STEM in situ thermal wave observations for investigating thermal diffusivity in nanoscale materials and devices.

Practical techniques to identify heat routes at the nanoscale are required for the thermal control of microelectronic, thermoelectric, and photonic devices. Nanoscale thermometry using various approaches has been extensively investigated, yet a reliable method has not been finalized. We developed an original technique using thermal waves induced by a pulsed convergent electron beam in a scanning transmission electron microscopy (STEM) mode at room temperature. By quantifying the relative phase delay at each irradiated position, we demonstrate the heat transport within various samples with a spatial resolution of ~10 nm and a temperature resolution of 0.01 K. Phonon-surface scatterings were quantitatively confirmed due to the suppression of thermal diffusivity. The phonon-grain boundary scatterings and ballistic phonon transport near the pulsed convergent electron beam were also visualized.

Direct Probe of the Ferromagnetic Proximity Effect at the Interface of SnTe/Fe Heterostructure by Polarized Neutron Reflectometry.

Introducing magnetic order into a topological insulator (TI) system has attracted much attention with an expectation of realizing exotic phenomena such as the quantum anomalous Hall effect (QAHE) and axion insulator states. The magnetic proximity effect (MPE) is one of the promising schemes to induce the magnetic order on the surface of a TI without introducing disorder accompanied by doping magnetic impurities in the TI. In this study, we investigate the MPE at the interface of a heterostructure consisting of the topological crystalline insulator (TCI) SnTe and Fe by employing polarized neutron reflectometry. The ferromagnetic order penetrates ∼2.2 nm deep into the SnTe layer from the interface with Fe, which persists up to room temperature. This is induced by the MPE on the surface of the TCI preserving the coherent topological states without introducing the disorder by doping magnetic impurities. This would open up a way for realizing next-generation spintronics and quantum computational devices.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.

Transport of intensity equation method and its applications.

A phase retrieval technique based on a transport of intensity equation (TIE) is one of the defocus series reconstruction techniques in microscopy. Since it does not require any dedicated devices like a biprism, and only three defocus images are enough to retrieve phase information, it has been applied to observe magnetic fields, magnetic domains, electrostatic potentials and strains. It is also used to improve image resolution by correcting spherical aberration. This technique is simple and easy to use, but some artifacts often appear in the retrieved phase map. One should pay careful attention to the experimental conditions and the algorithms and boundary conditions used to solve the TIE. This paper reviews the principle of the TIE method, the algorithms used to solve it and application results in materials science.

A stable LaB6 nanoneedle field-emission point electron source.

A material with a low work function exhibiting field-emission of electrons has long been sought as an ideal point electron source to generate a coherent electron beam with high brightness, long service life, low energy spread, and especially stable emission current. The quality and performance of the electron source are now becoming limiting factors for further improving the spatial resolution and analytical capabilities of the electron microscope. While tungsten (W) is still the only material of choice as a practically usable field emission filament since it was identified more than six decades ago, its electron optical performance remains unsatisfactory, especially the poor emission stability (>5% per hour), rapid current decay (20% in 10 hours), and relatively large energy spread (0.4 eV), even in an extremely high vacuum (10-9 Pa). Herein, we report a LaB6 nanoneedle structure having a sharpened tip apex with a radius of curvature of about 10 nm that is fabricated and finished using a focused ion beam (FIB) and show that it can produce a field emission electron beam meeting the application criteria with a high reduced brightness (1010 A m-2 sr-1 V-1), small energy spread (0.2 eV), and especially high emission stability (<1% fluctuation in 16 hours without decay). It can now be used practically as a next-generation field-emission point electron source.

Self-healing by design: universal kinetic model of strength recovery in self-healing ceramics.

We propose a new theoretical kinetic model of strength recovery by oxidation-induced self-healing of surface cracks in composites containing a healing agent (HA). The kinetics is a key parameter in the design of structural components that can self-heal the damage done in service. Based on three-dimensional (3D) observations of crack-gap filling, two crack-gap filling models, i.e., a bridging model and a tip-to-mouth filling model, are incorporated in the proposed kinetic model. These crack-gap filling models account for the microstructural features of the fracture surfaces, crack geometry, and oxidation kinetics of the healing-agent. Hence, the minimum and maximum remaining flaw sizes in the healed crack gaps are estimated for various healing temperatures, times, and oxygen partial pressure conditions. Further, the nonlinear elastic fracture mechanics suitable for small-sized remaining flaws, together with a statistical analysis of the original Weibull-type strength distribution, enables the prediction of upper and lower strength limits of the healed composites. Three sintered alumina matrix composites containing silicon carbide (SiC)-type HAs with various volume fractions and shapes, together with monolithic SiC ceramics, are considered. The strength of the healed-composite predicted by our model agrees well with the experimental values. This theoretical approach can be applied to HAs other than SiC and enables the design of self-healing ceramic components for various applications.

Electrical conduction and field emission of a single-crystalline GdB44Si2 nanowire.

The electronic transport and field emission properties of a single-crystalline GdB44Si2 nanowire are studied. The atomic structure and elemental composition of the GdB44Si2 nanowire are characterized by transmission electron microscopy (TEM) using atomic imaging, energy-dispersive X-ray spectroscopy (EDS), and electron energy-loss spectroscopic (EELS) mapping. The electrical conductivity of the single GdB44Si2 nanowire is in the range of 46.8-60.1 S m-1. The in situ TEM field emission measurement reveals that it has a low work function of 2.4 eV. To realize a converged electron emission, a field evaporation pretreatment was used to clean the emission surface and to make a sharpened tip. The field emission probe measurement results show that the electron emission from the sharp GdB44Si2 nanowire is converged to a single field emission spot and it has a work function of 2.6 eV which is in agreement with the in situ TEM measurement. The stability of field emission current is also very good with a fluctuation of 1.4% in 20 min. With a low work function and stable emission current, the GdB44Si2 nanowire shows great promise for field emission applications.

A controllable and efficient method for the fabrication of a single HfC nanowire field-emission point electron source aided by low keV FIB milling.

A single hafnium carbide (HfC) nanowire field-induced electron emitter with a sharp tip apex is fabricated by Pt deposition and focused ion beam (FIB) milling. The structure of the electron emitter is characterized by scanning transmission electron microscopy (STEM) and atom probe tomography (APT). The HfC nanowire is single-crystalline with a thin oxide layer on its tip surface. The field emission properties are determined by using both in situ transmission electron microscopy (TEM) and a field-emission probe in a high-vacuum chamber. A high current of 173 nA was obtained at a low extraction voltage of 631 V with an emission gap of 5 mm. The emission current is stable at 60 nA for 100 min with a fluctuation of 0.7%. The deduced work function was 3.1 eV. It is suggested that the implanted Ga ions and the oxide layer induce more downward dipoles that are beneficial for lowering the work function and creating a stable surface. When the low keV FIB processing is applied, it takes within 30 minutes to finish a HfC nanowire emitter, establishing an efficient procedure for the preparation of nanowire emitters. These results provide a controllable and fast production method for the fabrication of single nanowire field-emission point electron sources.

Intrinsic and Defect-Related Elastic Moduli of Boron Nitride Nanotubes As Revealed by in Situ Transmission Electron Microscopy.

Boron nitride nanotubes (BNNTs) are promising for mechanical applications owing to the high modulus, high strength, and inert chemical nature. However, up to now, precise evaluation of their elastic properties and their relation to defects have not been experimentally established. Herein, the intrinsic elastic modulus of BNNTs and its dependence on intrinsic and deliberately irradiation-induced extrinsic defects have been studied via an electric-field-induced high-order resonance technique inside a high-resolution transmission electron microscope (HRTEM). Resonances up to fourth order for normal modes and third order for parametric modes have been initiated in the cantilevered tubes, and the recorded frequencies are well consistent with the theoretical calculations with a discrepancy of ∼1%. The elastic moduli of the BNNTs measured from high-order resonance is about 906.2 GPa on average, with a standard deviation of 9.3%, which is found to be closely related to the intrinsic defect as cavities in the nanotube walls. Furthermore, electron irradiation in HRTEM has been used to study the effects of defects to elastic moduli and to evaluate the radiation resistance of the BNNTs. Along with an increase in the irradiation dose, the outer diameter has linearly reduced due to the knock-on effects. A defective shell with nearly constant thickness has been formed on the outer surface, and as a result, the elastic modulus decreases gradually to ∼662.9 GPa, which is still 3 times that of steel. Excellent intrinsic elastic properties and decent radiation-resistance prove that BNNTs could be a material of choice for applications in extreme environments, such as those existing in space.

Realization and direct observation of five normal and parametric modes in silicon nanowire resonators by in situ transmission electron microscopy.

Mechanical resonators have wide applications in sensing bio-chemical substances, and provide an accurate method to measure the intrinsic elastic properties of oscillating materials. A high resonance order with high response frequency and a small resonator mass are critical for enhancing the sensitivity and precision. Here, we report on the realization and direct observation of high-order and high-frequency silicon nanowire (Si NW) resonators. By using an oscillating electric-field for inducing a mechanical resonance of single-crystalline Si NWs inside a transmission electron microscope (TEM), we observed resonance up to the 5th order, for both normal and parametric modes at ∼100 MHz frequencies. The precision of the resonant frequency was enhanced, as the deviation reduced from 3.14% at the 1st order to 0.25% at the 5th order, correlating with the increase of energy dissipation. The elastic modulus of Si NWs was measured to be ∼169 GPa in the [110] direction, and size scaling effects were found to be absent down to the ∼20 nm level.

Chirality transitions and transport properties of individual few-walled carbon nanotubes as revealed by in situ TEM probing.

Physical properties of carbon nanotubes (CNTs) are closely related to the atomic structure, i.e. the chirality. It is highly desirable to develop a technique to modify their chirality and control the resultant transport properties. Herein, we present an in situ transmission electron microscopy (TEM) probing method to monitor the chirality transition and transport properties of individual few-walled CNTs. The changes of tube structure including the chirality are stimulated by programmed bias pulses and associated Joule heating. The chirality change of each shell is analyzed by nanobeam electron diffraction. Supported by molecular dynamics simulations, a preferred chirality transition path is identified, consistent with the Stone-Wales defect formation and dislocation sliding mechanism. The electronic transport properties are measured along with the structural changes, via fabricating transistors using the individual nanotubes as the suspended channels. Metal-to-semiconductor transitions are observed along with the chirality changes as confirmed by both the electron diffraction and electrical measurements. Apart from providing an alternative route to control the chirality of CNTs, the present work demonstrates the rare possibility of obtaining the dynamic structure-properties relationships at the atomic and molecular levels.

A Novel Design Approach for Self-Crack-Healing Structural Ceramics with 3D Networks of Healing Activator.

Self-crack-healing by oxidation of a pre-incorporated healing agent is an essential property of high-temperature structural ceramics for components with stringent safety requirements, such as turbine blades in aircraft engines. Here, we report a new approach for a self-healing design containing a 3D network of a healing activator, based on insight gained by clarifying the healing mechanism. We demonstrate that addition of a small amount of an activator, typically doped MnO localised on the fracture path, selected by appropriate thermodynamic calculation significantly accelerates healing by >6,000 times and significantly lowers the required reaction temperature. The activator on the fracture path exhibits rapid fracture-gap filling by generation of mobile supercooled melts, thus enabling efficient oxygen delivery to the healing agent. Furthermore, the activator promotes crystallisation of the melts and forms a mechanically strong healing oxide. We also clarified that the healing mechanism could be divided to the initial oxidation and additional two stages. Based on bone healing, we here named these stages as inflammation, repair, and remodelling stages, respectively. Our design strategy can be applied to develop new lightweight, self-healing ceramics suitable for use in high- or low-pressure turbine blades in aircraft engines.

Statistically Analyzed Photoresponse of Elastically Bent CdS Nanowires Probed by Light-Compatible In Situ High-Resolution TEM.

We demonstrate that high resolution transmission electron microscopy (HRTEM) paired with light illumination of a sample and its electrical probing can be utilized for the in situ study of initiated photocurrents in free-standing nanowires. Morphology, phase and crystallographic information from numerous individual CdS nanowires is obtained simultaneously with photocurrent measurements. Our results indicate that elastically bent CdS nanowires possessing a wurtzite structure show statistically unchanged values of ON/OFF (photocurrent/dark current) ratios. Photocurrent spectroscopy reveals red shifts of several nanometers in the cutoff wavelength after nanowire bending. This results from deformation-induced lattice strain and associated changes in the nanowire band structure, as confirmed by selected area electron diffraction (SAED) analyses and density functional tight binding (DFTB) simulations. The ON/OFF ratio stabilities and photocurrent spectroscopy shift of bent CdS nanowires are important clues for future flexible electronics, optoelectronics, and photovoltaics.

Constituent elements and their distribution in the radioactive Cs-bearing silicate glass microparticles released from Fukushima nuclear plant.

Microparticles of radioactive cesium (Cs)-bearing silicate glass emitted from the Fukushima Daiichi nuclear power plant were investigated mainly using state-of-the-art energy-dispersive X-ray spectroscopy in scanning transmission electron microscopes. Precise elemental maps of the particles were obtained using double silicon drift detectors with a large collection angle of X-rays, and qualitative elemental analysis was performed using high-resolution X-ray spectroscopy with a microcalorimetry detector. Beside the substantial elements (O, Si, Cl, K, Fe, Zn, Rb, Sn and Cs) as previously reported, Mn and Ba were also common, though their amounts were small. The atomic ratios of the substantial elements were not the same but varied among individual particles. Fe and Zn were relatively homogeneously distributed, whereas the concentration of alkali ions varied radially. Generally, Cs was rich and K and Rb were poor outward of the particles but the degree of such radial dependence was considerably different among the particles. A concentration of Sn on the particle surface was observed. High-resolution imaging indicated the formation of SnO2 (cassiterite) nanocrystals on the surface. Synthesis of the bulk glass with a similar composition to the microparticles was attempted by quenching the silicate melt from ∼1600°C. However, homogeneous silicate glass like that of the microparticles could not be obtained due to the segregation of nano-spherules rich in Fe and Zn, suggesting that the microparticles were formed in a very specific condition in the nuclear reactor.

Internal structure of cesium-bearing radioactive microparticles released from Fukushima nuclear power plant.

Microparticles containing substantial amounts of radiocesium collected from the ground in Fukushima were investigated mainly by transmission electron microscopy (TEM) and X-ray microanalysis with scanning TEM (STEM). Particles of around 2 µm in diameter are basically silicate glass containing Fe and Zn as transition metals, Cs, Rb and K as alkali ions, and Sn as substantial elements. These elements are homogeneously distributed in the glass except Cs which has a concentration gradient, increasing from center to surface. Nano-sized crystallites such as copper- zinc- and molybdenum sulfide, and silver telluride were found inside the microparticles, which probably resulted from the segregation of the silicate and sulfide (telluride) during molten-stage. An alkali-depleted layer of ca. 0.2 µm thick exists at the outer side of the particle collected from cedar leaves 8 months after the nuclear accident, suggesting gradual leaching of radiocesium from the microparticles in the natural environment.

Pollutant capturing SERS substrate: porous boron nitride microfibers with uniform silver nanoparticle decoration.

How to concentrate target molecules on the surface of a SERS substrate is a key problem in the practical application of SERS. Herein, we designed for the first time a pollutant capturing surface enhanced Raman spectroscopy (SERS) substrate, namely porous BN microfibers uniformly decorated with Ag nanoparticles, in which the BN microfibers adsorb pollutants, while the Ag nanoparticles provide SERS activity. This SERS substrate captures pollutants from an aqueous solution completely and accumulates them all on its surface without introducing noise signals. The pores of BN protect the silver particles from aggregation which makes BN/Ag a stable and recyclable SERS substrate. What's more, while the dyes are thoroughly concentrated from a diluted solution, the SERS detection limit is easily enhanced, from 10(-6) M to 10(-9) M.

Nanoscale characterization of the thermal interface resistance of a heat-sink composite material by in situ TEM.

We developed an original method of in situ nanoscale characterization of thermal resistance utilizing a high-resolution transmission electron microscope (HRTEM). The focused electron beam of the HRTEM was used as a contact-free heat source and a piezo-movable nanothermocouple was developed as a thermal detector. This method has a high flexibility of supplying thermal-flux directions for nano/microscale thermal conductivity analysis, and is a powerful way to probe the thermal properties of complex or composite materials. Using this method we performed reproducible measurements of electron beam-induced temperature changes in pre-selected sections of a heat-sink α-Al(2)O(3)/epoxy-based resin composite. Observed linear behavior of the temperature change in a filler reveals that Fourier's law holds even at such a mesoscopic scale. In addition, we successfully determined the thermal resistance of the nanoscale interfaces between neighboring α-Al(2)O(3) fillers to be 1.16 × 10(-8) m(2)K W(-1), which is 35 times larger than that of the fillers themselves. This method that we have discovered enables evaluation of thermal resistivity of composites on the nanoscale, combined with the ultimate spatial localization and resolution sample analysis capabilities that TEM entails.

Amorphization and Directional Crystallization of Metals Confined in Carbon Nanotubes Investigated by in Situ Transmission Electron Microscopy.

The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.

Magnetoresistance of drop-cast film of cobalt-substituted magnetite nanocrystals.

An oleic acid-coated Fe2.7Co0.3O4 nanocrystal (NC) self-assembled film was fabricated via drop casting of colloidal particles onto a three-terminal electrode/MgO substrate. The film exhibited a large coercivity (1620 Oe) and bifurcation of the zero-field-cooled and field-cooled magnetizations at 300 K. At 10 K, the film exhibited both a Coulomb blockade due to single electron charging as well as a magnetoresistance of ∼-80% due to spin-dependent electron tunneling. At 300 K, the film also showed a magnetoresistance of ∼-80% due to hopping of spin-polarized electrons. Enhanced magnetic coupling between adjacent NCs and the large coercivity resulted in a large spin-polarized current flow even at 300 K.

Three-dimensional strutted graphene grown by substrate-free sugar blowing for high-power-density supercapacitors.

Three-dimensional graphene architectures in the macroworld can in principle maintain all the extraordinary nanoscale properties of individual graphene flakes. However, current 3D graphene products suffer from poor electrical conductivity, low surface area and insufficient mechanical strength/elasticity; the interconnected self-supported reproducible 3D graphenes remain unavailable. Here we report a sugar-blowing approach based on a polymeric predecessor to synthesize a 3D graphene bubble network. The bubble network consists of mono- or few-layered graphitic membranes that are tightly glued, rigidly fixed and spatially scaffolded by micrometre-scale graphitic struts. Such a topological configuration provides intimate structural interconnectivities, freeway for electron/phonon transports, huge accessible surface area, as well as robust mechanical properties. The graphene network thus overcomes the drawbacks of presently available 3D graphene products and opens up a wide horizon for diverse practical usages, for example, high-power high-energy electrochemical capacitors, as highlighted in this work.