Noise reduction of electron holography observations for a thin-foiled Nd-Fe-B specimen using the wavelet hidden Markov model.

In this study, we investigate the effectiveness of noise reduction in electron holography, based on the wavelet hidden Markov model (WHMM), which allows the reasonable separation of weak signals from noise. Electron holography observations from a Nd2Fe14B thin foil showed that the noise reduction method suppressed artificial phase discontinuities generated by phase retrieval. From the peak signal-to-noise ratio, it was seen that the impact of denoising was significant for observations with a narrow spacing of interference fringes, which is a key parameter for the spatial resolution of electron holography. These results provide essential information for improving the precision of electron holography studies.

Phase control of solid-solution RuIn nanoparticles and their catalytic properties.

The properties of solids could be largely affected by their crystal structures. We achieved, for the first time, the phase control of solid-solution RuIn nanoparticles (NPs) from face-centred cubic (fcc) to hexagonal close-packed (hcp) crystal structures by hydrogen heat treatment. The effect of the crystal structure of RuIn alloy NPs on the catalytic performance in the hydrogen evolution reaction (HER) was also investigated. In the hcp RuIn NPs, enhanced HER catalytic performance was observed compared to the fcc RuIn NPs and monometallic Ru NPs. The intrinsic electronic structures of the NPs were investigated by valence-band X-ray photoelectron spectroscopy (VB-XPS). The d-band centre of hcp RuIn NPs obtained from VB-XPS was deeper than that of fcc RuIn NPs and monometallic Ru NPs, which is considered to enable the hcp RuIn NPs to exhibit enhanced HER catalytic performance.

High-precision charge analysis in a catalytic nanoparticle by electron holography.

The charge state of supported metal catalysts is the key to understanding the elementary processes involved in catalytic reactions. However, high-precision charge analysis of the metal catalysts at the atomic level is experimentally challenging. To address this critical challenge, high-sensitivity electron holography has recently been successfully applied for precisely measuring the elementary charges on individual platinum nanoparticles supported on a titanium dioxide surface. In this review, we introduce the latest advancements of high-precision charge analysis and discuss mechanisms of charge transfer at the metal-support interface. The development of charge measurements is entering a new era, and charge analyses under conditions closer to practical working environments, such as real-time, real-space, and reactive gas environments, are expected to be realized in near future.

Structural and electronic characterization of fluorine-doped La0.5Sr0.5CoO3-δ using electron energy-loss spectroscopy.

Perovskite oxides, ABO3, are potential catalysts for the oxygen evolution reaction, which is important in the production of hydrogen as a sustainable energy resource. Optimizing the chemical composition of such oxides by substitution or doping with additional elements is an effective approach to improving the activity of such catalysts. Here, we characterized the crystal and electronic structures of fluorine-doped La0.5Sr0.5CoO3-δ particles using scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). High-resolution STEM imaging demonstrated the formation of a disordered surface phase caused by fluorine doping. In addition, spatially resolved EELS data showed that fluorine anions were introduced into the interiors of the particles and that Co ions near the surfaces were slightly reduced by fluorine doping in conjunction with the loss of oxygen ions. Peak fitting of energy-loss near-edge structure data demonstrated an unexpected nanostructure in the vicinity of the surface. An EELS characterization comprising elemental mapping together with an energy-loss near-edge structure analysis indicated that this nanostructure could not be assigned to Co-based materials but rather to the solid electrolyte BaF2. Complementary structural and electronic characterizations using STEM and EELS as demonstrated herein evidently have the potential to play an increasingly important role in elucidating the nanostructures of functional materials.

Catalytic Behavior of K-doped Fe/MgO Catalysts for Ammonia Synthesis Under Mild Reaction Conditions.

An important part of realizing a carbon-neutral society using ammonia will be the development of an inexpensive yet efficient catalyst for ammonia synthesis under mild reaction conditions (<400 °C, <10 MPa). Here, we report Fe/K(3)/MgO, fabricated via an impregnation method, as a highly active catalyst for ammonia synthesis under mild reaction conditions (350 °C, 1.0 MPa). At the mentioned conditions, the activity of Fe/K(3)/MgO (17.5 mmol h-1 gcat -1 ) was greater than that of a commercial fused iron catalyst (8.6 mmol h-1 gcat -1 ) currently used in the Haber-Bosch process. K doping was found to increase the ratio of Fe0 on the surface and turnover frequency of Fe in our Fe/K(3)/MgO catalyst. In addition, increasing the pressure to 3.0 MPa at the same temperature led to a significant improvement of the ammonia synthesis rate to 29.6 mmol h-1 gcat -1 , which was higher than that of two more expensive, benchmark Ru-based catalysts, which are also potential alternative catalysts. A kinetics analysis revealed that the addition of K enhanced the ammonia synthesis activity at ≥300 °C by changing the main adsorbed species from NH to N which can accelerate dissociative adsorption of nitrogen as the rate limiting step in ammonia synthesis.

B2-structured indium-platinum group metal high-entropy intermetallic nanoparticles.

We first report the synthesis of B2-structured indium-platinum group metal high-entropy intermetallic nanoparticles (In-PGM HEI NPs). The synthesis was achieved by a wet-chemistry method and subsequent heat treatment. The crystal structure of these NPs is unique in the coexistence of completely orderly arranged indium and disorderly arranged PGMs.

Continuous-Flow Chemical Synthesis for Sub-2 nm Ultra-Multielement Alloy Nanoparticles Consisting of Group IV to XV Elements.

Multielement alloy nanoparticles have attracted much attention due to their attractive catalytic properties derived from the multiple interactions of adjacent multielement atoms. However, mixing multiple elements in ultrasmall nanoparticles from a wide range of elements on the periodic table is still challenging because the elements have different properties and miscibility. Herein, we developed a benchtop 4-way flow reactor for chemical synthesis of ultra-multielement alloy (UMEA) nanoparticles composed of d-block and p-block elements. BiCoCuFeGaInIrNiPdPtRhRuSbSnTi 15-element alloy nanoparticles composed of group IV to XV elements were synthesized by sequential injection of metal precursors using the reactor. This methodology realized the formation of UMEA nanoparticles at low temperature (66 °C), resulting in a 1.9 nm ultrasmall average particle size. The UMEA nanoparticles have high durability and activity for electrochemical alcohol oxidation reactions and high tolerance to CO poisoning. These results suggest that the multiple interactions of UMEA efficiently promote the multistep alcohol oxidation reaction.

Self-Assembled Crystalline Bundles in Soluble Metal-Organic Nanotubes.

The use of nanotubes in the solution state is crucial not only for the exploration of physical and chemical behaviors at the molecular level but also for application such as thin-film fabrication. Surface modification is generally used to solubilize carbon nanotubes (CNTs) and various synthetic nanotubes; however, this method may affect the surface properties of the original nanotubes, and the detailed crystal structure obtained after modification is unclear. Here, we report the synthesis of a crystalline and soluble metal-organic nanotube consisting of a cationic tubular framework and an anion with a long alkyl chain. The nanotubular structures are formed not only in the solid state but also in the solution state, as confirmed by an X-ray structural analysis, optical measurements, and electron microscopy studies. This nanotube system is realized in different states without any surface modification, which is quite different from typical CNTs and synthetic nanotubes. In addition, self-assembled crystalline bundles are directly observed using transmission electron microscopy (TEM) for the first time in a metal-organic nanotube system. The bundle structures are also confirmed by atomic force microscopy (AFM) observations of thin nanotube films. We envisage a systematic design of such soluble metal-organic nanotubes that will enable direct observation of mass transport behavior in channels of bundles or a single nanotube, as well as a wide range of thin-film applications.

Extraction of phase information approximating the demagnetization field within a thin-foiled magnet using electron holography observation.

This paper proposes a method that provides a phase image related to the demagnetization field (Hd) within a thin-foil permanent magnet using electron holography. The observation of Hd remains a significant challenge because electron holography in principle allows only imaging of the magnetic flux density (B), which is a mixture of the contributions from magnetization (M), stray magnetic field (Hs) outside of the specimen and Hd inside of the specimen. The phase map approximating Hd, which was determined by processing of the electron holography observation from a Nd2Fe14B single-crystalline specimen, showed a good agreement with the prediction by micromagnetic theory. With respect to permanent magnets, this method can be applied to examinations about the coercivity mechanism, which is sensitive to the demagnetization field. Graphical Abstract.

Direct identification of the charge state in a single platinum nanoparticle on titanium oxide.

A goal in the characterization of supported metal catalysts is to achieve particle-by-particle analysis of the charge state strongly correlated with the catalytic activity. Here, we demonstrate the direct identification of the charge state of individual platinum nanoparticles (NPs) supported on titanium dioxide using ultrahigh sensitivity and precision electron holography. Sophisticated phase-shift analysis for the part of the NPs protruding into the vacuum visualized slight potential changes around individual platinum NPs. The analysis revealed the number (only one to six electrons) and sense (positive or negative) of the charge per platinum NP. The underlying mechanism of platinum charging is explained by the work function differences between platinum and titanium dioxide (depending on the orientation relationship and lattice distortion) and by first-principles calculations in terms of the charge transfer processes.

Non-Hookean large elastic deformation in bulk crystalline metals.

Crystalline metals can have large theoretical elastic strain limits. However, a macroscopic block of conventional crystalline metals practically suffers a very limited elastic deformation of <0.5% with a linear stress-strain relationship obeying Hooke's law. Here, we report on the experimental observation of a large tensile elastic deformation with an elastic strain of >4.3% in a Cu-based single crystalline alloy at its bulk scale at room temperature. The large macroscopic elastic strain that originates from the reversible lattice strain of a single phase is demonstrated by in situ microstructure and neutron diffraction observations. Furthermore, the elastic reversible deformation, which is nonhysteretic and quasilinear, is associated with a pronounced elastic softening phenomenon. The increase in the stress gives rise to a reduced Young's modulus, unlike the traditional Hooke's law behaviour. The experimental discovery of a non-Hookean large elastic deformation offers the potential for the development of bulk crystalline metals as high-performance mechanical springs or for new applications via "elastic strain engineering."

Improved efficiency in automated acquisition of ultra-high-resolution electron holograms using automated target detection.

An automated hologram acquisition system for big-data analysis and for improving the statistical precision of phase analysis has been upgraded with automated particle detection technology. The coordinates of objects in low-magnification images are automatically detected using zero-mean normalized cross-correlation with preselected reference images. In contrast with the conventional scanning acquisitions from the whole area of a microgrid and/or a thin specimen, the new method allows efficient data collections only from the desired fields of view including the particles. The acquisition time of the cubic/triangular nanoparticles that were observed was shortened by about one-fifty eighth that of the conventional scanning acquisition method because of efficient data collections. The developed technology can improve statistical precision in electron holography with shorter acquisition time and is applicable to the analysis of electromagnetic fields for various kinds of nanoparticles.

Deep convolutional neural network image processing method providing improved signal-to-noise ratios in electron holography.

An image identification method was developed with the aid of a deep convolutional neural network (CNN) and applied to the analysis of inorganic particles using electron holography. Despite significant variation in the shapes of α-Fe2O3 particles that were observed by transmission electron microscopy, this CNN-based method could be used to identify isolated, spindle-shaped particles that were distinct from other particles that had undergone pairing and/or agglomeration. The averaging of images of these isolated particles provided a significant improvement in the phase analysis precision of the electron holography observations. This method is expected to be helpful in the analysis of weak electromagnetic fields generated by nanoparticles showing only small phase shifts.

Magnetic flux density measurements from narrow grain boundaries produced in sintered permanent magnets.

This review examines methods of magnetic flux density measurements from the narrow grain boundary (GB) regions, the thickness of which is of the order of nanometers, produced in Nd-Fe-B-based sintered magnets. Despite of the complex crystallographic microstructure and the significant stray magnetic field of the sintered magnet, recent progress in electron holography allowed for the determination of the intrinsic magnetic flux density due to the GB which is embedded in the polycrystalline thin-foil. The methods appear to be useful as well for intensive studies about interface magnetism in a variety of systems.

Automated acquisition of vast numbers of electron holograms with atomic-scale phase information.

An automated acquisition system for collecting a large number of electron holograms, to improve the statistical precision of phase analysis, was developed. A technique for shifting the electron beam in combination with stage movement allows data to be acquired over a wide area of a TEM-specimen grid. Undesired drift in the hologram position, which may occur during the hologram acquisition, can be corrected in real time by automated detection of the interference-fringe region in an image. To demonstrate the usefulness of the developed automated hologram acquisition system, gold nanoparticles dispersed on a carbon foil were observed with a 1.2-MV atomic resolution holography electron microscope. The system could obtain 1024 holograms, which provided phase maps for more than 500 nanoparticles with a lateral resolution of 0.14 nm, in just 1 h. The observation results revealed an anomalous increase in mean inner potential for a particle size smaller than 4 nm. The developed automated hologram acquisition system can be applied to improve the precision of phase measurement by averaging many phase images, as demonstrated by single particle analysis for biological entities. Moreover, the system makes it possible to study electrostatic potential of catalysts and other functional nanoparticles at atomic resolution.

Growth of vanadium dioxide thin films on hexagonal boron nitride flakes as transferrable substrates.

Vanadium dioxide (VO2) is an archetypal metal-insulator transition (MIT) material, which has been known for decades to show an orders-of-magnitude change in resistivity across the critical temperature of approximately 340 K. In recent years, VO2 has attracted increasing interest for electronic and photonic applications, along with advancement in thin film growth techniques. Previously, thin films of VO2 were commonly grown on rigid substrates such as crystalline oxides and bulk semiconductors, but the use of transferrable materials as the growth substrates can provide versatility in applications, including transparent and flexible devices. Here, we employ single-crystalline hexagonal boron nitride (hBN), which is an insulating layered material, as a substrate for VO2 thin film growth. VO2 thin films in the polycrystalline form are grown onto hBN thin flakes exfoliated onto silicon (Si) with a thermal oxide, with grains reaching up-to a micrometer in size. The VO2 grains on hBN are orientated preferentially with the (110) surface of the rutile structure, which is the most energetically favorable. The VO2 film on hBN shows a MIT at approximately 340 K, across which the resistivity changes by nearly three orders of magnitude, comparable to VO2 films grown on common substrates such as sapphire and titanium dioxide. The VO2/hBN stack can be picked up from the supporting Si and transferred onto arbitrary substrates, onto which VO2 thin films cannot be grown directly. Our results pave the way for new possibilities for practical and versatile applications of VO2 thin films in electronics and photonics.

Self-assembled structure of dendronized CdS nanoparticles.

Self-assembled dendronized CdS nanoparticles have been attracting considerable attention because of their photoluminescence properties depending on annealing treatments. In this study, their annealing-induced self-assembled structure was investigated via scanning transmission electron microscopy; thin foil specimens of self-assembled dendronized CdS nanoparticles were prepared by ultramicrotomy and the STEM images revealed their ordered structure and the effect of the annealing treatment. In addition, a structural order belonging to the P213 space group was identified via an autocorrelation analysis. The results indicated that this structural order could be achieved only over a few tens of nanometers.

Illumination semiangle of 10-9 rad achieved in a 1.2-MV atomic resolution holography transmission electron microscope.

The coherency of a 1.2-MV transmission electron microscope was evaluated through illumination semiangles calculated from lengths over which Fresnel fringes can be observed. These lengths were determined from the diameters of circular holes fully filled with Fresnel fringes, i.e. this method allows lengths to be accurately measured even if micrographs are subjected to distortions. The smallest illumination semiangle of 4.0 × 10-9 rad was obtained for a circular hole with a diameter of 191 µm. In addition, electron beam brightness was estimated to be approximately 3 × 1014 A/m2·sr from the obtained illumination semiangle values and current densities. The results provide us with essential information that can be referred to in future electron holography studies aimed at detecting weak electromagnetic fields in materials.

Synthesis of zero-valent iron nanoparticles via laser ablation in a formate ionic liquid under atmospheric conditions.

Transition metal nanoparticles (NPs) are promising materials for use as catalysts in many processes, although they are easily oxidized under ambient conditions. In this communication, a novel synthetic method is proposed for producing zero-valent iron (Fe) NPs by laser ablation under atmospheric conditions using the reducing properties of a formate-based ionic liquid solvent. The valence state of Fe was confirmed using X-ray absorption near edge structure (XANES) spectroscopy. The Fe NPs adopt a face centered cubic structure after synthesis, which gradually transforms to a body centered cubic structure after one month. The method can be extended to the synthesis of other transition metal NPs that are easily oxidized.