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.

Real-Space Observation of Topological Defects in Extended Skyrmion-Strings.

Exotic topological spin textures such as emergent magnetic monopole/anti-monopoles (hedgehog/anti-hedgehog) in the metastable extended skyrmion-strings attract much attention to the fundamental physics owing to their novel electromagnetic properties. However, the direct imaging of such spin textures is lacking. Here, we report the real-space observation of emergent magnetic monopoles involved in extended skyrmion-strings by Lorentz transmission electron microscopy (TEM) in combination with micromagnetic simulations. The in-plane extended skyrmion-strings are observed directly by Lorentz TEM to accompany the topological hedgehog-like defect, where the skyrmion-string terminates or merges with another skyrmion-string, as well as the surface-related defects where skyrmion-string bends 90° and ends on the surface. We also demonstrate the transformation of a metastabilized lattice of out-of-plane short skyrmion-strings into an in-plane array of extended skyrmion-strings by tuning the magnitude of oblique fields in a room-temperature helimagnet, revealing the stability of such topological spin textures and the possibility to control them.

Plasmonic p-n Junction for Infrared Light to Chemical Energy Conversion.

Infrared (IR) light represents an untapped energy source accounting for almost half of all solar energy. Thus, there is a need to develop systems to convert IR light to fuel and make full use of this plentiful resource. Herein, we report photocatalytic H2 evolution driven by near- to shortwave-IR light (up to 2500 nm) irradiation, based on novel CdS/Cu7S4 heterostructured nanocrystals. The apparent quantum yield reached 3.8% at 1100 nm, which exceeds the highest efficiencies achieved by IR light energy conversion systems reported to date. Spectroscopic results revealed that plasmon-induced hot-electron injection at p-n heterojunctions realizes exceptionally long-lived charge separation (>273 µs), which results in efficient IR light to hydrogen conversion. These results pave the way for the exploration of undeveloped low-energy light for solar fuel generation.

Atomic number dependence of Z contrast in scanning transmission electron microscopy.

Annular dark-field (ADF) imaging by scanning transmission electron microscopy (STEM) is a common technique for material characterization with high spatial resolution. It has been reported that ADF signal is proportional to the nth power of the atomic number Z, i.e., the Z contrast in textbooks and papers. Here we first demonstrate the deviation from the power-law model by quantitative experiments of a few 2D materials (graphene, MoS2 and WS2 monolayers). Then we elucidate ADF signal of single atoms using simulations to clarify the cause of the deviation. Two major causes of the deviation from the power-law model will be pointed out. The present study provides a practical guideline for the usage of the conventional power-law model for ADF imaging.

Quantitative annular dark-field imaging of single-layer graphene-II: atomic-resolution image contrast.

We have investigated how accurately atomic-resolution annular dark-field (ADF) images match between experiments and simulations to conduct more reliable crystal structure analyses. Quantitative ADF imaging, in which the ADF intensity at each pixel represents the fraction of the incident probe current, allows us to perform direct comparisons with simulations without the use of fitting parameters. Although the conventional comparison suffers from experimental uncertainties such as an amorphous surface layer and specimen thickness, in this study we eliminated such uncertainties by using a single-layer graphene as a specimen. Furthermore, to reduce image distortion and shot noises in experimental images, multiple acquisitions with drift correction were performed, and the atomic ADF contrast was quantitatively acquired. To reproduce the experimental ADF contrast, we used three distribution functions as the effective source distribution in simulations. The optimum distribution function and its full-width at half-maximum were evaluated by measuring the residuals between the experimental and simulated images. It was found that the experimental images could be explained well by a linear combination of a Gaussian function and a Lorentzian function with a longer tail than the Gaussian function.

Synthesis of single-walled carbon nanotubes on graphene layers.

Here, we report the synthesis of semiconducting single-walled carbon nanotubes with a narrow diameter distribution between 0.67 and 1.1 nm via chemical vapour deposition on graphene layers using Pt catalysts.

Single adatom dynamics at monatomic steps of free-standing few-layer reduced graphene.

Steps and their associated adatoms extensively exist and play prominent roles in affecting surface properties of materials. Such impacts should be especially pronounced in two-dimensional, atomically-thin membranes like graphene. However, how single adatom behaves at monatomic steps of few-layer graphene is still illusive. Here, we report dynamics of individual adatom at monatomic steps of free-standing few-layer reduced graphene under the electron beam radiations, and demonstrate the prevalent existence of monatomic steps even down to unexpectedly ultrasmall lateral size of a circular diameter of ~5 Å. Single adatom prefers to stay at the edges of the atomic steps of few-layer reduced graphene and evolve with the steps. Moreover, we also find that how the single adatom behaves at atomic step edges can be remarkably influenced by the type of adatoms and step edges. Such single adatoms at monatomic steps and ultrasmall atomic steps open up a new window for surface physics and chemistry for graphene-based as well as other two-dimensional materials.

Quantitative evaluation of temporal partial coherence using 3D Fourier transforms of through-focus TEM images.

We evaluate the temporal partial coherence of transmission electron microscopy (TEM) using the three-dimensional (3D) Fourier transform (FT) of through-focus images. Young's fringe method often indicates the unexpected high-frequency information due to non-linear imaging terms. We have already used the 3D FT of axial (non-tilted) through-focus images to reduce the effect of non-linear terms on the linear imaging term, and demonstrated the improvement of monochromated lower-voltage TEM performance [Kimoto et al., Ultramicroscopy 121 (2012) 31-39]. Here we apply the 3D FT method with intentionally tilted incidence to normalize various factors associated with a TEM specimen and an imaging device. The temporal partial coherence of two microscopes operated at 30, 60 and 80 kV is evaluated. Our method is applicable to such cases where the non-linear terms become more significant in lower acceleration voltage or aberration-corrected high spatial resolution TEM.

Assessment of lower-voltage TEM performance using 3D Fourier transform of through-focus series.

We assess the imaging performance of a transmission electron microscopy (TEM) system operated at a relatively low acceleration voltage using the three-dimensional (3D) Fourier transform of through-focus images. Although a single diffractogram and the Thon diagram cannot distinguish between the linear and non-linear TEM imaging terms, the 3D Fourier transform allows us to evaluate linear imaging terms, resulting in a conclusive assessment of TEM performance. Using this method, information transfer up to 98 pm is demonstrated for an 80 kV TEM system equipped with a spherical aberration corrector and a monochromator. We also revisit the Young fringe method in the light of the 3D Fourier transform, and have found a considerable amount of non-linear terms in Young fringes at 80 kV even from a typical standard specimen, such as an amorphous Ge thin film.

Entanglement-free fibrils of aligned polyacetylene films that produce single nanofibers.

An aligned polyacetylene (PA) film was synthesized in a macroscopically-aligned nematic liquid crystal (N-LC) solvent using a gravity-flow method. Long and single nanofibers of less than 100 nm in radius were successfully prepared by ultrasonication of the aligned PA film immersed in ethanol. The usual PA film was synthesized in an isotropic solvent, such as toluene, only yielding short and non-dispersed fibers after the ultrasonication due to the entangled fibril morphology. Entanglement-free fibrils of the aligned PA were well-separated into single fibrils through ultrasonication, even without a surfactant.

Local crystal structure analysis with several picometer precision using scanning transmission electron microscopy.

We report a local crystal structure analysis with a high precision of several picometers on the basis of scanning transmission electron microscopy (STEM). Advanced annular dark-field (ADF) imaging has been demonstrated using software-based experimental and data-processing techniques, such as the improvement of signal-to-noise ratio, the reduction of image distortion, the quantification of experimental parameters (e.g., thickness and defocus) and the resolution enhancement by maximum-entropy deconvolution. The accuracy in the atom position measurement depends on the validity of the incoherent imaging approximation, in which an ADF image is described as the convolution between the incident probe profile and scattering objects. Although the qualitative interpretation of ADF image contrast is possible for a wide range of specimen thicknesses, the direct observation of a crystal structure with deep-sub-angstrom accuracy requires a thin specimen (e.g., 10nm), as well as observation of the structure image by conventional high-resolution transmission electron microscopy.

Synthesis of orthorhombic Mo-V-Sb oxide species by assembly of pentagonal Mo6O21 polyoxometalate building blocks.

Mix and match: The pentagonal [Mo(6)O(21)](n-) polyoxomolybdate building block assembles with other sources of Mo, V, and Sb ions to form an orthorhombic Mo-V-Sb oxide. The first single-crystal X-ray analysis of an orthorhombic Mo-V-based oxide, a promising catalyst for light alkane selective oxidation known as the "M1 phase", revealed the structure of the compound.

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.

Helical carbon and graphitic films prepared from iodine-doped helical polyacetylene film using morphology-retaining carbonization.

In this communication, we report a novel preparation of the helical carbon nanofibril-fabricated thin film from the iodine-doped filmy helical polyacetylene through a carbonization process. Carbonization of the helical polyacetylene films by way of iodine doping is found to afford carbon and graphitic films completely preserving morphologies and even helical nanofibril structures.

Tubular-shaped nanocarbons prepared from polyaniline synthesized by a self-assembly process and their electrical conductivity.

A tubular-shaped polyaniline less than 5 microm in length and 170 nm in outer diameter was synthesized by a self-assembly process using D-camphorsulfonic acid as a dopant. A tubular-shaped nanocarbon was prepared from the tubular-shaped polyaniline by means of pyrolysis at 1000 degrees C in argon gas. The structural and electrical properties of the resultant tubular-shaped nanocarbons were investigated using Raman scattering spectrum, X-ray diffraction measurements, scanning and transmission electron microscopes, and a low resistivity meter. The tubular-shaped nanocarbons are very short in length and are an amorphous state. The short length and amorphous tubular-shaped nanocarbon were crystallized to some extent by heat-treatment at 2600 degrees C. The tubular-shaped nanocarbons mentioned in this work are appropriate for mass production, compared to the well-known multi-walled carbon nanotubes. The electrical conductively of the tubular-shaped polyaniline was remarkably improved by the carbonization and was enhanced by the heat-treatment.

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.

Spinel-to-CaFe2O4-type structural transformation in LiMn2O4 under high pressure.

A new form of LiMn2O4 is reported. The structure is the CaFe2O4-type and 6% denser than the spinel. The structure transformation was achieved by heating at 6 GPa. Analysis of the neutron diffraction pattern confirmed an average of the structure; the unit cell was orthorhombic at a = 8.8336(5) angstroms, b = 2.83387(18) angstroms, and c = 10.6535(7) angstroms (Pnma). Electron diffraction patterns indicated an order of superstructure 3a x b x c, which might be initiated by Li vacancies. The exact composition is estimated at Li(0.92)Mn2O4 from the structure analysis and quantity of intercalated Li. The polycrystalline CaFe2O4-type compound showed semiconducting-like characters over the studied range above 5 K. The activation energy was reduced to approximately 0.27 eV from approximately 0.40 eV at the spinel form, suggesting a possible enhancement of hopping mobility. Magnetic and specific-heat data indicated a magnetically glassy transition at approximately 10 K. As the CaFe2O4-type transition was observed for the mineral MgAl2O4, hence the new form of the lithium manganese oxide would provide valuable opportunities to study not only the magnetism of strongly correlated electrons but also the thermodynamics of the phase transition in the mantle.

BiScO3: centrosymmetric BiMnO3-type oxide.

With neutron powder diffraction, electron diffraction, and second-harmonic generation, we have shown that BiScO3 has a structure closely related to that of multiferroic BiMnO3, but BiScO3 crystallizes in the centrosymmetric space group of C2/c. These results bring up a question about the origin of ferroelectricity in BiMnO3. BiScO3 may serve as a model system to understand the role of Mn3+ ions in the ferroelectricity of BiMnO3.

0.23 eV energy resolution obtained using a cold field-emission gun and a streak imaging technique.

We demonstrate that a high energy resolution of 0.23 eV is possible by using a cold field-emission electron gun (CFEG) without a monochromator. We have used a 300 kV transmission electron microscope (Hitachi, HF-3000) equipped with a CFEG and an energy filter (Gatan, GIF2002). Since energy instability is critical for high energy resolution in electron energy-loss spectroscopy, we have applied a high-speed 'streak imaging' acquisition technique, in which a series of time-resolved spectra are acquired as a two-dimensional spectrum. With this technique, we can easily record 1000-20,000 spectra with an exposure time of 0.353 ms per spectrum. Instability of less than 1.4 kHz has been corrected in the time-resolved spectra, allowing the inherent performance of the CFEG to be realized.