鈴木 哲

Abstract Detection of a small amount of oxygen vacancies is often difficult. In this study, using near-ambient pressure hard X-ray photoelectron spectroscopy, oxygen vacancies were formed in situ in SnO_{2 − x} and WO_{3 − y} under a reducing gas atmosphere. The number of oxygen vacancies was so small that they could not be detected in the core-level photoelectron spectra. However, the effects of the vacancies were observed in the valence band spectra. This is because under the measurement conditions, the relative sensitivity of the metal outer orbitals (Sn 5s and W 5d) occupied when the oxygen vacancies are formed is significantly higher than that of the O 2p orbital predominantly forming the valence band. The x and y values were estimated to be ∼0.007–0.01 and ∼0.008–0.02, respectively, which correspond to vacancy ratios of sub-percent.

In recent years, enclosing liquid in a “liquid cell” (Fig. 1) has made it possible to analyze the chemical composition of the liquid sample and map samples in the liquid-solid interface using XPS, EDX, SEM in ultra-high vacuum (UHV). The most important part of the cell is the electron transmission window that allows electrons to input to or extract from the liquid sample. Silicon nitride (SiNx) is the most suitable material as the window, which has excellent mechanical properties. R. Endo et. al. has successfully measured the concentration of CsCl solution using a SiNx window with the film thickness of 5 nm¹. However, the transmittance of 1 keV photoelectron is about 10% with the thickness of SiNx membrane. When the membrane thickness is decreased to 2 nm, the transmittance can be improved to more than 40%, which means that even higher sensitivity can be achieved. However, the burst pressure must be 1 atm or more because the membrane needs to perform enclosing a liquid sample in UHV. In previous research, we demonstrated low damage etching of an SiNx film using gas cluster ion beam (GCIB) for thinning the window². Herein, GCIB is composed of aggregates of several thousands of atoms, and the energy of the individual atoms in the GCIB reduces to several eV/atom with an acceleration voltage of several kV. This enables irradiation on the target surface with little damage. Combining O₂-GCIB irradiation and exposure of acetylacetone (Hacac) gas enable reactive etching of SiNx². In this study, we utilized the above techniques to ultra-thin SiNx films and investigate whether the low-damage irradiation effect of GCIB is effective for SiNx films. In addition, Proof-of-principle of high sensitivity in liquid sample detection using ultra-thinning SiNx films is demonstrated using SEM/EDS. We have evaluated the burst pressure of ultra-thinned SiNx membranes of TEM window chips (SiMPore, Inc.) by reactive etching with O₂-GCIB and Hacac gas, where the thickness was originally 11 nm. The SiNx membrane was also etched in the same way using 400 eV Ar⁺ beam, and the burst pressure was evaluated. These irradiation doses were controlled so that the remaining SiNx membrane thickness was 4.5 nm. As a result, the burst pressure was 1 atm in the case of Ar⁺ beam, whereas it was 2.5 atm in the case of the GCIB etching. Therefore, it was found that low damage irradiation of GCIB was valid for thinning SiNx membrane. We sealed pure water in the liquid cell shown in Fig. 1 and performed EDS measurement. When electron beam with the energy of 5 keV was injected at the SiNx/water, generated characteristics X-ray of oxygen which photon energy is 0.52 keV could be observed. On the other hands, no O peak was observed in the SiNx/Si region. This result indicates that the O peak originated from the pure water under the SiNx membrane. Next, we carried out the measurements on a pristine SiNx membrane (t = 11 nm) and the GCIB-etched SiNx membrane (t = 4.5 nm), and compared their O peak characteristic X-ray intensities. Herein, the incident electron energies were 1.0 and 1.5 keV. The peak intensity of the GCIB-etched SiNx membrane was 1.6 times stronger than that of the pristine membrane at 1.5 keV. At 1.0 keV, the O peak was observed in GCIB-etched SiNx, but not in pristine SiNx. This is because the penetration depth of electrons in the SiNx film decreases with decreasing electron energy. From the above results, we have shown that the ultrathin SiNx membrane thinned by GCIB could be used for highly sensitive detection of pure water. Acknowledgement This work was supported by JSPS KAKENHI Grant Numbers 23K13236 and 22K04930. References [1] R. Endo, D. Watanabe, M. Shimamura et. al., Appl. Phys. Lett., 114, 173702 (2019). [2] M. Takeuchi R. Fujiwara, N. Toyoda, Jpn. J. Appl. Phys., 62, SG1051 (2023). Figure 1 <p></p>

Previous atomic force microscopy studies have suggested that surface micro- and nanobubbles exhibit a flat shape. In this study, we directly observed surface microbubbles formed in an NH3BH3 solution using an optical microscope. No flat microbubbles were observed. Instead, on an SiO2/Si substrate, we discovered a relationship where the sum of the contact angle of a microbubble and the contact angle of a droplet equaled ∼180°. This relationship allowed us to control the shape of surface microbubbles by manipulating the wettability of the surface and the surface tension of the liquid, similar to droplet control. We were able to produce almost perfectly spherical microbubbles. Conversely, on a Cu foil, this relationship did not hold, although we still observed the formation of nearly spherical microbubbles. In this scenario, the shape of microbubbles appeared to be influenced by contact line pinning.

Abstract We would like to improve detection sensitivity by making photoelectron transmission window (SiNx membrane) of liquid cell ultra-thin for liquid measurement using XPS or X-ray PEEM at UHV. In this study, thinning of the membrane using gas cluster ion beams (GCIB) was demonstrated and the burst pressure was compared with those thinned with atomic 400 eV Ar+ ions. It was shown that SiNx membranes thinned by GCIB was 2.5 times higher burst pressure than the Ar+ ions. In addition, improvement of sensitivity of characteristic X-ray from liquid-water induced by low-energy electrons was investigated. By using 4.5 nm thick SiNx membrane etched by GCIB, the X-ray intensity became 1.6 times higher than those from 11 nm thick pristine membrane at electron beam energy of 1.5 keV. This result showed good agreement with Monte Carlo simulation results of the electron-beam-induced X-ray emission from liquid-water beneath SiNx membrane.

We have completed a system that can achieve both deep x-ray lithography and submicron x-ray lithography with a single beamline by introducing the combination of x-ray plane and cylindrical mirrors. This x-ray lithography system can provide a large-scale microfabrication processing with 210 × 300 mm2 (A4 size). To exploit multiscale lithography, the beamline has a beam transport vacuum duct with a two-stage stacked structure and a 5-axis stage. This two-stage stacked structure allows us to fabricate both micron scale structures with high aspect ratios and submicron scale structures using the same beamline. In addition, x-ray imaging and computer tomography (CT) system are connected to the x-ray lithography system for nondestructive inspection and evaluation of the fabricated microstructures. The x-ray imaging system constructed this study has a relatively low energy range of x-ray energy in the beamline, which is in the range of 2–15 keV or less. Therefore, relatively good absorption contrast can be obtained for plastic materials, biomaterials, and the like. Since nondestructive imaging of the processed shape by x-ray lithography is possible, it is a very useful system in processing and evaluation can be performed simultaneously. This system also enables us to obtain the live images with keeping the creature alive in liquid using an indirect x-ray imaging system which converts x-ray images to visible light images through the fluorescent plate.

In near-ambient-pressure photoelectron spectroscopy, the photoelectron intensity is assumed to follow the Beer-Lambert law, that is, the intensity decreases exponentially with distance d between the sample and the aperture cone. In this study, the gas pressure dependence of photoelectron intensity is systematically studied in a wide range of d values from 0.3 up to 5 mm. The experimental results were reproduced by replacing d with d + do (do is a constant) in the Beer-Lambert law. The do value was evaluated as ∼1 mm, which is considerably larger than the normal d value of 0.3 mm. Fluid dynamics simulation results obtained using a structural model with a size close to that of the actual differential pumping system suggested that the residual gas in the long pumping path caused a large do value.

The competition between magnetic shape anisotropy and the induced uniaxial magnetic anisotropy in the heterojunction between a ferromagnetic layer and a ferroelectric substrate serves to control magnetic domain structures as well as magnetization reversal characteristics. The uniaxial magnetic anisotropy, originating from the symmetry breaking effect in the heterojunction, plays a significant role in modifying the characteristics of magnetization dynamics. Magnetoelastic phenomena are known to generate uniaxial magnetic anisotropy; however, the interfacial electronic states that may contribute to the uniaxial magnetic anisotropy have not yet been adequately investigated. Here, we report experimental evidence concerning the binding energy change in the ferromagnetic layer/ferroelectric substrate heterojunction using X-ray photoemission spectroscopy. The binding energy shifts, corresponding to the chemical shifts, reveal the binding states near the interface. Our results shed light on the origin of the uniaxial magnetic anisotropy induced from the heterojunction. This knowledge can provide a means for the simultaneous control of magnetism, mechanics, and electronics in a nano/microsystem consisting of ferromagnetic/ferroelectric materials.