Record-High Thermoelectric Performance in Al-Doped ZnO via Anderson Localization of Band Edge States.

Oxides are of interest for thermoelectrics due to their high thermal stability, chemical inertness, low cost, and eco-friendly constituting elements. Here, adopting a unique synthesis route via chemical co-precipitation at strongly alkaline conditions, one of the highest thermoelectric performances for ZnO ceramics ( P F max = $PF_{\text{max}} =$  21.5 µW cm-1 K-2 and z T max = $zT_{\text{max}} =$  0.5 at 1100 K in Zn 0.96 Al 0.04 O ${\rm Zn}_{0.96} {\rm Al}_{0.04}{\rm O}$ ) is achieved. These results are linked to a distinct modification of the electronic structure: charge carriers become trapped at the edge of the conduction band due to Anderson localization, evidenced by an anomalously low carrier mobility, and characteristic temperature and doping dependencies of charge transport. The bi-dimensional optimization of doping and carrier localization enable a simultaneous improvement of the Seebeck coefficient and electrical conductivity, opening a novel pathway to advance ZnO thermoelectrics.

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.

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.

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.

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.

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.

Chemical unzipping of WS2 nanotubes.

WS2 nanoribbons have been synthesized by chemical unzipping of WS2 nanotubes. Lithium atoms are intercalated in WS2 nanotubes by a solvothermal reaction with n-butyllithium in hexane. The lithiated WS2 nanotubes are then reacted with various solvents--water, ethanol, and long chain thiols. While the tubes break into pieces when treated with water and ethanol, they unzip through longitudinal cutting along the axes to yield nanoribbons when treated with long chain thiols, 1-octanethiol and 1-dodecanethiol. The slow diffusion of the long chain thiols reduces the aggression of the reaction, leading to controlled opening of the tubes.

Ternary modified TiO2 as a simple and efficient photocatalyst for green organic synthesis.

TiO2 ternary-modified with Fe(3+), Ni(2+), and Au nanoparticles exhibited a noticeable photocatalytic activity for selective cyclohexane oxidation with O2 under sunlight irradiation.

Revealing the anomalous tensile properties of WS2 nanotubes by in situ transmission electron microscopy.

Mechanical properties and fracture behaviors of multiwalled WS2 nanotubes produced by large scale fluidized bed method were investigated under uniaxial tension using in situ transmission electron microscopy probing; these were directly correlated to the nanotube atomic structures. The tubes with the average outer diameter ∼40 nm sustained tensile force of ∼2949 nN and revealed fracture strength of ∼11.8 GPa. Surprisingly, these rather thick WS2 nanotubes could bear much higher loadings than the thin WS2 nanotubes with almost "defect-free" structures studied previously. In addition, the fracture strength of the "thick" nanotubes did not show common size dependent degradation when the tube diameters increased from ∼20 to ∼60 nm. HRTEM characterizations and real time observations revealed that the anomalous tensile properties are related to the intershell cross-linking and geometric constraints from the inverted cone-shaped tube cap structures, which resulted in the multishell loading and fracturing.

Transmission electron microscope as an ultimate tool for nanomaterial property studies.

In this review, a non-standard application of high-resolution transmission electron microscope (HRTEM), namely the creation of so-called NanoLaboratory for the nanomaterial property studies within its pole piece, is presented. The most modern research trends with respect to nanotube, graphene and nanowire, as well as electrical, mechanical and electromechanical properties are demonstrated. In addition, the unique possibilities of modeling real technological processes inside HRTEM, for example, the performance of Li-ion batteries, are illustrated. The contribution particularly highlights the recent research endeavors of our Tsukuba group in line with all the above-mentioned directions of in situ TEM.

Mechanical properties of Si nanowires as revealed by in situ transmission electron microscopy and molecular dynamics simulations.

Deformation and fracture mechanisms of ultrathin Si nanowires (NWs), with diameters of down to ~9 nm, under uniaxial tension and bending were investigated by using in situ transmission electron microscopy and molecular dynamics simulations. It was revealed that the mechanical behavior of Si NWs had been closely related to the wire diameter, loading conditions, and stress states. Under tension, Si NWs deformed elastically until abrupt brittle fracture. The tensile strength showed a clear size dependence, and the greatest strength was up to 11.3 GPa. In contrast, under bending, the Si NWs demonstrated considerable plasticity. Under a bending strain of <14%, they could repeatedly be bent without cracking along with a crystalline-to-amorphous phase transition. Under a larger strain of >20%, the cracks nucleated on the tensed side and propagated from the wire surface, whereas on the compressed side a plastic deformation took place because of dislocation activities and an amorphous transition.

Local temperature measurements on nanoscale materials using a movable nanothermocouple assembled in a transmission electron microscope.

A nanoscale thermocouple consisting of merged Cu and Cu-Ni tips is developed for local temperature measurements on advanced nanomaterials by using a probing technique in a high-resolution transmission electron microscope (TEM) equipped with a double probe scanning tunneling microcopy (STM) unit. The fabricated nanothermocouple works as the so-called T-type thermocouple and displays a quick response and high spatial and thermal resolutions. A generated thermoelectromotive force which reflects rapid temperature changes controlled by electron beam intensity alternations on a metal nanoelectrode proves the technique's usefulness for high-precision local temperature measurements. The developed method demonstrates the effectiveness while also measuring temperature changes in Joule heated multi-walled carbon nanotubes (CNTs) and in a modeled electrical conductive composite nanosystem.