Mitsuhiro Saito

Element-selective imaging of atomic columns in a crystal using STEM and EELS

Microstructure characterization has become indispensable to the study of complex materials, such as strongly correlated oxides, and can obtain useful information about the origin of their physical properties. Although atomically resolved measurements have long been possible, an important goal in microstructure characterization is to achieve element-selective imaging at atomic resolution. A combination of scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) is a promising technique for atomic-column analysis. However, two-dimensional analysis has not yet been performed owing to several difficulties, such as delocalization in inelastic scattering or instrumentation instabilities. Here we demonstrate atomic-column imaging of a crystal specimen using localized inelastic scattering and a stabilized scanning transmission electron microscope. The atomic columns of La, Mn and O in the layered manganite La1.2Sr1.8Mn2O7 are visualized as two-dimensional images.

Atom-resolved imaging of ordered defect superstructures at individual grain boundaries

The ability to resolve spatially and identify chemically atoms in defects would greatly advance our understanding of the correlation between structure and property in materials. This is particularly important in polycrystalline materials, in which the grain boundaries have profound implications for the properties and applications of the final material. However, such atomic resolution is still extremely difficult to achieve, partly because grain boundaries are effective sinks for atomic defects and impurities, which may drive structural transformation of grain boundaries and consequently modify material properties. Regardless of the origin of these sinks, the interplay between defects and grain boundaries complicates our efforts to pinpoint the exact sites and chemistries of the entities present in the defective regions, thereby limiting our understanding of how specific defects mediate property changes. Here we show that the combination of advanced electron microscopy, spectroscopy and first-principles calculations can provide three-dimensional images of complex, multicomponent grain boundaries with both atomic resolution and chemical sensitivity. The high resolution of these techniques allows us to demonstrate that even for magnesium oxide, which has a simple rock-salt structure, grain boundaries can accommodate complex ordered defect superstructures that induce significant electron trapping in the bandgap of the oxide. These results offer insights into interactions between defects and grain boundaries in ceramics and demonstrate that atomic-scale analysis of complex multicomponent structures in materials is now becoming possible.

Selective Detection of Formaldehyde Gas Using a Cd-Doped TiO(2)-SnO(2) Sensor.

We report the microstructure and gas-sensing properties of a nonequilibrium TiO2-SnO2 solid solution prepared by the sol-gel method. In particular, we focus on the effect of Cd doping on the sensing behavior of the TiO2-SnO2 sensor. Of all volatile organic compound gases examined, the sensor with Cd doping exhibits exclusive selectivity as well as high sensitivity to formaldehyde, a main harmful indoor gas. The key gas-sensing quantities, maximum sensitivity, optimal working temperature, and response and recovery time, are found to meet the basic industrial needs. This makes the Cd-doped TiO2-SnO2 composite a promising sensor material for detecting the formaldehyde gas.

Micropolarizer made of the anodized alumina film

A novel micropolarizer has been fabricated from alumina and nickel by means of anodization and electroplating techniques. Making use of the anisotropic microstructure of the anodized alumina film, a lattice of nickel columns is easily constructed in the film, which works as a wire grid type polarizer. The fabricated polarizer has achieved an extinction ratio larger than 30 dB at the wavelength of 1.3 μm.

Dimensionality-driven insulator–metal transition in A-site excess non-stoichiometric perovskites

Coaxing correlated materials to the proximity of the insulator–metal transition region, where electronic wavefunctions transform from localized to itinerant, is currently the subject of intensive research because of the hopes it raises for technological applications and also for its fundamental scientific significance. In general, this tuning is achieved by either chemical doping to introduce charge carriers, or external stimuli to lower the ratio of Coulomb repulsion to bandwidth. In this study, we combine experiment and theory to show that the transition from well-localized insulating states to metallicity in a Ruddlesden-Popper series, La0.5Srn+1−0.5TinO3n+1, is driven by intercalating an intrinsically insulating SrTiO3 unit, in structural terms, by dimensionality n. This unconventional strategy, which can be understood upon a complex interplay between electron–phonon coupling and electron correlations, opens up a new avenue to obtain metallicity or even superconductivity in oxide superlattices that are normally expected to be insulators.

Polymorphism of dislocation core structures at the atomic scale

Dislocation defects together with their associated strain fields and segregated impurities are of considerable significance in many areas of materials science. However, their atomic-scale structures have remained extremely challenging to resolve, limiting our understanding of these ubiquitous defects. Here, by developing a complex modelling approach in combination with bicrystal experiments and systematic atomic-resolution imaging, we are now able to pinpoint individual dislocation cores at the atomic scale, leading to the discovery that even simple magnesium oxide can exhibit polymorphism of core structures for a given dislocation species. These polymorphic cores are associated with local variations in strain fields, segregation of defects, and electronic states, adding a new dimension to understanding the properties of dislocations in real materials. The findings advance our fundamental understanding of basic behaviours of dislocations and demonstrate that quantitative prediction and characterization of dislocations in real materials is possible.

Regulating Infrared Photoresponses in Reduced Graphene Oxide Phototransistors by Defect and Atomic Structure Control

Defects play significant roles in properties of graphene and related device performances. Most studies of defects in graphene focus on their influences on electronic or luminescent optical properties, while controlling infrared optoelectronic performance of graphene by defect engineering remains a challenge. In the meantime, pristine graphene has very low infrared photoresponses of ~0.01 A/W due to fast photocarrier dynamics. Here we report regulating infrared photoresponses in reduced graphene oxide phototransistors by defect and atomic structure control for the first time. The infrared optoelectronic transport and photocurrent generation are significantly influenced and well controlled by oxygenous defects and structures in reduced graphene oxide. Moreover, remarkable infrared photoresponses are observed in photoconductor devices based on reduced graphene oxide with an external responsivity of ~0.7 A/W, at least over one order of magnitude higher than that from pristine graphene. External quantum efficiencies of infrared devices reach ultrahigh values of ~97%, which to our knowledge is one of the best efficiencies for infrared photoresponses from nonhybrid, pure graphene or graphene-based derivatives. The flexible infrared photoconductor devices demonstrate no photoresponse degradation even after 1000 bending tests. The results open up new routes to control optoelectronic behaviors of graphene for high-performance devices.

Atomic-scale structure and electronic property of the LaAlO3/TiO2 interface

Combining advanced transmission electron microscopy with high-precision first-principles calculation, atomic-scale structures of the LaAlO3/TiO2 interface are investigated and bridged to their electronic property at the atomic level. Experimentally, the deposited TiO2 thin film is demonstrated to have an anatase phase and bond directly to the LaAlO3 substrate in an epitaxial, coherent, and atomically abrupt fashion. The atomic-resolution microscopic images reveal that the interface can be terminated with either AlO2 or LaO layer, which is predicted in theory to exhibit a semiconducting or metallic nature at interface, respectively. By applying several analytic methods, we characterize carefully the electronic structure and determine interfacial bonding to be of a mixed covalent-ionic character. The combined experimental and theoretical studies performed shed light on the complex atomic and electronic structures of the buried interface, which are fundamental for understanding the promising properties of fu...

Local crystal structure analysis with 10-pm accuracy using scanning transmission electron microscopy

We demonstrate local crystal structure analysis based on annular dark-field (ADF) imaging in scanning transmission electron microscopy (STEM). Using a stabilized STEM instrument and customized software, we first realize high accuracy of elemental discrimination and atom-position determination with a 10-pm-order accuracy, which can reveal major cation displacements associated with a variety of material properties, e.g. ferroelectricity and colossal magnetoresistivity. A-site ordered/disordered perovskite manganites Tb(0.5)Ba(0.5)MnO(3) are analysed; A-site ordering and a Mn-site displacement of 12 pm are detected in each specific atomic column. This method can be applied to practical and advanced materials, e.g. strongly correlated electron materials.

Structural characterization and iron detection at Σ3 grain boundaries in multicrystalline silicon

Transition-metal impurities gettered by grain boundaries (GBs) act as recombination centers of carriers and are regarded to be harmful defects in multicrystalline silicon (mc-Si) used for solar cell production. In this study, gettering of iron by Σ3 GBs in mc-Si was investigated by using transmission electron microscopy and annular dark-field (ADF) imaging. In the clean specimen, both straight Σ3{111} GB and zig-zag Σ3{110}, {112} GBs are not electrically active, whereas the zig-zag Σ3{110}, {112} GBs become electrically active when contaminated with iron. ADF images have shown that iron is preferentially gettered at the irregular parts of zig-zag Σ3{112} GB and exists in the form of clusters. The iron gettering abilities of these Σ3 GBs have been discussed.