Development and Application of a Sample Holder for In Situ Gaseous TEM Studies of Membrane Electrode Assemblies for Polymer Electrolyte Fuel Cells.

Polymer electrolyte fuel cells hold great potential for stationary and mobile applications due to high power density and low operating temperature. However, the structural changes during electrochemical reactions are not well understood. In this article, we detail the development of the sample holder equipped with gas injectors and electric conductors and its application to a membrane electrode assembly of a polymer electrolyte fuel cell. Hydrogen and oxygen gases were simultaneously sprayed on the surfaces of the anode and cathode catalysts of the membrane electrode assembly sample, respectively, and observation of the structural changes in the catalysts were simultaneously carried out along with measurement of the generated voltages.

Long-term biopersistence of tangled oxidized carbon nanotubes inside and outside macrophages in rat subcutaneous tissue.

Because of their mechanical strength, chemical stability, and low molecular weight, carbon nanotubes (CNTs) are attractive biological implant materials. Biomaterials are typically implanted into subcutaneous tissue or bone; however, the long-term biopersistence of CNTs in these tissues is unknown. Here, tangled oxidized multi-walled CNTs (t-ox-MWCNTs) were implanted into rat subcutaneous tissues and structural changes in the t-ox-MWCNTs located inside and outside of macrophages were studied for 2 years post-implantation. The majority of the large agglomerates were present in the intercellular space, maintained a layered structure, and did not undergo degradation. By contrast, small agglomerates were found inside macrophages, where they were gradually degraded in lysosomes. None of the rats displayed symptoms of cancer or severe inflammatory reactions such as necrosis. These results indicate that t-ox-MWCNTs have high biopersistence and do not evoke adverse events in rat subcutaneous tissue in vivo, demonstrating their potential utility as implantable biomaterials.

Effect of the state of distribution of supported Pt nanoparticles on effective Pt utilization in polymer electrolyte fuel cells.

In polymer electrolyte fuel cells, it is essential to minimize Pt loading, particularly at the cathode, without serious loss of performance. From this point of view, we will report an advanced concept for the design of high performance catalysts and membrane-electrode assemblies (MEAs): first, the evaluation of Pt particle distributions on both the interior and exterior walls of various types of carbon black (CB) particles used as supports with respect to the "effective surface (ES)"; second, control of both size and location of Pt particles by means of a new preparation method (nanocapsule method); and finally, a new evaluation method for the properties of MEAs based on the Pt utilization (UPt), mass activity (MA), and effectiveness of Pt (EfPt), based on the ES concept. The amounts of Pt catalyst particles located in the CB nanopores were directly evaluated using the transmission electron microscopy, scanning electron microscopy and corresponding three-dimensional images. By use of the nanocapsule method and optimization of the ionomer, increased MA and EfPt values for the MEA were achieved. The improvement in the cathode performance can be attributed to the sharp particle-size distribution for Pt and the highly uniform dispersion on the exterior surface of graphitized carbon black (GCB) supports.

New generation "nanohybrid supercapacitor".

To meet growing demands for electric automotive and regenerative energy storage applications, researchers all over the world have sought to increase the energy density of electrochemical capacitors. Hybridizing battery-capacitor electrodes can overcome the energy density limitation of the conventional electrochemical capacitors because they employ both the system of a battery-like (redox) and a capacitor-like (double-layer) electrode, producing a larger working voltage and capacitance. However, to balance such asymmetric systems, the rates for the redox portion must be substantially increased to the levels of double-layer process, which presents a significant challenge. An in situ material processing technology called "ultracentrifuging (UC) treatment" has been used to prepare a novel ultrafast Li4Ti5O12 (LTO) nanocrystal electrode for capacitive energy storage. This Account describes an extremely high-performance supercapacitor that utilizes highly optimized "nano-nano-LTO/carbon composites" prepared via the UC treatment. The UC-treated LTO nanocrystals are grown as either nanosheets or nanoparticles, and both have hyperlinks to two types of nanocarbons: carbon nanofibers and supergrowth (single-walled) carbon nanotubes. The spinel structured LTO has been prepared with two types of hyperdispersed carbons. The UC treatment at 75 000G stoichiometrically accelerates the in situ sol-gel reaction (hydrolysis followed by polycondensation) and further forms, anchors, and grafts the nanoscale LTO precursors onto the carbon matrices. The mechanochemical sol-gel reaction is followed by a short heat-treatment process in vacuo. This immediate treatment with heat is very important for achieving optimal crystallization, inhibiting oxidative decomposition of carbon matrices, and suppressing agglomeration. Such nanocrystal composites can store and deliver energy at the highest rate attained to this date. The charge-discharge profiles indicate a very high sustained capacity of 80 mAh g(-1) at an extremely high rate of 1200 C. Using this ultrafast material, we assembled a hybrid device called a "nanohybrid capacitor" that consists of a Faradaic Li-intercalating LTO electrode and a non-Faradaic AC electrode employing an anion (typically BF4(-)) adsorption-desorption process. The "nanohybrid capacitor" cell has demonstrated remarkable energy, power, and cycleability performance as an electrochemical capacitor electrode. It also exhibits the same ion adsorption-desorption process rates as those of standard activated carbon electrodes in electrochemical capacitors. The new-generation "nanohybrid capacitor" technology produced more than triple the energy density of a conventional electrochemical capacitor. Moreover, the synthetic simplicity of the high-performance nanostructures makes it possible to scale them up for large-volume material production and further applications in many other electrochemical energy storage devices.

Development of a technique for in situ high temperature TEM observation of catalysts in a highly moisturized air atmosphere.

To clarify the influence of moisture on the structural changes of heated nano materials, in situ high temperature transmission electron microscopy (TEM) has been carried out using a conventional analytical TEM combined with a gas injection-specimen heating holder. Air with high moisture content, above 94% relative humidity (RH), from a humidifier was directly injected onto the heated platinum catalyst dispersed on carbon black (Pt/CB), and the morphological changes of the specimens were observed at high magnification dynamically. The result of the experiment was compared with a result obtained from an experiment using air with a low moisture content, 34% RH. Active movement of the Pt particles, leading agglomeration and grain growth, occurred prior to degradation of the CB support at high moisture content. In contrast, the degradation of the CB support leading agglomeration and grain growth of the Pt particles occurred before the displacement of the Pt particles on the CB supports in a low humidity environment.

Development of a high temperature-atmospheric pressure environmental cell for high-resolution TEM.

An environmental cell for high-temperature, high-resolution transmission electron microscopy of nanomaterials in near atmospheric pressures is developed. The developed environmental cell is a side-entry type with built-in specimen-heating element and micropressure gauge. The relationship between the cell condition and the quality of the transmission electron microscopic (TEM) image and the diffraction pattern was examined experimentally and theoretically. By using the cell consisting of two electron-transparent silicon nitride thin films as the window material, the gas pressure inside the environmental cell is continuously controlled from 10(-5) Pa to the atmospheric pressure in a high-vacuum TEM specimen chamber. TEM image resolutions of 0.23 and 0.31 nm were obtained using 15-nm-thick silicon nitride film windows with the pressure inside the cell being around 5 × 10(-5) and 1 × 10(4) Pa, respectively.

In-situ TEM observations of the crystallization process of solution-prepared MoS2 amorphous particles.

The crystallization of polymer-mixed amorphous molybdenum sulfide was observed in-situ by a TEM equipped with a heated specimen holder. High electron beam irradiation induced the formation of a crystal structure with a lattice spacing of 0.62 nm, which corresponds to the layer spacing of MoS2. With a lower electron dose, a possible new crystal structure of molybdenum sulfide with several fringe spacings was identified at room temperature. An ordered layered structure of MoS2 appeared after annealing at 600 degrees C. The completely different crystal phase found here might be responsible for the high temperature required for the formation of the MoS2 layered structure.

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.

Observation of three-dimensional elemental distributions of a Si device using a 360 degrees -tilt FIB and the cold field-emission STEM system.

A technique for preparation of a pillar-shaped specimen and its multidirectional observation using a combination of a scanning transmission electron microscope (STEM) and a focused ion beam (FIB) instrument has been developed. The system employs an FIB/STEM compatible holder with a specially designed tilt mechanism, which allows the specimen to be tilted through 360 degrees [T. Yaguchi, M. Konno, T. Kamino, T. Hashimoto, T. Ohnishi, K. Umemura, K. Asayama, Microsc. Microanal. 9 (Suppl. 2) (2003) 118; T. Yaguchi, M. Konno, T. Kamino, T. Hashimoto, T. Ohnishi, M. Watanabe, Microsc. Microanal. 10 (Suppl. 2) (2004) 1030]. This technique was applied to obtain the three-dimensional (3D) elemental distributions around a contact plug of a Si device used in a 90-nm technology. A specimen containing only one contact plug was prepared in the shape of a pillar with a diameter of 200nm and a length of 5mum. Elemental maps were obtained from the pillar specimen using a 200-kV cold-field emission gun (FEG) STEM model HD-2300C equipped with the EDAX genesis X-ray energy-dispersive spectrometry (XEDS) system through a spectrum imaging technique. In this study, elemental distributions of minor elements with weak signals were enhanced by applying principal component analysis (PCA), which is a superior technique to extract weak signals from a large dataset. The distributions of elements, especially the metallization component Ti and minor dopant As in this particular device, were successfully extracted by PCA. Finally, the 3D elemental distributions around the contact plug could be visualized by reconstruction from the tilt series of maps.

In situ high temperature TEM observation of interaction between multi-walled carbon nanotube and in situ deposited gold nano-particles.

Interaction between multi-walled carbon nanotubes (MWNTs) and deposited gold nano-particles has been dynamically observed in a 200 kV transmission electron microscope (TEM) using a specimen heating holder. Gold particles with diameters of several tens of microns were mixed with MWNTs to mount on the heating element of a specimen heating holder. The gold particles were instantaneously heated to 1373 K to deposit gold nano-particles on the MWNTs from a very short distance. The MWNTs were then heated to 1073 K to observe interaction between the deposited gold nano-particles and MWNTs. Some gold nano-particles drilled through the wall of the MWNT and entered the capillary space of the MWNTs. To characterize the mechanism of the transition of the gold nano-particles into the capillary space of the MWNT, high resolution TEM observation of the deformed wall of MWNT was also carried out.

Development of a technique for high resolution electron microscopic observation of nano-materials at elevated temperatures.

A technique for high resolution transmission electron microscopic (TEM) observation of nano-materials at very high temperatures has been developed. A spirally wound tungsten wire, normally used as the heating element of a high resolution-high temperature-specimen heating holder, was coated with a thin carbon film and the carbon film was used as the substrate of nanometer-sized specimen. The carbon film was securely self-adhered on the heater and the form of the carbon film remained unchanged until the tungsten heater is heated to around 1173 K. Temperature distribution on the carbon film has been measured by observing the sublimation of ZnS particles. Behavior of gold atoms on a surface of gold nano-particles dispersed on the carbon film has been clearly observed at 773 K in a scanning transmission electron microscope (STEM).

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.

Improvements in performance of focused ion beam cross-sectioning: aspects of ion-sample interaction.

A gallium (Ga) focused ion beam (FIB) has been applied increasingly to 'site-specific' preparation of cross-sectional samples for transmission electron microscopy (TEM), scanning TEM, scanning electron microscopy and scanning ion microscopy. It is absolutely required for FIB cross-sectioning to prepare higher-quality samples in a shorter time without sacrificing the site specificity. The present paper clarifies the parameters that impose limitation on the following performances of the FIB cross-sectioning: milling rate, cross-sectioning at a right angle with respect to the sample surface, curtain structures formed on the cross sections, ion implantation and ion damage. All of these are discussed from the viewpoint of ion-sample interaction. Improvements for these performances achieved by diminishing their limiting origins or by correcting the resultants are described. Especially, the FIB scanning speed is significantly utilizable to improve the milling rate. A microsampling method, which allows the FIB incidence in a sidewards or upwards direction as well as downwards with respect to the microsample surface, is very effective to minimize the curtain structures.

Evaluation of TEM samples of an Mg-Al alloy prepared using FIB milling at the operating voltages of 10 kV and 40 kV.

Transmission electron microscopy (TEM) samples of an Mg-Al alloy has been prepared using a Ga-focused ion beam (FIB) milling at two different operating voltages of 10 kV and 40 kV to investigate the influence of the FIB energy on the sample quality. The fine structures of the samples have been studied using a high resolution TEM, and the concentration of the implanted Ga was analysed using an energy dispersive X-ray (EDX) analysis. The result of the TEM observation revealed that point defects were introduced to the sample finally milled at 40 kV but not at 10 kV. However, crystal lattice images and electron diffraction patterns were clearly observed on both the samples. The typical influence of the FIB energy was indicated in the elemental analysis. The relative Ga concentration in the thin sample finally milled at 10 kV was 1.0-2.0 at% that is less than half of 4.0-6.0 at% of the Ga concentration in the sample finally milled at 40 kV. A comparison between the experimental results of the Ga concentration measurement with simulation was also discussed.

Application of a FIB-STEM system for 3D observation of a resin-embedded yeast cell.

The combination of a focused ion beam (FIB) system and a scanning transmission electron microscope (STEM) has been applied to the three-dimensional (3D) observation of a resin-embedded yeast cell. Using a FIB microsampling technique, a sample with a thickness of tens of micrometres was extracted from a resin-embedded block sample. The extracted sample was transferred to a FIB-STEM-compatible specimen rotation holder and trimmed by FIB milling for 3D STEM observation. Although the FIB milling was carried out at an operating voltage of 40 KV, the sample was cross sectioned without forming a harmful damage layer on its surface. Cell structures, such as cell wall, cell membrane, mitochondria, peroxisomes, endoplasmic reticulum and vacuoles, were observed clearly in a pillar-shaped sample of 20 microm long, 4 microm wide and 3 microm deep.

A method for multidirectional TEM observation of a specific site at atomic resolution.

A new technique has been developed for the three-dimensional structure characterisation of a specific site at atomic resolution. In this technique, a focused ion beam (FIB) system is used to extract a specimen from a desired site as well as to fabricate the electron transparent specimen. A specimen holder with a specimen stage rotation mechanism has also been developed for use with both an FIB system and a high-resolution transmission electron microscope (TEM). The specimen holder allows both the FIB milling of a specimen and its observation in TEM without remounting the specimen from the specimen holder. A specimen for the three-dimensional TEM observation is extracted using the FIB micro-sampling technique and shaped into a pillar to mount on a tip of a needle stub enabling a multidirectional observation. The technique was applied to the multidirectional observation of the crystal structure of an Si single crystal at atomic resolution. The crystal lattice fringes of the two Si(111) planes with distances of 0.31 nm as well as the lattice fringes of the Si(200) with distances of 0.19 nm were clearly observed.

Method for Cross-sectional Thin Specimen Preparation from a Specific Site Using a Combination of a Focused Ion Beam System and Intermediate Voltage Electron Microscope and Its Application to the Characterization of a Precipitate in a Steel.

In this study, we discuss a method for cross-sectional thin specimen preparation from a specific site using a combination of a focused ion beam (FIB) system and an intermediate voltage transmission electron microscope (TEM). A FIB-TEM compatible specimen holder was newly developed for the method. The thinning of the specimen using the FIB system and the observation of inside structure of the ion milled area in a TEM to localize a specific site were alternately carried out. The TEM fitted with both scanning transmitted electron detector and secondary electron detector enabled us to localize the specific site in a halfway milled specimen with the positional accuracy of better than 0.1 &mgr;m. The method was applied to the characterization of a precipitate in a steel. A submicron large precipitate was thinned exactly at its center for the characterization by a high-resolution electron microscopy and an elemental mapping.