A Novel Monochromator with Offset Cylindrical Lenses and Its Application to a Low-Voltage Scanning Electron Microscope.

Low-voltage scanning electron microscopes (LV-SEMs) are widely used in nanoscience. However, image resolution for SEMs is restricted by chromatic aberration due to energy spread of the electron beam at low acceleration voltage. This study introduces a new monochromator (MC) with offset cylindrical lenses (CLs) as one solution for LV-SEMs. The MC optics, with highly excited CLs in offset layouts, has advantageous high performance and simple experimental setup, making it suitable for field emission LV-SEMs. In a preliminary evaluation, our MC reduced the energy spread from 770 to 67 meV. The MC was integrated into a commercial SEM equipped with an out-lens (a conventional objective lens without immersion magnetic or retarding electric fields) and an Everhart­Thornley detector. Comparing SEM images under two conditions with the MC turned on or off, the spatial resolution was improved by 58% at 0.5 and 1 keV. The filtering effect of the MC decreased the probe current with a ratio (i.e., transmittance) of 5.7%, which was consistent with estimations based on measured energy spreads. To the best of our knowledge, this is the first report on an effective MC with higher-energy resolution than 100 meV and the results offer encouraging prospects for LV-SEM technology.

Phase retrieval using through-focus images in Lorentz transmission electron microscopy.

In this study, we report on phase retrieval by the maximum likelihood method with conjugate gradient method (CG-MAL) using through-focus images in Lorentz transmission electron microscopy (LTEM). The method was evaluated using 32 simulated and experimentally obtained through-focus images of magnetic bubbles; these images were collected under a defocus range from approximately -3 mm to 3 mm. Consequently, we obtained the magnetic domain structures of the magnetic bubbles in both the simulation and the LTEM experiment. Furthermore, the CG-MAL method showed better convergence behavior than other iterative phase retrieval methods. Therefore, the method can also be widely and effectively applied to the observation of magnetic domain structures other than magnetic bubbles when highly defocused through-focus images are used.

Development of a real-time wave field reconstruction TEM system (II): correction of coma aberration and 3-fold astigmatism, and real-time correction of 2-fold astigmatism.

In this study, a function for the correction of coma aberration, 3-fold astigmatism and real-time correction of 2-fold astigmatism was newly incorporated into a recently developed real-time wave field reconstruction TEM system. The aberration correction function was developed by modifying the image-processing software previously designed for auto focus tracking, as described in the first article of this series. Using the newly developed system, the coma aberration and 3-fold astigmatism were corrected using the aberration coefficients obtained experimentally before the processing was carried out. In this study, these aberration coefficients were estimated from an apparent 2-fold astigmatism induced under tilted-illumination conditions. In contrast, 2-fold astigmatism could be measured and corrected in real time from the reconstructed wave field. Here, the measurement precision for 2-fold astigmatism was found to be ±0.4 nm and ±2°. All of these aberration corrections, as well as auto focus tracking, were performed at a video frame rate of 1/30 s. Thus, the proposed novel system is promising for quantitative and reliable in situ observations, particularly in environmental TEM applications.

Development of a real-time wave field reconstruction TEM system (I): incorporation of an auto focus tracking system.

We have developed a real-time wave field reconstruction transmission electron microscope system that enables auto focus tracking at a video rate. In the developed system, a high-speed image calculation technique using a graphical processing unit was incorporated along with two techniques facilitating high-speed focus control using high-voltage modulation and weighted image integration using exposure time control. By utilizing these techniques, the sample drift induced in the Z-axis direction can be measured and automatically corrected for every 1/30 of a second. The auto focus tracking system can be operated in the sample drift range of ±150 nm with a precision of ~0.4 nm. In addition to amorphous samples, the system can be used to examine thin crystalline samples, which indicates that atomic structure analysis can be performed in real time with high reliability even when heavy drift occurs in the Z-axis direction.

A new type of molybdenum oxide crystal encapsulated inside a single-walled carbon nanotube.

The crystal structure of a new type of molybdenum oxide crystal encapsulated in a single-walled carbon nanotube (CNT) was examined via diffraction and spectroscopic techniques using both X-rays and electron beams. This new type of molybdenum oxide crystal has a chemical bonding state of MoO3, as confirmed by X-ray absorption spectroscopy, and the MoO3 units exhibit axial symmetry, as clarified by electron diffraction from bundled and individual CNTs encapsulating the crystal. To obtain three-dimensional information on the structure, a cross-sectional sample was prepared using a conventional dimple and ion-mill method. High-resolution transmission electron microscopy images exhibit ring-like shapes that originated from the arrangement of the MoO3 units inside the CNTs, as observed along the tube axis. The units are spaced 0.36 nm from each other in a ring arrangement and the distance between each ring is 0.391 nm.

Cross-sectional transmission electron microscopy observation of sub-nano-sized molybdenum carbide crystals in carbon nanotubes.

Cross-sectional observation of molybdenum carbide nanocrystals inside carbon nanotubes was successfully conducted in this study. The nanocrystals were generated by irradiating as-synthesized encapsulated molybdenum oxide crystals with an intense electron beam; the most probable composition of the crystals was determined to be α-MoC1-x by electron diffraction, high-resolution transmission electron microscopy, and energy dispersive X-ray spectroscopy. Thinning processes using a focused ion beam and an Ar-ion mill enabled cross-sectional observations along the tube axis. As a result, it became clear that the molybdenum carbide crystals show translational symmetry with a parallelogram configuration having preferred {111} facets when observed from the [110] direction, despite the sub-nanometer order of the crystals.

Catalysis of nickel ferrite for photocatalytic water oxidation using [Ru(bpy)3]2+ and S2O8(2-).

Single or mixed oxides of iron and nickel have been examined as catalysts in photocatalytic water oxidation using [Ru(bpy)(3)](2+) as a photosensitizer and S(2)O(8)(2-) as a sacrificial oxidant. The catalytic activity of nickel ferrite (NiFe(2)O(4)) is comparable to that of a catalyst containing Ir, Ru, or Co in terms of O(2) yield and O(2) evolution rate under ambient reaction conditions. NiFe(2)O(4) also possesses robustness and ferromagnetic properties, which are beneficial for easy recovery from the solution after reaction. Water oxidation catalysis achieved by a composite of earth-abundant elements will contribute to a new approach to the design of catalysts for artificial photosynthesis.

High-resolution wave field reconstruction using a through-focus series of images taken under limited electron dose.

The three-dimensional Fourier filtering method and Schiske's Wiener filtering method are compared with the aim of high-resolution wave field reconstruction of an unstained deoxyribonucleic acid (DNA) molecular fiber using a through-focus series of images taken under a limited electron dose. There were some definite differences between the two reconstructed images, although the two kinds of processing are essentially equivalent except for the dimension and the filter used for processing. Through theoretical analyses together with computer simulations, the differences were proved to be primarily due to specimen drift during the experiment. Although the observed structure of the DNA molecular fiber was heavily damaged by electron beam irradiation, reconstructed images by the three-dimensional Fourier filtering method provided higher resolution information on the molecular structure even when relatively large specimen drift was included in the through-focus series. In contrast, in Schiske's Wiener filtering method, the detailed information of the structure was lost because of the drift, although the reconstructed image showed a higher signal-to-noise ratio. The three dimensional Fourier filtering method seems to be more applicable for observing radiation-sensitive materials under an extremely low electron dose, because specimen drift cannot be completely avoided.

Development of a parallel detection and processing system using a multidetector array for wave field restoration in scanning transmission electron microscopy.

A parallel image detection and image processing system for scanning transmission electron microscopy was developed using a multidetector array consisting of a multianode photomultiplier tube arranged in an 8 x 8 square array. The system enables the taking of 64 images simultaneously from different scattered directions with a scanning time of 2.6 s. Using the 64 images, phase and amplitude contrast images of gold particles on an amorphous carbon thin film could be separately reconstructed by applying respective 8 shaped bandpass Fourier filters for each image and multiplying the phase and amplitude reconstructing factors.

Development of computer-assisted minimal-dose system with beam blanker for TEM.

A computer-assisted minimal-dose system has been developed for the high-resolution observation of radiation-sensitive samples using a transmission electron microscope (TEM). This system consists of a CCD camera, a beam blanker and a control computer (PC) that also controls the TEM. A sample is illuminated by an electron beam only when the CCD camera takes images; otherwise, the beam blanker cuts off the electron beam. Emulated images, which are calculated from the images taken and the variable parameters of the TEM, such as magnification and sample stage position, are displayed on the control PC display. After a few times of repetition of exposures and emulations, the sample is positioned to final observation area. Subsequently to select the observation area, the system automatically adjusts the focus position from two different illuminating angle images and the TEM conditions are appropriate for taking a final image. The total electron dose before the final image is taken can be markedly decreased because the sample is irradiated by an electron beam only when images are taken. For the final image, a three-dimensional Fourier filtering method (3DFFM), which corrects the spherical aberration for the through-focus image series and enables the selection of the optimum focus condition later, is also included in our system.

Viologen-modified platinum clusters acting as an efficient catalyst in photocatalytic hydrogen evolution.

A highly efficient photocatalytic system for hydrogen evolution with dihydronicotinamide coenzyme (NADH) as a sacrificial agent in an aqueous solution has been constructed by using water-soluble platinum clusters functionalized with methyl viologen-alkanethiol (MVA2+) and a simple electron-donor dyad, 9-mesityl-10-methylacridinium ion (Acr+-Mes), which is capable of fast photoinduced electron transfer but extremely slow back electron transfer. The mean diameter of the platinum core was determined as R(CORE) = 1.9 nm with a standard deviation sigma = 0.5 nm by transmission electron microscopy (TEM). As a result, the hydrogen-evolution rate of the photocatalytic system with MVA2+-modified platinum clusters (MVA2+-PtC) is 10 times faster than the photocatalytic system with the mixture of the same amount of MVA2+ and platinum clusters as that of MVA2+-PtC under otherwise the same experimental conditions. The radical cation of NADH has been successfully detected by laser flash photolysis experiments. The decay of the absorbance due to NAD*, produced by the deprotonation from NADH*+, coincides with the appearance of the absorption band due to Acr*-Mes. This indicates electron transfer from NAD* to Acr+-Mes to give Acr*-Mes, which undergoes the electron-transfer reduction of MVA2+-PtC, leading to the efficient hydrogen evolution.

Separation of linear and non-linear imaging components in high-resolution transmission electron microscope images.

Linear and non-linear image components in high-resolution transmission electron microscope images were successfully separated by applying a bandpass filter to the three-dimensional Fourier spectrum of its through-focus series of images. In the observed lattice image of a wedgeshaped Si [110] crystal, we determined the magnitude of the contribution of the non-linear imaging components to the total image intensity distribution. The contribution was proved to become sometimes larger than that of the linear imaging component, even at a thickness of 13 nm.

Development of coincidence transmission electron microscope. III. Incorporation with gamma-type imaging energy filter.

We have developed a new analytical transmission electron microscope (TEM), called coincidence TEM, which, in principle, enables observation of elemental mapping images at a high signal-to-noise ratio. We have previously reported the successful observation of an elemental mapping image of a specimen, but over a very long period of time (168 h). To solve this inefficiency, we installed a gamma-type imaging energy filter in the coincidence TEM to remove the no-loss electrons, which are mainly transmitted electrons. This has enabled the intensity of the background signals in the coincidence measurement to be markedly reduced. The coincidence TEM with a gamma-type imaging energy filter allows the coincidence image to be observed in 3 h, thus, the measurement time is shortened by two orders of magnitude. Moreover, the use of a silicon drift detector (SDD) will shorten the measurement time.

Practical method to determine the filter shape function used in the three-dimensional Fourier filtering method.

The procedure to determine the appropriate filter shape function used in the three-dimensional Fourier filtering method (3D-FFM) is discussed from a practical point of view, so as to reduce the artificial contrast induced by the processing and to achieve a high signal-to-noise ratio. The effects of cutting off the high spatial frequency of the filter shape function and damping at low spatial frequency were investigated by using through-focus images of a gold (110) thin film. In addition, the effect of the width of the filtered area was discussed using through-focus images of a carbon nanotube. For reliable image processing, the filter shape function should be cut off beyond the information limit and attenuated with damping at low spatial frequency. Furthermore, the extraction area should include the distributed area of the relevant structural components appearing in the 3-D Fourier spectrum.

Quantitative analysis of surface atom positions in a thick crystal as determined by a reconstructed exit wave.

Atomic structures of an Au (110) 2 x 1 reconstructed surface were analysed quantitatively using an exit wave reconstructed by the three-dimensional Fourier filtering method in high-resolution transmission electron microscopy. To reconstruct the exit wave in a relatively thick crystal, a practical criterion was proposed in the present analysis. In the 'pseudo-exit wave' obtained by the proposed criterion, relaxation of surface atoms was clearly visible in the top three layers. The atoms' displacement was measured to be about 5-20 pm. For quantitative analysis of the atom column positions, image contrast calculations were performed using a structural model of the Au (110) reconstructed surface. Calculations confirmed that the reconstructed pseudo-exit wave could represent the atom column positions directly with an accuracy of several pm, even for a relaxed surface, provided the sample thickness was <7 nm.