Probing plasmonic excitation mechanisms and far-field radiation of single-crystalline gold tapers with electrons.

Conical metallic tapers represent an intriguing subclass of metallic nanostructures, as their plasmonic properties show interesting characteristics in strong correlation to their geometrical properties. This is important for possible applications such as in the field of scanning optical microscopy, as favourable plasmonic resonance behaviour can be tailored by optimizing structural parameters like surface roughness or opening angle. Here, we review our recent studies, where single-crystalline gold tapers were investigated experimentally by means of electron energy-loss and cathodoluminescence spectroscopy techniques inside electron microscopes, supported by theoretical finite-difference time-domain calculations. Through the study of tapers with various opening angles, the underlying resonance mechanisms are discussed. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

High spatiotemporal-resolution imaging in the scanning transmission electron microscope.

The temporal resolution in scanning transmission electron microscopy (STEM) is limited by the scanning system of an electron probe, leading to only a few frames per second (fps) at most in the current microscopes. To push the boundary of atomic-resolution STEM imaging into dynamic observations, an unprecedentedly faster scanning system combined with fast electron detection systems should be a prerequisite. Here we develop a new scanning probe system with the acquisition time of 83 nanoseconds per pixel and the fly-back time of 35 microseconds, leading to 25 fps STEM imaging with the image size of 512 × 512 pixels that is faster than a human perception speed. Using such high-speed probe scanning system, we have demonstrated the observations of shape-transformation of Pt nanoparticles and Pt single atomic motions on TiO2 (110) surface at atomic-resolution with the temporal resolution of 40 milliseconds. The present probe scanning system opens the door to use atomic-resolution STEM imaging for in situ observations of material dynamics under the temperatures of cooling or heating, the atmosphere of liquid or gas, electric-basing or mechanical test.

Atomic Resolution Imaging at an Ultralow Accelerating Voltage by a Monochromatic Transmission Electron Microscope.

Transmission electron microscopy using low-energy electrons would be very useful for atomic resolution imaging of specimens that would be damaged at higher energies. However, the resolution at low voltages is degraded because of geometrical and chromatic aberrations. In the present study, we diminish the effect of these aberrations by using a delta-type corrector and a monochromator. The dominant residual aberration in a delta-type corrector, which is the sixth-order three-lobe aberration, is counterbalanced by other threefold aberrations. Defocus spread caused by chromatic aberration is reduced by using a monochromated beam with an energy spread of 0.05 eV. We obtain images of graphene and demonstrate atomic resolution at an ultralow accelerating voltage of 15 kV.

Exciton mapping at subwavelength scales in two-dimensional materials.

Spatially resolved electron-energy-loss spectroscopy (EELS) is performed at diffuse interfaces between MoS2 and MoSe2 single layers. With a monochromated electron source (20 meV) we successfully probe excitons near the interface by obtaining the low loss spectra at the nanometer scale. The exciton maps clearly show variations even with a 10 nm separation between measurements; consequently, the optical band gap can be measured with nanometer-scale resolution, which is 50 times smaller than the wavelength of the emitted photons. By performing core-loss EELS at the same regions, we observe that variations in the excitonic signature follow the chemical composition. The exciton peaks are observed to be broader at interfaces and heterogeneous regions, possibly due to interface roughness and alloying effects. Moreover, we do not observe shifts of the exciton peak across the interface, possibly because the interface width is not much larger than the exciton Bohr radius.

Development of a monochromator for aberration-corrected scanning transmission electron microscopy.

In this article, we report the development of a new 200-kV analytical electron microscope equipped with a monochromator with an integrated double Wien-filter system. It enables us to study the electronic structures of materials in detail using electron energy-loss spectroscopy (EELS) analysis at an atomic scale. A highly monochromated and isotropically round electron probe is produced on the specimen plane. The ultimate energy resolutions with 0.1-s acquisition times are measured to be 36 meV at 200 kV and 30 meV at 60 kV. In an EELS mapping experiment performed on SrTiO3 with a monochromated electron probe whose energy resolution is 146 meV, an elemental map exhibits atomic resolution.

Measurement of vibrational spectrum of liquid using monochromated scanning transmission electron microscopy-electron energy loss spectroscopy.

Investigations on the dynamic behavior of molecules in liquids at high spatial resolution are greatly desired because localized regions, such as solid-liquid interfaces or sites of reacting molecules, have assumed increasing importance with respect to improving material performance. In application to liquids, electron energy loss spectroscopy (EELS) observed with transmission electron microscopy (TEM) is a promising analytical technique with the appropriate resolutions. In this study, we obtained EELS spectra from an ionic liquid, 1-ethyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C2mim-TFSI), chosen as the sampled liquid, using monochromated scanning TEM (STEM). The molecular vibrational spectrum and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap of the liquid were investigated. The HOMO-LUMO gap measurement coincided with that obtained from the ultraviolet-visible spectrum. A shoulder in the spectrum observed ∼0.4 eV is believed to originate from the molecular vibration. From a separately performed infrared observation and first-principles calculations, we found that this shoulder coincided with the vibrational peak attributed to the C-H stretching vibration of the [C2mim(+)] cation. This study demonstrates that a vibrational peak for a liquid can be observed using monochromated STEM-EELS, and leads one to expect observations of chemical reactions or aids in the analysis of the dynamic behavior of molecules in liquid.

The development of a 200 kV monochromated field emission electron source.

We report the development of a monochromator for an intermediate-voltage aberration-corrected electron microscope suitable for operation in both STEM and TEM imaging modes. The monochromator consists of two Wien filters with a variable energy selecting slit located between them and is located prior to the accelerator. The second filter cancels the energy dispersion produced by the first filter and after energy selection forms a round monochromated, achromatic probe at the specimen plane. The ultimate achievable energy resolution has been measured as 36 meV at 200 kV and 26 meV at 80 kV. High-resolution Annular Dark Field STEM images recorded using a monochromated probe resolve Si-Si spacings of 135.8 pm using energy spreads of 218 meV at 200 kV and 217 meV at 80 kV respectively. In TEM mode an improvement in non-linear spatial resolution to 64 pm due to the reduction in the effects of partial temporal coherence has been demonstrated using broad beam illumination with an energy spread of 134 meV at 200 kV.

Isolation and identification of phytate-degrading bacteria and their contribution to phytate mineralization in soil.

To better understand the phosphorus (P) cycling in an agricultural soil environment, amounts of total, organic and inorganic P in 10 agricultural soil samples were analyzed. Since a large proportion (57.8%) of the total P in the soils was in organic form, a method was developed to evaluate the mineralization rate of organic P in the soil by adding phytate to the soil and analyzing the change in water-soluble P (WSP) content after incubating it for 3 days. Moreover, the relationship between the phytate mineralization activity and bacterial biomass in 60 agricultural soils was also investigated, where the phytate mineralization activity ranged from 0 to 61.7% (average: 18.8%), and the R² value between phytate mineralization activity and indigenous bacterial biomass was 0.11 only. Phytate-degrading bacteria were isolated from the soil environment, and identified as Pseudomonas rhodesiae JT29, JT32, JT33, JT34, JT35, Pseudomonas sp. JT30, and Flavobacterium johnsoniae JT31. When P. rhodesiae JT29 and F. johnsoniae JT31 were inoculated into the agricultural soils, the phytate mineralization activities were increased up to 16 and 27 times, respectively. It was concluded that promotion of effective phytate-degrading bacterial strains could improve the sustainable P management in the agricultural soils.

Distribution of hydrocarbon-degrading bacteria in the soil environment and their contribution to bioremediation.

A real-time PCR quantification method for indigenous hydrocarbon-degrading bacteria (HDB) carrying the alkB gene in the soil environment was developed to investigate their distribution in soil. The detection limit of indigenous HDB by the method was 1 × 10(6) cells/g-soil. The indigenous HDB were widely distributed throughout the soil environment and ranged from 3.7 × 10(7) to 5.0 × 10(8) cells/g-soil, and the ratio to total bacteria was 0.1-4.3 %. The dynamics of total bacteria, indigenous HDB, and Rhodococcus erythropolis NDKK6 (carrying alkB R2) during bioremediation were analyzed. During bioremediation with an inorganic nutrient treatment, the numbers of these bacteria were slightly increased. The numbers of HDB (both indigenous bacteria and strain NDKK6) were gradually decreased from the middle stage of bioremediation. Meanwhile, the numbers of these bacteria were highly increased and were maintained during bioremediation with an organic nutrient. The organic treatment led to activation of not only the soil bacteria but also the HDB, so an efficient bioremediation was carried out.

Dislocation-driven deformations in graphene.

The movement of dislocations in a crystal is the key mechanism for plastic deformation in all materials. Studies of dislocations have focused on three-dimensional materials, and there is little experimental evidence regarding the dynamics of dislocations and their impact at the atomic level on the lattice structure of graphene. We studied the dynamics of dislocation pairs in graphene, recorded with single-atom sensitivity. We examined stepwise dislocation movement along the zig-zag lattice direction mediated either by a single bond rotation or through the loss of two carbon atoms. The strain fields were determined, showing how dislocations deform graphene by elongation and compression of C-C bonds, shear, and lattice rotations.

Atomic structure of ABC rhombohedral stacked trilayer graphene.

We distinguish between Bernal and rhombohedral stacked trilayer graphene using aberration-corrected high-resolution transmission electron microscopy. By using a monochromator to reduce chromatic aberration effects, angstrom resolution can be achieved at an accelerating voltage of 80 kV, which enables the atomic structure of ABC rhombohedral trilayer graphene to be unambiguously resolved. Our images of ABC rhombohedral trilayer graphene provide a clear signature for its identification. Few-layer graphene interfaces with ABC:BC:BCAB structure have also been studied, and we have determined the stacking sequence of each graphene layer and consequently the 3D structure. These results confirm that CVD-grown few-layer graphene can adopt an ABC rhombohedral stacking.

High energy-resolution electron energy-loss spectroscopy study of the dielectric properties of bulk and nanoparticle LaB6 in the near-infrared region.

The dielectric properties of LaB(6) crystals and the plasmonic behavior of LaB(6) nanoparticles, which have been applied to solar heat-shielding filters, were studied by high energy-resolution electron energy-loss spectroscopy (HR-EELS). An EELS spectrum of a LaB(6) crystal showed a peak at 2.0 eV, which was attributed to volume plasmon excitation of carrier electrons. EELS spectra of single LaB(6) nanoparticles showed peaks at 1.1-1.4 eV depending on the dielectric effect from the substrates. The peaks were assigned to dipole oscillation excitations. These peak energies almost coincided with the peak energy of optical absorption of a heat-shielding filter with LaB(6) nanoparticles. On the other hand, those energies were a smaller than a dipole oscillation energy predicted using the dielectric function of bulk LaB(6) crystal. It is suggested that the lower energy than expected is due to an excitation at 1.2 eV, which was observed for oxidized LaB(6) area.