Takehito Seki

Electric field imaging of single atoms

In scanning transmission electron microscopy (STEM), single atoms can be imaged by detecting electrons scattered through high angles using post-specimen, annular-type detectors. Recently, it has been shown that the atomic-scale electric field of both the positive atomic nuclei and the surrounding negative electrons within crystalline materials can be probed by atomic-resolution differential phase contrast STEM. Here we demonstrate the real-space imaging of the (projected) atomic electric field distribution inside single Au atoms, using sub-Å spatial resolution STEM combined with a high-speed segmented detector. We directly visualize that the electric field distribution (blurred by the sub-Å size electron probe) drastically changes within the single Au atom in a shape that relates to the spatial variation of total charge density within the atom. Atomic-resolution electric field mapping with single-atom sensitivity enables us to examine their detailed internal and boundary structures.

Local cluster symmetry of a highly ordered quasicrystalline Al58Cu26Ir16 extracted through multivariate analysis of STEM images

The structure of a highly ordered Al58Cu26Ir16 decagonal quasicrystal (d-QC), which is constructed by a periodic stack of quasiperiodic atomic planes, was investigated using aberration-corrected scanning transmission electron microscopy. The entire quasiperiodic structure can be well described based on the pentagonal Penrose lattice decorated with a decagonal columnar cluster 2 nm across, and the individual clusters apparently showed up with localized atomic disorder to various degree that blurs the underlying cluster symmetry. Multivariate analysis of the cluster images with principal component analysis has successfully extracted two fundamental clusters, which are with definite mirror and 10-fold-rotation symmetries; this is the first solid example of the d-QC composed of multiple fundamental clusters with different symmetry. Consequently, it is found that all the observed variations can be reasonably interpreted by a linear combination between these two fundamental clusters of mirror and 10-fold symmetries, indicating that the possible atomic disorder is strongly restricted by these particular symmetries. Characteristic distributions of the mirror/10-fold clusters on the pentagonal Penrose lattice are also described.

Direct Visualization of Local Electromagnetic Field Structures by Scanning Transmission Electron Microscopy

The functional properties of materials and devices are critically determined by the electromagnetic field structures formed inside them, especially at nanointerface and surface regions, because such structures are strongly associated with the dynamics of electrons, holes and ions. To understand the fundamental origin of many exotic properties in modern materials and devices, it is essential to directly characterize local electromagnetic field structures at such defect regions, even down to atomic dimensions. In recent years, rapid progress in the development of high-speed area detectors for aberration-corrected scanning transmission electron microscopy (STEM) with sub-angstrom spatial resolution has opened new possibilities to directly image such electromagnetic field structures at very high-resolution. In this Account, we give an overview of our recent development of differential phase contrast (DPC) microscopy for aberration-corrected STEM and its application to many materials problems. In recent years, we have developed segmented-type STEM detectors which divide the detector plane into 16 segments and enable simultaneous imaging of 16 STEM images which are sensitive to the positions and angles of transmitted/scattered electrons on the detector plane. These detectors also have atomic-resolution imaging capability. Using these segmented-type STEM detectors, we show DPC STEM imaging to be a very powerful tool for directly imaging local electromagnetic field structures in materials and devices in real space. For example, DPC STEM can clearly visualize the local electric field variation due to the abrupt potential change across a p-n junction in a GaAs semiconductor, which cannot be observed by normal in-focus bright-field or annular type dark-field STEM imaging modes. DPC STEM is also very effective for imaging magnetic field structures in magnetic materials, such as magnetic domains and skyrmions. Moreover, real-time imaging of electromagnetic field structures can now be realized through very fast data acquisition, processing, and reconstruction algorithms. If we use DPC STEM for atomic-resolution imaging using a sub-angstrom size electron probe, it has been shown that we can directly observe the atomic electric field inside atoms within crystals and even inside single atoms, the field between the atomic nucleus and the surrounding electron cloud, which possesses information about the atomic species, local chemical bonding and charge redistribution between bonded atoms. This possibility may open an alternative way for directly visualizing atoms and nanostructures, that is, seeing atoms as an entity of electromagnetic fields that reflect the intra- and interatomic electronic structures. In this Account, the current status of aberration-corrected DPC STEM is highlighted, along with some applications in real material and device studies.

Quantitative electric field mapping in thin specimens using a segmented detector: Revisiting the transfer function for differential phase contrast

Differential phase contrast in scanning transmission electron microscopy can visualize local electromagnetic fields inside specimens. The contrast derived from first moments, the so-called center of mass, of the diffraction patterns for each probe position can be quantitatively related to the local electromagnetic field under the phase object approximation. While only approximate first moments can be obtained with a segmented detector, in weak phase objects the fields can be accurately quantified on the basis of a phase contrast transfer function. Through systematic image simulations we further show that the quantification based on the approximated first moment is a good approximation also for strong phase objects.

True Vapor–Liquid–Solid Process Suppresses Unintentional Carrier Doping of Single Crystalline Metal Oxide Nanowires

Single crystalline nanowires composed of semiconducting metal oxides formed via a vapor-liquid-solid (VLS) process exhibit an electrical conductivity even without an intentional carrier doping, although these stoichiometric metal oxides are ideally insulators. Suppressing this unintentional doping effect has been a challenging issue not only for metal oxide nanowires but also for various nanostructured metal oxides toward their semiconductor applications. Here we demonstrate that a pure VLS crystal growth, which occurs only at liquid-solid (LS) interface, substantially suppresses an unintentional doping of single crystalline SnO2 nanowires. By strictly tailoring the crystal growth interface of VLS process, we found the gigantic difference of electrical conduction (up to 7 orders of magnitude) between nanowires formed only at LS interface and those formed at both LS and vapor-solid (VS) interfaces. On the basis of investigations with spatially resolved single nanowire electrical measurements, plane-view electron energy-loss spectroscopy, and molecular dynamics simulations, we reveal the gigantic suppression of unintentional carrier doping only for the crystal grown at LS interface due to the higher annealing effect at LS interface compared with that grown at VS interface. These implications will be a foundation to design the semiconducting properties of various nanostructured metal oxides.

Boundary-artifact-free determination of potential distribution from differential phase contrast signals

The differential phase contrast (DPC) imaging in STEM was mainly used for a study of magnetic material in a medium resolution. An ideal DPC signals give the center of mass of the diffraction pattern, which is proportional to an electric field. Recently, the possibility of the DPC imaging at atomic resolution was demonstrated. Thus, the DPC imaging opens up the possibility to observe the object phase that is proportional to the electrostatic potential.In this report we investigate the numerical procedures to obtain the object phase from the two perpendicular DPC signals. Specifically, we demonstrate that the discrete cosine transform (DCT) is the method to solve the Poisson equation, since we can use the Neumann boundary condition directly specified by the DPC signals. Furthermore, based on the fast Fourier transform (FFT) of an extended DPC signal we introduce the scheme that gives an equivalent result that is obtained with the DCT. The results obtained with the DCT and extended FFT method are superior to the results obtained with commonly used FFT. In addition, we develop real-time integration schemes that update the result with the progress of the scan. Our real-time integration gives the reasonable result, and can be used in a view mode. We demonstrate that our numerical procedures work excellently with the experimental DPC signals obtained from SrTiO3 single crystal.

Direct Determination of Atomic Structure and Magnetic Coupling of Magnetite Twin Boundaries

Clarifying how the atomic structure of interfaces/boundaries in materials affects the magnetic coupling nature across them is of significant academic value and will facilitate the development of state-of-the-art magnetic devices. Here, by combining atomic-resolution transmission electron microscopy, atomistic spin-polarized first-principles calculations, and differential phase contrast imaging, we conduct a systematic investigation of the atomic and electronic structures of individual Fe3O4 twin boundaries (TBs) and determine their concomitant magnetic couplings. We demonstrate that the magnetic coupling across the Fe3O4 TBs can be either antiferromagnetic or ferromagnetic, which directly depends on the TB atomic core structures and resultant electronic structures within a few atomic layers. Revealing the one-to-one correspondence between local atomic structures and magnetic properties of individual grain boundaries will shed light on in-depth understanding of many interesting magnetic behaviors of widely used polycrystalline magnetic materials, which will surely promote the development of advanced magnetic materials and devices.

Direct observations of local electronic states in an Al-based quasicrystal by STEM-EELS

Most quasicrystals (QCs) reveal pseudogaps in their density of states around Fermi level, and hence the stability of QCs have been discussed in terms of energetic gains in electron systems. In fact, many QCs have been discovered by tuning valence electron density based on Hume-Rothery rule. Therefore, understanding electronic structures in QCs may provide an important clue for their stabilization mechanism. Generally, it has been frequently discussed based on an interaction between Fermi surface and Brillouin zone boundary within the framework of nearly free electron model, which is believed to be an underlying physics of a Hume-Rotherys empirical criteria. However the hybridization effect also stabilize electron system, particularly in Al-transition metal system, in which a lot of quasicrystalline phases were discovered. Therefore, the electronic structures of QCs have not yet been fully understood, whereas their atomic structures have been studied well in terms of configuration entropy by scanning transmission electron microscopy (STEM) [1]. In the present work, we investigate local electronic states in Al-based QCs using electron energy loss spectroscopy (EELS) combined with STEM, by which EELS spectra with sub-Å probe and atomic structure can be obtained simultaneously. We report STEM-EELS results on AlCuIr decagonal phases [2].jmicro;63/suppl_1/i17-a/DFU069F1F1DFU069F1Fig. 1.Core-loss edges obtained from cluster-centers and cluster-edges. Al L1 (left) Ir O23, Ir N67 (center) and Cu L23 (right). Principal components analysis clearly shows up the atomic-site dependence of plasmon loss spectra in a two-dimensional map. Qualitatively, there seems to be certain correlations between the plasmon peaks and the core-loss edges, Al L1, Ir O23, Ir N67 and Cu L23, all of which reveal different behaviors at the cluster centers and the edges (Fig. 1). All results indicate the cluster centers have metallic states and the cluster edges have covalent states in comparison. First-principles calculations confirm the unusual electronic state. On the basis of the calculated DOS and charge-density map, we conclude Al-Ir pairs, which are mainly located at the cluster edges, hybridize their orbitals and Cu atoms are localized at cluster center without hybridization. We analyze a distribution of the hybridized orbitals by Fourier transformation of electron localization function. The distribution seems like a 10-fold standing wave with Fermi wave length. It suggests that the Hume-Rothery mechanism works even when hybridization effect mainly contributes to pseudogap formation. In other words, global distribution of hybridized orbitals is important to stabilize structures whereas usually only local atomic configurations are discussed. Moreover, in the 10-fold standing wave, no distinct peak appears at the cluster centers. It means hybridized orbitals located at cluster centers are unable to contribute to the Hume-Rothery mechanism. It may be the reason why the metallic regions appear at the cluster centers.

Integrated contrast-transfer-function for aberration-corrected phase-contrast STEM

We describe the optical conditions that are essentially necessary for phase-contrast imaging with aberration-corrected scanning transmission electron microscopy (STEM), whose depth of field has reached almost comparable to the specimen thickness. For such state-of-the-art STEM, contrast-transfer-function (CTF) should be defined not solely for the projected potential but multiply for each wavefront during the beam propagation across the specimen thickness; an integration of multiple CTFs (iCTF). We show that the iCTF concept explains fairly well characteristic annular-bright-field (ABF) imaging behaviors of heavy/light atom sites against the defocus changes, and also provide notable concerns on possible artifacts that arise from different imaging-depth dependences between the heavy/light atom sites.

Theoretical framework of statistical noise in scanning transmission electron microscopy

Statistical noise, or shot noise, dominates experimental image quality in scanning transmission electron microscopy because efficiencies of recent detectors are close to ideal. We establish a general framework for the statistical noise taking into account two random processes in the electron incidence and the electron scattering. Using this framework, in terms of signal-to-noise ratio, we evaluate several STEM coherent imaging techniques: annular bright field, enhanced annular bright field, differential phase contrast, and ptychography and show that ptychography is the most efficient imaging for weak phase objects. Moreover, we find that normalizing annular-bright-field image by total electron count in the bright field significantly suppress the noise.