Atom-by-atom imaging of moiré transformations in 2D transition metal dichalcogenides.

Understanding the atomic-scale mechanisms that govern the structure of interfaces is critical across materials systems but particularly so for two-dimensional (2D) moiré materials. Here, we image, atom-by-atom, the thermally induced structural evolution of twisted bilayer transition metal dichalcogenides using in situ transmission electron microscopy. We observe low-temperature, local conversion of moiré superlattice into nanoscale aligned domains. Unexpectedly, this process occurs by nucleating a new grain within one monolayer, whose crystal orientation is templated by the other. The aligned domains grow through collective rotation of moiré supercells and hopping of 5|7 defect pairs at moiré boundaries. This provides mechanistic insight into the atomic-scale interactions controlling moiré structures and illustrates the potential to pattern interfacial structure and properties of 2D materials at the nanoscale.

Achieving sub-0.5-angstrom-resolution ptychography in an uncorrected electron microscope.

Subangstrom resolution has long been limited to aberration-corrected electron microscopy, where it is a powerful tool for understanding the atomic structure and properties of matter. Here, we demonstrate electron ptychography in an uncorrected scanning transmission electron microscope (STEM) with deep subangstrom spatial resolution down to 0.44 angstroms, exceeding the conventional resolution of aberration-corrected tools and rivaling their highest ptychographic resolutions​. Our approach, which we demonstrate on twisted two-dimensional materials in a widely available commercial microscope, far surpasses prior ptychographic resolutions (1 to 5 angstroms) of uncorrected STEMs. We further show how geometric aberrations can create optimized, structured beams for dose-efficient electron ptychography. Our results demonstrate that expensive aberration correctors are no longer required for deep subangstrom resolution.

Thermally induced atomic reconstruction into fully commensurate structures of transition metal dichalcogenide layers.

Twist angle between two-dimensional layers is a critical parameter that determines their interfacial properties, such as moiré excitons and interfacial ferro-electricity. To achieve better control over these properties for fundamental studies and various applications, considerable efforts have been made to manipulate twist angle. However, due to mechanical limitations and the inevitable formation of incommensurate regions, there remains a challenge in attaining perfect alignment of crystalline orientation. Here we report a thermally induced atomic reconstruction of randomly stacked transition metal dichalcogenide multilayers into fully commensurate heterostructures with zero twist angle by encapsulation annealing, regardless of twist angles of as-stacked samples and lattice mismatches. We also demonstrate the selective formation of R- and H-type fully commensurate phases with a seamless lateral junction using chemical vapour-deposited transition metal dichalcogenides. The resulting fully commensurate phases exhibit strong photoluminescence enhancement of the interlayer excitons, even at room temperature, due to their commensurate structure with aligned momentum coordinates. Our work not only demonstrates a way to fabricate zero-twisted, two-dimensional bilayers with R- and H-type configurations, but also provides a platform for studying their unexplored properties.

Bend-Induced Ferroelectric Domain Walls in α-In2Se3.

The low bending stiffness of atomic membranes from van der Waals ferroelectrics such as α-In2Se3 allow access to a regime of strong coupling between electrical polarization and mechanical deformation at extremely high strain gradients and nanoscale curvatures. Here, we investigate the atomic structure and polarization at bends in multilayer α-In2Se3 at high curvatures down to 0.3 nm utilizing atomic-resolution scanning transmission electron microscopy, density functional theory, and piezoelectric force microscopy. We find that bent α-In2Se3 produces two classes of structures: arcs, which form at bending angles below ∼33°, and kinks, which form above ∼33°. While arcs preserve the original polarization of the material, kinks contain ferroelectric domain walls that reverse the out-of-plane polarization. We show that these kinks stabilize ferroelectric domains that can be extremely small, down to 2 atoms or ∼4 Å wide at their narrowest point. Using DFT modeling and the theory of geometrically necessary disclinations, we derive conditions for the formation of kink-induced ferroelectric domain boundaries. Finally, we demonstrate direct control over the ferroelectric polarization using templated substrates to induce patterned micro- and nanoscale ferroelectric domains with alternating polarization. Our results describe the electromechanical coupling of α-In2Se3 at the highest limits of curvature and demonstrate a strategy for nanoscale ferroelectric domain patterning.

Angstrom-scale imaging of magnetization in antiferromagnetic Fe2As via 4D-STEM.

We demonstrate a combination of computational tools and experimental 4D-STEM methods to image the local magnetic moment in antiferromagnetic Fe2As with 6 angstrom spatial resolution. Our techniques utilize magnetic diffraction peaks, common in antiferromagnetic materials, to create imaging modes that directly visualize the magnetic lattice. Using this approach, we show that center-of-mass analysis can determine the local magnetization component in the plane perpendicular to the path of the electron beam. Moreover, we develop Magnstem, a quantum mechanical electron scattering simulation code, to model electron scattering of an angstrom-scale probe from magnetic materials. Using these tools, we identify optimal experimental conditions for separating weak magnetic signals from the much stronger interactions of an angstrom-scale probe with electrostatic potentials. Our techniques should be useful for characterizing the local magnetic order in systems such in thin films, interfaces, and domain boundaries of antiferromagnetic materials, which are difficult to probe with existing methods.

In Situ Imaging of an Anisotropic Layer-by-Layer Phase Transition in Few-Layer MoTe2.

Understanding the phase transition mechanisms in two-dimensional (2D) materials is a key to precisely tailor their properties at the nanoscale. Molybdenum ditelluride (MoTe2) exhibits multiple phases at room temperature, making it a promising candidate for phase-change applications. Here, we fabricate lateral 2H-Td interfaces with laser irradiation and probe their phase transitions from micro- to atomic scales with in situ heating in the transmission electron microscope (TEM). By encapsulating the MoTe2 with graphene protection layers, we create an in situ reaction cell compatible with atomic resolution imaging. We find that the Td-to-2H phase transition initiates at phase boundaries at low temperatures (200-225 °C) and propagates anisotropically along the b-axis in a layer-by-layer fashion. We also demonstrate a fully reversible 2H-Td-2H phase transition cycle, which generates a coherent 2H lattice containing inversion domain boundaries. Our results provide insights on fabricating 2D heterophase devices with atomically sharp and coherent interfaces.

Atomic-Resolution Imaging of Small Organic Molecules on Graphene.

Here, we demonstrate atomic-resolution scanning transmission electron microscopy (STEM) imaging of light elements in small organic molecules on graphene. We use low-dose, room-temperature, aberration-corrected STEM to image 2D monolayer and bilayer molecular crystals, followed by advanced image processing methods to create high-quality composite images from ∼102-104 individual molecules. In metalated porphyrin and phthalocyanine derivatives, these images contain an elementally sensitive contrast with up to 1.3 Å resolution─sufficient to distinguish individual carbon and nitrogen atoms. Importantly, our methods can be applied to molecules with low masses (∼0.6 kDa) and nanocrystalline domains containing just a few hundred molecules, making it possible to study systems for which large crystals cannot easily be grown. Our approach is enabled by low-background graphene substrates, which we show increase the molecules' critical dose by 2-7×. These results indicate a new route for low-dose, atomic-resolution electron microscopy imaging to solve the structures of small organic molecules.

Wafer-Scale Programmed Assembly of One-Atom-Thick Crystals.

Crystalline films offer various physical properties based on the modulation of their thicknesses and atomic structures. The layer-by-layer assembly of atomically thin crystals provides a powerful means to arbitrarily design films at the atomic level, which are unattainable with existing growth technologies. However, atomically clean assembly of the materials with high scalability and reproducibility remains challenging. We report programmed crystal assembly of graphene and monolayer hexagonal boron nitride, assisted by van der Waals interactions, to form wafer-scale films of pristine interfaces with near-unity yield. The atomic configurations of the films are tailored with layer-resolved compositions and in-plane crystalline orientations. We demonstrate batch-fabricated tunnel device arrays with modulation of the resistance over orders of magnitude by thickness control of the hexagonal boron nitride barrier with single-atom precision and large-scale, twisted multilayer graphene with programmable electronic band structures and crystal symmetries. Our results constitute an important development in the artificial design of large-scale films.

Designing the Bending Stiffness of 2D Material Heterostructures.

2D monolayers represent some of the most deformable inorganic materials, with bending stiffnesses approaching those of lipid bilayers. Achieving 2D heterostructures with similar properties would enable a new class of deformable devices orders of magnitude softer than conventional thin-film electronics. Here, by systematically introducing low-friction twisted or heterointerfaces, interfacial engineering is leveraged to tailor the bending stiffness of 2D heterostructures over several hundred percent. A bending model is developed and experimentally validated to predict and design the deformability of 2D heterostructures and how it evolves with the composition of the stack, the atomic arrangements at the interfaces, and the geometry of the structure. Notably, when each atomic layer is separated by heterointerfaces, the total bending stiffness reaches a theoretical minimum, equal to the sum of the constituent layers regardless of scale of deformation-lending the extreme deformability of 2D monolayers to device-compatible multilayers.

Enhanced Photoluminescence of Multiple Two-Dimensional van der Waals Heterostructures Fabricated by Layer-by-Layer Oxidation of MoS2.

Monolayer transition metal dichalcogenides (TMDs) are promising for optoelectronics because of their high optical quantum yield and strong light-matter interaction. In particular, the van der Waals (vdW) heterostructures consisting of monolayer TMDs sandwiched by large gap hexagonal boron nitride have shown great potential for novel optoelectronic devices. However, a complicated stacking process limits scalability and practical applications. Furthermore, even though lots of efforts, such as fabrication of vdW heterointerfaces, modification of the surface, and structural phase transition, have been devoted to preserve or modulate the properties of TMDs, high environmental sensitivity and damage-prone characteristics of TMDs make it difficult to achieve a controllable technique for surface/interface engineering. Here, we demonstrate a novel way to fabricate multiple two-dimensional (2D) vdW heterostructures consisting of alternately stacked MoS2 and MoOx with enhanced photoluminescence (PL). We directly oxidized multilayer MoS2 to a MoOx/1 L-MoS2 heterostructure with atomic layer precision through a customized oxygen plasma system. The monolayer MoS2 covered by MoOx showed an enhanced PL intensity 3.2 and 6.5 times higher in average than the as-exfoliated 1 L- and 2 L-MoS2 because of preserved crystallinity and compensated dedoping by MoOx. By using layer-by-layer oxidation and transfer processes, we fabricated the heterostructures of MoOx/MoS2/MoOx/MoS2, where the MoS2 monolayers are separated by MoOx. The heterostructures showed the multiplied PL intensity as the number of embedded MoS2 layers increases because of suppression of the nonradiative trion formation and interlayer decoupling between stacked MoS2 layers. Our work shows a novel way toward the fabrication of 2D material-based multiple vdW heterostructures and our layer-by-layer oxidation process is beneficial for the fabrication of high performance 2D optoelectronic devices.

Deep Learning Enabled Strain Mapping of Single-Atom Defects in Two-Dimensional Transition Metal Dichalcogenides with Sub-Picometer Precision.

Two-dimensional (2D) materials offer an ideal platform to study the strain fields induced by individual atomic defects, yet challenges associated with radiation damage have so far limited electron microscopy methods to probe these atomic-scale strain fields. Here, we demonstrate an approach to probe single-atom defects with sub-picometer precision in a monolayer 2D transition metal dichalcogenide, WSe2-2xTe2x. We utilize deep learning to mine large data sets of aberration-corrected scanning transmission electron microscopy images to locate and classify point defects. By combining hundreds of images of nominally identical defects, we generate high signal-to-noise class averages which allow us to measure 2D atomic spacings with up to 0.2 pm precision. Our methods reveal that Se vacancies introduce complex, oscillating strain fields in the WSe2-2xTe2x lattice that correspond to alternating rings of lattice expansion and contraction. These results indicate the potential impact of computer vision for the development of high-precision electron microscopy methods for beam-sensitive materials.

Stochastic Stress Jumps Due to Soliton Dynamics in Two-Dimensional van der Waals Interfaces.

The creation and movement of dislocations determine the nonlinear mechanics of materials. At the nanoscale, the number of dislocations in structures become countable, and even single defects impact material properties. While the impact of solitons on electronic properties is well studied, the impact of solitons on mechanics is less understood. In this study, we construct nanoelectromechanical drumhead resonators from Bernal stacked bilayer graphene and observe stochastic jumps in frequency. Similar frequency jumps occur in few-layer but not twisted bilayer or monolayer graphene. Using atomistic simulations, we show that the measured shifts are a result of changes in stress due to the creation and annihilation of individual solitons. We develop a simple model relating the magnitude of the stress induced by soliton dynamics across length scales, ranging from <0.01 N/m for the measured 5 µm diameter to ∼1.2 N/m for the 38.7 nm simulations. These results demonstrate the sensitivity of 2D resonators are sufficient to probe the nonlinear mechanics of single dislocations in an atomic membrane and provide a model to understand the interfacial mechanics of different kinds of van der Waals structures under stress, which is important to many emerging applications such as engineering quantum states through electromechanical manipulation and mechanical devices like highly tunable nanoelectromechanical systems, stretchable electronics, and origami nanomachines.

Author Correction: Ultrasoft slip-mediated bending in few-layer graphene.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Ultrasoft slip-mediated bending in few-layer graphene.

Continuum scaling laws often break down when materials approach atomic length scales, reflecting changes in their underlying physics and the opportunities to access unconventional properties. These continuum limits are evident in two-dimensional materials, where there is no consensus on their bending stiffnesses or how they scale with thickness. Through combined computational and electron microscopy experiments, we measure the bending stiffness of graphene, obtaining 1.2-1.7 eV for a monolayer. Moreover, we find that the bending stiffness of few-layer graphene decreases sharply as a function of bending angle, tuning by almost 400% for trilayer graphene. This softening results from shear, slip and the onset of superlubricity between the atomic layers and corresponds with a gradual change in scaling power from cubic to linear. Our results provide a unified model for bending in two-dimensional materials and show that their multilayers can be orders of magnitude softer than previously thought, among the most flexible electronic materials currently known.

Quantitative Imaging of Organic Ligand Density on Anisotropic Inorganic Nanocrystals.

A longstanding challenge in nanoparticle characterization is to understand anisotropic distributions of organic ligands at the surface of inorganic nanoparticles. Here, we show that using electron energy loss spectroscopy in an aberration-corrected scanning transmission electron microscope we can directly visualize and quantify ligand distributions on gold nanorods (AuNRs). These experiments analyze dozens of particles on graphene substrates, providing insight into how ligand binding densities vary within and between individual nanoparticles. We demonstrate that the distribution of cetyltrimethylammonium bromide (CTAB) on AuNRs is anisotropic, with a 30% decrease in ligand density at the poles of the nanoparticles. In contrast, the distribution of (16-mercaptohexadecyl)trimethylammonium bromide (MTAB) is more uniform. These results are consistent with literature reported higher reactivity at the ends of CTAB-coated AuNRs. Our results demonstrate the impact of electron spectroscopy to probe molecular distributions at soft-hard interfaces and how they produce spatially heterogeneous properties in colloidal nanoparticles.

Ultrasonic Nebulization for TEM Sample Preparation on Single-Layer Graphene Grids.

Spray-coating using ultrasonic nebulization is reported for depositing nanoparticles on a TEM grid without many of the drying artifacts that are often associated with drop-casting. Spray-coating is suitable for preparing TEM samples on fragile support materials, such as suspended single-layer graphene, that rupture when samples are prepared by drop-casting. Additionally, because ultrasonic nebulization produces uniform droplets, nanoparticles deposited by spray-coating occur on the TEM grid in clusters, whose size is dependent on the concentration of the nanoparticle dispersion, which may allow the concentration of nanoparticle dispersions to be estimated using TEM.

Spin-Orbit Torque Switching in a Nearly Compensated Heusler Ferrimagnet.

Ferrimagnetic materials combine the advantages of the low magnetic moment of an antiferromagnet and the ease of realizing magnetic reading of a ferromagnet. Recently, it was demonstrated that compensated ferrimagnetic half metals can be realized in Heusler alloys, where high spin polarization, zero magnetic moment, and low magnetic damping can be achieved at the same time. In this work, by studying the spin-orbit torque induced switching in the Heusler alloy Mn2 Ru1- x Ga, it is found that efficient current-induced magnetic switching can be realized in a nearly compensated sample with strong perpendicular anisotropy and large film thickness. This work demonstrates the possibility of employing compensated Heusler alloys for fast, energy-efficient spintronic devices.

Author Correction: Atomically precise graphene etch stops for three dimensional integrated systems from two dimensional material heterostructures.

The original version of this Article contained an error in the second sentence of the second paragraph of the 'Electrical properties of fluorinated graphene contacts' section of the Results, which incorrectly read 'The mobility was calculated by the Drude model, µ = ne/σ where µ, n, e, and σ are the carrier mobility, carrier density, electron charge, and sheet conductivity, respectively'. The correct version states 'µ = σ/ne ' in place of 'µ = ne/σ '. This has been corrected in both the PDF and HTML versions of the Article.

Selective-Area Superconductor Epitaxy to Ballistic Semiconductor Nanowires.

Semiconductor nanowires such as InAs and InSb are promising materials for studying Majorana zero modes and demonstrating non-Abelian particle exchange relevant for topological quantum computing. While evidence for Majorana bound states in nanowires has been shown, the majority of these experiments are marked by significant disorder. In particular, the interfacial inhomogeneity between the superconductor and nanowire is strongly believed to be the main culprit for disorder and the resulting "soft superconducting gap" ubiquitous in tunneling studies of hybrid semiconductor-superconductor systems. Additionally, a lack of ballistic transport in nanowire systems can create bound states that mimic Majorana signatures. We resolve these problems through the development of selective-area epitaxy of Al to InSb nanowires, a technique applicable to other nanowires and superconductors. Epitaxial InSb-Al devices generically possess a hard superconducting gap and demonstrate ballistic 1D superconductivity and near-perfect transmission of supercurrents in the single mode regime, requisites for engineering and controlling 1D topological superconductivity. Additionally, we demonstrate that epitaxial InSb-Al superconducting island devices, the building blocks for Majorana-based quantum computing applications, prepared using selective-area epitaxy can achieve micron-scale ballistic 1D transport. Our results pave the way for the development of networks of ballistic superconducting electronics for quantum device applications.