Judy S. Kim

Imaging of Transient Structures Using Nanosecond in Situ TEM

The microstructure and properties of a material depend on dynamic processes such as defect motion, nucleation and growth, and phase transitions. Transmission electron microscopy (TEM) can spatially resolve these nanoscale phenomena but lacks the time resolution for direct observation. We used a photoemitted electron pulse to probe dynamic events with “snapshot” diffraction and imaging at 15-nanosecond resolution inside of a dynamic TEM. With the use of this capability, the moving reaction front of reactive nanolaminates is observed in situ. Time-resolved images and diffraction show a transient cellular morphology in a dynamically mixing, self-propagating reaction front, revealing brief phase separation during cooling, and thus provide insights into the mechanisms driving the self-propagating high-temperature synthesis.

Dynamics of single Fe atoms in graphene vacancies.

Focused electron beam irradiation has been used to create mono and divacancies in graphene within a defined area, which then act as trap sites for mobile Fe atoms initially resident on the graphene surface. Aberration-corrected transmission electron microscopy at 80 kV has been used to study the real time dynamics of Fe atoms filling the vacancy sites in graphene with atomic resolution. We find that the incorporation of a dopant atom results in pronounced displacements of the surrounding carbon atoms of up to 0.5 Å, which is in good agreement with density functional theory calculations. Once incorporated into the graphene lattice, Fe atoms can transition to adjacent lattice positions and reversibly switch their bonding between four and three nearest neighbors. The C atoms adjacent to the Fe atoms are found to be more susceptible to Stone-Wales type bond rotations with these bond rotations associated with changes in the dopant bonding configuration. These results demonstrate the use of controlled electron beam irradiation to incorporate dopants into the graphene lattice with nanoscale spatial control.

Single-shot dynamic transmission electron microscopy

A dynamic transmission electron microscope (DTEM) has been designed and implemented to study structural dynamics in condensed matter systems. The DTEM is a conventional in situ transmission electron microscope (TEM) modified to drive material processes with a nanosecond laser, “pump” pulse and measure it shortly afterward with a 30-ns-long probe pulse of ∼107 electrons. An image with a resolution of <20nm may be obtained with a single pulse, largely eliminating the need to average multiple measurements and enabling the study of unique, irreversible events with nanosecond- and nanometer-scale resolution. Space charge effects, while unavoidable at such a high current, may be kept to reasonable levels by appropriate choices of operating parameters. Applications include the study of phase transformations and defect dynamics at length and time scales difficult to access with any other technique. This single-shot approach is complementary to stroboscopic TEM, which is capable of much higher temporal resolution ...

Nanosecond time-resolved investigations using the in situ of dynamic transmission electron microscope (DTEM)

Most biological processes, chemical reactions and materials dynamics occur at rates much faster than can be captured with standard video rate acquisition methods in transmission electron microscopes (TEM). Thus, there is a need to increase the temporal resolution in order to capture and understand salient features of these rapid materials processes. This paper details the development of a high-time resolution dynamic transmission electron microscope (DTEM) that captures dynamics in materials with nanosecond time resolution. The current DTEM performance, having a spatial resolution <10nm for single-shot imaging using 15ns electron pulses, will be discussed in the context of experimental investigations in solid state reactions of NiAl reactive multilayer films, the study of martensitic transformations in nanocrystalline Ti and the catalytic growth of Si nanowires. In addition, this paper will address the technical issues involved with high current, electron pulse operation and the near-term improvements to the electron optics, which will greatly improve the signal and spatial resolutions, and to the laser system, which will allow tailored specimen and photocathode drive conditions.

The development of a 200 kV monochromated field emission electron source

We report the development of a monochromator for an intermediate-voltage aberration-corrected electron microscope suitable for operation in both STEM and TEM imaging modes. The monochromator consists of two Wien filters with a variable energy selecting slit located between them and is located prior to the accelerator. The second filter cancels the energy dispersion produced by the first filter and after energy selection forms a round monochromated, achromatic probe at the specimen plane. The ultimate achievable energy resolution has been measured as 36 meV at 200 kV and 26 meV at 80 kV. High-resolution Annular Dark Field STEM images recorded using a monochromated probe resolve Si-Si spacings of 135.8 pm using energy spreads of 218 meV at 200 kV and 217 meV at 80 kV respectively. In TEM mode an improvement in non-linear spatial resolution to 64 pm due to the reduction in the effects of partial temporal coherence has been demonstrated using broad beam illumination with an energy spread of 134 meV at 200 kV.

Unusual Stacking variations in liquid-phase exfoliated Transition Metal Dichalcogenides

Liquid-phase exfoliation of layered materials offers a large-scale approach toward the synthesis of 2D nanostructures. Structural properties of materials can however change during transition from bulk to the 2D state. Any such changes must be examined and understood for successful implementation of 2D nanostructures. In this work, we demonstrate nonbulk stacking sequences in the few-layer MoS2 and WS2 nanoflakes produced by liquid-phase exfoliation. Our analysis shows that nonbulk stacking sequences can be derived from its bulk counterparts by translational shifts of the layers. No structural changes within the layers were observed. Twenty-seven MoS2 and five WS2 nanoflakes were imaged and analyzed. Nine MoS2 and four WS2 nanoflakes displayed nonbulk stacking. Such dominance of the nonbulk stacking suggests high possibility of unusual stacking sequences in other 2D nanostructures. Notably, the electronic structure of some non bulk stacked bilayers presents characteristics which are uncommon to either the bulk phase or the single monolayer, for instance, a spin-split conduction band bottom. Our main characterization technique was annular dark-field scanning transmission electron microscopy, which offers direct and reliable imaging of atomic columns. The stacking characterization approach employed here can be readily applied toward other few-layer transition metal chalcogenides and oxides.

Controlled radiation damage and edge structures in boron nitride membranes.

We show that hexagonal boron nitride membranes synthesized by chemical exfoliation are more resistant to electron beam irradiation at 80 kV than is graphene, consistent with quantum chemical calculations describing the radiation damage processes. Monolayer hexagonal boron nitride does not form vacancy defects or amorphize during extended electron beam irradiation. Zigzag edge structures are predominant in thin membranes for both a freestanding boron nitride monolayer and for a supported multilayer step edge. We have also determined that the elemental termination species in the zigzag edges is predominantly N.

Quantifying transient states in materials with the dynamic transmission electron microscope

The dynamic transmission electron microscope (DTEM) offers a means of capturing rapid evolution in a specimen through in situ microscopy experiments by allowing 15-ns electron micrograph exposure times. The rapid exposure time is enabled by creating a burst of electrons at the emitter by ultraviolet pulsed laser illumination. This burst arrives at a specified time after a second laser initiates the specimen reaction. The timing of the two Q-switched lasers is controlled by high-speed pulse generators with a timing error much less than the pulse duration. Both diffraction and imaging experiments can be performed, just as in a conventional TEM. The brightness of the emitter and the total current control the spatial and temporal resolutions. We have demonstrated 7-nm spatial resolution in single 15-ns pulsed images. These single-pulse imaging experiments have been used to study martensitic transformations, nucleation and crystallization of an amorphous metal and rapid chemical reactions. Measurements have been performed on these systems that are possible by no other experimental approaches currently available.

Laser‐based in situ techniques: Novel methods for generating extreme conditions in TEM samples

The dynamic transmission electron microscope (DTEM) is introduced as a novel tool for in situ processing of materials. Examples of various types of dynamic studies outline the advantages and differences of laser‐based heating in the DTEM in comparison to conventional (resistive) heating in situ TEM methods. We demonstrate various unique capabilities of the drive laser, namely, in situ processing of nanoscale materials, rapid and high temperature phase transformations, and controlled thermal activation of materials. These experiments would otherwise be impossible without the use of the DTEM drive laser. Thus, the potential of the DTEM as a new technique to process and characterize the growth of a myriad of micro and nanostructures is demonstrated. Microsc. Res. Tech., 2009. Published 2009 Wiley‐Liss, Inc.

Temperature dependence of atomic vibrations in mono-layer graphene

We have measured the mean square amplitude of both in- and out-of-plane lattice vibrations for mono-layer graphene at temperatures ranging from ∼100 K to 1300 K. The amplitude of lattice vibrations was calculated from data extracted from selected area electron diffraction patterns recorded across a known temperature range with over 80 diffraction peaks measured per diffraction pattern. Using an analytical Debye model, we have also determined values for the maximum phonon wavelength that can be supported by a mono-layer graphene crystal and the magnitude of quantum mechanical zero point vibrations. For in-plane phonons, the quantum mechanical zero point contribution dominates the measured atomic displacement at room temperature, whereas for out-of-plane modes, thermally populated phonons must be considered. We find a value for the maximum phonon wavelength sampled that is several orders of magnitudes smaller than the physical crystallite size.