Low energy Si+, SiCH5+, or C+ beam injections to silicon substrates during chemical vapor deposition with dimethylsilane.

We found that the atomic-concentration-ratio of carbon to silicon (C/Si ratio) in silicon carbide (SiC) films formed by thermal chemical vapor deposition (CVD) was much greater than 1 when the source gas for CVD was dimethylsilane (DMS). Thus, we tried to change carbon-inclusion levels in the film by injecting some ion beams into a depositing SiC film during the CVD process with DMS. Three ion beams, i.e., Si+, SiCH5+, or C+ ions were injected to depositing SiC films. The energy of Si+, SiCH5+, and C+ ions was 110 eV. The temperature of the substrate was 800 °C. X-ray diffraction of the deposited films showed that 3C-SiC was included in all three samples. X-ray photoelectron spectroscopy (XPS) showed that the C/Si ratio of the obtained SiC film increased significantly following the Si+ or C+ ion beam irradiations. The XPS measurements also showed that the C/Si ratio of the SiC film obtained by injecting SiCH5+ beam during thermal CVD with DMS was lower than that of the SiC film formed by thermal CVD with DMS alone.

Optical Study of the Surface Film Formed during Li-Metal Deposition and Dissolution Investigated by Surface Plasmon Resonance Spectroscopy.

The features of the electrode surface film during Li-metal deposition and dissolution cycles are essential for understanding the mechanism of the negative electrode reaction in Li-metal battery cells. The physical and chemical property changes of the interface during the initial stages of the reaction should be investigated under operando conditions. In this study, we focused on the changes in the optical properties of the electrode surface film of the negative electrode of a Li-metal battery. Cu-based electrochemical surface plasmon resonance spectroscopy (EC-SPR) was applied because of its high sensitivity to optical phenomena on the electrode surface and its stability against Li-metal deposition. The feature of SPR reflectance dip depends on the optical properties of the electrode surface; namely, the wavelength and depth of the reflectance dip directly connected the refractive index and extinction coefficient (color of electrode surface film), which was confirmed by reflectance simulation. In the operando EC-SPR experiment, various changes in optical properties were clearly observed during the cycles. In particular, the change in the extinction coefficient was more remarkable at the second process than the first process of Li-metal deposition. By electrochemical quartz-crystal microbalance (EQCM) measurements, surface film formation was confirmed during the first Li-metal deposition process. The remarkable change in the extinction coefficient is based on the color change of the surface film, which is caused by the chemical condition change during Li-metal deposition cycles.

Low-energy Ar+ and N+ ion beam induced chemical vapor deposition using hexamethyldisilazane for the formation of nitrogen containing SiC and carbon containing SiN films.

We proposed an experimental methodology for producing films on substrates with an ion beam induced chemical vapor deposition (IBICVD) method using hexamethyldisilazane (HMDS) as a source material. In this study, both HMDS and ion beam were simultaneously injected onto a Si substrate. We selected Ar+ and N+ as the ion beam. The energy of the ion beam was 101 eV. Temperature of the Si substrate was set at 540 °C. After the experiments, films were found to be deposited on the substrates. The films were then analyzed by Fourier transform infrared (FTIR) spectroscopy, stylus profilometer, X-ray diffraction, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The FTIR and XPS results showed that silicon carbide films containing small amount of nitrogen were formed when Ar+ ions were injected in conjunction with HMDS. On the other hand, in the cases of N+ ion beam irradiation, silicon nitride films involving small amount of carbon were formed. It was noted that no film deposition was observed when HMDS alone was supplied to the substrates without any ion beam injections.

Electrochemical Surface Plasmon Resonance Spectroscopy for Investigation of the Initial Process of Lithium Metal Deposition.

The initial process of Li-metal electrodeposition on the negative electrode surface determines the charging performance of Li-metal secondary batteries. However, minute depositions or the early processes of nucleation and growth of Li metal are generally difficult to detect under operando conditions. In this study, we propose an optical diagnostic approach to address these challenges. Surface plasmon resonance (SPR) spectroscopy coupled with electrochemical operation is a promising technique that enables the ultrasensitive detection of the initial stage of Li-metal electrodeposition. The SPR is excited in a thin copper film deposited on a glass substrate, which also serves as a current collector enabling electrochemical Li-metal deposition. For a propylene carbonate (PC)-based Li-ion battery electrolyte, under both cyclic voltammetry and constant-current operation, Li-metal deposition is readily detected by changes in the SPR absorption dip in the reflectance spectrum. Electrochemical SPR is highly sensitive to metal deposition, with a demonstrated capability of detecting an average thickness of approximately 0.1 nm, corresponding to a few atomic layers of Li. To identify the growth mechanism, the SPR reflectance spectra of various possible Li-metal deposition processes were simulated. Comparison of the simulated spectra with the experimental data found good agreement with the well-known nucleation and growth model for Li-metal deposition from PC-based electrolytes. The demonstrated operando electrochemical SPR measurement should be a valuable tool for basic research on the initial Li-metal deposition process.

Identification of fragment ions produced by the decomposition of tetramethyltin and the production of low-energy Sn+ ion beam.

Tetramethyltin was decomposed in an ion source and the fragment ions produced were identified using a low-energy mass-selected ion beam machine. Dominant fragment ions were found to be H+, CH2+, and Sn+. Subsequently, fragment ions were mass-selected. The mass spectrum of the selected ions indicated that only a single peak appeared at the mass number of 120 u, being suggestive of the presence of 120Sn+ ions. The ion energy was set at the range of 20-100 eV. The Sn+ ion beam was irradiated to a Si substrate, and a film was then found deposited on the substrate after the ion beam irradiation. An X-ray diffraction measurement showed that the film obtained was metallic Sn. Then, the Sn+ ion beam was irradiated to a quartz crystal microbalance substrate. We found that most of the irradiated Sn+ ions were adhered to the substrate, at the ion energy levels of 25 and 58 eV, producing the Sn film, whereas a 107 eV Sn+ beam caused a significant proportion of Sn atoms in the film to detach from the substrate, probably due to sputtering.

Dogs can discriminate human smiling faces from blank expressions.

Dogs have a unique ability to understand visual cues from humans. We investigated whether dogs can discriminate between human facial expressions. Photographs of human faces were used to test nine pet dogs in two-choice discrimination tasks. The training phases involved each dog learning to discriminate between a set of photographs of their owner's smiling and blank face. Of the nine dogs, five fulfilled these criteria and were selected for test sessions. In the test phase, 10 sets of photographs of the owner's smiling and blank face, which had previously not been seen by the dog, were presented. The dogs selected the owner's smiling face significantly more often than expected by chance. In subsequent tests, 10 sets of smiling and blank face photographs of 20 persons unfamiliar to the dogs were presented (10 males and 10 females). There was no statistical difference between the accuracy in the case of the owners and that in the case of unfamiliar persons with the same gender as the owner. However, the accuracy was significantly lower in the case of unfamiliar persons of the opposite gender to that of the owner, than with the owners themselves. These results suggest that dogs can learn to discriminate human smiling faces from blank faces by looking at photographs. Although it remains unclear whether dogs have human-like systems for visual processing of human facial expressions, the ability to learn to discriminate human facial expressions may have helped dogs adapt to human society.