Liquid Cell Electron Microscopy Research Articles

In-Situ Liquid-Electrochemical X-Ray and Electron Microscopy for Multi-Modal Energy Materials Characterization

In-situ liquid cell electron and x-ray microscopy have enabled dynamic studies of electrochemical reactions in energy materials and revealed relationships between the performance, structure, and chemical composition of these material systems. Such fundamental relationships are critical to improving the performance of batteries, catalysts, and other energy materials. Growing research interest in energy materials systems has accelerated the development of in-situ liquid-electrochemical microscopy techniques into mature and robust characterization workflows using novel and versatile scientific hardware.Multiple characterization techniques or in-situ processing steps are often required to fully understand the mechanisms governing the behavior of energy materials for all relevant length scales and environmental conditions. A multi-modal workflow combining in-situ liquid-electrochemical transmission electron, X-ray synchrotron and scanning electron microscopy methods is presented. The breadth of research applications is discussed, including the study of chemical dynamics and structural changes to micron-scale LixFePO4 battery particles during lithium-ion insertion/extraction, electrocatalytic behavior of β-Co(OH)2 platelet particles, and electrochemical oxidation of copper nanoparticles under reductive electrolytic conditions. New insights into these materials systems provided by these experiments will directly inform the development of predictive models for material performance and guide improvement of material design and synthesis.New scientific hardware and method development has been critical to in-situ nano-scale liquid cell microscopy and spectroscopy of electrochemical systems. Therefore, best-practice hardware and method design and development for these in-situ liquid-electrochemical microscopy experiments are also discussed. The connections between potentiostat, holder, and on-chip leads must be carefully considered with respect to different ground potentials, and the incorporation of real bulk-scale reference electrodes in this hardware has yielded quantitatively higher fidelity data with less degradation from further electrochemical cycling. Heating the sample or illuminating with light during in-situ electrochemical data collection has begun to further expand the range of environmental conditions that can be incorporated into experiments.

Liquid Cell Electron Microscopy with Self-Supervised Machine-Learning Denoising Framework

Liquid Cell Electron Microscopy with Self-Supervised Machine-Learning Denoising Framework

Unveiling Corrosion Pathways of Sn Nanocrystals through High-Resolution Liquid Cell Electron Microscopy.

Unveiling materials' corrosion pathways is significant for understanding the corrosion mechanisms and designing corrosion-resistant materials. Here, we investigate the corrosion behavior of Sn@Ni3Sn4 and Sn nanocrystals in an aqueous solution in real time by using high-resolution liquid cell transmission electron microscopy. Our direct observation reveals an unprecedented level of detail on the corrosion of Sn metal with/without a coating of Ni3Sn4 at the nanometric and atomic levels. The Sn@Ni3Sn4 nanocrystals exhibit "pitting corrosion", which is initiated at the defect sites in the Ni3Sn4 protective layer. The early stage isotropic etching transforms into facet-dependent etching, resulting in a cavity terminated with low-index facets. The Sn nanocrystals under fast etching kinetics show uniform corrosion, and smooth surfaces are obtained. Sn nanocrystals show "creeping-like" etching behavior and rough surfaces. This study provides critical insights into the impacts of coating, defects, and ion diffusion on corrosion kinetics and the resulting morphologies.

The ergodicity question when imaging DNA conformation using liquid cell electron microscopy.

Assessing the ergodicity of graphene liquid cell electron microscope measurements, we report that loop states of circular DNA interconvert reversibly and that loop numbers follow the Boltzmann distribution expected for this molecule in bulk solution, provided that the electron dose is low (80-keV electron energy and electron dose rate 1-20 e- Å-2 s-1). This imaging technique appears to act as a "slow motion" camera that reveals equilibrated distributions by imaging the time average of a few molecules without the need to image a spatial ensemble.

The effect of nanochannel length on in situ loading times of diffusion-propelled nanoparticles in liquid cell electron microscopy

Liquid cell transmission electron microscopy is a powerful tool for visualizing nanoparticle (NP) assemblies in liquid environments with nanometer resolution. However, it remains a challenge to control the NP concentration in the high aspect ratio liquid enclosure where the diffusion of dispersed NPs is affected by the exposed surface of the liquid cell walls. Here, we introduce a semi-empirical model based on the 1D diffusion equation, to predict the NP loading time as they pass through the nanochannel into the imaging volume of the liquid cell. We show that loading of NPs into the imaging volume of the liquid cell may take several days if NPs are prone to attach to the surface of the mm-long nanochannel when using an industry-standard flat microchip. As a means to facilitate mass transport via diffusion, we tested a liquid cell incorporating a microchannel geometry resulting in a NP loading time in the order minutes that allowed us to observe the formation of a randomly oriented self-assembled monolayer in situ using scanning transmission electron microscopy.

Robust fully controlled nanometer liquid layers for high resolution liquid-cell electron microscopy.

Liquid cell electron microscopy (LCEM) has long suffered from irreproducibility and its inability to confer high-quality images over a wide field of view. LCEM demands the encapsulation of the in-liquid sample between two ultrathin membranes (windows). In the vacuum environment of the electron microscope, the windows bulge, drastically reducing the achievable resolution and the usable viewing region. Herein, we introduce a shape-engineered nanofluidic cell architecture and an air-free drop-casting sample loading technique, which combined, provide robust bulgeless imaging conditions. We demonstrate the capabilities of our stationary approach through the study of in-liquid model samples and quantitative measurements of the liquid layer thickness. The presented LCEM method confers high throughput, lattice resolution across the complete viewing window, and sufficient contrast for the observation of unstained liposomes, paving the way to high-resolution movies of biospecimens in their near native environment.

Tacking Directional Movement of Nanomotors with Liquid Cell Electron Microscopy

Tacking Directional Movement of Nanomotors with Liquid Cell Electron Microscopy

Lithium metal stripping mechanisms revealed through electrochemical liquid cell electron microscopy

An understanding of lithium stripping is as important as that of lithium plating to achieve significant advances in using lithium metal anodes for high-energy rechargeable batteries. However, there have been limited studies on lithium stripping compared to lithium plating. Here we report the lithium stripping mechanisms revealed through in-situ electrochemical liquid cell transmission electron microscopy (TEM). We directly observe and compare the stripping behavior of the in-situ grown lithium dendrites and lithium nanograins covered by a lithium fluoride-rich solid-electrolyte interphase (SEI). We find the sporadic lithium stripping behavior and three important modes that can describe the stripping of individual lithium deposits, regardless of their morphology: (i) symmetric stripping, (ii) surface-preferred asymmetric stripping, and (iii) interface-preferred asymmetric stripping. In addition, SEI chemical mapping with high spatial resolution shows a remarkable SEI loss at the end of the lithium metal stripping, which illustrates the importance of SEI protection in the subsequent cycles.

DFT calculations and machine learning approach to predict catalytic properties of nanoscale electrocatalysts in solution for clean fuel generation

<h2>Abstract</h2> A nanocatalyst is at the central position as a promoter of various chemical. Innovative design of highly functional catalyst materials has been, however, delayed. In molecular level computational electrochemistry new research paradigm has been established, which substantially incorporates IT-based artificial intelligence (AI) technology into machine learning algorism. Using the new computational methodology high-throughput screening of promising nanoparticle candidates has been attempted for various desired applications. Whether the frontier approach is successful or not is significantly controlled by the reliability and accuracy of input database. It is true that substantial amounts of the data are come by previous literatures and often ab-initio calculations with idealized model systems. The conditions in which the data were generated may be so different from the operando circumstances of the target materials. To secure extreme-level integrity of the database the in-situ measurement of nanoparticle structures should be carried out, from which the reliable correlation of the structure-performance-design principle can be identified. Using first-principles calculations we studied nanoparticles with adsorbate ligands in liquid solution to establish three-dimensional (3D) structure and property database, which are, then, analyzed through AI-based neural-network approach with high speed and accuracy. The information includes sizes, lattice distortions, and defects with picometer resolution under non-vacuum conditions. The computational outcomes are rigorously validated from the 3D liquid-cell electron microscopy. The approach is indeed ‘knowledge-based' AI, which can be expected to make groundbreaking ways toward the quantum nanoarchitecture for hybrid interface materials.

Real-space imaging of nanoparticle transport and interaction dynamics by graphene liquid cell TEM.

Thermal motion of colloidal nanoparticles and their cohesive interactions are of fundamental importance in nanoscience but are difficult to access quantitatively, primarily due to the lack of the appropriate analytical tools to investigate the dynamics of individual particles at nanoscales. Here, we directly monitor the stochastic thermal motion and coalescence dynamics of gold nanoparticles smaller than 5 nm, using graphene liquid cell (GLC) transmission electron microscopy (TEM). We also present a novel model of nanoparticle dynamics, providing a unified, quantitative explanation of our experimental observations. The nanoparticles in a GLC exhibit non-Gaussian, diffusive motion, signifying dynamic fluctuation of the diffusion coefficient due to the dynamically heterogeneous environment surrounding nanoparticles, including organic ligands on the nanoparticle surface. Our study shows that the dynamics of nanoparticle coalescence is controlled by two elementary processes: diffusion-limited encounter complex formation and the subsequent coalescence of the encounter complex through rotational motion, where surface-passivating ligands play a critical role.

Hydroxyapatite as a scavenger of reactive radiolysis species in graphene liquid cells for in situ electron microscopy

Liquid cell electron microscopy is an imaging technique allowing for the investigation of the interaction of liquids and solids at nanoscopic length scales. Such in situ observations are increasingly in-demand in an array of fields, from biological sciences to medicine to batteries. Graphene liquid cells (GLCs), in particular, have generated a great interest as a low-scattering window material with the potential for increasing the quality of both imaging and spectroscopy. However, preserving the stability of the liquid and of the sample in the GLC remains a considerable challenge. In the present work we encapsulate water and hydroxyapatite (HAP), a pH-sensitive biological material, in GLCs to observe the interactions between the graphene, HAP, and the electron beam. HAP was chosen for several reasons. One is its ubiquity in biological specimens such as bones and teeth, and the second is the presence of phosphate ions in common buffer solutions. Finally, there is its sensitivity to changes in pH, which result from beam-induced hydrolysis in liquid cells. A dynamic process of dissolution and recrystallization of HAP was observed, which correlated with the production of H+ ions by the beam during imaging. In addition, a large increase in the stability of the GLC under irradiation was noted. Specifically, no stable hydrogen bubbles were detected under the electron fluxes routinely exceeding 170 e− Å−2 s−1. With the measured threshold dose for the bubble formation in pure water equaling 9 e− Å−2 s−1, it was concluded that the presence of HAP increases the resistance of water against radiolysis in the GLC by more than an order of magnitude. These results confirm the possibility of using biological materials, such as HAP, as stabilizers in liquid cell electron microscopy. They outline a potential route for stabilization of specimens in liquid cells through the addition of a scavenger of reactive species generated by the beam-induced hydrolysis of water. These improvements are essential for enhancing both the resolution of imaging and the available imaging time, as well as avoiding the beam-induced artifacts.

Versatile Printing of Substantial Liquid Cells for Efficiently Imaging In Situ Liquid-Phase Dynamics.

Through its ability to image liquid-phase dynamics at nano/atomic-scale resolution, liquid-cell electron microscopy is essential for a wide range of applications, including wet-chemical synthesis, catalysis, and nanoparticle tracking, for which involved structural features are critical. However, statistical investigations by usual techniques remain challenging because of the difficulty in fabricating substantial liquid cells with appreciable efficiency. Here, we report a general approach for efficiently printing huge numbers of ready-to-use liquid cells (∼9000) within 30 s by electrospinning, with the unique feature of statistical liquid-phase studies requiring only one experimental time slot. Our solution efficiently resolves a complete transition picture of bubble evolution and also the induced nanoparticle motion. We statistically quantify the effect of the electron dose rate on the bubble variation and conclude that the bubble-driven nanoparticle motion is a ballistic-like behavior insignificant to morphological asymmetries. The versatile approach here is critical for statistical research, offering great opportunities in liquid-phase-associated dynamic studies.

Redox Mediated Control of Electrochemical Potential in Liquid Cell Electron Microscopy.

Liquid cell electron microscopy enables the study of nanoscale transformations in solvents with high spatial and temporal resolution, but for the technique to achieve its potential requires a new level of control over the reactivity caused by radical generation under electron beam irradiation. An understanding of how to control electron-solvent interactions is needed to further advance the study of structural dynamics for complex materials at the nanoscale. We developed an approach that scavenges radicals with redox species that form well-defined redox couples and control the electrochemical potential in situ. This approach enables the observation of electrochemical structural dynamics at near-atomic resolution with precise control of the liquid environment. Analysis of nanocrystal etching trajectories indicates that this approach can be generalized to several chemical systems. The ability to simultaneously observe heterogeneous reactions at near-atomic resolution and precisely control the electrochemical potential enables the fundamental study of complex nanoscale dynamics with unprecedented detail.

Tunability of Interactions between the Core and Shell in Rattle-Type Particles Studied with Liquid-Cell Electron Microscopy.

Yolk–shell or rattle-type particles consist of a core particle that is free to move inside a thin shell. A stable core with a fully accessible surface is of interest in fields such as catalysis and sensing. However, the stability of a charged nanoparticle core within the cavity of a charged thin shell remains largely unexplored. Liquid-cell (scanning) transmission electron microscopy is an ideal technique to probe the core–shell interactions at nanometer spatial resolution. Here, we show by means of calculations and experiments that these interactions are highly tunable. We found that in dilute solutions adding a monovalent salt led to stronger confinement of the core to the middle of the geometry. In deionized water, the Debye length κ–1 becomes comparable to the shell radius Rshell, leading to a less steep electric potential gradient and a reduced core–shell interaction, which can be detrimental to the stability of nanorattles. For a salt concentration range of 0.5–250 mM, the repulsion was relatively long-ranged due to the concave geometry of the shell. At salt concentrations of 100 and 250 mM, the core was found to move almost exclusively near the shell wall, which can be due to hydrodynamics, a secondary minimum in the interaction potential, or a combination of both. The possibility of imaging nanoparticles inside shells at high spatial resolution with liquid-cell electron microscopy makes rattle particles a powerful experimental model system to learn about nanoparticle interactions. Additionally, our results highlight the possibilities for manipulating the interactions between core and shell that could be used in future applications.

Ligand-Induced Motion and Self-Assembly Pathways between Nanocubes.

Nanoparticle motion and self-assembly have been regarded as a promising pathway for forming ordered nanostructures. However, the detailed dynamics processes induced by ligand involvement remained poorly understood. Here, we used in situ liquid-cell electron microscopy technology to image the formation of face-to-face Pt cube ordered structures: pairs, linear chains, and squares. The van der Waals interaction between the two neighboring cubes was quantified in real time. Interestingly, the two different formation processes of the square phase were achieved via a rotational and translational method. It is found that the space between two neighboring cubes was the same as the ex-TEM results. The density functional theory calculation demonstrated that it was attributed to the DMF ligand interactions of the cubes that promoted their face-to-face attachment.

Graphene Liquid Cell Electron Microscopy: Progress, Applications, and Perspectives.

Graphene liquid cell electron microscopy (GLC-EM), a cutting-edge liquid-phase EM technique, has become a powerful tool to directly visualize wet biological samples and the microstructural dynamics of nanomaterials in liquids. GLC uses graphene sheets with a one carbon atom thickness as a viewing window and a liquid container. As a result, GLC facilitates atomic-scale observation while sustaining intact liquids inside an ultra-high-vacuum transmission electron microscopy chamber. Using GLC-EM, diverse scientific results have been recently reported in the material, colloidal, environmental, and life science fields. Here, the developments of GLC fabrications, such as first-generation veil-type cells, second-generation well-type cells, and third-generation liquid-flowing cells, are summarized. Moreover, recent GLC-EM studies on colloidal nanoparticles, battery electrodes, mineralization, and wet biological samples are also highlighted. Finally, the considerations and future opportunities associated with GLC-EM are discussed to offer broad understanding and insight on atomic-resolution imaging in liquid-state dynamics.

Probing Thermoresponsive Polymerization-Induced Self-Assembly with Variable-Temperature Liquid-Cell Transmission Electron Microscopy

Summary We directly initiate and visualize the formation of polymeric nanomaterials via variable-temperature liquid-cell transmission electron microscopy (VT-LCTEM). With temperature control in the liquid cell, reversible addition-fragmentation chain transfer polymerization was thermally initiated, leading to the formation of amphiphilic block copolymers that assemble upon dispersion polymerization-induced self-assembly (PISA). In combination with traditional ex situ analyses, VT-LCTEM enabled not only the characterization of the nanoparticles in situ but also the observation of a thermal phase transition. Critically, because these assemblies form from thermoresponsive components, any temperature changes during sample preparation and analysis can alter morphologies, necessitating direct in situ characterization of reaction progression. We believe that the findings and the technique described herein will lead to unprecedented possibilities for the development and characterization of self-organizing soft matter.

Real-Time Electron Microscopy of Nanocrystal Synthesis, Transformations, and Self-Assembly in Solution

Solution-phase processes such as colloidal synthesis and transformations have enabled the formation of nanocrystals with exquisite control over size, shape, and composition. Self-assembly, in solution or at phase boundaries, can arrange such nanocrystal building blocks into ordered superlattices and dynamically reconfigurable "smart" materials. Ultimately, continued improvements in our ability to direct nanocrystal matter depend on progress in understanding colloidal chemistry and self-assembly in solution. The traditional approach for investigating the underlying, inherently dynamic processes involves sampling at different stages combined with ex situ characterization, for example, using electron microscopy. In situ studies have been restricted to a few methods capable of measuring in bulk liquids, either in reciprocal space by diffraction or scattering or using spatially averaging (e.g., optical) measurements. These strategies face clear limitations in obtaining mechanistic information, and they are unable to address heterogeneous systems that may harbor rich sets of configurations with different local properties. The development of microfabricated cells that hermetically encapsulate bulk solutions between ultrathin (electron transparent) membranes has paved the way for studying processes in liquids in real time by electron microscopy at resolution down to the atomic scale. Electrons interact much more strongly with matter than other probes, for example, X-rays. In ordinary inorganic samples, the main effects are atom displacements and defect formation via knock-on and ionization damage. In liquid-cell electron microscopy, the interaction of the beam with both the suspended nanostructures and the solution creates more diverse effects, so the straightforward scenario of imaging unperturbed nanocrystal chemistry in solution is rarely realized.In this Account, we discuss applications of real-time electron microscopy to the analysis of nanocrystal synthesis, transformations, and self-assembly in solution. While in the simplest case the effects of the electron beam are negligible, the interaction with high-energy electrons often provides excitation or stimulus for solution-phase processes or opens up competing chemical pathways. Real-time observations of self-assembly demonstrate particularly clearly the power of in situ microscopy in identifying key nucleation and growth mechanisms and providing information about preferred structural motifs that can be analyzed to quantify the balance of forces and the role of entropy in stabilizing ordered assemblies. Modifications of the solution by the electron beam can provide stimuli for on-demand self-assembly, for example, via an acid spike due to water radiolysis that locally lowers the pH in the imaged area. While in this and other cases (e.g., colloidal synthesis), beam-induced radicals become part of the experimental design, in imaging redox reactions such as galvanic transformations of nanocrystal templates, radicals need to be managed and if possible eliminated by suitable scavengers. Finally, excitation by the imaging electron beam can transfer energy to individual nanocrystals in solution, thus driving nonthermal (e.g., plasmon-mediated) synthesis or other chemistry while following the reaction progress with high resolution. Overall, with validation by ex situ control experiments, the unique ability of observing processes in solution at the nanometer scale should make liquid-cell electron microscopy an integral part of the toolkit for designing novel inorganic nanocrystal architectures.

In situ Electron Microscopy of Complex Biological and Nanoscale Systems: Challenges and Opportunities

In situ imaging for direct visualization is important for physical and biological sciences. Research endeavors into elucidating dynamic biological and nanoscale phenomena frequently necessitate in situ and time-resolved imaging. In situ liquid cell electron microscopy (LC-EM) can overcome certain limitations of conventional electron microscopies and offer great promise. This review aims to examine the status-quo and practical challenges of in situ LC-EM and its applications, and to offer insights into a novel correlative technique termed microfluidic liquid cell electron microscopy. We conclude by suggesting a few research ideas adopting microfluidic LC-EM for in situ imaging of biological and nanoscale systems.

Low‐dose liquid cell electron microscopy investigation of the complex etching mechanism of rod‐shaped silica colloids

AbstractUnderstanding the chemical structure of rod‐shaped silica colloidal particles is attainable by investigating their etching mechanism in solution. Liquid Cell (Scanning) Transmission Electron Microscopy (LC‐(S)TEM) is a promising technique through which the etching of these particles can be observed in real time, and at the single particle level, without possible deformations induced by the surface tension of dried particles. However, the presence of high energy electrons, and the different geometry in LC experiments may alter the conditions of in situ experiments compared to their ex situ counterparts. Here we present a controlled low‐dose LC‐STEM study of the basic etching process of micron‐sized silica rods that are immobilized on the SiN window of a liquid cell. The results show that using low‐dose imaging conditions, combined with a low accumulated electron dose, and optimized flow rates of solutions allow for investigation of the chemical etching mechanism of silica colloidal particles using the LC‐(S)TEM technique with negligible effects of the electron beam. A comparison of ex situ etching experiments with LC‐STEM observations show that the LC geometry can play a crucial role in LC‐STEM experiments where the diffusion of the etching particles is important, which should be considered during the interpretations of LC‐STEM results.