Jong Min Yuk

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.

Raman Spectroscopy Study of Rotated Double-Layer Graphene: Misorientation-Angle Dependence of Electronic Structure

We present a systematic Raman study of unconventionally stacked double-layer graphene, and find that the spectrum strongly depends on the relative rotation angle between layers. Rotation-dependent trends in the position, width and intensity of graphene 2D and G peaks are experimentally established and accounted for theoretically. Our theoretical analysis reveals that changes in electronic band structure due to the interlayer interaction, such as rotational-angle dependent Van Hove singularities, are responsible for the observed spectral features. Our combined experimental and theoretical study provides a deeper understanding of the electronic band structure of rotated double-layer graphene, and leads to a practical way to identify and analyze rotation angles of misoriented double-layer graphene.

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.

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.

Freeze-Dried Sulfur–Graphene Oxide–Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells

The ambient-temperature rechargeable lithium/sulfur (Li/S) cell is a strong candidate for the beyond lithium ion cell since significant progress on developing advanced sulfur electrodes with high sulfur loading has been made. Here we report on a new sulfur electrode active material consisting of a cetyltrimethylammonium bromide-modified sulfur-graphene oxide-carbon nanotube (S-GO-CTA-CNT) nanocomposite prepared by freeze-drying. We show the real-time formation of nanocrystalline lithium sulfide (Li2S) at the interface between the S-GO-CTA-CNT nanocomposite and the liquid electrolyte by in situ TEM observation of the reaction. The combination of GO and CNT helps to maintain the structural integrity of the S-GO-CTA-CNT nanocomposite during lithiation/delithiation. A high S loading (11.1 mgS/cm2, 75% S) S-GO-CTA-CNT electrode was successfully prepared using a three-dimensional structured Al foam as a substrate and showed good S utilization (1128 mAh/g S corresponding to 12.5 mAh/cm2), even with a very low electrolyte to sulfur weight ratio of 4. Moreover, it was demonstrated that the ionic liquid in the electrolyte improves the Coulombic efficiency and stabilizes the morphology of the Li metal anode.

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.

Direct Fabrication of Zero- and One-Dimensional Metal Nanocrystals by Thermally Assisted Electromigration

Zero- and one-dimensional metal nanocrystals were successfully fabricated with accurate control in size, shape, and position on semiconductor surfaces by using a novel in situ fabrication method of the nanocrystal with a biasing tungsten tip in transmission electron microscopy. The dominant mechanism of nanocrystal formation was identified mainly as local Joule heating-assisted electromigration through the direct observation of formation and growth processes of the nanocrystal. This method was applied to extracting metal atoms with an exceedingly faster growth rate ( approximately 10(5) atoms/s) from a metal-oxide thin film to form a metal nanocrystal with any desired size and position. By real-time observation of the microstructure and concurrent electrical measurements, it was found that the nanostructure formation can be completely controlled into various shapes such as zero-dimensional nanodots and one-dimensional nanowires/nanorods.

Initial formation mechanisms of the supersaturation region and the columnar structure in ZnO thin films grown on n-Si (001) substrates

ZnO thin films were grown on n-Si (001) substrates by using plasma-assisted molecular beam epitaxy. A cross-sectional bright-field transmission electron microscopy (TEM) image showed that small ZnO columnar grains were embedded into large columnar grains, and a selected-area electron diffraction pattern, and an x-ray diffraction pattern showed that the ZnO thin film were nearly c-axis oriented. The evolution of the ZnO columnar structure was analyzed by using the evolution of the strain due to the interaction of the columnar grains, as observed by using high-resolution TEM. The initial formation mechanisms of the supersaturation region and the columnar grains are described.

Transformation mechanisms from metallic Zn nanocrystals to insulating ZnSiO3 nanocrystals in a SiO2 matrix due to thermal treatment

Transmission electron microscopy (TEM), high-resolution TEM, and x-ray energy dispersive spectroscopy results showed that Zn metallic nanocrystals and ZnSiO3 insulating nanocrytals embedded in a SiO2 matrix were created from the ZnO thin films deposited on n-Si (001) substrates due to rapid thermal annealing. The formed Zn metallic nanocrystals were transformed into monoclinic ZnSiO3 insulating nanocrystals with increasing number of Zn atoms resulting from an increase in the annealing time up to 10 min. The transformation mechanisms from metallic Zn nanocrystals to insulating ZnSiO3 nanocrystals in a SiO2 matrix due to rapid thermal annealing are described on the basis of the experimental results.

Formation mechanisms of metallic Zn nanodots by using ZnO thin films deposited on n-Si substrates

High-resolution transmission electron microscopy and energy dispersive x-ray spectroscopy results showed that metallic Zn nanodots (NDs) were fabricated through transformation of ZnO thin films by deposition of SiOx on ZnO/n-Si (100) heterostructures. The Zn NDs with various sizes and densities were formed due to the occurrence of the mass diffusion of atoms along the grain boundaries in the ZnO thin films. The fabrication mechanisms of metallic Zn NDs through transformation of ZnO thin films deposited on n-Si substrates are described on the basis of the experimental results.