomically-sharp boundary, the core-shell interface is found to be atomically diffuse with an average thickness of 4.2 Å, irrespective of the particle’s morphology or crystallographic texture. The high concentration of Pd in the diffusive interface is highly related to the free Pd atoms dissolved from the Pd seeds, which is confirmed by atomic images of Pd and Pt single atoms and sub-nanometer clusters using cryogenic electron microscopy. These results advance our understanding of core-shell structures at the fundamental level, providing potential strategies into precise nanomaterial manipulation and chemical property regulation.

Abstract A fast, robust pipeline for strain mapping of crystalline materials is important for many technological applications. Scanning electron nanodiffraction allows us to calculate strain maps with high accuracy and spatial resolutions, but this technique is limited when the electron beam undergoes multiple scattering. Deep-learning methods have the potential to invert these complex signals, but require a large number of training examples. We implement a Fourier space, complex-valued deep-neural network, FCU-Net, to invert highly nonlinear electron diffraction patterns into the corresponding quantitative structure factor images. FCU-Net was trained using over 200,000 unique simulated dynamical diffraction patterns from different combinations of crystal structures, orientations, thicknesses, and microscope parameters, which are augmented with experimental artifacts. We evaluated FCU-Net against simulated and experimental datasets, where it substantially outperforms conventional analysis methods. Our code, models, and training library are open-source and may be adapted to different diffraction measurement problems.

Understanding 3D interfacial strain at the atomic level has been a long-sought challenge in the field of core-shell nanomaterials. Here, the authors address this challenge by revealing the full 3D atomic structures of Pd@Pt core-shell nanoparticles

The structure of hydrated interfaces is essential for understanding of geochemical processes and behavior of layered minerals. The authors show that waves of hydrated ions emerge at curved aqueous interfaces and couple mineral deformation to the chemistry of the solution.

Studying organic molecular nanocrystals with electron microscopy has been challenging due to complex structures and radiation sensitivity. Here, the authors present 4D-scanning confocal electron diffraction, and demonstrate direct in situ observation of structural evolution of bulk heterojunction thin films.

To use skyrmions to store information, an effective method for writing and deleting them is required. Here, Chen et al demonstrate the writing and deleting of skyrmions at room temperature by using hydrogen adsorption to change the magnetic anisotropy of the metallic multilayer hosting the skyrmions.

Materials discovery and design require characterizing material structures at the nanometer and sub-nanometer scale. Four-Dimensional Scanning Transmission Electron Microscopy (4D-STEM) resolves the crystal structure of materials, but many 4D-STEM data analysis pipelines are not suited for the identification of anomalous and unexpected structures. This work introduces improvements to the iterative Non-Negative Matrix Factorization (NMF) method by implementing consensus clustering for ensemble learning. We evaluate the performance of models during parameter tuning and find that consensus clustering improves performance in all cases and is able to recover specific grains missed by the best performing model in the ensemble. The methods introduced in this work can be applied broadly to materials characterization datasets to aid in the design of new materials.

Abstract Efforts to map atomic-scale chemistry at low doses with minimal noise using electron microscopes are fundamentally limited by inelastic interactions. Here, fused multi-modal electron microscopy offers high signal-to-noise ratio (SNR) recovery of material chemistry at nano- and atomic-resolution by coupling correlated information encoded within both elastic scattering (high-angle annular dark-field (HAADF)) and inelastic spectroscopic signals (electron energy loss (EELS) or energy-dispersive x-ray (EDX)). By linking these simultaneously acquired signals, or modalities, the chemical distribution within nanomaterials can be imaged at significantly lower doses with existing detector hardware. In many cases, the dose requirements can be reduced by over one order of magnitude. This high SNR recovery of chemistry is tested against simulated and experimental atomic resolution data of heterogeneous nanomaterials.

The response of the electronic structure to the non-trivial polarization texture in PbTiO3/SrTiO3 superlattices has not been explored. Here, the authors reveal how the peaks of the spectra shift and change their local electronic structure depending on the position of the Ti cation.

In ultrafast electron diffraction (UED) experiments, accurate retrieval of time-resolved structural parameters, such as atomic coordinates and thermal displacement parameters, requires an accurate scattering model. Unfortunately, kinematical models are often inaccurate even for relativistic electron probes, especially for dense, oriented single crystals where strong channeling and multiple scattering effects are present. This article introduces and demonstrates dynamical scattering models tailored for quantitative analysis of UED experiments performed on single-crystal films. As a case study, we examine ultrafast laser heating of single-crystal gold films. Comparison of kinematical and dynamical models reveals the strong effects of dynamical scattering within nm-scale films and their dependence on sample topography and probe kinetic energy. Applying to UED experiments on an 11 nm thick film using 750 keV electron probe pulses, the dynamical models provide a tenfold improvement over a comparable kinematical model in matching the measured UED patterns. Also, the retrieved lattice temperature rise is in very good agreement with predictions based on previously measured optical constants of gold, whereas fitting the Debye–Waller factor retrieves values that are more than three times lower. Altogether, these results show the importance of a dynamical scattering theory for quantitative analysis of UED and demonstrate models that can be practically applied to single-crystal materials and heterostructures.

Advanced time-resolved structural probes are enabling new views of rapid interactions and optical switching between symmetry-broken phases in quantum materials. Here, using relativistic ultrafast electron diffraction the authors investigate the dynamics of TaTe2 and chart the evolution of a distinct superstructure of trimer clusters which dissolve and form on picosecond time scales.

Nanocrystallography has transformed our ability to interrogate the atomic structures of proteins, peptides, organic molecules and materials. By probing atomic level details in ordered sub-10 nm regions of nanocrystals, scanning nanobeam electron diffraction extends the reach of nanocrystallography and in principle obviates the need for diffraction from large portions of one or more crystals. Scanning nanobeam electron diffraction is now applied to determine atomic structures from digitally defined regions of beam-sensitive peptide nanocrystals. Using a direct electron detector, thousands of sparse diffraction patterns over multiple orientations of a given crystal are recorded. Each pattern is assigned to a specific location on a single nanocrystal with axial, lateral and angular coordinates. This approach yields a collection of patterns that represent a tilt series across an angular wedge of reciprocal space: a scanning nanobeam diffraction tomogram. Using this diffraction tomogram, intensities can be digitally extracted from any desired region of a scan in real or diffraction space, exclusive of all other scanned points. Intensities from multiple regions of a crystal or from multiple crystals can be merged to increase data completeness and mitigate missing wedges. It is demonstrated that merged intensities from digitally defined regions of two crystals of a segment from the OsPYL/RCAR5 protein produce fragment-based ab initio solutions that can be refined to atomic resolution, analogous to structures determined by selected-area electron diffraction. In allowing atomic structures to now be determined from digitally outlined regions of a nanocrystal, scanning nanobeam diffraction tomography breaks new ground in nanocrystallography.

Summary: Understanding and visualizing the heterogeneous structure of immiscible semicrystalline polymer systems is critical for optimizing their morphology and microstructure. We demonstrate a cryogenic 4D-STEM technique using a combination of amorphous radial profile mapping and correlative crystalline growth processing methods to map both the crystalline and amorphous phase distribution in an isotactic polypropylene (iPP)/ethylene-octene copolymer (EO) multilayer film with 5-nm step size. The resulting map shows a very sharp interface between the amorphous iPP and EO with no preferential crystalline structure near or at the interface, reinforcing the expected incompatibility and immiscibility of iPP and EO, which is a short-chain branched polyethylene. This technique provides a method for direct observation of interfacial structure in an unstained semicrystalline complex multicomponent system with a single cryogenic 4D-STEM dataset.

Deviations of local structure and chemistry from the average crystalline unit cell are increasingly recognized to have a significant influence on the properties of many technologically important materials. Here, we present the vector pair correlation function (vPCF) as a new real-space crystallographic analysis method, which can be applied to atomic-resolution scanning transmission electron microscopy (STEM) images to quantify and analyze structural order/disorder correlations. Our STEM-based vPCFs have several advantages over radial PCFs and/or 3D pair distribution functions from x-ray total scattering: vPCFs explicitly retain crystallographic orientation information, are spatially resolved, can be applied directly on a sublattice basis, and are suitable for any material that can be imaged with STEM. To show the utility of our approach, we measure partial vPCFs in Ba5SmSn3Nb7O30 (BSSN), a tetragonal tungsten bronze (TTB) structured complex oxide. Many TTBs are known to be classical or relaxor ferroelectrics, and these properties have been correlated with the presence of superlattice ordering. BSSN, specifically, exhibits relaxor behavior and an incommensurate structural modulation. From the vPCF data, we observe that, of the cation sites, only the Ba (A2) sublattice is structurally modulated. We then infer the local modulation vector and reveal a marked anisotropy in its correlation length. Finally, short-range correlated polar displacements on the B2 cation sites are observed. This work introduces the vPCF as a powerful real-space crystallography technique, which enables direct, robust quantification of short-to-long range order on a sublattice-specific basis and is applicable to a wide range of complex material types.

Observing defect formation during bulk metallic glass deformation remains challenging. Here, the authors combine in situ nanobeam electron diffraction and large-scale molecular dynamics simulations to directly link changes to the local atomic ordering with shear band formation in a metallic glass.

Imaging electrostatic field around individual atoms or defective areas in monolayer 2D materials is crucial to understand their structural coordination. Here, the authors report local changes in specific atomic bonds and provide in-depth structural information of complex defective monolayer MoS2 and WS2 systems by 4D STEM.

The average crystal structure largely governs the Li diffusion kinetics in well-ordered cathode materials. Here the authors show this rule does not hold true for cation-disordered analogues. Cation short-range order is not only ubiquitous but also controls the Li transport behavior.

Chiral domain walls in magnetic films can be electrically controlled, which makes them attractive for applications, but domain walls in ultrathin films are normally non-chiral. Here, the authors observe chiral domain walls in ultrathin Fe/Ni bilayers that are stabilized by the magnetic anisotropy.

Feynman once asked physicists to build better electron microscopes to be able to watch biology at work. While electron microscopes can now provide atomic resolution, electron beam induced specimen damage precludes high resolution imaging of sensitive materials, such as single proteins or polymers. Here, we use simulations to show that an electron microscope based on a multi-pass measurement protocol enables imaging of single proteins, without averaging structures over multiple images. While we demonstrate the method for particular imaging targets, the approach is broadly applicable and is expected to improve resolution and sensitivity for a range of electron microscopy imaging modalities, including, for example, scanning and spectroscopic techniques. The approach implements a quantum mechanically optimal strategy which under idealized conditions can be considered interaction-free.

Future technologies based on ferroelectric materials will require new routes to control the nature of polar order. Through a combined experimental and theoretical study of compositionally and strain-graded Ba1-xSrxTiO3 heterostructures, Damodaranet al. demonstrate the ability to engineer large polarization gradients and temperature-stable susceptibilities.

Three-dimensional phase-contrast imaging of multiply-scattering samples in x-ray and electron microscopy is challenging due to small numerical apertures, the unavailability of wave front shaping optics, and the highly nonlinear inversion required from intensity-only measurements. In this work, we present an algorithm using the scattering matrix formalism to solve the scattering from a noncrystalline medium from scanning diffraction measurements and simultaneously recover the illumination aberrations. We demonstrate our method experimentally in a scanning transmission electron microscope, recovering the scattering matrix of a heterogeneous sample with two layers of multiwall carbon nanotubes filled with TaTe_{2} core-shell structures, spaced 10nm apart in the axial direction. Our work enables phase contrast imaging and materials characterization in multiply-scattering samples at high resolution for a wide range of materials.

The Dzyaloshinskii-Moriya interaction (DMI) has drawn much attention, as it stabilizes magnetic chirality, with important implications in fundamental and applied research. This antisymmetric exchange interaction is induced by the broken inversion symmetry at interfaces or in noncentrosymmetric lattices. Significant interfacial DMIs are often found at magnetic/heavy-metal interfaces with large spin-orbit coupling. Recent studies have shown promise for induced DMI at interfaces involving light elements such as carbon (graphene) or oxygen. Here, we report direct observation of induced DMI by chemisorption of the lightest element, hydrogen, on a ferromagnetic layer at room temperature, which is supported by density functional theory calculations. We further demonstrate a reversible chirality transition of the magnetic domain walls due to the induced DMI via hydrogen chemisorption and desorption. These results shed new light on the understanding of DMI in low atomic number materials and the design of novel chiral spintronics and magneto-ionic devices.

Competing phases in layered complex oxides are believed to be relevant for emergent phenomena, which still await to be witnessed. Here, Stone et al. report direct atomic-scale imaging of a multitude of polar phases in Ruddlesden-Popper oxide thin films, exhibiting diverse phenomena in a single structure.

Scanning transmission electron microscopy is a powerful material probe, but constrained to large atomic number samples due to the issues of beam damage and weak scattering. Here, Ophus et al.propose a method that produces linear phase contrast in a focused electron beam to image dose-sensitive objects.

Strong multiple scattering of the probe in scanning transmission electron microscopy (STEM) means image simulations are usually required for quantitative interpretation and analysis of elemental maps produced by electron energy-loss spectroscopy (EELS). These simulations require a full quantum-mechanical treatment of multiple scattering of the electron beam, both before and after a core-level inelastic transition. Current algorithms scale quadratically and can take up to a week to calculate on desktop machines even for simple crystal unit cells and do not scale well to the nanoscale heterogeneous systems that are often of interest to materials science researchers. We introduce an algorithm with linear scaling that typically results in an order of magnitude reduction in computation time for these calculations without introducing additional error and discuss approximations that further improve computational scaling for larger-scale objects with modest penalties in calculation error. We demonstrate these speedups by calculating the atomic resolution STEM-EELS map using the L-edge transition of Fe, for a nanoparticle 80 Å in diameter, in 16 hours, a calculation that would have taken at least 80 days using a conventional multislice approach.