Athermal Solid Phase Reaction in Pt/SiO x Thin Films Induced by Electron Irradiation.

Microelectronics based on Si requires metal silicide contacts. The ability to form platinum silicide (Pt2Si) by electronic excitation instead of thermal processes would benefit the field. We studied the effects of electron irradiation on Pt2Si formation in composite films-composed of Pt and amorphous silicon oxides (a-SiO x )-by transmission electron microscopy and electron diffraction. Pt2Si formed in Pt/a-SiO x bilayer and a-SiO x /Pt/a-SiO x sandwiched films by 75 keV electron irradiation, at 298 and 90 K. The reaction is attributable to dissociation of SiO x triggered by electronic excitation. In a-SiO x /Pt/a-SiO x sandwiched films, reflections of pure Pt were not present after irradiation, i.e., Pt was completely consumed in the reaction to form Pt2Si at 298 K. However, in Pt/a-SiO x bilayer films, unreacted Pt remained under the same irradiation conditions. Thus, it can be said that the extent of the interfacial area is the predominant factor in Pt2Si formation. The morphology of Pt islands extensively changed during Pt2Si formation even at 90 K. Coalescence and growth of metallic particles (Pt and Pt-Si) are not due to thermal effects during electron irradiation but to athermal processes accompanied by silicide formation. To maintain the reaction interface between metallic particles and the dissociation product (i.e., Si atoms) by electronic excitation, a considerable concomitant morphology change occurs. Elemental analysis indicates that the decrease in Si concentration near Pt is faster than the decrease in O concentration, suggesting formation of a Si depletion zone in the amorphous silicon oxide matrix associated with formation of Pt2Si.

Research on nanoprocess of non-equilibrium materials by in situ ultra-high voltage electron microscopy.

Ultra-high voltage electron microscopy is useful for research utilizing high-penetration thickness of electron beam, in situ observation, or irradiation effects by the particle characteristics of electrons. In this review, the importance of non-equilibrium materials science research by a combination with irradiation effects and in situ observation is shown, and examples of some research are introduced. For example, crystal-amorphous-crystalline phase transition in intermetallic compounds, non-equilibrium phase transition in pure metallic nanoparticles and nucleation and growth process of electron irradiation-induced crystallization in amorphous nanoparticles will be discussed. Finally, we want to suggest the importance of exploring non-equilibrium materials science based on dynamic structures which has been unexplored.

Quantum de-trapping and transport of heavy defects in tungsten.

The diffusion of defects in crystalline materials1 controls macroscopic behaviour of a wide range of processes, including alloying, precipitation, phase transformation and creep2. In real materials, intrinsic defects are unavoidably bound to static trapping centres such as impurity atoms, meaning that their diffusion is dominated by de-trapping processes. It is generally believed that de-trapping occurs only by thermal activation. Here, we report the direct observation of the quantum de-trapping of defects below around one-third of the Debye temperature. We successfully monitored the de-trapping and migration of self-interstitial atom clusters, strongly trapped by impurity atoms in tungsten, by triggering de-trapping out of equilibrium at cryogenic temperatures, using high-energy electron irradiation and in situ transmission electron microscopy. The quantum-assisted de-trapping leads to low-temperature diffusion rates orders of magnitude higher than a naive classical estimate suggests. Our analysis shows that this phenomenon is generic to any crystalline material.

Fast, vacancy-free climb of prismatic dislocation loops in bcc metals.

Vacancy-mediated climb models cannot account for the fast, direct coalescence of dislocation loops seen experimentally. An alternative mechanism, self climb, allows prismatic dislocation loops to move away from their glide surface via pipe diffusion around the loop perimeter, independent of any vacancy atmosphere. Despite the known importance of self climb, theoretical models require a typically unknown activation energy, hindering implementation in materials modeling. Here, extensive molecular statics calculations of pipe diffusion processes around irregular prismatic loops are used to map the energy landscape for self climb in iron and tungsten, finding a simple, material independent energy model after normalizing by the vacancy migration barrier. Kinetic Monte Carlo simulations yield a self climb activation energy of 2 (2.5) times the vacancy migration barrier for 1/2〈111〉 (〈100〉) dislocation loops. Dislocation dynamics simulations allowing self climb and glide show quantitative agreement with transmission electron microscopy observations of climbing prismatic loops in iron and tungsten, confirming that this novel form of vacancy-free climb is many orders of magnitude faster than what is predicted by traditional climb models. Self climb significantly influences the coarsening rate of defect networks, with important implications for post-irradiation annealing.

In-Situ High-Resolution Transmission Electron Microscopy Investigation of Overheating of Cu Nanoparticles.

Synthesizing and functionalizing metal nanoparticles supported on substrates is currently the subject of intensive study owing to their outstanding catalytic performances for heterogeneous catalysis. Revealing the fundamental effect of the substrates on metal nanoparticles represents a key step in clarifying mechanisms of stability and catalytic properties of these heterogeneous systems. However, direct identification of these effects still poses a significant challenge due to the complicacy of interactions between substrates and nanoparticles and also for the technical difficulty, restraining our understanding of these heterogeneous systems. Here, we combine in situ high-resolution transmission electron microscopy with molecular dynamics simulations to investigate Cu nanoparticles supported on graphite and Cu2O substrates, and demonstrate that melting behavior and thermal stability of Cu nanoparticles can be markedly influenced by substrates. The graphite-supported Cu nanoparticles do not melt during annealing at 1073 K until they vanish completely, i.e. only the sublimation occurs, while the Cu2O-supported Cu nanoparticles suffer melting during annealing at 973 K. Such selective superheating of the Cu nanoparticles can be attributed to the adsorption of a thin carbon layer on the surface of the Cu nanoparticles, which helps guide further stability enhancement of functional nanoparticles for realistic applications.

Collagen production of osteoblasts revealed by ultra-high voltage electron microscopy.

In the bone, collagen fibrils form a lamellar structure called the "twisted plywood-like model." Because of this unique structure, bone can withstand various mechanical stresses. However, the formation of this structure has not been elucidated because of the difficulty of observing the collagen fibril production of the osteoblasts via currently available methods. This is because the formation occurs in the very limited space between the osteoblast layer and bone matrix. In this study, we used ultra-high-voltage electron microscopy (UHVEM) to observe collagen fibril production three-dimensionally. UHVEM has 3-MV acceleration voltage and enables us to use thicker sections. We observed collagen fibrils that were beneath the cell membrane of osteoblasts elongated to the outside of the cell. We also observed that osteoblasts produced collagen fibrils with polarity. By using AVIZO software, we observed collagen fibrils produced by osteoblasts along the contour of the osteoblasts toward the bone matrix area. Immediately after being released from the cell, the fibrils run randomly and sparsely. But as they recede from the osteoblast, the fibrils began to run parallel to the definite direction and became thick, and we observed a periodical stripe at that area. Furthermore, we also observed membrane structures wrapped around filamentous structures inside the osteoblasts. The filamentous structures had densities similar to the collagen fibrils and a columnar form and diameter. Our results suggested that collagen fibrils run parallel and thickly, which may be related to the lateral movement of the osteoblasts. UHVEM is a powerful tool for observing collagen fibril production.

Detection and in situ switching of unreversed interfacial antiferromagnetic spins in a perpendicular-exchange-biased system.

By using the perpendicular-exchange-biased Pt/Co/α-Cr(2)O(3) system, we provide experimental evidence that the unreversed uncompensated Cr spins exist at the Co/α-Cr(2)O(3) interface. The unreversed uncompensated Cr spin manifests itself in both the vertical shift of an element-specific magnetization curve and the relative peak intensity of soft-x-ray magnetic circular dichroism spectrum. We also demonstrate an in situ switching of the interfacial Cr spins and correspondingly a reversal of the exchange bias without interfacial atomic diffusion. Such switching shows the direct relationship between the interfacial antiferromagnetic spins and origin of the exchange bias. The demonstrated switching of exchange bias would likely offer a new design of advanced spintronics devices, using the perpendicular-exchange-biased system, with low power consumption and ultrafast operation.

Topics in recent studies with high-voltage electron microscopes.

In this article, topics in recent studies with high-voltage electron microscopes (HVEMs) are reviewed. High-voltage electron microscopy possesses a number of advantages that cannot be afforded by conventional electron microscopy, thus providing a unique microscopy technique in both materials science and biological science. One of these advantages is the capability of continuously observing phenomena using a variety of electron microscopy techniques simultaneously with the introduction of the displacement of atoms from lattice points. This has enabled in-depth studies on such fundamental subjects as the crystalline-to-amorphous-to-crystalline transition, the motion properties of point defects and the one-dimensional diffusion of dislocation loops. Electron tomography studies using HVEMs take advantage of the large observable thickness of a specimen. In addition, by combining different advantages, a number of advanced applications in materials science have been carried out, including analyses of the atomic structure of a reduction-induced reconstructed surface and the atomic mechanism behind the self-catalytic vapor-liquid-solid growth of an oxide nanowire. As long as excellent and invaluable studies that cannot be carried out without HVEMs appear in succession, it is necessary to make the utmost efforts to improve these microscopes.

Magnetic Cu-Ni (core-shell) nanoparticles in a one-pot reaction under microwave irradiation.

We successfully prepared face-centered cubic (fcc) Cu-Ni (core-shell) nanoparticles by intramolecular reduction of formate complexes of Cu(2+) and Ni(2+) with long-chain amine ligands in a one-pot reaction within an extremely short time realized only under microwave irradiation. Observation by an HAADF-STEM technique showed that the nanostructure in one particle consisted of a Ni-rich shell and a Cu-rich core. Cu(4)Ni(6) nanoparticles with an average size of 11.7 nm were comprised of a Cu core with a diameter of ca. 6.0 nm, a Ni shell ca. 1.6 nm thick and a 0.9 nm thick interlayer of mixed Cu-Ni alloy between the Cu core and the Ni shell. Both the oxidation characteristics and the magnetic properties were dramatically affected by the molar ratios of Cu : Ni in the Cu-Ni nanoparticles. The magnetization of Cu(3)Ni(7) and Cu(4)Ni(6) comprised of a diamagnetic Cu-rich core, ferromagnetic Ni-rich shell and antiferromagnetic NiO-rich layer on the particle surface showed an exchange bias (209 and 143 Oe, respectively).

In situ atomic-scale observation of melting point suppression in nanometer-sized gold particles.

Phase stabilities of nanometer-sized materials are quite different from those of the corresponding bulk materials. Among the phase stabilities, melting point suppression is one of the most fundamentally important issues. In this work, real-time, atomic-scale direct observation of melting point suppression in nanometer-sized Au particles, along with simple size reduction, was carried out by means of in situ high resolution electron microscopy. Namely, it was confirmed in real space on an atomic scale that a solid-to-liquid transition occurred when the size of a particle, placed on a graphite substrate maintained at 1100 K, decreased to 5 nm during diminution. Furthermore, a monolayer-thick hole was formed on the substrate at the position of the liquid Au particle, probably due to carbon dissolution into the liquid Au particle.

Synthesis of highly dispersed platinum nanoparticles on Ti-containing mesoporous silica using photo-assisted deposition.

A simple and unique route to synthesize the nano-size Pt particles using mesoporous silica support including single-site Ti-oxide moiety (Ti-HMS) under UV-light irradiation has been developed. By the photo-assisted deposition (PAD) method, a Pt precursor can be deposited from aqueous solution of H2PtCl6 directly on the photo-excited isolated Ti-oxide moiety. The subsequent reduction with H2 generates the nano-sized Pt metal particles (PAD-Pt/Ti-HMS). The deposition of Pt precursor onto the Ti-HMS can be recognized by the observation of the decrease in the intensity of the preedge in the Ti K-edge XANES spectrum, demonstrating that the Pt precursor underwent anchoring on the single framework Ti4+ center of Ti-HMS under UV-light irradiation. The lower intensity of the Pt-Pt bond of the PAD-Pt/Ti-HMS than that of Pt foil in the Fourier transforms of Pt L(III)-edge EXAFS spectra clearly suggests the formation of the Pt nanoparticles. The PAD-Pt/Ti-HMS exhibited the higher catalytic activity for the hydrogenation of nitrobenzene to aniline and the NO reduction than the catalyst prepared by the conventional impregnation.

Behavior of fluorescent molecules bound to the interior of silica nanocapsules in various solvents.

Porous silica nanocapsules with 20% 3-aminopropyltrimethoxysilane (APS)-bound 6-carboxy-fluorescein (APS-fluorescein) and 80% APS molecules adsorbed on the surface of a 50-nm-diameter Au core were prepared by a modified core-shell method. Silica mesoporous nanocapsules were obtained after the Au cores were dissolved in sodium cyanide. The size of the pores in the silica shells corresponded to the area of the fluorescein (approximately 1.02 nm(2)) in each APS-fluorescein molecule, which was bound to the silica shell by coupling between the silanol groups of APS in the APS-fluorescein molecule and the silica shell. The amino group of APS bound to the silica inside the shell is also reactive. Dy485XL N-hydroxysuccinimide ester (NHS) molecules were then added to the mesoporous silica nanocapsules in the solution and bonded to the amino group of the interior. Thus, mesoporous (fluorescein and Dy485XL)-bound silica nanocapsules were obtained. The fluorescence of Dy485XL was only observed in the mesoporous (fluorescein and Dy485XL)-bound silica nanocapsules in aqueous solution after ultrafiltration. However, the fluorescence of fluorescein reappeared after the addition of acetonitrile. Furthermore, upon adding various solvents to the mesoporous (fluorescein and Dy485XL)-bound silica nanocapsules, their fluorescence varied with that of fluorescein or Dy485XL. In the case of a mixture of 6-carboxy-fluorescein-N-hydroxysuccinimide (FLUOS) and Dy485XL-NHS free molecules in aqueous solution, the fluorescence of FLUOS was observed. Such different fluorescence phenomena demonstrated that Dy485XL-NHS molecules can easily penetrate into the nanocapsule interior via the pores and that the interior of the silica nanocapsules can bind to Dy485XL molecules. These fluorescence behaviors are discussed in terms of fluorescence resonance energy transfer (FRET) and solvatochromism.

High sintering resistance of platinum nanoparticles embedded in a microporous hollow carbon shell fabricated through a photocatalytic reaction.

Platinum (Pt) nanoparticles encapsulated in microporous carbon with a hollow structure (nPt@hC) were fabricated on the basis of a titanium(IV) oxide (TiO2) photocatalytic reaction. From the tomogram of a sample studied by using a transmission electron microscope (TEM), the Pt nanoparticles were found to be embedded in the carbon shell and were physically separated from each other by the carbon matrix. Owing to this unique structure, the Pt particles showed high resistance to sintering when subjected to thermal treatment at temperatures up to 800 degrees C. As a result, hydrogenation reactions using various heat-treated nPt@hCs as catalysts indicated that loss of catalytic activity was minimized. Thus, the present system will be a promising system for optimizing catalyst nanostructures utilized in processes requiring rigorous conditions.

Microscopic tomography with ultra-HVEM and applications.

The ultra-HVEM with an accelerating voltage of 3 MV at Osaka University is capable of achieving excellent penetration and resolution for thick specimens. We obtained images of 5-microm-thick slices tilted at angles of up to 70 degrees for biological samples and observed stick-shaped samples of Si devices free from missing zone. These features make the ultra-HVEM an invaluable extension of 3D observation by electron tomography. In this paper, we introduce aspects of ultra-HVEM tomography; specifically, the magnification, the amount of image blurring for thick samples and the electron staining method. Finally, we give some typical applications in the fields of cell biology, pathology and electrical engineering.

Synthesis and photophysical properties of EuS nanoparticles from the thermal reduction of novel Eu(III) complex.

EuS nanoparticles were synthesized by the thermal reduction of single source precursor (SSP), (PPh4)[Eu(S2CNEt2)4].2H2O, under microwave irradiation. The average size of the EuS nanoparticles was found to be 8 nm (3-16 nm in size). The organic products on the EuS surface were observed by using FT-IR, NMR, and MS analyses. We have found that these are resulted from the chemical reactions of SSP and cover the nanocrystal surface. A thermal reaction of SSP gave EuS nanoparticles and the organic product (*SCN(Et)2). The organic product would make a dimmer, (Et)2NC(S)-(S)CN(Et)2, by the couping of the radicals formed in the thermal reaction and/or thiopolymer in the solution through the polymerization of the radicals. The effective surface modification by the organic products led to protection of the EuS surface, resulting in the formation of the strongly luminescent EuS nanoparticles at room temperature (emission peak = 350 nm, fwhm = 58 nm, emission quantum yield = 27 +/- 5%).

Scientific Grid activities and PKI deployment in the Cybermedia Center, Osaka University.

The Cybermedia Center (CMC), Osaka University, is a research institution that offers knowledge and technology resources obtained from advanced researches in the areas of large-scale computation, information and communication, multimedia content and education. Currently, CMC is involved in Japanese national Grid projects such as JGN II (Japan Gigabit Network), NAREGI and BioGrid. Not limited to Japan, CMC also actively takes part in international activities such as PRAGMA. In these projects and international collaborations, CMC has developed a Grid system that allows scientists to perform their analysis by remote-controlling the world's largest ultra-high voltage electron microscope located in Osaka University. In another undertaking, CMC has assumed a leadership role in BioGrid by sharing its experiences and knowledge on the system development for the area of biology. In this paper, we will give an overview of the BioGrid project and introduce the progress of the Telescience unit, which collaborates with the Telescience Project led by the National Center for Microscopy and Imaging Research (NCMIR). Furthermore, CMC collaborates with seven Computing Centers in Japan, NAREGI and National Institute of Informatics to deploy PKI base authentication infrastructure. The current status of this project and future collaboration with Grid Projects will be delineated in this paper.

Porous polystyrene microspheres having dimpled surface structures prepared within micellar assemblies of amphiphilic silica particles in water.

Production of porous polystyrene microspheres having dimpled surface structures was demonstrated using amphiphilic and hydrophobic silica particles as structure-directing agents.

In situ HVEM study on copper oxidation using an improved environmental cell.

A window-type environmental cell that can be used over the temperature range from room temperature to approximately 1000 K was improved by incorporating a new window material that increases resolution and contrast in high voltage electron microscopy. With this improvement, the resolution was a few nanometers and the maximum pressure in the cell was approximately 1.3 x 10(4) Pa. Using this new window-type environmental cell, oxidation of copper and reduction of copper oxides, which occur through gas (oxygen or hydrogen)-solid (copper metal) reactions, have been successfully observed in situ, i.e. the formation process of oxides (Cu --> Cu2O --> CuO) and their subsequent reduction (CuO --> Cu) in the cell. The growth process of CuO whiskers on a thick (50 microm) Cu film was also observed in situ. It was found that whisker growth occurs at the tips of whiskers.