Direct identification of the charge state in a single platinum nanoparticle on titanium oxide.

A goal in the characterization of supported metal catalysts is to achieve particle-by-particle analysis of the charge state strongly correlated with the catalytic activity. Here, we demonstrate the direct identification of the charge state of individual platinum nanoparticles (NPs) supported on titanium dioxide using ultrahigh sensitivity and precision electron holography. Sophisticated phase-shift analysis for the part of the NPs protruding into the vacuum visualized slight potential changes around individual platinum NPs. The analysis revealed the number (only one to six electrons) and sense (positive or negative) of the charge per platinum NP. The underlying mechanism of platinum charging is explained by the work function differences between platinum and titanium dioxide (depending on the orientation relationship and lattice distortion) and by first-principles calculations in terms of the charge transfer processes.

Improved efficiency in automated acquisition of ultra-high-resolution electron holograms using automated target detection.

An automated hologram acquisition system for big-data analysis and for improving the statistical precision of phase analysis has been upgraded with automated particle detection technology. The coordinates of objects in low-magnification images are automatically detected using zero-mean normalized cross-correlation with preselected reference images. In contrast with the conventional scanning acquisitions from the whole area of a microgrid and/or a thin specimen, the new method allows efficient data collections only from the desired fields of view including the particles. The acquisition time of the cubic/triangular nanoparticles that were observed was shortened by about one-fifty eighth that of the conventional scanning acquisition method because of efficient data collections. The developed technology can improve statistical precision in electron holography with shorter acquisition time and is applicable to the analysis of electromagnetic fields for various kinds of nanoparticles.

Deep convolutional neural network image processing method providing improved signal-to-noise ratios in electron holography.

An image identification method was developed with the aid of a deep convolutional neural network (CNN) and applied to the analysis of inorganic particles using electron holography. Despite significant variation in the shapes of α-Fe2O3 particles that were observed by transmission electron microscopy, this CNN-based method could be used to identify isolated, spindle-shaped particles that were distinct from other particles that had undergone pairing and/or agglomeration. The averaging of images of these isolated particles provided a significant improvement in the phase analysis precision of the electron holography observations. This method is expected to be helpful in the analysis of weak electromagnetic fields generated by nanoparticles showing only small phase shifts.

Automated acquisition of vast numbers of electron holograms with atomic-scale phase information.

An automated acquisition system for collecting a large number of electron holograms, to improve the statistical precision of phase analysis, was developed. A technique for shifting the electron beam in combination with stage movement allows data to be acquired over a wide area of a TEM-specimen grid. Undesired drift in the hologram position, which may occur during the hologram acquisition, can be corrected in real time by automated detection of the interference-fringe region in an image. To demonstrate the usefulness of the developed automated hologram acquisition system, gold nanoparticles dispersed on a carbon foil were observed with a 1.2-MV atomic resolution holography electron microscope. The system could obtain 1024 holograms, which provided phase maps for more than 500 nanoparticles with a lateral resolution of 0.14 nm, in just 1 h. The observation results revealed an anomalous increase in mean inner potential for a particle size smaller than 4 nm. The developed automated hologram acquisition system can be applied to improve the precision of phase measurement by averaging many phase images, as demonstrated by single particle analysis for biological entities. Moreover, the system makes it possible to study electrostatic potential of catalysts and other functional nanoparticles at atomic resolution.

Beam brightness and its reduction in a 1.2-MV cold field-emission transmission electron microscope.

In this paper we discuss probe properties in terms of probe currents, probe sizes, energy spread, virtual source sizes, and brightness in a 1.2-MV cold field-emission (cold FE) transmission electron microscope (TEM) equipped with a magnetic gun lens. The probe size increased gradually in proportion to the (3/8)th power of the probe current, very unusual behavior in cold FE guns but typical behavior in thermionic guns. This is due to the magnetic gun lens, which caused large emission angles for electron beams in the probe before being limited by aberrations at the gun and acceleration tube. The brightness reached the maximum at 1.62 × 1014 A/(m2sr) and then decreased with increasing the emission current. The energy spread of the beam, including the Boersch effect, was 0.32-0.50 eV, comparable to that of conventional cold FE guns without magnetic gun lens. Experimental analysis indicated that neither noises nor aberrations caused the probe size increase under the optimized illumination condition. The virtual source size increased from 11.1 to 24.7 nm with the increase in the emission current. To describe this behavior, we conjecture that this brightness reduction is due to increase in the virtual source size caused by trajectory displacement created by stochastic Coulomb interactions near the emitter.

Electron holography on Fraunhofer diffraction.

Electron holography in Fraunhofer region was realized by using an asymmetric double slit. A Fraunhofer diffraction wave from a wider slit worked as an objective wave interfered with a plane wave from a narrower slit as a reference wave under the pre-Fraunhofer condition and recorded as a hologram. Here, the pre-Fraunhofer condition means that the following conditions are simultaneously satisfied: single-slit observations are performed under the Fraunhofer condition and the double-slit observations are performed under the Fresnel condition. Amplitude and phase distributions of the Fraunhofer diffraction wave were reconstructed from the hologram by the Fourier transform reconstruction method. The reconstructed amplitude and phase images corresponded to Fraunhofer diffraction patterns; in particular, the phase steps of π at each band pattern in the phase image were confirmed. We hope that the developed Fraunhofer electron holography can be extended to a direct phase detection method in the reciprocal space.

Illumination semiangle of 10-9 rad achieved in a 1.2-MV atomic resolution holography transmission electron microscope.

The coherency of a 1.2-MV transmission electron microscope was evaluated through illumination semiangles calculated from lengths over which Fresnel fringes can be observed. These lengths were determined from the diameters of circular holes fully filled with Fresnel fringes, i.e. this method allows lengths to be accurately measured even if micrographs are subjected to distortions. The smallest illumination semiangle of 4.0 × 10-9 rad was obtained for a circular hole with a diameter of 191 µm. In addition, electron beam brightness was estimated to be approximately 3 × 1014 A/m2·sr from the obtained illumination semiangle values and current densities. The results provide us with essential information that can be referred to in future electron holography studies aimed at detecting weak electromagnetic fields in materials.

Interference experiment with asymmetric double slit by using 1.2-MV field emission transmission electron microscope.

Advanced electron microscopy technologies have made it possible to perform precise double-slit interference experiments. We used a 1.2-MV field emission electron microscope providing coherent electron waves and a direct detection camera system enabling single-electron detections at a sub-second exposure time. We developed a method to perform the interference experiment by using an asymmetric double-slit fabricated by a focused ion beam instrument and by operating the microscope under a "pre-Fraunhofer" condition, different from the Fraunhofer condition of conventional double-slit experiments. Here, pre-Fraunhofer condition means that each single-slit observation was performed under the Fraunhofer condition, while the double-slit observations were performed under the Fresnel condition. The interference experiments with each single slit and with the asymmetric double slit were carried out under two different electron dose conditions: high-dose for calculation of electron probability distribution and low-dose for each single electron distribution. Finally, we exemplified the distribution of single electrons by color-coding according to the above three types of experiments as a composite image.

Current-Driven Motion of Domain Boundaries between Skyrmion Lattice and Helical Magnetic Structure.

To utilize magnetic skyrmions, nanoscale vortex-like magnetic structures, experimental elucidation of their dynamics against current application in various circumstances such as in confined structure and mixture of different magnetic phases is indispensable. Here, we investigate the current-induced dynamics of the coexistence state of magnetic skyrmions and helical magnetic structure in a thin plate of B20-type helimagnet FeGe in terms of in situ real-space observation using Lorentz transmission electron microscopy. Current pulses with various heights and widths were applied, and the change of the magnetic domain distribution was analyzed using a machine-learning technique. The observed average driving direction of the two-magnetic-state domain boundary is opposite to the applied electric current, indicating ferromagnetic s-d exchange coupling in the spin-transfer torque mechanism. The evaluated driving distance tends to increase with increasing the pulse duration time, current density (>1 × 109 A/m2), and sample temperature, providing valuable information about hitherto unknown current-induced dynamics of the skyrmion-lattice ensemble.

Magnetic field observations in CoFeB/Ta layers with 0.67-nm resolution by electron holography.

Nanometre-scale magnetic field distributions in materials such as those at oxide interfaces, in thin layers of spintronics devices, and at boundaries in magnets have become important research targets in materials science and applied physics. Electron holography has advantages in nanometric magnetic field observations, and the realization of aberration correctors has improved its spatial resolution. Here we show the subnanometre magnetic field observations inside a sample at 0.67-nm resolution achieved by an aberration-corrected 1.2-MV holography electron microscope with a pulse magnetization system. A magnetization reduction due to intermixing in a CoFeB/Ta multilayer is analyzed by observing magnetic field and electrostatic potential distributions simultaneously. Our results demonstrate that high-voltage electron holography can be widely applied to pin-point magnetization analysis with structural and composition information in physics, chemistry, and materials science.

Information transfer of 25.5 nm-1 in a 1-MV field-emission transmission electron microscope.

Information transfer of a 1-MV field-emission transmission electron microscope (TEM) was improved by reducing mechanical vibrations and improving the stability of an acceleration voltage. The resulting mechanical stability was estimated from lattice fringes with an obtained spacing of 19.6 pm under achromatic conditions. This value corresponds to a vibration amplitude of <19.6 pm. The stability of the acceleration voltage was improved by reducing thermal noises in the power supply. As a result, 39.2-pm-spacing linear lattice fringes were obtained under chromatic conditions. This indicates that 25.5 nm(-1) information transfer was accomplished in the 1 MV field-emission TEM.