Improving the Long-Term Stability of PbTe-Based Thermoelectric Modules: From Nanostructures to Packaged Module Architecture.

Nanostructured lead telluride PbTe is among the best-performing thermoelectric materials, for both p- and n-types, for intermediate temperature applications. However, the fabrication of power-generating modules based on nanostructured PbTe still faces challenges related to the stability of the materials, especially nanoprecipitates, and the bonding of electric contacts. In this study, in situ high-temperature transmission electron microscopy observation confirmed the stability of nanoprecipitates in p-type PbNaGeTe up to at least ∼786 K.

Direct Observation of Locally Modified Excitonic Effects within a Moiré Unit Cell in Twisted Bilayer Graphene.

Bilayer graphene, which forms moiré superlattices, possesses distinct electronic and optical properties owing to its hybridized energy band and the emergence of van Hove singularities depending on its twist angle. Extensive research has been conducted on the characteristics of moiré superlattices induced by their long-range periodicity. However, the properties, which differ owing to the variations in the three-dimensional atomic arrangement, within a moiré unit cell have been rarely explored.

Momentum-Dependent Oscillator Strength Crossover of Excitons and Plasmons in Two-Dimensional PtSe.

The 1T-phase layered PtX chalcogenide has attracted widespread interest due to its thickness dependent metal-semiconductor transition driven by strong interlayer coupling. While the ground state properties of this paradigmatic material system have been widely explored, its fundamental excitation spectrum remains poorly understood. Here we combine first-principles calculations with momentum () resolved electron energy loss spectroscopy (-EELS) to study the collective excitations in 1T-PtSe from the monolayer limit to the bulk.

Multiple 2D Phase Transformations in Monolayer Transition Metal Chalcogenides.

Phase transformation lies at the heart of materials science because it allows for the control of structural phases of solids with desired properties. It has long been a challenge to manipulate phase transformations in crystals at the nanoscale with designed interfaces and compositions. Here in situ electron microscopy is employed to fabricate novel 2D phases with different stoichiometries in monolayer MoS and MoSe .

Deciphering the Intense Postgap Absorptions of Monolayer Transition Metal Dichalcogenides.

Rich valleytronics and diverse defect-induced or interlayer pre-bandgap excitonics have been extensively studied in transition metal dichalcogenides (TMDCs), a system with fascinating optical physics. However, more intense high-energy absorption peaks (∼3 eV) above the bandgaps used to be long ignored and their underlying physical origin remains to be unveiled. Here, we employ momentum resolved electron energy loss spectroscopy to measure the dispersive behaviors of the valley excitons and intense higher-energy peaks at finite momenta.

Unexpected Huge Dimerization Ratio in One-Dimensional Carbon Atomic Chains.

Peierls theory predicted atomic distortion in one-dimensional (1D) crystal due to its intrinsic instability in 1930. Free-standing carbon atomic chains created in situ in transmission electron microscope (TEM)1-3 are an ideal example to experimentally observe the dimerization behavior of carbon atomic chain within a finite length. We report here a surprisingly huge distortion found in the free-standing carbon atomic chains at 773 K, which is 10 times larger than the value expected in the system.

Application of preparative disk gel electrophoresis for antigen purification from inclusion bodies.

Specific antibodies are a reliable tool to examine protein expression patterns and to determine the protein localizations within cells. Generally, recombinant proteins are used as antigens for specific antibody production. However, recombinant proteins from mammals and plants are often overexpressed as insoluble inclusion bodies in Escherichia coli.

Structural and Chemical Dynamics of Pyridinic-Nitrogen Defects in Graphene.

High density and controllable nitrogen doping in graphene is a critical issue to realize high performance graphene-based devices. In this paper, we demonstrate an efficient method to selectively produce graphitic-N and pyridinic-N defects in graphene by using the mixture plasma of ozone and nitrogen. The atomic structure, electronic structure, and dynamic behavior of these nitrogen defects are systematically studied at the atomic level by using a scanning transmission electron microscopy.

Structure and local chemical properties of boron-terminated tetravacancies in hexagonal boron nitride.

Imaging and spectroscopy performed in a low-voltage scanning transmission electron microscope are used to characterize the structure and chemical properties of boron-terminated tetravacancies in hexagonal boron nitride. We confirm earlier theoretical predictions about the structure of these defects and identify new features in the electron energy-loss spectra of B atoms using high resolution chemical maps, highlighting differences between these areas and pristine sample regions. We correlate our experimental data with calculations which help explain our observations.

Single molecular spectroscopy: identification of individual fullerene molecules.

We report the molecule-by-molecule spectroscopy of individual fullerenes by means of electron spectroscopy based on scanning transmission electron microscopy. Electron energy-loss fine structure analysis of carbon 1s absorption spectra is used to discriminate carbon allotropes with known symmetries. C(60) and C(70) molecules randomly stored inside carbon nanotubes are successfully identified at a single-molecular basis.

Stability and spectroscopy of single nitrogen dopants in graphene at elevated temperatures.

Single nitrogen (N) dopants in graphene are investigated using atomic-resolution scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS). Using an in situ heating holder at 500 °C provided us with clean graphene surfaces, and we demonstrate that isolated N substitutional atoms remain localized and stable in the graphene lattice even during local sp(2) bond reconstruction. The high stability of isolated N dopants enabled us to acquire 2D EELS maps with simultaneous ADF-STEM images to map out the local bonding variations.

Atomic level spatial variations of energy states along graphene edges.

The local atomic bonding of carbon atoms around the edge of graphene is examined by aberration-corrected scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS). High-resolution 2D maps of the EELS combined with atomic resolution annular dark field STEM images enables correlations between the carbon K-edge EELS and the atomic structure. We show that energy states of graphene edges vary across individual atoms along the edge according to their specific C-C bonding, as well as perpendicular to the edge.

Multiple reaction pathways of metallofullerenes investigated by transmission electron microscopy.

Recent advances in molecule-by-molecule transmission electron microscopy (TEM) have provided time-series structural information of individual molecules supported by nano-carbon materials, enabling researchers to trace their motions and reactions. In this paper, the chemical reactions of fullerenes and metallofullerene derivatives, focusing on their deformation process, are reviewed and discussed based on the single-molecule-resolved TEM analysis.

Conformational analysis of single perfluoroalkyl chains by single-molecule real-time transmission electron microscopic imaging.

Whereas a statistical average of molecular ensembles has been the conventional source of information on molecular structures, atomic resolution movies of single organic molecules obtained by single-molecule real-time transmission electron microscopy have recently emerged as a new tool to study the time evolution of the structures of individual molecules. The present work describes a proof-of-principle study of the determination of the conformation of each C-C bond in single perfluoroalkyl fullerene molecules encapsulated in a single-walled carbon nanotube (CNT) as well as those attached to the outer surface of a carbon nanohorn (CNH). Analysis of 82 individual molecules in CNTs under a 120 kV electron beam indicated that 6% of the CF2-CF2 bonds and about 20% of the CH2-CH2 bonds in the corresponding hydrocarbon analogue are in the gauche conformation.

Heterogeneous nucleation of organic crystals mediated by single-molecule templates.

Fundamental understanding of how crystals of organic molecules nucleate on a surface remains limited because of the difficulty of probing rare events at the molecular scale. Here we show that single-molecule templates on the surface of carbon nanohorns can nucleate the crystallization of two organic compounds from a supersaturated solution by mediating the formation of disordered and mobile molecular nanoclusters on the templates. Single-molecule real-time transmission electron microscopy indicates that each nanocluster consists of a maximum of approximately 15 molecules, that there are fewer nanoclusters than crystals in solution, and that in the absence of templates physisorption, but not crystal formation, occurs.

Atomic imaging and spectroscopy of low-dimensional materials with interrupted periodicities.

Identification of individual atoms and examination of their electronic properties in materials are the ultimate goal of all microscopy-based analytical techniques. Here, we demonstrate successful single-atom imaging and spectroscopy in low-dimensional materials using (scanning) transmission electron microscopy together with electron energy-loss spectroscopy (EELS). Edges and point defects in single-layered materials such as graphene, hexagonal boron nitride and WS(2) nanoribbons are investigated by annular dark-field imaging and EELS fine-structure analysis.

Core-level spectroscopy of point defects in single layer h-BN.

Electron energy-loss spectroscopy (EELS) is used to analyze single-layered hexagonal boron-nitride with or without point defects. EELS profiles using a 0.1 nm probe clearly discriminate the chemical species of single atoms but show different delocalization of the boron and nitrogen K edges.

Electron microscopic imaging of a single Group 8 metal atom catalyzing C-C bond reorganization of fullerenes.

Heating a bulk sample of [60]fullerene complexes, (η(5)-C(5)H(5))MC(60)R(5) (M = Fe, Ru, R = Me, Ph), produces small hydrocarbons because of coupling of R and C(5)H(5) via C-C and C-H bond activation. Upon observation by transmission electron microscopy, these complexes, encapsulated in single-walled carbon nanotubes, underwent C-C bond reorganization reactions to form new C-C bond networks, including a structure reminiscent of [70]fullerene. Quantitative comparison of the electron dose required to effect the C-C bond reorganization of fullerenes and organofullerenes in the presence of a single atom of Ru, Fe, or Ln and in the the absence of metal atoms indicated high catalytic activity of Ru and Fe atoms, as opposed to no catalytic activity of Ln.

Atomically resolved images of I(h) ice single crystals in the solid phase.

The morphology and crystal structure of nanoparticles of ice were examined by high-resolution transmission electron microscopy. Two different crystal structures were found and unambiguously assigned to hexagonal (I(h)) and cubic (I(c)) ice crystals. Direct observation of oxygen columns clearly revealed the hexagonal packing of water molecules.

Atom-by-atom spectroscopy at graphene edge.

The properties of many nanoscale devices are sensitive to local atomic configurations, and so elemental identification and electronic state analysis at the scale of individual atoms is becoming increasingly important. For example, graphene is regarded as a promising candidate for future devices, and the electronic properties of nanodevices constructed from this material are in large part governed by the edge structures. The atomic configurations at graphene boundaries have been investigated by transmission electron microscopy and scanning tunnelling microscopy, but the electronic properties of these edge states have not yet been determined with atomic resolution.

Analysis of the reactivity and selectivity of fullerene dimerization reactions at the atomic level.

High-resolution transmission electron microscopy has proved useful for its ability to provide time-resolved images of small molecules and their movements. One of the next challenges in this area is to visualize chemical reactions by monitoring time-dependent changes in the atomic positions of reacting molecules. Such images may provide information that is not available with other experimental methods.

Study of structures at the boundary and defects in organic thin films of perchlorocoronene by high-resolution and analytical transmission electron microscopy.

Both the periodic and non-periodic structures of perchlorocoronene (C(24)Cl(12)) crystals were characterized by high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), electron energy-loss spectroscopy (EELS), and energy-filtered transmission electron microscopy (EFTEM). The HRTEM images at the boundary of the C(24)Cl(12) crystals exhibit the flexibility of defect structures, where molecules align to compensate for the discontinuity between two different domains. Emphasized by the filtered images, it was found that the non-periodic regions are created everywhere with a small electron beam irradiation (∼ 10(6)electrons nm(-2)) and then spread over the entire regions to completely destroy the periodic structures after a higher electron dose (∼ 2 × 10(6)electrons nm(-2)).

Imaging the passage of a single hydrocarbon chain through a nanopore.

Molecular transport through nanoscale pores in films, membranes and wall structures is of fundamental importance in a number of physical, chemical and biological processes. However, there is a lack of experimental methods that can obtain information on the structure and orientation of the molecules as they pass through the pore, and their interactions with the pore during passage. Imaging with a transmission electron microscope is a powerful method for studying structural changes in single molecules as they move and for imaging molecules confined inside carbon nanotubes.

Imaging active topological defects in carbon nanotubes.

A single-walled carbon nanotube (SWNT) is a wrapped single graphene layer, and its plastic deformation should require active topological defects--non-hexagonal carbon rings that can migrate along the nanotube wall. Although in situ transmission electron microscopy (TEM) has been used to examine the deformation of SWNTs, these studies deal only with diameter changes and no atomistic mechanism has been elucidated experimentally. Theory predicts that some topological defects can form through the Stone-Wales transformation in SWNTs under tension at 2,000 K, and could act as a dislocation core.

Imaging of conformational changes of biotinylated triamide molecules covalently bonded to a carbon nanotube surface.

A diamide molecule bearing a biotin terminus was bonded via an amide linkage to the surface of an aminated single-walled carbon nanotube and examined by a high-resolution transmission electron microscope. The still and movie images allowed us to study not only the conformation of the molecule but also its time evolution. An iterative sequence of modeling and simulation allowed us to assign one plausible conformation out of >10(8) possibilities.