Boosting Thermoelectric Performance in Epitaxial GeTe Film/Si by Domain Engineering and Point Defect Control.

This study demonstrates a simultaneous realization of ultralow thermal conductivity and high thermoelectric power factor in epitaxial GeTe thin films/Si substrates by a combination of the interface introduction by domain engineering and the suppression of Ge vacancy generation by point defect control. We formed epitaxial Te-poor GeTe thin films having low-angle grain boundaries with a misorientation angle close to 0° or twin interfaces with a misorientation angle close to 180°. The control of interfaces and point defects gave rise to ultralow lattice thermal conductivity of ∼0.7 ± 0.2 W m-1 K-1. This value was the same in the order of magnitude as the theoretical minimum lattice thermal conductivity of ∼0.5 W m-1 K-1 calculated by the Cahill-Pohl model. At the same time, the GeTe thin films exhibited a high thermoelectric power factor because of the suppression of Ge vacancy generation and a small contribution of grain boundary carrier scattering. The outstanding combined technique of domain engineering and point defect control can be a great approach for developing high-performance thermoelectric films.

Curcumin tautomerization in the mechanism of pentameric amyloid- ß42 oligomers disassembly.

Alzheimer's disease is a neurologic disorder characterized by the accumulation of extracellular deposits of amyloid-ß (Aß) fibrils in the brain of patients. The key etiologic agent in Alzheimer's disease is not known; however oligomeric Aß appears detrimental to neuronal functions and increases Aß fibrils deposition. Previous research has shown that curcumin, a phenolic pigment of turmeric, has an effect on Aß assemblies, although the mechanism remains unclear. In this study, we demonstrate that curcumin disassembles pentameric oligomers made from synthetic Aß42 peptides (pentameric oAß42), using atomic force microscopy imaging followed by Gaussian analysis. Since curcumin shows keto-enol structural isomerism (tautomerism), the effect of keto-enol tautomerism on its disassembly was investigated. We have found that curcumin derivatives capable of keto-enol tautomerization also disassemble pentameric oAß42, while, a curcumin derivative incapable of tautomerization did not affect the integrity of pentameric oAß42. These experimental findings indicate that keto-enol tautomerism plays an essential role in the disassembly. We propose a mechanism for oAß42 disassembly by curcumin based on molecular dynamics calculations of the tautomerism. When curcumin and its derivatives bind to the hydrophobic regions of oAß42, the keto-form changes predominantly to the enol-form; this transition is associated with structural (twisting, planarization and rigidification) and potential energy changes that give curcumin enough force to act as a torsion molecular-spring that eventually disassembles pentameric oAß42. This proposed mechanism sheds new light on keto-enol tautomerism as a relevant chemical feature for designing such novel therapeutic drugs that target protein aggregation.

The Effect of Ethanol on Disassembly of Amyloid-ß1-42 Pentamer Revealed by Atomic Force Microscopy and Gel Electrophoresis.

The most common type of dementia, Alzheimer's disease, is associated with senile plaques formed by the filamentous aggregation of hydrophobic amyloid-ß (Aß) in the brains of patients. Small oligomeric assemblies also occur and drugs and chemical compounds that can interact with such assemblies have attracted much attention. However, these compounds need to be solubilized in appropriate solvents, such as ethanol, which may also destabilize their protein structures. As the impact of ethanol on oligomeric Aß assembly is unknown, we investigated the effect of various concentrations of ethanol (0 to 7.2 M) on Aß pentameric assemblies (Aßp) by combining blue native-PAGE (BN-PAGE) and ambient air atomic force microscopy (AFM). This approach was proven to be very convenient and reliable for the quantitative analysis of Aß assembly. The Gaussian analysis of the height histogram obtained from the AFM images was correlated with band intensity on BN-PAGE for the quantitative estimation of Aßp. Our observations indicated up to 1.4 M (8.3%) of added ethanol can be used as a solvent/vehicle without quantitatively affecting Aß pentamer stability. Higher concentration induced significant destabilization of Aßp and eventually resulted in the complete disassembly of Aßp.

Phonon transport in the nano-system of Si and SiGe films with Ge nanodots and approach to ultralow thermal conductivity.

Phonon transport in the nano-system has been studied using well-designed nanostructured materials to observe and control the interesting phonon behaviors like ballistic phonon transport. Recently, we observed drastic thermal conductivity reduction in the films containing well-controlled nanodots. Here, we investigate whether this comes from the interference effect in ballistic phonon transport by comparing the thermal properties of the Si or Si0.75Ge0.25 films containing Ge nanodots. The experimentally-obtained thermal resistance of the nanodot layer shows peculiar nanodot size dependence in the Si films and a constant value in the SiGe films. From the phonon simulation results, interestingly, it is clearly found that in the nanostructured Si film, phonons travel in a non-diffusive way (ballistic phonon transport). On the other hand, in the nanostructured SiGe film, although simple diffusive phonon transport occurs, extremely-low thermal conductivity (∼0.81 W m-1 K-1) close to that of amorphous Si0.7Ge0.3 (∼0.7 W m-1 K-1) is achieved due to the combination of the alloy phonon scattering and Ge nanodot scattering.

A Chiral Metal-Organic 1D-Coordination Polymer Upon Complexation of Phenylene-Bridged Bipyrrole and Palladium (II) Ion.

Metal-organic 1D-coordination polymers, having unique electronic and optical properties, are expected to be a novel advanced functional material capable of fabricating smart plastics, films, and fibers. In this study, we have synthesized a novel metal-organic 1D-coordination polymer composed of a phenylene-bridged bipyrrole bearing N-alkylimino groups (BPI) and palladium(II) ion. The BPI and Pd(II) form square planar bis(bidentate) complex to form a metal coordinated π-conjugation polymer (Poly-BPI/Pd). It is stable in solutions at room temperature, and allowed measurement of its average molecular weight in SEC (M w = 106,000 and M n = 18,000, M w/M n = 5.88). It also provided a reversible multi redox profile in cyclic voltammetry, most likely originating from strong π-electronic interactions between the BPI components via Pd ion. A variety of substituent groups can be attached to the imino-nitrogens of BPI. A coordination polymer composed of a BPI derivative bearing chiral alkyl chains and Pd(II) showed strong circular dichroism (CD) in the solution due to the unidirectional chiral conformation of the BPI components in the polymer backbone.

Correlation between musculoskeletal structure of the hand and primate locomotion: Morphometric and mechanical analysis in prehension using the cross- and triple-ratios.

Biometric ratios of the relative length of the rays in the hand have been analyzed between primate species in the light of their hand function or phylogeny. However, how relative lengths among phalanges are mechanically linked to the grasping function of primates with different locomotor behaviors remains unclear. To clarify this, we calculated cross and triple-ratios, which are related to the torque distribution, and the torque generation mode at different joint angles using the lengths of the phalanges and metacarpal bones in 52 primates belonging to 25 species. The torque exerted on the finger joint and traction force of the flexor tendons necessary for a cylindrical grip and a suspensory hand posture were calculated using the moment arm of flexor tendons measured on magnetic resonance images, and were compared among Hylobates spp., Ateles sp., and Papio hamadryas. Finally, the torques calculated from the model were validated by a mechanical study detecting the force exerted on the phalanx by pulling the digital flexor muscles during suspension in these three species. Canonical discriminant analysis of cross and triple-ratios classified primates almost in accordance with their current classification based on locomotor behavior. The traction force was markedly reduced with flexion of the MCP joint parallel to the torque in brachiating primates; this was notably lower in the terrestrial quadrupedal primates than in the arboreal primates at mild flexion. Our mechanical study supported these features in the torque and traction force generation efficiencies. Our results suggest that suspensory or terrestrial quadrupedal primates have hand structures that can exert more torque at a suspensory posture, or palmigrade and digitigrade locomotion, respectively. Furthermore, our study suggests availability of the cross and triple-ratios as one of the indicators to estimate the hand function from the skeletal structure.

High Thermoelectric Power Factor Realization in Si-Rich SiGe/Si Superlattices by Super-Controlled Interfaces.

A Si-based superlattice is one of the promising thermoelectric films for realizing a stand-alone single-chip power supply. Unlike a p-type superlattice (SL) achieving a higher power factor due to strain-induced high hole mobility, in the n-type SL, the strain can degrade the power factor due to lifting conduction band degeneracy. Here, we propose epitaxial Si-rich SiGe/Si SLs with ultrathin Ge segregation interface layers. The ultrathin interface layers are designed to be sufficiently strained, not to give strain to the above Si layers. Therein, a drastic thermal conductivity reduction occurs by larger phonon scattering at the interfaces with the large atomic size difference between Si layers and Ge segregation layers, while unstrained Si layers preserve a high conduction band degeneracy leading to a high Seebeck coefficient. As a result, the n-type Si0.7Ge0.3/Si SL with controlled interfaces achieves a higher power factor of ∼25 µW cm-1 K-2 in the in-plane direction at room temperature, which is superior to ever reported SiGe-based films: SiGe-based SLs and SiGe films. The Si0.7Ge0.3/Si SL with controlled interfaces also exhibits a low thermal conductivity of ∼2.5 W m-1 K-1 in the cross-plane direction, which is ∼5 times lower than the reported value in a conventional Si0.7Ge0.3/Si SL. These results demonstrate that strain and atomic differences controlled by ultrathin layers can bring a breakthrough for realizing high-performance light-element-based thermoelectric films.

Resistive switching memory performance in oxide hetero-nanocrystals with well-controlled interfaces.

For realization of new informative systems, the memristor working like synapse has drawn much attention. We developed isolated high-density Fe3O4 nanocrystals on Ge nuclei/Si with uniform and high resistive switching performance using low-temperature growth. The Fe3O4 nanocrystals on Ge nuclei had a well-controlled interface (Fe3O4/GeOx/Ge) composed of high-crystallinity Fe3O4 and high-quality GeOx layers. The nanocrystals showed uniform resistive switching characteristics (high switching probability of ~90%) and relatively high Off/On resistance ratio (~58). The high-quality interface enables electric field application to Fe3O4 and GeOx near the interface, which leads to effective positively charged oxygen vacancy movement, resulting in high-performance resistive switching. Furthermore, we successfully observed memory effect in nanocrystals with well-controlled interface. The experimental confirmation of the memory effect existence even in ultrasmall nanocrystals is significant for realizing non-volatile nanocrystal memory leading to neuromorphic devices.

Methodology of Thermoelectric Power Factor Enhancement by Controlling Nanowire Interface.

The simultaneous realization of low thermal conductivity and high thermoelectric power factor in materials has long been the goal for the social use of high-performance thermoelectric modules. Nanostructuring approaches have drawn considerable attention because of the success in reducing thermal conductivity. On the contrary, enhancement of the thermoelectric power factor, namely, the simultaneous increase of the Seebeck coefficient and electrical conductivity, has been difficult. We propose a method for the power factor enhancement by introducing coherent homoepitaxial interfaces with controlled dopant concentration, which enables the quasiballistic transmission of high-energy carriers. The wavenumber of the high-energy carriers is nearly conserved through the interfaces, resulting in simultaneous realization of a high Seebeck coefficient and relatively high electrical mobility. Here, we experimentally demonstrate the dopant-controlled epitaxial interface effect for the thermoelectric power factor enhancement using our "embedded-ZnO nanowire structure" having high-quality nanowire interfaces. This presents the methodology for substantial power factor enhancement by interface carrier scattering.

Mechanically activated switching of Si-based single-molecule junction as imaged with three-dimensional dynamic probe.

Understanding and extracting the full functions of single-molecule characteristics are key factors in the development of future device technologies, as well as in basic research on molecular electronics. Here we report a new methodology for realizing a three-dimensional (3D) dynamic probe of single-molecule conductance, which enables the elaborate 3D analysis of the conformational effect on molecular electronics, by the formation of a Si/single molecule/Si structure using scanning tunnelling microscopy (STM). The formation of robust covalent bonds between a molecule and Si electrodes, together with STM-related techniques, enables the stable and repeated control of the conformational modulation of the molecule. By 3D imaging of the conformational effect on a 1,4-diethynylbenzene molecule, a binary change in conductance with hysteresis is observed for the first time, which is considered to originate from a mechanically activated conformational change.

Probing ultrafast spin dynamics with optical pump-probe scanning tunnelling microscopy.

Studies of spin dynamics in low-dimensional systems are important from both fundamental and practical points of view. Spin-polarized scanning tunnelling microscopy allows localized spin dynamics to be characterized and plays important roles in nanoscale science and technology. However, nanoscale analysis of the ultrafast dynamics of itinerant magnetism, as well as its localized characteristics, should be pursued to advance further the investigation of quantum dynamics in functional structures of small systems. Here, we demonstrate the optical pump-probe scanning tunnelling microscopy technique, which enables the nanoscale probing of spin dynamics with the temporal resolution corresponding, in principle, to the optical pulse width. Spins are optically oriented using circularly polarized light, and their dynamics are probed by scanning tunnelling microscopy based on the optical pump-probe method. Spin relaxation in a single quantum well with a width of 6 nm was observed with a spatial resolution of ∼ 1 nm. In addition to spin relaxation dynamics, spin precession, which provides an estimation of the Landé g factor, was observed successfully.

Bases for time-resolved probing of transient carrier dynamics by optical pump-probe scanning tunneling microscopy.

The tangled mechanism that produces optical pump-probe scanning tunneling microscopy spectra from semiconductors was analyzed by comparing model simulation data with experimental data. The nonlinearities reflected in the spectra, namely, the excitations generated by paired laser pulses with a delay time, the logarithmic relationship between carrier density and surface photovoltage (SPV), and the effect of the change in tunneling barrier height depending on SPV, were examined along with the delay-time-dependent integration process used in measurement. The optimum conditions required to realize reliable measurement, as well as the validity of the microscopy technique, were demonstrated for the first time.

Nanoprobe fourier-transform photoabsorption spectroscopy using a supercontinuum light source.

A scheme of photoabsorption spectroscopy based on scanning tunneling microscopy (STM) has been developed by using a supercontinuum light as the wideband light source of a Fourier transform interferometer for spectroscopic measurements. The performance was demonstrated for a sample of GaAs. The proof-of-concept test showed that the use of the supercontinuum light instead of halogen lamps greatly enhances the signal-to-noise ratio due to the high brilliance of the supercontinuum light emitted from a small core of the photonic crystal fiber that enables tight focusing of the spectroscopy light onto the sample beneath the STM tip.

Response analysis for identifying the origin of photo-modulated current contrasts in scanning tunneling microscopic imaging semiconductor surfaces.

Inhomogeneities in semiconductor solids can be imaged by two-dimensional mapping of the amplitude of periodically modulated tip current in scanning tunneling microscopy that is induced by illumination of semiconductor samples with a chopped light. It has been shown that it is possible to distinguish between plural origins of the photo-modulated current by analyzing the response properties of the current signal. A judicial choice of the modulation frequency is important for the required contrasts to be obtained.

Nanoscale imaging of electronic surface transport probed by atom movements induced by scanning tunneling microscope current.

The hopping movements of Cl atoms on a Si(111)-(7 x 7) surface that are enhanced by an electron injection from tips of a scanning tunneling microscope (STM) exhibit a spatial spread from the electron injection point with an anisotropic distribution. The enhanced hopping effect becomes greatest at a sample bias voltage being resonant with the Si-Cl antibonding states and also exhibits an oscillatory decay with the distance from the injection point characterized by the wavelength depending on the bias voltage. All of these facts can be interpreted in terms of the coherent expansion of the electron wave packets locally formed at the STM tip.