Jungwon Park

High-resolution EM of colloidal nanocrystal growth using graphene liquid cells.

Liquid Nanocrystals In high-resolution transmission electron microscopy, grid materials are used to support solid samples while providing a means for preventing a build-up of static charge. Liquids are difficult to study at the same atomic resolution and require encapsulation to prevent excess sample movement, sample damage, or evaporation. Materials that have been used for liquid cells, like silicon nitride or silicon oxide, need thick layers and have poor electron transmittance at the thicknesses required because they contain high atomic number elements. Yuk et al. (p. 61; see the Perspective by Colliex) show that liquids can be encapsulated in graphene sheets, and through this technique, they studied the formation of platinum nanocrystals with atomic resolution. The crystals could be tracked as they selectively coalesced, modified their shape, and formed surface facets. Encapsulating a liquid film between two graphene layers allows the film and growing crystals from the graphene sheets to be studied at an atomic scale. We introduce a new type of liquid cell for in situ transmission electron microscopy (TEM) based on entrapment of a liquid film between layers of graphene. The graphene liquid cell facilitates atomic-level resolution imaging while sustaining the most realistic liquid conditions achievable under electron-beam radiation. We employ this cell to explore the mechanism of colloidal platinum nanocrystal growth. Direct atomic-resolution imaging allows us to visualize critical steps in the process, including site-selective coalescence, structural reshaping after coalescence, and surface faceting.

Hetero-Epitaxial Anion Exchange Yields Single-Crystalline Hollow Nanoparticles

Anion exchange with S was performed on ZnO colloidal nanoparticles. The resulting hollow ZnS nanoparticles are crystal whose shape is dictated by the initial ZnO. Crystallographic and elemental analyses provide insight into the mechanism of the anion exchange.

Direct Observation of Nanoparticle Superlattice Formation by Using Liquid Cell Transmission Electron Microscopy

Direct imaging of nanoparticle solutions by liquid phase transmission electron microscopy has enabled unique in situ studies of nanoparticle motion and growth. In the present work, we report on real-time formation of two-dimensional nanoparticle arrays in the very low diffusive limit, where nanoparticles are mainly driven by capillary forces and solvent fluctuations. We find that superlattice formation appears to be segregated into multiple regimes. Initially, the solvent front drags the nanoparticles, condensing them into an amorphous agglomerate. Subsequently, the nanoparticle crystallization into an array is driven by local fluctuations. Following the crystallization event, superlattice growth can also occur via the addition of individual nanoparticles drawn from outlying regions by different solvent fronts. The dragging mechanism is consistent with simulations based on a coarse-grained lattice gas model at the same limit.

3D structure of individual nanocrystals in solution by electron microscopy

Looking at teeny tiny platinum particles Electron microscopy is a powerful technique for taking snapshots of particles or images at near-atomic resolution. Park et al. studied free-floating platinum nanoparticles using electron microscopy and liquid cells (see the Perspective by Colliex). Using analytical techniques developed to study biological molecules, they reconstructed the threedimensional features of the Pt particles at near-atomic resolution. This approach has the scope to study a mixed population of particles one at a time and to study their synthesis as it occurs in solution. Science, this issue p. 290; see also p. 232 Individual platinum nanoparticles are imaged in solution at near-atomic resolution. [Also see Perspective by Colliex] Knowledge about the synthesis, growth mechanisms, and physical properties of colloidal nanoparticles has been limited by technical impediments. We introduce a method for determining three-dimensional (3D) structures of individual nanoparticles in solution. We combine a graphene liquid cell, high-resolution transmission electron microscopy, a direct electron detector, and an algorithm for single-particle 3D reconstruction originally developed for analysis of biological molecules. This method yielded two 3D structures of individual platinum nanocrystals at near-atomic resolution. Because our method derives the 3D structure from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unordered nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale.

Revealing Bismuth Oxide Hollow Nanoparticle Formation by the Kirkendall Effect

We study the formation of bismuth oxide hollow nanoparticles by the Kirkendall effect using liquid cell transmission electron microscopy (TEM). Rich dynamics of bismuth diffusion through the bismuth oxide shell have been captured in situ. The diffusion coefficient of bismuth through bismuth oxide shell is 3-4 orders of magnitude higher than that of bulk. Observation reveals that defects, temperature, sizes of the particles, and so forth can affect the diffusion of reactive species and modify the kinetics of the hollowing process.

3D Motion of DNA-Au Nanoconjugates in Graphene Liquid Cell Electron Microscopy

Liquid-phase transmission electron microscopy (TEM) can probe and visualize dynamic events with structural or functional details at the nanoscale in a liquid medium. Earlier efforts have focused on the growth and transformation kinetics of hard material systems, relying on their stability under electron beam. Our recently developed graphene liquid cell technique pushed the spatial resolution of such imaging to the atomic scale but still focused on growth trajectories of metallic nanocrystals. Here, we adopt this technique to imaging three-dimensional (3D) dynamics of soft materials instead, double strand (dsDNA) connecting Au nanocrystals as one example, at nanometer resolution. We demonstrate first that a graphene liquid cell can seal an aqueous sample solution of a lower vapor pressure than previously investigated well against the high vacuum in TEM. Then, from quantitative analysis of real time nanocrystal trajectories, we show that the status and configuration of dsDNA dictate the motions of linked nanocrystals throughout the imaging time of minutes. This sustained connecting ability of dsDNA enables this unprecedented continuous imaging of its dynamics via TEM. Furthermore, the inert graphene surface minimizes sample-substrate interaction and allows the whole nanostructure to rotate freely in the liquid environment; we thus develop and implement the reconstruction of 3D configuration and motions of the nanostructure from the series of 2D projected TEM images captured while it rotates. In addition to further proving the nanoconjugate structural stability, this reconstruction demonstrates 3D dynamic imaging by TEM beyond its conventional use in seeing a flattened and dry sample. Altogether, we foresee the new and exciting use of graphene liquid cell TEM in imaging 3D biomolecular transformations or interaction dynamics at nanometer resolution.

Direct Observation of Wet Biological Samples by Graphene Liquid Cell Transmission Electron Microscopy

Recent development of liquid phase transmission electron microscopy (TEM) enables the study of specimens in wet ambient conditions within a liquid cell; however, direct structural observation of biological samples in their native solution using TEM is challenging since low-mass biomaterials embedded in a thick liquid layer of the host cell demonstrate low contrast. Furthermore, the integrity of delicate wet samples is easily compromised during typical sample preparation and TEM imaging. To overcome these limitations, we introduce a graphene liquid cell (GLC) using multilayer graphene sheets to reliably encapsulate and preserve biological samples in a liquid for TEM observation. We achieve nanometer scale spatial resolution with high contrast using low-dose TEM at room temperature, and we use the GLC to directly observe the structure of influenza viruses in their native buffer solution at room temperature. The GLC is further extended to investigate whole cells in wet conditions using TEM. We also demonstrate the potential of the GLC for correlative studies by TEM and fluorescence light microscopy imaging.

Graphene-templated directional growth of an inorganic nanowire

Assembling inorganic nanomaterials on graphene is of interest in the development of nanodevices and nanocomposite materials, and the ability to align such inorganic nanomaterials on the graphene surface is expected to lead to improved functionalities, as has previously been demonstrated with organic nanomaterials epitaxially aligned on graphitic surfaces. However, because graphene is chemically inert, it is difficult to precisely assemble inorganic nanomaterials on pristine graphene. Previous techniques based on dangling bonds of damaged graphene, intermediate seed materials and vapour-phase deposition at high temperature(,) have only formed randomly oriented or poorly aligned inorganic nanostructures. Here, we show that inorganic nanowires of gold(I) cyanide can grow directly on pristine graphene, aligning themselves with the zigzag lattice directions of the graphene. The nanowires are synthesized through a self-organized growth process in aqueous solution at room temperature, which indicates that the inorganic material spontaneously binds to the pristine graphene surface. First-principles calculations suggest that this assembly originates from lattice matching and π interaction to gold atoms. Using the synthesized nanowires as templates, we also fabricate nanostructures with controlled crystal orientations such as graphene nanoribbons with zigzag-edged directions.

Control of Emergent Properties at a Correlated Oxide Interface with Graphene

Electrolyte gating of complex oxides enables investigation of electronic phase boundaries and collective response to strong electric fields. The origin of large conductance modulations and associated emergent properties in such field effect structures is a matter of intense study due to competing contributions from electrostatic (charge accumulation) and electrochemical (crystal chemistry changes) effects. Vanadium dioxide (VO2) is a prototypical correlated insulator that shows an insulator-to-metal transition at ∼67 °C and recent studies have noted a vast range of electronic effects in electric double-layer transistors (EDLT). In this study, we demonstrate that the response of electrolyte gated VO2 devices can be deterministically controlled by inserting a monolayer of graphene at the oxide-electrolyte interface. Several electrolytes as well as dopants (such as lithium ions and protons) were employed in EDL transistors to show that graphene serves as an inert barrier that successfully protects the oxide surface from chemical reactions. This monolayer interface has a striking effect on resistance modulation in the vanadium dioxide transistor channel up to several orders of magnitude and enables retention of the insulating phase. The studies allow new insights into the response of correlated insulators in EDLTs and inform design of correlated oxide-2D heterostructures for electronics and sensors.

Liquid Cell Electron Microscopy of Nanoparticle Self-Assembly Driven by Solvent Drying

Drying a colloidal solution of nanoparticles is a versatile method to construct self-assembled structures of nanoparticles. However, mechanistic understanding has mostly relied on empirical knowledge obtained from the final structures of self-assembly as relevant processes during solvent drying are likely kinetic and far from equilibrium. Here, we present in situ TEM studies of nanoparticle self-assembly under various conditions, including the concentrations of the initial solution and the types of nanoparticles and substrates. The capability of tracking trajectories of individual nanoparticles enables us to understand the mechanisms of drying-mediated self-assembly at the single-nanoparticle level. Our results consistently show that a solvent boundary primarily affects nanoparticle motions and the resulting self-assembly processes regardless of different conditions. The solvent boundary drives nanoparticles to form two-dimensional assembly mainly through two pathways, transporting scattered nanoparticles by lateral dragging and flattening aggregated nanoparticles by vertical pressing.