External-Stimuli-Assisted Control over Assemblies of Plasmonic Metals.

Assembly of plasmonic nanoparticles (NPs) in suspensions is a promising approach for the control of optical and sensing properties that depend on the assembled states of plasmonic NPs. This review focuses on the controlling methods to assemble the NP via external stimuli such as pH, temperature, light, magnetic field, and electric field. External stimuli are introduced as powerful tools to assemble the NPs because of various operational factors, such as the intensity, application time, and frequency, which can be employed. In addition to a summary of recent studies on the controlling methods, a future study on the reversible control over assembled states of the plasmonic NPs via external stimuli is proposed.

Microstructure characterization of defects in cubic silicon carbide using transmission electron microscopy.

Microstructures of 3C-SiC grown by chemical vapor deposition (CVD) technique on undulant silicon substrate and a further developed technique called switch-back epitaxy (SBE) were studied using transmission electron microscopy (TEM). In case of the CVD sample, the density of the stacking faults was found to be significantly decreasing along growth direction. Sites of collision of stacking faults were observed using high-resolution transmission electron microscopy. Some of the stacking faults were observed to have disappeared after colliding into each other. The stacking faults were identified to be on the same type of plane and had the same type of displacement vector not only in CVD and SBE but also in the epitaxial layer on the SBE SiC samples.

High temperature in-situ observations of multi-segmented metal nanowires encapsulated within carbon nanotubes by in-situ filling technique.

Multi-segmented one-dimensional metal nanowires were encapsulated within carbon nanotubes (CNTs) through in-situ filling technique during plasma-enhanced chemical vapor deposition process. Transmission electron microscopy (TEM) and environmental TEM were employed to characterize the as-prepared sample at room temperature and high temperature. The selected area electron diffractions revealed that the Pd4Si nanowire and face-centered-cubic Co nanowire on top of the Pd nanowire were encapsulated within the bottom and tip parts of the multiwall CNT, respectively. Although the strain-induced deformation of graphite walls was observed, the solid-state phases of Pd4Si and Co-Pd remain even at above their expected melting temperatures and up to 1,550 ± 50°C. Finally, the encapsulated metals were melted and flowed out from the tip of the CNT after 2 h at the same temperature due to the increase of internal pressure of the CNT.

Growth and structure analysis of tungsten oxide nanorods using environmental TEM.

WO3 nanorods targeted for applications in electric devices were grown from a tungsten wire heated in an oxygen atmosphere inside an environmental transmission electron microscope, which allowed the growth process to be observed to reveal the growth mechanism of the WO3 nanorods. The initial growth of the nanorods did not consist of tungsten oxide but rather crystal tungsten. The formed crystal tungsten nanorods were then oxidized, resulting in the formation of the tungsten oxide nanorods. Furthermore, it is expected that the nanorods grew through cracks in the natural surface oxide layer on the tungsten wire.

In-situ TEM studies of the sintering behavior of copper nanoparticles covered by biopolymer nanoskin.

Sintering behavior of copper nanoparticles with a protective layer of gelatin synthesized by wet-chemical process with an average diameter of 45 nm has been observed using in-situ transmission electron microscopy (TEM). Copper nanoparticles were sublimated without sintering at about 925 degrees C at 2.0 x 10(-)(5) Pa, and carbonized gelatin remained and retained the shape of the initial layer of nanoparticles. Copper nanoparticles were sintered without sublimation at about 250 degrees C with between 1.0 x 10(-)(4) and 6.0 x 10(-)(4) Pa of oxygen gas flow. It was found that the surface of the sintered copper was covered by a gelatin layer.

Measurement of electric field distribution using a conventional transmission electron microscope.

A simple and quick method to measure the electric field distribution near a specimen using a conventional transmission electron microscope has been developed. The electric field distribution around a field emitter needle was measured to evaluate the performance of the method. It was found that this method allows us to measure the 2D distribution of electric field quantitatively with error of <10% with submicron spatial resolution. The dedicated aperture and software to construct an automated analysis system have been developed.

Development of an analytical environmental TEM system and its application.

Many automotive materials, such as catalysts and fuel cell materials, undergo significant changes in structure or properties when subjected to temperature change or the addition of a gas. For this reason, in the development of these materials, it is important to study the behavior of the material under controlled temperatures and gaseous atmospheres. Recently, a new environmental transmission electron microscope (TEM) has been developed for observation with a high resolution at high temperatures and under gaseous atmospheres, thus making it possible to analyze reaction processes in details. Also, the new TEM provides a high degree of reproducibility of observation conditions, thus making it possible to compare and validate observation of various specimens under a given set of conditions. Furthermore, easiness of gas condition and temperature control can provide a powerful tool for the studying of the mechanism of material change, such as oxidation and reduction reactions.

In situ observation of oxidation of liquid droplets of tin and melting behavior of a tin particle covered with a tin oxide layer.

Oxidation of a liquid droplet of tin (Sn) was observed using an in situ specimen heating holder in an oxygen environment. The surface of the Sn liquid droplet was covered with a tin oxide layer, Sn(3)O(4), the thickness of which depended on the oxygen pressure and temperature. Subsequent cooling of the droplet resulted in the formation of a solid Sn particle covered with a Sn(3)O(4) layer. The solid Sn particle was then heated above the melting temperature of Sn, and the melting behavior of Sn was observed.

Focused ion beam preparation techniques dedicated for the fabrication of TEM lamellae of fibre-reinforced composites.

Two Focused Ion Beam based transmission electron microscopy (TEM) thin film preparation techniques are introduced. One is dedicated to the preparation of single fibres, the other to fibre/matrix interfaces of fibre reinforced composites. Due to their thin film quality, reliability and predictable processing times both techniques are suited for routine applications in material science like TEM studies of fibre microtextures and fibre/matrix interfaces. Exemplarily they are applied to Carbon Fibres and Carbon Fibre reinforced Carbon Matrix Composites (C/C). The achieved preparation standard in both cases is substantiated by TEM investigations.

Development of a gas injection/specimen heating holder for use with transmission electron microscope.

A new gas injection/specimen heating holder is developed for the purpose of in situ observation of gas reaction of materials at high temperatures in a transmission electron microscope at near-atomic resolution. A fine tungsten wire is employed as a heating element of the holder and a battery is used as the power source. Gas was injected onto specimens in the form of particles lying on the heating element via a nozzle. The maximum pressure near specimens was middle of 10(-2) Pa, while the pressure in the electron-gun chamber was kept to 2 x 10(-4) Pa. This gas injection/specimen heating holder was applied to observe solid-gas reactions. The reactions observed include oxidation of pure In into In2O3, reduction of SiO2 into Si and re-oxidation of Si into SiO2.

Application of focused ion beam techniques and transmission electron microscopy to thin-film transistor failure analysis.

The locations of process-induced defects in hydrogenated amorphous silicon thin-film transistors (a-Si:H TFTs), which are used as elements of active-matrix liquid crystal displays, were investigated by combining focused ion beam techniques with cross-sectional transmission electron microscopy (X-TEM). The FIB technique is applied to TFT failure analysis problems, which require considerable localised etching without inducing mechanical stress or damage at fragile failure locations. We demonstrate the manner in which these techniques are used to characterise TFT defects such as pinholes and portions of the multilayer damaged by mechanical stress. A dramatic improvement brought about by the FIB technique is the increase in temporal efficiency of sample preparations. X-TEM observations also lead to identification of the fault and analysis of its cause, which in turn lead to a marked yield improvement.

Microstructural investigation of ceria-zirconia solid solution with oxygen vacancies.

The microstructural change in CeO2-ZrO2 solid solution (Ce2Zr2O7 + x; 0 < or = x < or = 1) with an ordered arrangement of Ce and Zr associated with the absorption/release of oxygen was observed by transmission electron microscopy (TEM). The oxidation of Ce2Zr2O7 was observed in TEM by electron diffraction analysis. The change in the electron diffraction pattern shows that Ce2Zr2O7 was easily oxidized in the TEM and that the oxidation was completed, giving an intermediate phase Ce2Zr2O7.5. Three different lattice images corresponding to x = 0, 0.5 and 1.0 were observed in high-resolution photographs of Ce2Zr2O7 + x. This difference in contrast image may be used for determining the local amount of oxygen absorbed.