Direct Visualization of Defect-Controlled Diffusion in van der Waals Gaps.

Diffusion processes govern fundamental phenomena such as phase transformations, doping, and intercalation in van der Waals (vdW) bonded materials. Here, the diffusion dynamics of W atoms by visualizing the motion of individual atoms at three different vdW interfaces: hexagonal boron nitride (BN)/vacuum, BN/BN, and BN/WSe2, by recording scanning transmission electron microscopy movies is quantified. Supported by density functional theory (DFT) calculations, it is inferred that in all cases diffusion is governed by intermittent trapping at electron beam-generated defect sites. This leads to diffusion properties that depend strongly on the number of defects. These results suggest that diffusion and intercalation processes in vdW materials are highly tunable and sensitive to crystal quality. The demonstration of imaging, with high spatial and temporal resolution, of layers and individual atoms inside vdW heterostructures offers possibilities for direct visualization of diffusion and atomic interactions, as well as for experiments exploring atomic structures, their in situ modification, and electrical property measurements of active devices combined with atomic resolution imaging.

Field-Driven Solid-State Defect Control of Bilayer Switching Devices.

We develop a framework for controlling and investigating reversible ionic transfer between two solid metal oxides layers by examining field-driven changes in electrical properties of the thin film bilayer oxide system Pr0.1Ce0.9O2/La1.85Ce0.15CuO4 (PCO/LCCO). We show that we can reversibly redistribute oxygen ions by applied voltage in a highly controlled and reversible fashion near ambient temperatures over large oxygen ion activity limits, which, for the first time, is directly interpretable by defect chemical models. This allowed us to determine how defect concentrations in each layer systematically varied with voltage and the subsequent impact on each film's conductance. These results showcase the relevance and applicability of defect chemical models, traditionally considered only at elevated temperatures, to the development of bilayer devices of importance to neuromorphic memory applications. This allows for a more systematic approach for studying and understanding the solid-solid exchange process in electrochemically controlled microelectronic devices. Moreover, our work sets the foundation for the development of large-area field-driven defect-controlled bilayer switching devices with potential application to a broad array of functionally modulated devices.

Simultaneous 2D Projection and 3D Topographic Imaging of Gas-Dependent Dynamics of Catalytic Nanoparticles.

Catalyst deactivation through pathways such as sintering of nanoparticles and degradation of the support is a critical factor when designing high-performance catalysts. Here, structural changes of supported nanoparticle catalysts are investigated in controlled gas environments (O2, H2O, and H2) at different temperatures by imaging simultaneously the nanoparticle structures in 2D projection and the 3D surface-sensitive topography. Platinum nanoparticles on carbon support as a model system are imaged in an environmental transmission electron microscope (ETEM), with concurrent acquisition of high-angle annular dark field scanning TEM (HAADF-STEM) and secondary electron (SE) images. Particle migration and coalescence occurs and shows gas-dependent kinetics, with nanoparticles moving across and through the support during and after coalescence. The temperature required for motion is lower in O2 than in H2O and H2, explained through the nature of the gas/nanoparticle interactions. In O2 and H2, the carbon support degrades by trench formation along migration pathways, and the particles move continuously, indicating a chemical reaction between gas and support. In H2O gas, motion is more discontinuous and oriented particle attachment occurs, as expected from theoretical predictions. These results suggest that multimodal imaging in ETEM that combines HAADF-STEM and SE data provides comprehensive information regarding catalyst dynamics and degradation mechanisms.

Temperature Dependent Growth Kinetics of Pd Nanocrystals: Insights from Liquid Cell Transmission Electron Microscopy.

Quantifying the role of experimental parameters on the growth of metal nanocrystals is crucial when designing synthesis protocols that yield specific structures. Here, the effect of temperature on the growth kinetics of radiolytically-formed branched palladium (Pd) nanocrystals is investigated by tracking their evolution using liquid cell transmission electron microscopy (TEM) and applying a temperature-dependent radiolysis model. At early times, kinetics consistent with growth limited is measured by the surface reaction rate, and it is found that the growth rate increases with temperature. After a transition time, kinetics consistent with growth limited by Pd atom supply is measured, which depends on the diffusion rate of Pd ions and atoms and the formation rate of Pd atoms by reduction of Pd ions by hydrated electrons. Growth in this regime is not strongly temperature-dependent, which is attributed to a balance between changes in the reducing agent concentration and the Pd ion diffusion rate. The observations suggest that branched rough surfaces, generally attributed to diffusion-limited growth, can form under surface reaction-limited kinetics. It is further shown that the combination of liquid cell TEM and radiolysis calculations can help identify the processes that determine crystal growth, with prospects for strategies for control during the synthesis of complex nanocrystals.

Anisotropic 2D van der Waals Magnets Hosting 1D Spin Chains.

The exploration of 1D magnetism, frequently portrayed as spin chains, constitutes an actively pursued research field that illuminates fundamental principles in many-body problems and applications in magnonics and spintronics. The inherent reduction in dimensionality often leads to robust spin fluctuations, impacting magnetic ordering and resulting in novel magnetic phenomena. Here, structural, magnetic, and optical properties of highly anisotropic 2D van der Waals antiferromagnets that uniquely host spin chains are explored. First-principle calculations reveal that the weakest interaction is interchain, leading to essentially 1D magnetic behavior in each layer. With the additional degree of freedom arising from its anisotropic structure, the structure is engineered by alloying, varying the 1D spin chain lengths using electron beam irradiation, or twisting for localized patterning, and spin textures are calculated, predicting robust stability of the antiferromagnetic ordering. Comparing with other spin chain magnets, these materials are anticipated to bring fresh perspectives on harvesting low-dimensional magnetism.

Effect of Surface Oxidation and Crystal Thickness on the Magnetic Properties and Magnetic Domain Structures of Cr2Ge2Te6.

van der Waals (vdW) magnetic materials, such as Cr2Ge2Te6 (CGT), show promise for memory and logic applications. This is due to their broadly tunable magnetic properties and the presence of topological magnetic features such as skyrmionic bubbles. A systematic study of thickness and oxidation effects on magnetic domain structures is important for designing devices and vdW heterostructures for practical applications. Here, we investigate thickness effects on magnetic properties, magnetic domains, and bubbles in oxidation-controlled CGT crystals. We find that CGT exposed to ambient conditions for 5 days forms an oxide layer approximately 5 nm thick. This oxidation leads to a significant increase in the oxidation state of the Cr ions, indicating a change in local magnetic properties. This is supported by real-space magnetic texture imaging through Lorentz transmission electron microscopy. By comparing the thickness-dependent saturation field of oxidized and pristine crystals, we find that oxidation leads to a nonmagnetic surface layer that is thicker than the oxide layer alone. We also find that the stripe domain width and skyrmionic bubble size are strongly affected by the crystal thickness in pristine crystals. These findings underscore the impact of thickness and surface oxidation on the properties of CGT, such as saturation field and domain/skyrmionic bubble size, and suggest a pathway for manipulating magnetic properties through a controlled oxidation process.

High energy density in artificial heterostructures through relaxation time modulation.

Electrostatic capacitors are foundational components of advanced electronics and high-power electrical systems owing to their ultrafast charging-discharging capability. Ferroelectric materials offer high maximum polarization, but high remnant polarization has hindered their effective deployment in energy storage applications. Previous methodologies have encountered problems because of the deteriorated crystallinity of the ferroelectric materials. We introduce an approach to control the relaxation time using two-dimensional (2D) materials while minimizing energy loss by using 2D/3D/2D heterostructures and preserving the crystallinity of ferroelectric 3D materials. Using this approach, we were able to achieve an energy density of 191.7 joules per cubic centimeter with an efficiency greater than 90%. This precise control over relaxation time holds promise for a wide array of applications and has the potential to accelerate the development of highly efficient energy storage systems.

Salt-Assisted Vapor-Liquid-Solid Growth of 1D van der Waals Materials.

The method of salt-assisted vapor-liquid-solid (VLS) growth is introduced to synthesize 1D nanostructures of trichalcogenide van der Waals (vdW) materials, exemplified by niobium trisulfide (NbS3). The method uses a unique catalyst consisting of an alloy of Au and an alkali metal halide (NaCl) to enable rapid and directional growth. High yields of two types of NbS3 1D nanostructures, nanowires and nanoribbons, each with sub-ten nanometer diameter, tens of micrometers length, and distinct 1D morphology and growth orientation are demonstrated. Strategies to control the location, size, and morphology of growth, and extend the growth method to synthesize other transition metal trichalcogenides, NbSe3 and TiS3, as nanowires are demonstrated. Finally, the role of the Au-NaCl alloy catalyst in guiding VLS synthesis is described and the growth mechanism based on the relationships measured between structure (growth orientation, morphology, and dimensions) and growth conditions (catalyst volume and growth time) is discussed. These results introduce opportunities to expand the library of emerging 1D vdW materials to make use of their unique properties through controlled growth at nanoscale dimensions.

Controlled formation of three-dimensional cavities during lateral epitaxial growth.

Epitaxial growth is a fundamental step required to create devices for the semiconductor industry, enabling different materials to be combined in layers with precise control of strain and defect structure. Patterning the growth substrate with a mask before performing epitaxial growth offers additional degrees of freedom to engineer the structure and hence function of the semiconductor device. Here, we demonstrate that conditions exist where such epitaxial lateral overgrowth can produce complex, three-dimensional structures that incorporate cavities of deterministic size. We grow germanium on silicon substrates patterned with a dielectric mask and show that fully-enclosed cavities can be created through an unexpected self-assembly process that is controlled by surface diffusion and surface energy minimization. The result is confined cavities enclosed by single crystalline Ge, with size and position tunable through the initial mask pattern. We present a model to account for the observed cavity symmetry, pinch-off and subsequent evolution, reflecting the dominant role of surface energy. Since dielectric mask patterning and epitaxial growth are compatible with conventional device processing steps, we suggest that this mechanism provides a strategy for developing electronic and photonic functionalities.

Electrochemical Intercalation and Exfoliation of CrSBr into Ferromagnetic Fibers and Nanoribbons.

Recent studies dedicated to layered van der Waals crystals have attracted significant attention to magnetic atomically thin crystals offering unprecedented opportunities for applications in innovative magnetoelectric, magneto-optic, and spintronic devices. The active search for original platforms for the low-dimensional magnetism study has emphasized the entirely new magnetic properties of two dimensional (2D) semiconductor CrSBr. Herein, for the first time, the electrochemical exfoliation of bulk CrSBr in a non-aqueous environment is demonstrated. Notably, crystal cleavage governed by the structural anisotropy occurred along two directions forming atomically thin and few-layered nanoribbons. The exfoliated material possesses an orthorhombic crystalline structure and strong optical anisotropy, showing the polarization dependencies of Raman signals. The antiferromagnetism exhibited by multilayered CrSBr gives precedence to ferromagnetic ordering in the revealed CrSBr nanostructures. Furthermore, the potential application of CrSBr nanoribbons is pioneered for electrochemical photodetector fabrication and demonstrates its responsivity up to 30 µA cm-2 in the visible spectrum. Moreover, the CrSBr-based anode for lithium-ion batteries exhibited high performance and self-improving abilities. This anticipates that the results will pave the way toward the future study of CrSBr and practical applications in magneto- and optoelectronics.

Atomic-Scale Mechanisms of MoS2 Oxidation for Kinetic Control of MoS2/MoO3 Interfaces.

Oxidation of transition metal dichalcogenides (TMDs) occurs readily under a variety of conditions. Therefore, understanding the oxidation processes is necessary for successful TMD handling and device fabrication. Here, we investigate atomic-scale oxidation mechanisms of the most widely studied TMD, MoS2. We find that thermal oxidation results in α-phase crystalline MoO3 with sharp interfaces, voids, and crystallographic alignment with the underlying MoS2. Experiments with remote substrates prove that thermal oxidation proceeds via vapor-phase mass transport and redeposition, a challenge to forming thin, conformal films. Oxygen plasma accelerates the kinetics of oxidation relative to the kinetics of mass transport, forming smooth and conformal oxides. The resulting amorphous MoO3 can be grown with subnanometer to several-nanometer thickness, and we calibrate the oxidation rate for different instruments and process parameters. Our results provide quantitative guidance for managing both the atomic scale structure and thin-film morphology of oxides in the design and processing of TMD devices.

High-Resolution Nanoanalytical Insights into Particle Formation in SnO2/ZnO Core/Shell Nanowire Lithium-Ion Battery Anodes.

Tin oxide (SnO2)/zinc oxide (ZnO) core/shell nanowires as anode materials in lithium-ion batteries (LIBs) were investigated using a combination of classical electrochemical analysis and high-resolution electron microscopy to correlate structural changes and battery performance. The combination of the conversion materials SnO2 and ZnO is known to have higher storage capacities than the individual materials. We report the expected electrochemical signals of SnO2 and ZnO for SnO2/ZnO core/shell nanowires as well as unexpected structural changes in the heterostructure after cycling. Electrochemical measurements based on charge/discharge, rate capability, and electrochemical impedance spectroscopy showed electrochemical signals for SnO2 and ZnO and partial reversibility of lithiation and delithiation. We find an initially 30% higher capacity for the SnO2/ZnO core/shell NW heterostructure compared to the ZnO-coated substrate without the SnO2 NWs. However, electron microscopy characterization revealed pronounced structural changes upon cycling, including redistribution of Sn and Zn, formation of ∼30 nm particles composed of metallic Sn, and a loss of mechanical integrity. We discuss these changes in terms of the different reversibilities of the charge reactions of both SnO2 and ZnO. The results show stability limitations of SnO2/ZnO heterostructure LIB anodes and offer guidelines on material design for advanced next-generation anode materials for LIBs.

Strain-tunable Berry curvature in quasi-two-dimensional chromium telluride.

Magnetic transition metal chalcogenides form an emerging platform for exploring spin-orbit driven Berry phase phenomena owing to the nontrivial interplay between topology and magnetism. Here we show that the anomalous Hall effect in pristine Cr2Te3 thin films manifests a unique temperature-dependent sign reversal at nonzero magnetization, resulting from the momentum-space Berry curvature as established by first-principles simulations. The sign change is strain tunable, enabled by the sharp and well-defined substrate/film interface in the quasi-two-dimensional Cr2Te3 epitaxial films, revealed by scanning transmission electron microscopy and depth-sensitive polarized neutron reflectometry. This Berry phase effect further introduces hump-shaped Hall peaks in pristine Cr2Te3 near the coercive field during the magnetization switching process, owing to the presence of strain-modulated magnetic layers/domains. The versatile interface tunability of Berry curvature in Cr2Te3 thin films offers new opportunities for topological electronics.

Temperature Dependent Nanochemistry and Growth Kinetics Using Liquid Cell Transmission Electron Microscopy.

Liquid cell transmission electron microscopy has become a powerful and increasingly accessible technique for in situ studies of nanoscale processes in liquid and solution phase. Exploring reaction mechanisms in electrochemical or crystal growth processes requires precise control over experimental conditions, with temperature being one of the most critical factors. Here we carry out a series of crystal growth experiments and simulations at different temperatures in the well-studied system of Ag nanocrystal growth driven by the changes in redox environment caused by the electron beam. Liquid cell experiments show strong changes in both morphology and growth rate with temperature. We develop a kinetic model to predict the temperature-dependent solution composition, and we discuss how the combined effect of temperature-dependent chemistry, diffusion, and the balance between nucleation and growth rates affect the morphology. We discuss how this work may provide guidance in interpreting liquid cell TEM and potentially larger-scale synthesis experiments for systems controlled by temperature.

The Bulk van der Waals Layered Magnet CrSBr is a Quasi-1D Material.

Correlated quantum phenomena in one-dimensional (1D) systems that exhibit competing electronic and magnetic order are of strong interest for the study of fundamental interactions and excitations, such as Tomonaga-Luttinger liquids and topological orders and defects with properties completely different from the quasiparticles expected in their higher-dimensional counterparts. However, clean 1D electronic systems are difficult to realize experimentally, particularly for magnetically ordered systems. Here, we show that the van der Waals layered magnetic semiconductor CrSBr behaves like a quasi-1D material embedded in a magnetically ordered environment. The strong 1D electronic character originates from the Cr-S chains and the combination of weak interlayer hybridization and anisotropy in effective mass and dielectric screening, with an effective electron mass ratio of mXe/mYe ∼ 50. This extreme anisotropy experimentally manifests in strong electron-phonon and exciton-phonon interactions, a Peierls-like structural instability, and a Fano resonance from a van Hove singularity of similar strength to that of metallic carbon nanotubes. Moreover, because of the reduced dimensionality and interlayer coupling, CrSBr hosts spectrally narrow (1 meV) excitons of high binding energy and oscillator strength that inherit the 1D character. Overall, CrSBr is best understood as a stack of weakly hybridized monolayers and appears to be an experimentally attractive candidate for the study of exotic exciton and 1D-correlated many-body physics in the presence of magnetic order.

Direct Visualization of Subnanometer Variations in the Excitonic Spectra of 2D/3D Semiconductor/Metal Heterostructures.

The integration of metallic contacts with two-dimensional (2D) semiconductors is routinely required for the fabrication of nanoscale devices. However, nanometer-scale variations in the 2D/metal interface can drastically alter the local optoelectronic properties. Here, we map local excitonic changes of the 2D semiconductor MoS2 in contact with Au. We utilize a suspended and epitaxially grown 2D/metal platform that allows correlated electron energy-loss spectroscopy (EELS) and angle resolved photoelectron spectroscopy (nanoARPES) mapping. Spatial localization of MoS2 excitons uncovers an additional EELS peak related to the MoS2/Au interface. NanoARPES measurements indicate that Au-S hybridization decreases substantially with distance from the 2D/metal interface, suggesting that the observed EELS peak arises due to dielectric screening of the excitonic Coulomb interaction. Our results suggest that increasing the van der Waals distance could optimize excitonic spectra of mixed-dimensional 2D/3D interfaces and highlight opportunities for Coulomb engineering of exciton energies by the local dielectric environment or moiré engineering.

Sensing the Local Magnetic Environment through Optically Active Defects in a Layered Magnetic Semiconductor.

Atomic-level defects in van der Waals (vdW) materials are essential building blocks for quantum technologies and quantum sensing applications. The layered magnetic semiconductor CrSBr is an outstanding candidate for exploring optically active defects because of a direct gap, in addition to a rich magnetic phase diagram, including a recently hypothesized defect-induced magnetic order at low temperature. Here, we show optically active defects in CrSBr that are probes of the local magnetic environment. We observe a spectrally narrow (1 meV) defect emission in CrSBr that is correlated with both the bulk magnetic order and an additional low-temperature, defect-induced magnetic order. We elucidate the origin of this magnetic order in the context of local and nonlocal exchange coupling effects. Our work establishes vdW magnets like CrSBr as an exceptional platform to optically study defects that are correlated with the magnetic lattice. We anticipate that controlled defect creation allows for tailor-made complex magnetic textures and phases with direct optical access.

Strong and Localized Luminescence from Interface Bubbles Between Stacked hBN Multilayers.

Extraordinary optoelectronic properties of van der Waals (vdW) heterostructures can be tuned via strain caused by mechanical deformation. Here, we demonstrate strong and localized luminescence in the ultraviolet region from interface bubbles between stacked multilayers of hexagonal boron nitride (hBN). Compared to bubbles in stacked monolayers, bubbles formed by stacking vdW multilayers show distinct mechanical behavior. We use this behavior to elucidate radius- and thickness-dependent bubble geometry and the resulting strain across the bubble, from which we establish the thickness-dependent bending rigidity of hBN multilayers. We then utilize the polymeric material confined within the bubbles to modify the bubble geometry under electron beam irradiation, resulting in strong luminescence and formation of optical standing waves. Our results open a route to design and modulate microscopic-scale optical cavities via strain engineering in vdW materials, which we suggest will be relevant to both fundamental mechanical studies and optoelectronic applications.

Nanosecond protonic programmable resistors for analog deep learning.

Nanoscale ionic programmable resistors for analog deep learning are 1000 times smaller than biological cells, but it is not yet clear how much faster they can be relative to neurons and synapses. Scaling analyses of ionic transport and charge-transfer reaction rates point to operation in the nonlinear regime, where extreme electric fields are present within the solid electrolyte and its interfaces. In this work, we generated silicon-compatible nanoscale protonic programmable resistors with highly desirable characteristics under extreme electric fields. This operation regime enabled controlled shuttling and intercalation of protons in nanoseconds at room temperature in an energy-efficient manner. The devices showed symmetric, linear, and reversible modulation characteristics with many conductance states covering a 20× dynamic range. Thus, the space-time-energy performance of the all-solid-state artificial synapses can greatly exceed that of their biological counterparts.

Suspended Graphene Membranes to Control Au Nucleation and Growth.

Control of nucleation sites is an important goal in materials growth: nuclei in regular arrays may show emergent photonic or electronic behavior, and once the nuclei coalesce into thin films, the nucleation density influences parameters such as surface roughness, stress, and grain boundary structure. Tailoring substrate properties to control nucleation is therefore a powerful tool for designing functional thin films and nanomaterials. Here, we examine nucleation control for metals deposited on two-dimensional materials in a situation where substrate effects are absent and heterogeneous nucleation sites are minimized. Through quantification of faceted, epitaxial Au island nucleation on graphene, we show that ultralow nucleation densities with nuclei several micrometers apart can be achieved on suspended graphene under conditions where we measure 2-3 orders of magnitude higher nucleation density on the adjacent supported substrate. We estimate diffusion distances using nucleation theory and find a strong sensitivity of nucleation and diffusion to suspended graphene thickness. Finally, we discuss the role of surface roughness as the main factor determining nucleation density on clean free-standing graphene.