神田 一浩

Abstract X-ray lithography was performed using synchrotron radiation to fabricate a nozzle array filter with submicron-order aperture diameters for a mesh nebulizer, as generating mist with a high yield of submicron-sized droplets is essential for delivering medication deep into the lungs. Utilizing polymethylmethacrylate as the resist material, precise control of X-ray exposure with distribution was performed to achieve submicron-order aperture fabrication, using a two-axis lead zirconate titanate stage with nanometer-scale positioning resolution. By precisely controlling the exposure process and development time on a minute scale, we successfully fabricated a nozzle array with submicron-order aperture diameters.

Abstract Positron annihilation spectroscopy was used to investigate vacancy-type defects in diamond-like carbon (DLC) films. From Doppler broadening measurements of the γ-rays produced by annihilation and positron annihilation lifetime (PAL) using a slow positron beam on DLC films deposited by various deposition methods and conditions, it was found that there is a good correlation between the S parameter obtained by Doppler broadening and PAL. The result of PAL correlates well with film density and hardness, indicating that PAL measurements can be used as an indicator of these film properties. The hydrogen content in the DLC film was roughly proportional to the PAL. However, there were also cases in which PAL differed greatly even with almost the same hydrogen content, and the sp²/(sp²+sp³) ratio of carbon in DLC films has no direct relationship with PAL.

<jats:title>Abstract</jats:title> <jats:p>The effects of soft X-ray irradiation and atomic hydrogen annealing (AHA) on the reduction of graphene oxide (GO) to obtain graphene were investigated. To clarify the interaction between soft X-rays and GO, soft X-rays of 300 eV and 550 eV were used for C 1s and O 1s inner-shell electron excitation, respectively at the NewSUBARU synchrotron radiation facility. Low-temperature reduction of the GO film was achieved by using soft X-ray at temperatures below 150 °C at 300 eV, and 60 °C at 550 eV. O-related peaks in X-ray photoelectron spectroscopy, such as the C–O–C peak, were smaller at 550 eV than those at 300 eV. This result indicates that excitation of the core–shell electrons of O enhances the reduction of GO. Soft X-rays preferentially break C–C and C–O bonds at 300 and 550 eV, respectively.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The reduction of graphene oxide (GO) through atomic hydrogen annealing (AHA) and soft X-ray irradiation is investigated using microwell substrates with μm-sized holes with and without Ni underlayers. The GO film is reduced through AHA at 170 °C and soft X-ray irradiation at 150 °C. In contrast, some GO films are not only reduced but also amorphized through soft X-ray irradiation. The effect of the Ni underlayer on GO reduction differs between AHA and soft X-ray irradiation. In AHA, the difference in GO reduction between SiO<jats:sub>2</jats:sub> and Ni underlayer was originated from the atomic hydrogen density on sample surface. On the other hand, in soft X-ray irradiation, the difference in GO reduction between SiO<jats:sub>2</jats:sub> and the Ni underlayer originates from the excited electrons generated by soft X-ray irradiation. Reduction without damage is more likely to occur in the suspended GO than in the supported GO.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>A demonstration test of a newly developed double crystal monochromator was performed on beamline BL06 in the NewSUBARU synchrotron radiation facility of Hyogo University. Due to the symmetrical layout of the 1st crystal and 2nd crystal units of the monochromator, a maximum rotation speed of the main axis of up to 5.0 degrees/sec could be achieved. The monochromator is controlled by a newly developed control board programmed with an electronic cam algorithm. The control system allows the speed of both Z<jats:sub>1</jats:sub> and Z<jats:sub>2</jats:sub> axes to be successively synchronized as the Bragg angle changes. The <jats:italic>Z</jats:italic> <jats:sub>1</jats:sub> and <jats:italic>Z</jats:italic> <jats:sub>2</jats:sub> axes are moved apart by equal amounts from the center of gravity of the monochromator as the Bragg angle is increased. Also, the speed at which the Z<jats:sub>1</jats:sub> and Z<jats:sub>2</jats:sub> axes are moved apart increases with larger Bragg angle. This newly developed monochromator can maintain a stable exit beam height just as well as previous mechanical cam type monochromators proved on the height of the exit beam measured by an encoder system and observed by fluorescent screen. Due to the symmetrical layout and newly developed control system, the monochromator is suitable for industrial use because it can handle a wide energy range and allows high-throughput experiments to be carried out.</jats:p>

Soft X-rays excite the inner shells of materials more efficiently than any other form of light. The investigation of synchrotron radiation (SR) processes using inner-shell excitation requires the beamline to supply a single-color and high-photon-flux light in the soft X-ray region. A new integrated computing multi-layered-mirror (MLM) monochromator was installed at beamline 07A (BL07A) of NewSUBARU, which has a 3 m undulator as a light source for irradiation experiments with high-photon-flux monochromatic light. The MLM monochromator has a high reflectivity index in the soft X-ray region; it eliminates unnecessary harmonic light from the undulator and lowers the temperature of the irradiated sample surfaces. The monochromator can be operated in a high vacuum, and three different mirror pairs are available for different experimental energy ranges; they can be exchanged without exposing the monochromator to the atmosphere. Measurements of the photon current of a photodiode on the sample stage indicated that the photon flux of the monochromatic beam was more than 10¹⁴ photons s⁻¹ cm⁻² in the energy range 80–400 eV and 10¹³ photons s⁻¹ cm⁻² in the energy range 400–800 eV. Thus, BL07A is capable of performing SR-stimulated process experiments.

The effect of soft X-ray irradiation on hydrogenated silicon-containing diamond-like carbon (Si-DLC) films intended for outer space applications was investigated by using synchrotron radiation (SR). We found that the reduction in film thickness was about 60 nm after 1600 mA·h SR exposure, whereas there was little change in their elemental composition. The reduction in volume was attributable to photoetching caused by SR, unlike the desorption of hydrogen in the case of exposure of hydrogenated DLC (H-DLC) film to soft X-rays. The ratio of the sp2 hybridization carbon and sp3 hybridization carbon in the hydrogenated Si-DLC films, sp2/(sp2 + sp3) ratio, increased rapidly from ~0.2 to ~0.5 for SR doses of less than 20 mA·h. SR exposure significantly changed the local structure of carbon atoms near the surface of the hydrogenated Si-DLC film. The rate of volume reduction in the irradiated hydrogenated Si-DLC film was 80 times less than that of the H-DLC film. Doping DLC film with Si thus suppresses the volume reduction caused by exposure to soft X-rays.

Diamond-like carbon (DLC) films have been extensively applied in industries owing to their excellent characteristics such as high hardness. In particular, there is a growing demand for their use as protective films for mechanical parts owing to their excellent wear resistance and low friction coefficient. DLC films have been deposited by various methods and many deviate from the DLC regions present in the ternary diagrams proposed for sp3 covalent carbon, sp2 covalent carbon, and hydrogen. Consequently, redefining the DLC region on ternary diagrams using DLC coatings for mechanical and electrical components is urgently required. Therefore, we investigate the sp3 ratio, hydrogen content, and other properties of 74 types of amorphous carbon films and present the classification of amorphous carbon films, including DLC. We measured the sp3 ratios and hydrogen content using near-edge X-ray absorption fine structure and Rutherford backscattering-elastic recoil detection analysis under unified conditions. Amorphous carbon films were widely found with nonuniform distribution. The number of carbon atoms in the sp3 covalent carbon without bonding with hydrogen and the logarithm of the hydrogen content were inversely proportional. Further, we elucidated the DLC regions on the ternary diagram, classified the amorphous carbon films, and summarized the characteristics and applications of each type of DLC.

In this paper, the local structure of silicon-containing diamond-like carbon (Si-DLC) films is discussed based on the measurement of C K-edge and Si K-edge near-edge x-ray absorption fine structure (NEXAFS) spectra using the synchrotron radiation of 11 types of Si-DLC film fabricated with various synthesis methods and having different elemental compositions. In the C K-edge NEXAFS spectra of the Si-DLC films, the σ* band shrunk and shifted to the lower-energy side, and the π* peak broadened with an increase in the Si content in the Si-DLC films. However, there were no significant changes observed in the Si K-edge NEXAFS spectra with an increase in the Si content. These results indicate that Si–Si bonding is not formed with precedence in Si-DLC film.

&lt;p&gt;アミノ酸やその前駆体は、炭素質コンドライトのような地球外物質で発見されており、これらは、地球上での最初の生命の誕生に必要な有機物の供給源と考えられている。これらの有機物が地球に運ばれたと考えるならば分子雲、原始太陽系円盤、小惑星、彗星、宇宙塵などの様々な宇宙環境での安定性を考慮する必要がある。本研究ではアミノ酸やアミノ酸前駆体、模擬星間物質に宇宙線を模擬した重粒子線、小惑星中での26Alの放射性崩壊によるγ線を模擬したγ線、原始太陽系円盤での原始太陽からの光を模擬した軟X線を照射し、安定性を評価することを目的とした。今回の実験を通して、複雑態アミノ酸前駆体が最も種々のエネルギーに対して、安定であることが示唆された。また、複雑態アミノ酸前駆体は150 nm ∼ 300 nm 付近に高い吸収があるにもかかわらず、軟X線照射実験で最も安定であった。このことから複雑態アミノ酸前駆体が種々の宇宙環境で安定であることが示唆され

The low-temperature formation of nanocrystalline Si (nc-Si) in SiO<inf>x</inf>film is one of the key technologies in the realization of Si-based photonics and memories. We proposed a low-temperature nc-Si formation method with soft X-ray irradiation. The nc-Si formation depended on the Si/O atomic ratio in the pristine SiO<inf>x</inf>film. The Si-rich regions in SiO<inf>x</inf>films with Si/O ratios higher than 0.67 were crystallized by atomic migration via electron excitation with soft X-ray irradiation at a photon energy near the core level of Si 2p. nc-Si with a mean size of 20 nm was formed by soft X-ray irradiation at a low temperature of 660 °C.

Hydrogenated amorphous silicon carbide films have been fabricated by the decomposition of hexamethyldisilane with a microwave discharge flow of Ar. Mechanically hard films were obtained by applying radio-frequency (RF) bias voltages to the substrate. The atomic compositions of the films were analyzed by a combination of Rutherford backscattering and elastic recoil detection, X-ray photoelectron spectroscopy (XPS), and glow discharge optical emission spectroscopy. The chemical structure was analyzed by carbon-K near-edge X-ray absorption fine structure spectroscopy, high-resolution XPS, and Fourier transform infrared absorption spectroscopy. The structural changes upon the application of RF bias were investigated, and the concentration of O atoms near the film surface was found to play a key role in the mechanical hardness of the present films.

A novel activation method for a B dopant implanted in a Si substrate using a soft X-ray undulator was examined. As the photon energy of the irradiated soft X-ray approached the energy of the core level of Si 2p, the activation ratio increased. The effect of soft X-ray irradiation on B activation was remarkable at temperatures lower than 400°C. The activation energy of B activation by soft X-ray irradiation (0.06 eV) was lower than that of B activation by furnace annealing (0.18 eV). The activation of the B dopant by soft X-ray irradiation occurs at low temperature, although the activation ratio shows small values of 6.2×10-3 at 110°C. The activation by soft X-ray is caused not only by thermal effects, but also electron excitation and atomic movement.

The compositions and bonding states of the amorphous hydrogenated carbon films at various thicknesses were evaluated via near-edge X-ray absorption fine-structure (NEXAFS) and elastic recoil detection analysis combined with Rutherford backscattering spectrometry. The absolute carbon<italic>sp</italic>²contents were determined to decrease to 65% from 73%, while the hydrogen contents increase from 26 to 33 at.% as the film thickness increases. In addition, as the film thickness increases, the<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M1"><mml:mrow><mml:msup><mml:mrow><mml:mi>π</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C=C),<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M2"><mml:mrow><mml:msup><mml:mrow><mml:mi>σ</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C–H),<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M3"><mml:mrow><mml:msup><mml:mrow><mml:mi>σ</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C=C), and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M4"><mml:mrow><mml:msup><mml:mrow><mml:mi>σ</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C≡C) bonding states were found to increase, whereas the<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M5"><mml:mrow><mml:msup><mml:mrow><mml:mi>π</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C≡C) and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" id="M6"><mml:mrow><mml:msup><mml:mrow><mml:mi>σ</mml:mi></mml:mrow><mml:mrow><mml:mo>⁎</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math>(C–C) bonding states were observed to decrease in the NEXAFS spectra. Consequently, the film thickness is a key factor to evaluate the composition and bonding state of the films.