Eiji Okunishi

Robust atomic resolution imaging of light elements using scanning transmission electron microscopy

We show that an annular detector placed within the bright field cone in scanning transmission electron microscopy allows direct imaging of light elements in crystals. In contrast to common high angle annular dark field imaging, both light and heavy atom columns are visible simultaneously. In contrast to common bright field imaging, the images are directly and robustly interpretable over a large range of thicknesses. We demonstrate this through systematic simulations and present a simple physical model to obtain some insight into the scattering dynamics.

Dynamics of annular bright field imaging in scanning transmission electron microscopy

We explore the dynamics of image formation in the so-called annular bright field mode in scanning transmission electron microscopy, whereby an annular detector is used with detector collection range lying within the cone of illumination, i.e. the bright field region. We show that this imaging mode allows us to reliably image both light and heavy columns over a range of thickness and defocus values, and we explain the contrast mechanisms involved. The role of probe and detector aperture sizes is considered, as is the sensitivity of the method to intercolumn spacing and local disorder.

Visualization of Light Elements at Ultrahigh Resolution by STEM Annular Bright Field Microscopy

In the field of materials sciences such as studies on ceramics, semi-conducting material and metals, role of light elements is important, because it is one of mainly composing elements or determiner of character i. e. dopants. The light elements at high resolution have been observed by ultrahigh voltage electron microscopy or aberration corrected electron microscopy in Transmission Electron Microscopy (TEM), since the visualization of light requires highly resolving power. Recently, a high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) has become widely used in this field because of high-resolution capability and easily interpretable image contrast, which is roughly proportional to square of atomic number Z (Z). However, the HAADF image sometimes gives lack of light element because of excess contrast originated from Z, when the specimen contains the light and heavy elements. The TEM bright field imaging gives an image contrast roughly proportional to the Z, when the specimen is thin enough to be able to apply the ‘thin film approximation’. We have examined to apply an STEM annular bright field (ABF) imaging, which is equivalent to TEM hollow cone illumination imaging technique [1-2], to the oxide or nitride samples for simultaneous visualization of light and heavier elements. According to the article on hollow cone illumination in TEM [2], the contrast transfer in ABF expected to give better resolution than conventional BF STEM and to give non-oscillating contrast transfer, which gives easily-interpretable images unlike the BF STEM. This paper reports characteristics and the experimental result of the ABF imaging technique.

Monolayer PtSe2, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt

Single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe2), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. A combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe2/Pt(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe2 (in contrast to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe2 film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe2 has also potential applications in valleytronics.

Direct imaging of lithium atoms in LiV2O4 by spherical aberration-corrected electron microscopy

We visualized lithium atom columns in LiV₂O₄ crystals by combining scanning transmission electron microscopy with annular bright field (ABF) imaging using a spherical aberration-corrected electron microscope (R005) viewed from the [110] direction. The incident electron beam was coherent with a convergent angle of 30 mrad (semi-angle), and the detector collected scattered electrons over 20-30 mrad (semi-angle). The ABF image showed dark dots corresponding to lithium, vanadium and oxygen columns.

Probe integrated scattering cross sections in the analysis of atomic resolution HAADF STEM images

The physical basis for using a probe-position integrated cross section (PICS) for a single column of atoms as an effective way to compare simulation and experiment in high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) is described, and the use of PICS in order to make quantitative use of image intensities is evaluated. It is based upon the calibration of the detector and the measurement of scattered intensities. Due to the predominantly incoherent nature of HAADF STEM, it is found to be robust to parameters that affect probe size and shape such as defocus and source coherence. The main imaging parameter dependencies are on detector angle and accelerating voltage, which are well known. The robustness to variation in other parameters allows for a quantitative comparison of experimental data and simulation without the need to fit parameters. By demonstrating the application of the PICS to the chemical identification of single atoms in a heterogeneous catalyst and in thin, layered-materials, we explore some of the experimental considerations when using this approach.

Evidence of drug confinement into silica mesoporous matrices by STEM spherical aberration corrected microscopy

For the first time it has been possible to detect drug molecules confined into the inner part of pore channels of ordered mesoporous materials. This has been possible using spherical aberration correctors incorporated to a STEM microscope, which allows illuminating an individual atom with the electron beam to identify an unknown substance.

Detection of photons emitted from single erbium atoms in energy-dispersive X-ray spectroscopy

Researchers use energy-dispersive X-ray spectroscopy to detect X-ray emission from a single erbium atom. Although the measured intensities are relatively weak, the work may allow single-atom X-ray spectra to be obtained from other atomic species.

Measurement of vibrational spectrum of liquid using monochromated scanning transmission electron microscopy–electron energy loss spectroscopy

Investigations on the dynamic behavior of molecules in liquids at high spatial resolution are greatly desired because localized regions, such as solid-liquid interfaces or sites of reacting molecules, have assumed increasing importance with respect to improving material performance. In application to liquids, electron energy loss spectroscopy (EELS) observed with transmission electron microscopy (TEM) is a promising analytical technique with the appropriate resolutions. In this study, we obtained EELS spectra from an ionic liquid, 1-ethyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C2mim-TFSI), chosen as the sampled liquid, using monochromated scanning TEM (STEM). The molecular vibrational spectrum and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap of the liquid were investigated. The HOMO-LUMO gap measurement coincided with that obtained from the ultraviolet-visible spectrum. A shoulder in the spectrum observed ∼0.4 eV is believed to originate from the molecular vibration. From a separately performed infrared observation and first-principles calculations, we found that this shoulder coincided with the vibrational peak attributed to the C-H stretching vibration of the [C2mim(+)] cation. This study demonstrates that a vibrational peak for a liquid can be observed using monochromated STEM-EELS, and leads one to expect observations of chemical reactions or aids in the analysis of the dynamic behavior of molecules in liquid.

Direct oxygen imaging within a ceramic interface, with some observations upon the dark contrast at the grain boundary.

Annular bright field scanning transmission electron microscopy, which has recently been established to produce directly interpretable images with both light and heavier atomic columns visible simultaneously, is shown to allow directly interpretable imaging of the oxygen columns within the Σ13[12¯10](101¯4) pyramidal twin grain boundary in α-Al(2)O(3). By using information in the high-angle annular dark field image and annular bright field images simultaneously, we estimate the specimen thickness and finite source size, and use them to explore in simulation the issue of dark contrast in the vicinity of the grain boundary in the annular dark field image.