Diffraction contrast of ferroelectric domains in DPC STEM images.

Differential phase contrast scanning transmission electron microscopy (DPC STEM) is a powerful technique for directly visualizing electromagnetic fields inside materials at high spatial resolution. Electric field observation within ferroelectric materials is potentially possible by DPC STEM, but concomitant diffraction contrast hinders the quantitative electric field evaluation. Diffraction contrast is basically caused by the diffraction-condition variation inside a field-of-view, but in the case of ferroelectric materials, the diffraction conditions can also change with respect to the polarization orientations. To quantitatively observe electric field distribution inside ferroelectric domains, the formation mechanism of diffraction contrast should be clarified in detail. In this study, we systematically simulated diffraction contrast of ferroelectric domains in DPC STEM images based on the dynamical diffraction theory, and clarify the issues for quantitatively observing electric fields inside ferroelectric domains. Furthermore, we conducted experimental DPC STEM observations for a ferroelectric material to confirm the influence of diffraction contrast predicted by the simulations.

Incommensurate grain-boundary atomic structure.

Grain-boundary atomic structures of crystalline materials have long been believed to be commensurate with the crystal periodicity of the adjacent crystals. In the present study, we experimentally observed a Σ9 grain-boundary atomic structure of a bcc crystal (Fe-3%Si). It is found that the Σ9 grain-boundary structure is largely reconstructed and forms a dense packing of icosahedral clusters in its core. Combining with the detailed theoretical calculations, the Σ9 grain-boundary atomic structure is discovered to be incommensurate with the adjacent crystal structures. The present findings shed new light on the study of stable grain-boundary atomic structures in crystalline materials.

Magnetic Field Observation in a Magnetic Tunnel Junction by Scanning Transmission Electron Microscopy.

A magnetic tunnel junction (MTJ) consists of two ferromagnetic layers separated by a thin insulating layer. MTJs show tunnel magnetoresistance effect, where the resistance in the direction perpendicular to the insulator layer drastically changes depending on the magnetization directions (parallel or antiparallel) in the ferromagnetic layers. However, direct observation of local magnetizations inside MTJs have been challenging. In this study, we demonstrate direct observation of magnetic flux density distribution inside epitaxially grown Fe/MgO/Fe layers using differential phase contrast scanning transmission electron microscopy. By utilizing newly-developed tilt-scan averaging system for suppressing diffraction contrasts, we clearly visualize parallel and antiparallel states of ferromagnetic layers at nanometer resolution.

Direct imaging of local atomic structures in zeolite using optimum bright-field scanning transmission electron microscopy.

Zeolites are used in industries as catalysts, ion exchangers, and molecular sieves because of their unique porous atomic structures. However, direct observation of zeolitic local atomic structures via electron microscopy is difficult owing to low electron irradiation resistance. Subsequently, their fundamental structure-property relationships remain unclear. A low-electron-dose imaging technique, optimum bright-field scanning transmission electron microscopy (OBF STEM), has recently been developed. It reconstructs images with a high signal-to-noise ratio and a dose efficiency approximately two orders of magnitude higher than that of conventional methods. Here, we performed low-dose atomic-resolution OBF STEM observations of two types of zeolite, effectively visualizing all atomic sites in their frameworks. In addition, we visualized the complex local atomic structure of the twin boundaries in a faujasite (FAU)-type zeolite and Na+ ions with low occupancy in eight-membered rings in a Na-Linde Type A (LTA) zeolite. The results of this study facilitate the characterization of local atomic structures in many electron beam-sensitive materials.

Real-space observation of a two-dimensional electron gas at semiconductor heterointerfaces.

Mobile charge carriers are essential components in high-performance, nano-engineered semiconductor devices. Employing charge carriers confined to heterointerfaces, the so-called two-dimensional electron gas, is essential for improving device performance. The real-space visualization of a two-dimensional electron gas at the nanometre scale is desirable. However, it is challenging to accomplish by means of electron microscopy due to an unavoidable strong diffraction contrast formation at the heterointerfaces. We performed direct, nanoscale electric field imaging across a GaN-based semiconductor heterointerface using differential phase contrast scanning transmission electron microscopy by suppressing diffraction contrasts. For both nearly the lattice-matched GaN/Al0.81In0.19N interface and pseudomorphic GaN/Al0.88In0.12N interface, the extracted quantitative electric field profiles show excellent agreement with profiles predicted using Poisson simulation. Furthermore, we used the electric field profiles to quantify the density and distribution of the two-dimensional electron gas across the heterointerfaces with nanometre precision. This study is expected to guide the real-space characterization of local charge carrier density and distribution in semiconductor devices.

Linear imaging theory for differential phase contrast and other phase imaging modes in scanning transmission electron microscopy.

We propose a linear imaging theory for differential phase contrast under the weak-phase-weak-amplitude object approximation. Contrast transfer functions are defined for thin and thick weak objects, and they successfully describe several imaging characteristics of differential phase contrast. We discuss the defocus dependence of the contrast for several examples: atomic resolution, a p-n junction, a heterointerface, and grain boundaries. Understanding the imaging characteristics helps in adjusting aberrations in DPC STEM.

Quantitative electric field mapping in semiconductor heterostructures via tilt-scan averaged DPC STEM.

Differential phase contrast (DPC) in scanning transmission electron microscopy can be used to visualize electric field distributions within specimens in real space. However, for electric field mapping in crystalline specimens, the concomitant diffraction contrast is seriously problematic. In particular, for heterostructures with large lattice distortions, such as GaN-based semiconductor devices, the diffraction contrast cannot be reduced using conventional methods such as DPC image acquisition under off-axis conditions. In the present study, the electric field imaging of heterostructures is shown to suppress the diffraction contrast by averaging multiple DPC signals, obtained under various beam-tilt conditions near the zone axis. The remaining diffraction contrast was quantitatively estimated through simulations. This technique was demonstrated to enable the quantitative evaluation of electric field distributions across GaN/AlGaN multi-heterostructures, with errors possibly attributed to the residual diffraction contrast.

Real-space visualization of intrinsic magnetic fields of an antiferromagnet.

Characterizing magnetic structures down to atomic dimensions is central to the design and control of nanoscale magnetism in materials and devices. However, real-space visualization of magnetic fields at such dimensions has been extremely challenging. In recent years, atomic-resolution differential phase contrast scanning transmission electron microscopy (DPC STEM)1 has enabled direct imaging of electric field distribution even inside single atoms2. Here we show real-space visualization of magnetic field distribution inside antiferromagnetic haematite (α-Fe2O3) using atomic-resolution DPC STEM in a magnetic-field-free environment3. After removing the phase-shift component due to atomic electric fields and improving the signal-to-noise ratio by unit-cell averaging, real-space visualization of the intrinsic magnetic fields in α-Fe2O3 is realized. These results open a new possibility for real-space characterization of many magnetic structures.

Experimental Observation of Long-Range Magnetic Order in Icosahedral Quasicrystals.

Quasicrystals (QCs), first discovered in 1984, generally do not exhibit long-range magnetic order. Here, we report on long-range magnetic order in the real icosahedral quasicrystals (i QCs) Au-Ga-Gd and Au-Ga-Tb. The Au65Ga20Gd15 i QC exhibits a ferromagnetic transition at TC = 23 K, manifested as a sharp anomaly in both magnetic susceptibility and specific heat measurements, along with an appearance of magnetic Bragg peak below TC. This is the first observation of long-range magnetic order in a real quasicrystal, in contrast to the spin-glass-like behaviors observed for the other magnetic quasicrystals found to date. Moreover, when Gd is replaced by Tb, i.e., for the Au65Ga20Tb15 i QC, a ferromagnetic behavior is still retained with TC = 16 K. Although the sharp anomaly in the specific heat observed for the Au65Ga20Gd15 i QC becomes broadened upon Tb substitution, neutron diffraction experiments clearly show marked development of magnetic Bragg peaks just below TC, indicating long-range magnetic order for the Au65Ga20Tb15 i QC also. Our findings can contribute to the further investigation of exotic magnetic orders formed on real quasiperiodic lattices with unprecedented highest global symmetry, i.e., icosahedral symmetry.

Nanometre imaging of Fe3GeTe2 ferromagnetic domain walls.

Fe3GeTe2 is a layered crystal which has recently been shown to maintain its itinerant ferromagnetic properties even when atomically thin. Here, differential phase contrast scanning transmission electron microscopy is used to investigate the domain structure in a Fe3GeTe2 cross-sectional lamella at temperatures ranging from 95 to 250 K and at nanometre spatial resolution. Below the experimentally determined Curie temperature (T C) of 191 K, stripe domains magnetised along 〈0001〉, bounded with 180◦ Bloch type domain walls, are observed, transitioning to mixed Bloch-Néel type where the cross-sectional thickness is reduced below 50 nm. When warming towards T C, these domains undergo slight restructuring towards uniform size, before abruptly fading at T C. Localised loss of ferromagnetic order is seen over time, hypothesised to be a frustration of ferromagnetic order from ambient oxidation and basal cracking, which could enable selective modification of the magnetic properties for device applications.

Ultra-high contrast STEM imaging for segmented/pixelated detectors by maximizing the signal-to-noise ratio.

Atomic-resolution low-dose imaging for beam-sensitive materials is one of the most challenging topics in electron microscopy research. In this study, we theoretically developed a new scanning transmission electron microscopy (STEM) imaging technique by maximizing the signal-to-noise ratio of an obtainable image under the weak phase object approximation (WPOA), which we will call optimum bright-field (OBF) imaging. OBF images are obtained by processing multiple images acquired by segmented/pixelated detectors through complex frequency filtering. This method has been confirmed through a systematic image simulation to be highly dose-efficient. Furthermore, we experimentally demonstrate the high dose efficiency of the OBF technique by visualizing the atomic structure in a lithium-ion battery material using a high-speed segmented detector. Furthermore, it was shown that OBF imaging is usable for real-time imaging, which makes low-dose observations of beam-sensitive materials much easier to achieve.

Toward quantitative electromagnetic field imaging by differential-phase-contrast scanning transmission electron microscopy.

Differential-phase-contrast scanning transmission electron microscopy (DPC STEM) is a technique to directly visualize local electromagnetic field distribution inside materials and devices at very high spatial resolution. Owing to the recent progress in the development of high-speed segmented and pixelated detectors, DPC STEM now constitutes one of the major imaging modes in modern aberration-corrected STEM. While qualitative imaging of electromagnetic fields by DPC STEM is readily possible, quantitative imaging by DPC STEM is still under development because of the several fundamental issues inherent in the technique. In this report, we review the current status and future prospects of DPC STEM for quantitative electromagnetic field imaging from atomic scale to mesoscopic scale.

Oxygen-Induced Reversible Sn-Dopant Deactivation between Indium Tin Oxide and Single-Crystalline Oxide Nanowire Leading to Interfacial Switching.

An impurity doping in semiconductors is an important irreversible process of manipulating the electrical properties of advanced electron devices. Here, we report an unusual reversible dopant activation/deactivation phenomenon, which emerges at an interface between indium tin oxide (ITO) and single-crystalline oxide channel. We found that the interface electrical resistance between ITO electrodes and single-crystalline oxide nanowire channel can be repeatedly switched between a metallic state and a near-insulative state by applying thermal treatments in air or vacuum. Interestingly, this electrical switching phenomenon disappears when the oxide nanowire changes from the single-crystalline structure to the lithography-defined polycrystalline structure. Atmosphere-controlled annealing experiments reveal that atmospheric oxygen induces repeatable change in the interfacial electrical resistance. Systematic investigations on metal cation species and channel crystallinity demonstrate that the observed electrical switching is related to an interface-specific reversible Sn-dopant activation/deactivation of ITO electrode in contact with a single-crystalline oxide channel.

Quantitative electric field mapping of a p-n junction by DPC STEM.

Local electromagnetic fields in a specimen is measured at high spatial resolutions using differential phase contrast (DPC) imaging in scanning transmission electron microscopy (STEM). According to previous studies, DPC signals can be quantified by measuring the center of mass of the diffraction pattern intensity and/or performing a deconvolution method based on a phase contrast transfer function (PCTF). However, when using a segmented detector, the field strength has been considerably underestimated for a very thick specimen. The main cause of the underestimation is assumed to be inelastic scattering, mainly bulk plasmon scattering. In this study, we develop a method to remove this inelastic scattering effect from segmented detector DPC signals by modifying the PCTF deconvolution method. Field quantification results using this new technique are compared with those using pixelated detector DPC and electron holography, and all results indicated good agreement within an error margin.

Magnetic-structure imaging in polycrystalline materials by specimen-tilt series averaged DPC STEM.

Differential phase contrast (DPC) imaging in scanning transmission electron microscopy is a technique to visualize electromagnetic field distribution inside specimens at high spatial resolution. However, diffraction contrast strongly hampers electromagnetic contrast in DPC images especially in polycrystalline samples. In this paper, we develop an imaging technique to effectively suppress diffraction contrast in DPC images. It is shown that a magnetic structure in a Nd-Fe-B permanent magnet was clearly visualized by averaging 64 DPC images with various specimen-tilt conditions. This is because the diffraction contrast in DPC images sensitively and randomly varies with crystal orientation and thus almost vanishes by averaging specimen-tilt image series. We further investigated two types of residual diffraction contrast in the tilt-series averaged DPC images: weak contrast inside grains and strong contrast at grain boundaries. We found that the former can be suppressed by averaging more DPC images, whereas the latter can be suppressed by the tilt-series averaging with wider range of specimen tilt. The tilt-series averaging method enables DPC to visualize electromagnetic structures even inside polycrystalline materials.

One-pot synthesis of cyclic oligosaccharides by the polyglycosylation of monothioglycosides.

Cyclic oligosaccharides such as cyclodextrins (CyDs) have been known as excellent host molecules for the inclusion of various organic guest molecules. The development of new synthetic methods for preparing cyclic oligosaccharides from simple and readily available glycosyl donors would be highly desirable, since the current traditional synthetic routes include multiple reaction steps (glycosylation reactions and deprotections). We herein report on the synthesis of cyclic oligosaccharides by polyglycosylation of monothioglycosides, typically, 2,3,4-protected 1-thioglycosides. A series of promoters and solvents were tested for the glycosylation of thiogalactosides that contain a hydroxy group at the 6-position, and glycosylation using a N-iodosuccinimide (NIS)/trimethylsilyl triflate (TMSOTf) promoter system in dichloromethane afforded cyclic oligosaccharides which consist of tri~penta galactosides containing repeating ß-(1→6) glycosidic linkage as major products, as evidenced by a single crystal X-ray structure analysis of the cyclic tetragalactoside. The effect of reaction temperature and reactant concentrations on the glycosylation products was also investigated. The cyclic glucosides were obtained by the glycosylation of the thioglucosides. Moreover, protecting groups of the synthesized cyclic tetragalactoside were removed to obtain deprotected cyclic tetragalactoside.

Redox-Inactive CO2 Determines Atmospheric Stability of Electrical Properties of ZnO Nanowire Devices through a Room-Temperature Surface Reaction.

Emerging interactive electronics for the Internet of Things era inherently require the long-term stability of semiconductor devices exposed to air. Nanostructured metal oxides are promising options for such atmospherically stable semiconductor devices owing to their inherent stability in air. Among various oxide nanostructures, ZnO nanowires have been the most intensively studied for electrical and optical device applications. Here, we demonstrate a strategy for achieving the atmospheric electrical stability of ZnO nanowire devices. Although the chemically active oxygen and water in air are strong candidates for affecting the electrical stability of nanoscale metal oxides, we found that the ppm-level redox-inactive CO2 in air critically determines the atmospheric electrical stability of hydrothermally grown single-crystalline ZnO nanowires. A series of analyses using atmosphere-controlled electrical characterization of single nanowire devices, Fourier transform infrared spectroscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy consistently revealed that atmospheric CO2 reacts substantially with the ZnO nanowire surfaces, even at room temperature, to form an electrically insulative zinc carbonate thin layer. The formation of this layer essentially limits the atmospheric electrical stability of the ZnO nanowire devices. Based on this surface carbonation mechanism, we propose a strategy to suppress the detrimental surface reaction, which is based on (1) reducing the density of surface hydroxyl groups and (2) improving the nanowire crystallinity by thermal pretreatment. This approach improves the atmospheric electrical stability to at least 40 days in air.

High contrast STEM imaging for light elements by an annular segmented detector.

Annular bright-field scanning transmission electron microscopy (ABF STEM) has been actively used to directly observe the light element atoms inside materials and devices. However, the detector angle condition for conventional ABF STEM has been empirically selected and thus is not always optimized for observing ultra-light element atoms such as hydrogen and lithium atoms. In this study, the detector conditions for ABF STEM were reexamined by calculating a new type of phase contrast transfer function (PCTF) for an annularly segmented detector to maximize the image contrast of ultra-light element atoms such as lithium. Using this new PCTF, an improved detector geometry for observing lithium atoms is demonstrated, which is confirmed by the image simulations and experiments in several types of lithium cathode materials.

Unusual Oxygen Partial Pressure Dependence of Electrical Transport of Single-Crystalline Metal Oxide Nanowires Grown by the Vapor-Liquid-Solid Process.

In general, the electrical conductivities of n-type semiconducting metal oxide nanostructures increase with the decrease in the oxygen partial pressure during crystal growth owing to the increased number of crystal imperfections including oxygen vacancies. In this paper, we report an unusual oxygen partial pressure dependence of the electrical conductivity of single-crystalline SnO2 nanowires grown by a vapor-liquid-solid (VLS) process. The electrical conductivity of a single SnO2 nanowire, measured using the four-probe method, substantially decreases by 2 orders of magnitude when the oxygen partial pressure for the crystal growth is reduced from 10-3 to 10-4 Pa. This contradicts the conventional trend of n-type SnO2 semiconductors. Spatially resolved single-nanowire electrical transport measurements, microstructure analysis, plane-view electron energy-loss spectroscopy, and molecular dynamics simulations reveal that the observed unusual oxygen partial pressure dependence of the electrical transport is attributed to the intrinsic differences between the two crystal growth interfaces (LS and VS interfaces) in the critical nucleation of the crystal growth and impurity incorporation probability as a function of the oxygen partial pressure. The impurity incorporation probability at the LS interface is always lower than that at the VS interface, even under reduced oxygen partial pressures.

Direct electric field imaging of graphene defects.

Material properties are sensitive to atomistic structure defects such as vacancies or impurities, and it is therefore important to determine not only the local atomic configuration but also their chemical bonding state. Annular dark-field scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy has been utilized to investigate the local electronic structures of such defects down to the level of single atoms. However, it is still challenging to two-dimensionally map the local bonding states, because the electronic fine-structure signal from a single atom is extremely weak. Here, we show that atomic-resolution differential phase-contrast STEM imaging can directly visualize the anisotropy of single Si atomic electric fields in monolayer graphene. We also visualize the atomic electric fields of Stone-Wales defects and nanopores in graphene. Our results open the way to directly examine the local chemistry of the defective structures in materials at atomistic dimensions.