Electron holography observation of individual ferrimagnetic lattice planes.

Atomic-scale observations of a specific local area would be considerably beneficial when exploring new fundamental materials and devices. The development of hardware-type aberration correction1,2 in electron microscopy has enabled local structural observations with atomic resolution3-5 as well as chemical and vibration analysis6-8. In magnetic imaging, however, atomic-level spin configurations are analysed by electron energy-loss spectroscopy by placing samples in strong magnetic fields9-11, which destroy the nature of the magnetic ordering in the samples. Although magnetic-field-free observations can visualize the intrinsic magnetic fields of an antiferromagnet by unit-cell averaging12, directly observing the magnetic field of an individual atomic layer of a non-uniform structure is challenging. Here we report that the magnetic fields of an individual lattice plane inside materials with a non-uniform structure can be observed under magnetic-field-free conditions by electron holography with a hardware-type aberration corrector assisted by post-digital aberration correction. The magnetic phases of the net magnetic moments of (111) lattice planes formed by opposite spin orderings between Fe3+ and Mo5+ in a ferrimagnetic double-perovskite oxide (Ba2FeMoO6) were successfully observed. This result opens the door to direct observations of the magnetic lattice in local areas, such as interfaces and grain boundaries, in many materials and devices.

Depth sectioning using environmental and atomic-resolution STEM.

(Scanning) transmission electron microscopy (TEM) images of samples in gas and liquid media are acquired with an environmental cell (EC) via silicon nitride membranes. The ratio of sample signal against the background is a significant factor for resolution. Depth-sectioning scanning TEM (STEM) is a promising technique that enhances the signal for a sample embedded in a matrix. It can increase the resolution to the atomic level, thereby enabling EC-STEM applications in important areas. This review introduces depth-sectioning STEM and its applications to high-resolution EC-STEM imaging of samples in gases and in liquids.

The Atomic Observation of the Structural Change Process in Pt Networks in Air Using Environmental Cell Scanning Transmission Electron Microscopy.

The structural change in Pt networks composed of multiple chain connections among grains was observed in air at 1 atm using atomic-resolution environmental cell scanning transmission electron microscopy. An aberration-corrected incident electron probe with a wide convergence angle made it possible to increase the depth resolution that contributes to enhancing the signal-to-noise ratio of Pt network samples in air in an environmental cell, resulting in the achievement of atomic-resolution imaging. The exposure of the Pt networks to gas molecules under Brownian motion, stimulated by electron beams in the air, increases the collision probability between gas molecules and Pt networks, and the Pt networks are more intensely stressed from all directions than in a situation without electron irradiation. By increasing the electron beam dose rate, the structural change of the Pt networks became significant. Dynamic observation on an atomic scale suggested that the structural change of the networks was not attributed to the surface atomic-diffusion-induced step motion but mainly caused by the movement and deformation of unstable grains and grain boundaries. The oxidized surface layers may be one of the factors hindering the surface atomic step motion, mitigating the change in the size of the grains and grain boundaries.

High Cathode Loading and Low-Temperature Operating Garnet-Based All-Solid-State Lithium Batteries - Material/Process/Architecture Optimization and Understanding of Cell Failure.

All-solid-state lithium batteries (ASSLBs) are prepared using garnet-type solid electrolytes by quick liquid phase sintering (Q-LPS) without applying high pressure during the sintering. The cathode layers are quickly sintered with a heating rate of 50-100 K min-1 and a dwell time of 10 min. The battery performance is dramatically improved by simultaneously optimizing materials, processes, and architectures, and the initial discharge capacity of the cell with a LiCoO2 -loading of 8.1 mg reaches 1 mAh cm-2 and 130 mAh g-1 at 25 °C. The all-solid-state cell exhibits capacity at a reduced temperature (10 °C) or a relatively high rate (0.1 C) compared to the previous reports. The Q-LPS would be suitable for large-scale manufacturing of ASSLBs. The multiphysics analyses indicate that the internal stress reaches 1 GPa during charge/discharge, which would induce several mechanical failures of the cells: broken electron networks, broken ion networks, separation of interfaces, and delamination of layers. The experimental results also support these failures.

Development of temporal series 4D-STEM and application to relaxation time measurement.

Diffraction patterns contain useful information about the materials. Recent developments in four-dimensional scanning transmission electron microscopy and the acquisition of the spatial distribution of diffraction patterns have produced significant results. The acquisition of a temporal series of diffractions is achieved for a stationary beam. However, the acquisition of spatiotemporal distribution of diffraction patterns has only been established under limited conditions. In this study, we developed a simple method that enables the recording of the spatiotemporal distribution of diffraction patterns and applied it to the relaxation time measurement that is robust to sample drift.

Direct observation of Cu in high-silica chabazite zeolite by electron ptychography using Wigner distribution deconvolution.

Direct observation of Cu in Cu-chabazite (CHA) zeolite has been achieved by electron ptychography using the Wigner distribution deconvolution. The imaging properties of ptychographically reconstructed images were evaluated by comparing the intensities of six-membered-ring columns of the zeolite with and without Cu using simulated ptychography images. It was concluded that although false contrast may appear at Cu-free columns for some acquisition conditions, ptychography can discriminate columns with and without Cu. Experimental observation of CHA with and without Cu was performed. Images obtained from the Cu-containing sample showed contrast at the six-membered-rings, while no contrast was observed for the Cu-free sample. The results show that ptychography is a promising technique for visualizing the atomic structures of beam-sensitive materials.

Fabrication of Oxide-Based All-Solid-State Batteries by a Sintering Process Based on Function Sharing of Solid Electrolytes.

Garnet-type Li7La3Zr2O12 (LLZ) has advantages of stability with Li metal and high Li+ ionic conductivity, achieving 1 × 10-3 S cm-1, but it is prone to react with electrode active materials during the sintering process. LISICON-type Li3.5Ge0.5V0.5O4 (LGVO) has the advantage of less reactivity with the electrode active material during the sintering process, but its ionic conductivity is on the order of 10-5 S cm-1. In this study, these two solid electrolytes are combined as a multilayer solid electrolyte sheet, where 2 µm thick LGVO films are coated on LLZ sheets to utilize the advantages of these two solid electrolytes. These two solid electrolytes adhere well through Ge diffusion without significant interfacial resistance. The LLZ-LGVO multilayer is combined with a LiCoO2 positive electrode and a lithium metal anode through annealing at 700 °C. The resultant all-solid-state battery can undergo repeated charge-discharge reactions for over 100 cycles at 25 or 60 °C. The LGVO coating suppresses the increases in the resistance from the solid electrolyte and interfacial resistance induced by annealing by ca. 1/40. As with sulfide-based all-solid-state batteries, function sharing of solid electrolytes will be a promising method for developing advanced oxide-based all-solid-state batteries through a sintering process.

Effect of amorphous carbon coating on the performance of liquid phase transmission electron microscopy (LP-TEM) and the dynamics of enclosed Pt nano-colloids.

Ultra-thin silicon nitride (SiN) membranes are critical in microfabrication-based liquid cells (LCs) for transmission electron microscopy (TEM). This study used a homemade LC with a 50-nm SiN membrane to study the dynamics of 2.58-nm platinum (Pt) nanoparticles (NPs) in approximately 200-nm-deep water. When a strong beam with electron flux ranging from 2.5 × 103 to 1.4 × 106 e-/(nm2 s) was applied to resolve the NPs, the beam caused NP aggregation and even drilled a hole on the top membrane. The hole drilling was prevented by coating a 1-4-nm-thick amorphous carbon layer on both sides of the membrane. The NP aggregation rate also decreased with increasing carbon thickness. After overcoming the aforementioned issues, lattice fringes of the Pt NPs were visible when the NPs were attached to the membrane of the 4-nm-carbon-coated LC containing a thin liquid layer. The effects of the electron beam and carbon on the LC and Pt NPs were investigated and discussed. This work provides a reference for LC-TEM research using strong electron beams.

Tracking the emergence of epitaxial metal-oxide interfaces from precursor alloys.

Heterointerfaces with an epitaxial relationship, self-assembled nanocomposites of Pt(111)/CeO2(111) 60°, were successfully formed by simple oxidation of Pt5Ce alloy. Oxygen dissolution into the alloy causes spacial periodic compositional perturbation by atomic segregation, specifically, by local diffusion of Pt and Ce atoms. A striped pattern of Pt and CeO2 with a 4-5 nm periodicity formed through phase transformation of the Pt-rich alloy and oxidation of the Ce-rich alloy, respectively. Notably, a fully epitaxial relationship between the Pt and CeO2 phases was observed even in the initial stage. With continued annealing, the crystals rotated into an energetically favorable orientation with respect to the remaining (111)Pt//(111)CeO2. The alloy oxidation and its resulting nanoscale phase-separation behavior were verified in an ex situ annealing experiment of an alloy specimen, which had been first thinned by a focused ion beam. Changing the oxygen partial pressure to the reaction interface may alter the orientation relationship between the hexagonal close-packed Pt5Ce structure and face-centered cubic Pt/CeO2 structure, thereby altering the growth direction of the separated phases. These findings present a pathway for the self-assembly of epitaxial Pt(111)/CeO2(111) interface and are expected to assist the structural design of metal-oxide nanocomposites.

Phase-transition-induced jumping, bending, and wriggling of single crystal nanofibers of coronene.

For decades, it has been reported that some organic crystals suddenly crack, break, or jump when they are heated from room temperature. Recently, such crystals have been intensively studied both in fundamental science and for high-speed mechanical device applications. According to these studies, the sudden crystal motions have been attributed to structural phase transitions induced by heating. Stress created by the phase transition is released through the sudden and rapid motion of the crystals. Here we report that single crystal nanofibers of coronene exhibit a new type of ultrafast motion when they are cooled from room temperature and subsequently heated to room temperature. The nanofibers make centimeter-scale jumps accompanied by surprisingly unique behaviors such as sharp bending and wriggling. We found that the motions are caused by a significantly fast structural phase transition between two polymorphs of coronene. A theoretical investigation revealed that the sudden force generated by the phase transition together with the nanoscale dimensions and elastic properties create dynamical instability in the nanofibers that results in the motions. Our finding demonstrates the novel mechanism that leads to ultrafast, large deformation of organic crystals.

Fabrication of a liquid cell for in situ transmission electron microscopy.

Liquid cell transmission electron microscopy (LCTEM) enables imaging of dynamic processes in liquid with high spatial and temporal resolution. The widely used liquid cell (LC) consists of two stacking microchips with a thin wet sample sandwiched between them. The vertically overlapped electron-transparent membrane windows on the microchips provide passage for the electron beam. However, microchips with imprecise dimensions usually cause poor alignment of the windows and difficulty in acquiring high-quality images. In this study, we developed a new and efficient microchip fabrication process for LCTEM with a large viewing area (180 µm × 40 µm) and evaluated the resultant LC. The new positioning reference marks on the surface of the Si wafer dramatically improve the precision of dicing the wafer, making it possible to accurately align the windows on two stacking microchips. The precise alignment led to a liquid thickness of 125.6 nm close to the edge of the viewing area. The performance of our LC was demonstrated by in situ transmission electron microscopy imaging of the dynamic motions of 2-nm Pt particles. This versatile and cost-effective microchip production method can be used to fabricate other types of microchips for in situ electron microscopy.

The electric double layer effect and its strong suppression at Li+ solid electrolyte/hydrogenated diamond interfaces.

The electric double layer (EDL) effect at solid electrolyte/electrode interfaces has been a key topic in many energy and nanoelectronics applications (e.g., all-solid-state Li+ batteries and memristors). However, its characterization remains difficult in comparison with liquid electrolytes. Herein, we use a novel method to show that the EDL effect, and its suppression at solid electrolyte/electronic material interfaces, can be characterized on the basis of the electric conduction characteristics of hydrogenated diamond(H-diamond)-based EDL transistors (EDLTs). Whereas H-diamond-based EDLT with a Li-Si-Zr-O Li+ solid electrolyte showed EDL-induced hole density modulation over a range of up to three orders of magnitude, EDLT with a Li-La-Ti-O (LLTO) Li+ solid electrolyte showed negligible enhancement, which indicates strong suppression of the EDL effect. Such suppression is attributed to charge neutralization in the LLTO, which is due to variation in the valence state of the Ti ions present. The method described is useful for quantitatively evaluating the EDL effect in various solid electrolytes.

Non-negative matrix factorization for mining big data obtained using four-dimensional scanning transmission electron microscopy.

Scientific instruments for material characterization have recently been improved to yield big data. For instance, scanning transmission electron microscopy (STEM) allows us to acquire many diffraction patterns from a scanning area, which is referred to as four-dimensional (4D) STEM. Here we study a combination of 4D-STEM and a statistical technique called non-negative matrix factorization (NMF) to deduce sparse diffraction patterns from a 4D-STEM data consisting of 10,000 diffraction patterns. Titanium oxide nanosheets are analyzed using this combined technique, and we discriminate the two diffraction patterns from pristine TiO2 and reduced Ti2O3 areas, where the latter is due to topotactic reduction induced by electron irradiation. The combination of NMF and 4D-STEM is expected to become a standard characterization technique for a wide range materials.

Highly Monochromatic Electron Emission from Graphene/Hexagonal Boron Nitride/Si Heterostructure.

In this work, a planar electron emission device based on a graphene/hexagonal boron nitride (h-BN)/n-Si heterostructure is fabricated to realize highly monochromatic electron emission from a flat surface. The h-BN layer is used as an insulating layer to suppress electron inelastic scattering within the planar electron emission device. The energy spread of the emission device using the h-BN insulating layer is 0.28 eV based on the full-width at half-maximum (FWHM), which is comparable to a conventional tungsten field emitter. The characteristic spectral shape of the electron energy distributions reflected the electron distribution in the conduction band of the n-Si substrate. The results indicate that the inelastic scattering of electrons at the insulating layer is drastically suppressed by the h-BN layer. Furthermore, the maximum emission current density reached 2.4 A/cm2, which is comparable to that of a conventional thermal cathode. Thus, the graphene/h-BN heterostructure is a promising material for planar electron emission devices to obtain a highly monochromatic electron beam and a high electron emission current density.

Comparative Analysis of Defects in Mg-Implanted and Mg-Doped GaN Layers on Freestanding GaN Substrates.

Inefficient Mg-induced p-type doping has been remained a major obstacle in the development of GaN-based electronic devices for solid-state lighting and power applications. This study reports comparative structural analysis of defects in GaN layers on freestanding GaN substrates where Mg incorporation is carried out via two approaches: ion implantation and epitaxial doping. Scanning transmission electron microscopy revealed the existence of pyramidal and line defects only in Mg-implanted sample whereas Mg-doped sample did not show presence of these defects which suggests that nature of defects depends upon incorporation method. From secondary ion mass spectrometry, a direct correspondence is observed between Mg concentrations and location and type of these defects. Our investigations suggest that these pyramidal and line defects are Mg-rich species and their formation may lead to reduced free hole densities which is still a major concern for p-GaN-based material and devices. As freestanding GaN substrates offer a platform for realization of p-n junction-based vertical devices, comparative structural investigation of defects originated due to different Mg incorporation processes in GaN layers on such substrates is likely to give more insight towards understanding Mg self-compensation mechanisms and then optimizing Mg doping and/or implantation process for the advancement of GaN-based device technology.

Direct observation of curvature of the wave surface in transmission electron microscope using transport intensity equation.

In optics it is well known that the image surface is curved, even when an illumination is an ideal plane wave. However, in transmission electron microscopy (TEM) the curvature of field, or wave surface, has not been discussed seriously. We have observed the curvature of field in TEM using the transport of intensity equation (TIE). The TIE describes the relation between the phase and intensity distributions of the wave that propagates in vacuum. The common way to obtain the phase distribution using the TIE requires solving the Poisson equation, which needs the information on the boundary (boundary condition). In this report, we observe the images that pass through a selected area (SA) aperture on the intermediate image plane in order to resolve the boundary value problem. Then, we have developed a new iterative scheme to solve the TIE based on the discrete cosine transform (DCT) valid for the Neumann boundary condition. Using the iterative DCT solver we have observed the phase modulation that shows curvature of field within the SA aperture. To the authors' knowledge this is the first direct observation of the additional phase term corresponding to the curvature of field on the image plane in transmission electron microscope. We have also explained why electron holography does not detect this spherical wave on the image plane.

Strain Relaxation in GaSb/GaAs(111)A Heteroepitaxy Using Thin InAs Interlayers.

We have systematically studied the strain relaxation processes in GaSb heteroepitaxy on GaAs(111)A using thin InAs interlayers. The growth with 1 ML- and 2 ML-InAs leads to formation of an InAsSb-like layer, which induces tensile strain in GaSb films, whereas the GaSb films grown with thicker InAs layers (≥3 ML) are under compressive strain. As the InAs thickness is increased above 5 ML, the insertion of the InAs layer becomes less effective in the strain relaxation, leaving residual strain in GaSb films. This leads to the elastic deformation of the GaSb lattice, giving rise to the increase in the peak width of X-ray rocking curves.

Two-dimensional Gaussian fitting for precise measurement of lattice constant deviation from a selected-area diffraction map.

Unlike X-ray diffraction or Raman techniques, which suffer from low spatial resolution, transmission electron microscopy can be used to obtain strain maps of nanoscaled materials and devices. Convergent-beam electron diffraction (CBED) and nanobeam electron diffraction (NBED) techniques detect the deviation of a lattice constant (i.e. an indicator of strain) within 0.01%; however, their use is restricted to beam-insensitive samples. Selected-area electron diffraction (SAED) does not have such limitations but has low spatial resolution and precision. The use of a spherical aberration corrector and a nanosized selected-area aperture improves the spatial resolution, but the precision is still low. In this study, a two-dimensional stage-scanning system is used to acquire arrays of diffraction patterns at different positions of the sample under fixed beam conditions. Data processing with iterative nonlinear least-squares fitting enabled the spot displacement for each point of the scan area to be measured with precision comparable to that of the CBED or NBED technique. The precise strain determination, in combination with the simplicity of the measurement process, makes the nanosized SAED technique competitive with other methods for strain mapping at nanoscale dimensions.

Fixation mechanisms of nanoparticles on substrates by electron beam irradiation.

For applications such as the fabrication of plasmonic waveguides we developed a patterning technique to fabricate an array of nanoparticles on a substrate using focused electron beams (Noriki, T.; Abe, S.;.Kajikawa, K.; Shimojo, M. Beilstein J. Nanotechnol.2015,6, 1010-1015). This technique consists of three steps: Firstly, nanoparticles are placed over the entire surface of a substrate. Secondly, the nanoparticles are fixed on the substrate by focused electron beam irradiation. The electron beam decomposes the organic molecules located around the particle into amorphous carbon. The amorphous carbon immobilizes the particle on the substrate. Finally, the unfixed nanoparticles are removed. However, in this original technique, the area in which the nanoparticles were fixed was wider than the electron-probe size of a few nanometers. To understand this widening mechanisms, the effects of accelerating voltage, particle size and substrate material are investigated by means of both experiments and simulation. It is demonstrated that the fixing area is greatly affected by the electrons back-scattered by the substrate. The back-scattering leads to an increase in line width and thus reduces the resolution of this patterning technique.

Microstructural analysis and transport properties of MoO and MoC nanostructures prepared by focused electron beam-induced deposition.

By electron-beam-induced deposition, we have succeeded in the direct fabrication of nanowires of molybdenum oxide (MoOx) and molybdenum carbide (MoC) on a SiO2 substrate set in a scanning electron microscope. In order to prepare MoOx specimens of high purity, a precursor gas of molybdenum hexacarbonyl [Mo(CO)6] is used, mixed with oxygen gas. On the other hand, MoC is grown by mixing H2O gas with the precursor gas. The electrical transport properties of the nanowires are investigated by the DC four-terminal method. A highly resistive MoOx nanowire prepared from an as-deposited specimen by annealing in air shows nonlinear current-voltage characteristics and a high photoconductivity. The resistivity ρ of an as-deposited amorphous MoC (a-MoC) nanowire takes its maximum at a temperature T ≈ 10 K and decreases to ≈ 0 with decreasing temperature. This behavior of ρ(T) indicates the possible occurrence of superconductivity in a-MoC nanowires. The characteristic of ρ(T) below the superconducting transition temperature Tc ≈ 4 K can be well explained by the quantum phase-slip model with a coherence length ξ(0) ≈ 8 nm at T = 0.