Graphene Liquid Cell Electron Microscopy Research Articles

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.

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.

Tracking the Effects of Ligands on Oxidative Etching of Gold Nanorods in Graphene Liquid Cell Electron Microscopy.

Surface ligands impact the properties and chemistry of nanocrystals, but observing ligand binding locations and their effect on nanocrystal shape transformations is challenging. Using graphene liquid cell electron microscopy and the controllable, oxidative etching of gold nanocrystals, the effect of different ligands on nanocrystal etching can be tracked with nanometer spatial resolution. The chemical environment of liquids irradiated with high-energy electrons is complex and potentially harsh, yet it is possible to observe clear evidence for differential binding properties of specific ligands to the nanorods' surface. Exchanging CTAB ligands for PEG-alkanethiol ligands causes the nanorods to etch at a different, constant rate while still maintaining their aspect ratio. Adding cysteine ligands that bind preferentially to nanorod tips induces etching predominantly on the sides of the rods. This etching at the sides leads to Rayleigh instabilities and eventually breaks apart the nanorod into two separate nanoparticles. The shape transformation is controlled by the interplay between atom removal and diffusion of surface atoms and ligands. These in situ observations are confirmed with ex situ colloidal etching reactions of gold nanorods in solution. The ability to monitor the effect of ligands on nanocrystal shape transformations will enable future in situ studies of nanocrystals surfaces and ligand binding positions.

(Invited) Electrochemical Energy Harvesters Based on Stress-Composition Coupling in Li Alloys

Efforts to harvest human-induced energies into electricity has garnered a significant amount of research attention, with potential applications in powering wireless sensors or Internet of Things (IoT) devices. Successful integration of energy harvesters into small-scale sensor systems may operate sensors without battery exchange for years or in remote environments where battery charging is not applicable. Energy harvesters may also provide additional efficiency to the overall electric grid, since the amount of generated electricity scales directly with human activities; providing electricity at the peak time and location where electricity is needed the most alleviates the burden from the electric grid.To realize successful energy harvesters, researchers have developed energy harvesters from different sources such as thermal, vibrational, acoustic or contact electrification-based energies. Many of these types, however, face severe challenges to commercialization due to the limited efficiencies linked to their fundamental working mechanisms. For instance, piezoelectric and triboelectric generators suffer from the mismatch between their natural output frequencies and human motion timescales. The generated electricity from these two types often has current peak widths below 100 msec, making them limited in the human activities timescales of 0.55 Hz[1,2].In this talk, we develop and demonstrate an electrochemically driven mechanical energy harvesters based on stress-composition coupling in Li binary alloys[3]. We first demonstrate the presence of stress-composition coupling among Li-alloys, by using in situ graphene liquid cell electron microscopy.[3] With the unveiled stress-composition coupling, we demonstrate two distinct device concepts utilizing this stress-composition coupling, with Li x Si thin films and yolk-shell nanoparticles[4].[1] Chun J., Ye B. U., Lee J. W., Choi D., Kang C.-Y., Kim S.-W., Wang Z. L., Baik J. M., “Boosted output performance of triboelectric nanogenerator via electric double layer effect” Nature Communications 7, 12985 2016.[2] Hwang G.-T., Park H., Lee J.-H., Oh S., Park K.-I., Byun M., Park H., Ahn G., Jeong C. K., No K., Kwon H., Lee S.-G., Joung B., Lee K. J., “Self-powered cardiac pacemaker enabled by flexible single crystalline PMN-PT piezoelectric energy harvester” Advanced Materials 26, 4880 2014.[3] Seo H., Park J.Y., Chang J.H., Dae K.S., Noh M.S., Kim S.S., Kang C.-Y., Zhao K., Kim S., Yuk J., "Strong stress composition coupling in Lithium alloy nanoparticles" Nature Communications 10, 3428 2019[4] Kim S., Choi S.J., Zhao K., Yang H., Gobbi G., Zhang S., Li J., “Electrochemically driven mechanical energy harvesting” Nature Communications 7, 10146 2016

Direct Visualization of Lithium Polysulfides and Their Suppression in Liquid Electrolyte.

Understanding of lithium polysulfide (Li-PS) formation and the shuttle phenomenon is essential for practical application of the lithium/sulfur (Li/S) cell, which has superior theoretical specific energy (2600 Wh/kg). However, it suffers from the lack of direct observation on behaviors of soluble Li-PS in liquid electrolytes. Using in situ graphene liquid cell electron microscopy, we have visualized formation and diffusion of Li-PS simultaneous with morphological and phase evolutions of sulfur nanoparticles during lithiation. We found that the morphological changes and Li-PS diffusion are retarded by ionic liquid (IL) addition into electrolyte. Chronoamperometric shuttle current measurement confirms that IL addition lowers the experimental diffusion coefficient of Li-PS by 2 orders of magnitude relative to that in IL-free electrolyte and thus suppresses the Li-PS shuttle current, which accounts for better cyclability and Coulombic efficiency of the Li/S cell. This study provides significant insights into electrolyte design to inhibit the polysulfide shuttle phenomenon.

Intermediate states of molecular self-assembly from liquid-cell electron microscopy

Traditional single-molecule methods do not report whole-molecule kinetic conformations, and their adaptive shape changes during the process of self-assembly. Here, using graphene liquid-cell electron microscopy with electrons of low energy at low dose, we show that this approach resolves the time dependence of conformational adaptations of macromolecules for times up to minutes, the resolution determined by motion blurring, with DNA as the test case. Single-stranded DNA molecules are observed in real time as they hybridize near the solid surface to form double-stranded helices; we contrast molecules the same length but differing in base-pair microstructure (random, blocky, and palindromic hairpin) whose key difference is that random sequences possess only one stable final state, but the others offer metastable intermediate structures. Hybridization is observed to couple with enhanced translational mobility and torsion-induced rotation of the molecule. Prevalent transient loops are observed in error-correction processes. Transient melting and other failed encounters are observed in the competitive binding of multiple single-stranded molecules. Among the intermediate states reported here, some were predicted but not observed previously, and the high incidence of looping and enhanced mobility come as surprises. The error-producing mechanisms, failed encounters, and transient intermediate states would not be easily resolved by traditional single-molecule methods. The methods generalize to visualize motions and interactions of other organic macromolecules.

Strong stress-composition coupling in lithium alloy nanoparticles

The stress inevitably imposed during electrochemical reactions is expected to fundamentally affect the electrochemistry, phase behavior and morphology of electrodes in service. Here, we show a strong stress-composition coupling in lithium binary alloys during the lithiation of tin-tin oxide core-shell nanoparticles. Using in situ graphene liquid cell electron microscopy imaging, we visualise the generation of a non-uniform composition field in the nanoparticles during lithiation. Stress models based on density functional theory calculations show that the composition gradient is proportional to the applied stress. Based on this coupling, we demonstrate that we can directionally control the lithium distribution by applying different stresses to lithium alloy materials. Our results provide insights into stress-lithium electrochemistry coupling at the nanoscale and suggest potential applications of lithium alloy nanoparticles.

Graphene Liquid Cell Electron Microscopy of Initial Lithiation in Co3O4 Nanoparticles.

As it governs the overall performance of lithium-ion batteries, understanding the reaction pathway of lithiation is highly desired. For Co3O4 nanoparticles as anode material, here, we report an initial conversion reaction pathway during lithiation. Using graphene liquid cell electron microscopy (GLC-EM), we reveal a CoO phase of the initial conversion product as well as morphological dynamics during Co3O4 lithiation. In accordance with the in situ TEM observation, we confirmed that the Co3O4 to CoO conversion is a thermodynamically favorable process by calculating the theoretical average voltage based on density functional theory. Our observation will provide a useful insight into the oxide electrode that undergoes conversion reaction.

Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy.

Graphene liquid cell electron microscopy has the necessary temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. However, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl3, on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these results with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl3 provides further insight into the liquid cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, allowing new nanoscale materials science experiments to be conducted systematically in a reproducible manner.

Sequential Growth and Etching of Gold Nanocrystals Revealed by High‐Resolution Liquid Electron Microscopy

Sequential growth and etching of Au nanoparticles in solution are observed in situ using the graphene liquid cell electron microscopy. Observation reveals that concentration of etching ions in aqueous growth solution leads transition from nanoparticle growth to its etching. At each step, the authors demonstrate different kinetics for both morphological evolutions and reaction rates. This study will likely benefit design strategies of nanoparticles with specific size or shape.

On the structure and chemistry of iron oxide cores in human heart and human spleen ferritins using graphene liquid cell electron microscopy.

Ferritin is a protein that regulates the iron ions in humans by storing them in the form of iron oxides. Despite extensive efforts to understand the ferritin iron oxide structures, it is still not clear how ferritin proteins with a distinct light (L) and heavy (H) chain subunit ratio impact the biomineralization process. In situ graphene liquid cell-transmission electron microscopy (GLC-TEM) provides an indispensable platform to study the atomic structure of ferritin mineral cores in their native liquid environment. In this study, we report differences in the iron oxide formation in human spleen ferritins (HSFs) and human heart ferritins (HHFs) using in situ GLC-TEM. Scanning transmission electron microscopy (STEM) along with selected area electron diffraction (SAED) of the mineral core and electron energy loss spectroscopy (EELS) analyses enabled the visualization of morphologies, crystal structures and the chemistry of iron oxide cores in HSFs and HHFs. Our study revealed the presence of metastable ferrihydrite (5Fe2O3·9H2O) as a dominant phase in hydrated HSFs and HHFs, while a stable hematite (α-Fe2O3) phase predominated in non-hydrated HSFs and HHFs. In addition, a higher Fe3+/Fe2+ ratio was found in HHFs in comparison with HSFs. This study provides new understanding on iron-oxide phases that exist in hydrated ferritin proteins from different human organs. Such new insights are needed to map ferritin biomineralization pathways and possible correlations with various iron-related disorders in humans.

Using Graphene Liquid Cell Electron Microscopy to Elucidate Nanocrystal Etching Mechanisms

Using Graphene Liquid Cell Electron Microscopy to Elucidate Nanocrystal Etching Mechanisms

Using Graphene Liquid Cell Transmission Electron Microscopy to Study <em>in Situ</em> Nanocrystal Etching

Graphene liquid cell electron microscopy provides the ability to observe nanoscale chemical transformations and dynamics as the reactions are occurring in liquid environments. This manuscript describes the process for making graphene liquid cells through the example of graphene liquid cell transmission electron microscopy (TEM) experiments of gold nanocrystal etching. The protocol for making graphene liquid cells involves coating gold, holey-carbon TEM grids with chemical vapor deposition graphene and then using those graphene-coated grids to encapsulate liquid between two graphene surfaces. These pockets of liquid, with the nanomaterial of interest, are imaged in the electron microscope to see the dynamics of the nanoscale process, in this case the oxidative etching of gold nanorods. By controlling the electron beam dose rate, which modulates the etching species in the liquid cell, the underlying mechanisms of how atoms are removed from nanocrystals to form different facets and shapes can be better understood. Graphene liquid cell TEM has the advantages of high spatial resolution, compatibility with traditional TEM holders, and low start-up costs for research groups. Current limitations include delicate sample preparation, lack of flow capability, and reliance on electron beam-generated radiolysis products to induce reactions. With further development and control, graphene liquid cell may become a ubiquitous technique in nanomaterials and biology, and is already being used to study mechanisms governing growth, etching, and self-assembly processes of nanomaterials in liquid on the single particle level.

Using Graphene Liquid Cell Transmission Electron Microscopy to Study in Situ Nanocrystal Etching.

Graphene liquid cell electron microscopy provides the ability to observe nanoscale chemical transformations and dynamics as the reactions are occurring in liquid environments. This manuscript describes the process for making graphene liquid cells through the example of graphene liquid cell transmission electron microscopy (TEM) experiments of gold nanocrystal etching. The protocol for making graphene liquid cells involves coating gold, holey-carbon TEM grids with chemical vapor deposition graphene and then using those graphene-coated grids to encapsulate liquid between two graphene surfaces. These pockets of liquid, with the nanomaterial of interest, are imaged in the electron microscope to see the dynamics of the nanoscale process, in this case the oxidative etching of gold nanorods. By controlling the electron beam dose rate, which modulates the etching species in the liquid cell, the underlying mechanisms of how atoms are removed from nanocrystals to form different facets and shapes can be better understood. Graphene liquid cell TEM has the advantages of high spatial resolution, compatibility with traditional TEM holders, and low start-up costs for research groups. Current limitations include delicate sample preparation, lack of flow capability, and reliance on electron beam-generated radiolysis products to induce reactions. With further development and control, graphene liquid cell may become a ubiquitous technique in nanomaterials and biology, and is already being used to study mechanisms governing growth, etching, and self-assembly processes of nanomaterials in liquid on the single particle level.

Growth dynamics of solid electrolyte interphase layer on SnO2 nanotubes realized by graphene liquid cell electron microscopy

Formation of stable solid electrolyte interphase (SEI) layer is critical to outstanding performance of energy storage devices, because it acts as a passive layer that allows facile transport of ions but forbids electron transport between the electrolyte and electrode. Although much study has been devoted to investigate the morphology and structure of SEI layer using a myriad of analytical devices on past decades, the direct observation of SEI layer on a real time scale has remained as a formidable challenge. In addition, it has been difficult to observe both the decomposition of electrolytes and formation process of stable SEI layer at nanometer scale. Here we utilize in situ transmission electron microscopy (TEM) using graphene liquid cell (GLC) to realize the observation of stable SEI layer formation in a sequential time scale. Upon e− beam irradiation, Li salts in the electrolytes react with reduced electrolytes and form gel-like agglomerates, which are deposited on the surface of the active material as a passivation layer and later stabilized to become more uniform in overall thickness. Additionally, growth dynamics of stable SEI layer were suggested, where the deposition of decomposed electrolytes eventually result in relatively uniform SEI layer. This paper demonstrates that it is possible to observe not only the formation of non-crystalline SEI layer but also the movement of decomposed electrolytes onto the surface of active materials which account for broader understanding of SEI layer, and has the potential to detect important interfacial phenomena in electrochemical devices that were overlooked so far.

Real-Time Observation of Water-Soluble Mineral Precipitation in Aqueous Solution by In Situ High-Resolution Electron Microscopy.

The precipitation and dissolution of water-soluble minerals in aqueous systems is a familiar process occurring commonly in nature. Understanding mineral nucleation and growth during its precipitation is highly desirable, but past in situ techniques have suffered from limited spatial and temporal resolution. Here, by using in situ graphene liquid cell electron microscopy, mineral nucleation and growth processes are demonstrated in high spatial and temporal resolution. We precipitate the mineral thenardite (Na2SO4) from aqueous solution with electron-beam-induced radiolysis of water. We demonstrate that minerals nucleate with a two-dimensional island structure on the graphene surfaces. We further reveal that mineral grains grow by grain boundary migration and grain rotation. Our findings provide a direct observation of the dynamics of crystal growth from ionic solutions.

Anisotropic lithiation onset in silicon nanoparticle anode revealed by in situ graphene liquid cell electron microscopy.

Recent real-time analyses have provided invaluable information on the volume expansion of silicon (Si) nanomaterials during their electrochemical reactions with lithium ions and have thus served as useful bases for robust design of high capacity Si anodes in lithium ion batteries (LIBs). In an effort to deepen the understanding on the critical first lithiation of Si, especially in realistic liquid environments, herein, we have engaged in situ graphene liquid cell transmission electron microscopy (GLC-TEM). In this technique, chemical lithiation is stimulated by electron-beam irradiation, while the lithiation process is being monitored by TEM in real time. The real-time analyses informing of the changes in the dimensions and diffraction intensity indicate that the very first lithiation of Si nanoparticle shows anisotropic volume expansion favoring the ⟨110⟩ directions due to the smaller Li diffusion energy barrier at the Si-electrolyte interface along such directions. Once passing this initial volume expansion stage, however, Li diffusion rate becomes isotropic in the inner region of the Si nanoparticle. The current study suggests that the in situ GLC-TEM technique can be a useful tool in understanding battery reactions of various active materials, particularly those whose initial lithiation plays a pivotal role in overall electrochemical performance and structural stability of the active materials.

Studies of the dynamics of biological macromolecules using Au nanoparticle-DNA artificial molecules.

The recent development of graphene liquid cells, a nanoscale version of liquid bubble wrap, is a breakthrough for in situ liquid phase electron microscopy (EM). Using ultrathin graphene sheets as the liquid sample container, graphene liquid cells have allowed the unprecedented atomic resolution observation of solution phase growth and dynamics of nanocrystals. Here we explore the potential of this technique to probe nanoscale structure and dynamics of biomolecules in situ, using artificial Au nanoparticle-DNA artificial molecules as model systems. The interactions of electrons with both the artificial molecules and the liquid environment have been demonstrated and discussed, revealing both the opportunities and challenges of using graphene liquid cell EM as a new method of bio-imaging.