Gas barrier properties of chemical vapor-deposited graphene to oxygen imparted with sub-electronvolt kinetic energy

Ogawa, Shuichi*; Yamaguchi, Hisato*; Holby, E. F.*; Yamada, Takatoshi*; Yoshigoe, Akitaka; Takakuwa, Yuji*

Journal of Physical Chemistry Letters (Internet), 11(21), p.9159 - 9164, 2020/11

https://doi.org/10.1021/acs.jpclett.0c02112

Atomically thin layers of graphene have been proposed to protect surfaces through the direct blocking of corrosion reactants such as oxygen with low added weight. The long term efficacy of such an approach, however, is unclear due to the long-term desired protection of decades and the presence of defects in as-synthesized materials. Here, we demonstrate catalytic permeation of oxygen molecules through previously-described impermeable graphene by imparting sub-eV kinetic energy to molecules. These molecules represent a small fraction of a thermal distribution thus this exposure serves as an accelerated stress test for understanding decades-long exposures. The permeation rate of the energized molecules increased 2 orders of magnitude compared to their non-energized counterpart. Graphene maintained its relative impermeability to non-energized oxygen molecules even after the permeation of energized molecules indicating that the process is non-destructive and a fundamental property of the exposed material.

Synchrotron radiation real-time photoelectron spectroscopy study on adsorption reactions of oxygen molecule at semiconductor surfaces

Yoshigoe, Akitaka

Hoshako, 32(4), p.185 - 198, 2019/07

Synchrotron radiation photoelectron spectroscopy is a beneficial technique for precise analysis of chemical states of solid surfaces. Owing to its high luminosity, it ensures availability of termed synchrotron radiation real-time photoelectron spectroscopy which enables "" observation of chemical reactions with gas molecules occurring at surfaces. In this review, oxygen adsorption reactions in the oxidation of silicon single crystal surfaces are focused. Through the demonstration of our research, the usefulness of synchrotron radiation real-time photoelectron spectroscopy to study molecular adsorption reactions at solid surfaces is briefly described and the future perspective would also be shown.

Simultaneous observation of Si oxidation rate and oxidation-induced strain using XPS

Ogawa, Shuichi*; Yoshigoe, Akitaka; Takakuwa, Yuji*

Vacuum and Surface Science, 62(6), p.350 - 355, 2019/06

https://doi.org/10.1380/vss.62.350

Thermal oxidation of Si substrate is an indispensable process for the Si device fabrication. However, the influence of oxidation induced strain cannot be ignored for thin films. Synchrotron radiation real-time photoelectron spectroscopy was used as a method to measure simultaneously oxidation induced strain and oxidation rate. It was found that the acceleration of interfacial oxidation induced by thermal strain was observed for the rapid thermal oxidation. The results can be explained by the model in which point defects caused by strain become reaction sites at the SiO/Si interface.

Biodegradability of disulfide-organosilica nanoparticles evaluated by soft X-ray photoelectron spectroscopy; Cancer therapy implications

Mekaru, Harutaka*; Yoshigoe, Akitaka; Nakamura, Michihiro*; Doura, Tomohiro*; Tamanoi, Fuyuhiko*

ACS Applied Nano Materials (Internet), 2(1), p.479 - 488, 2019/01

https://pubs.acs.org/doi/10.1021/acsanm.8b02023

Organosilica nanoparticles are attractive for use as drug delivery systems for cancer therapy. Ideally, the nanoparticles need to degrade in the body after drug delivery to minimize their risk. However, the biodegradation of organosilica nanoparticles has not been thoroughly investigated. In this study, we used X-ray photoelectron spectroscopy and field-emission scanning electron microscopy to investigate the degradation of organosilica nanoparticles by glutathione, a peptide found in cells. Our results indirectly indicate that glutathione is able to reduce the disulfide bonds present in the network of one type of the nanoparticles, promoting dissociation of these nanoparticles. The dissociated nanoparticles form large maple leaf-shaped structures under certain conditions. We consider the formation mechanism of these symmetrical structures.

STM-induced SiO decomposition on Si(110)

Yano, Masahiro; Uozumi, Yuki*; Yasuda, Satoshi; Asaoka, Hidehito; Tsukada, Chie*; Yoshida, Hikaru*; Yoshigoe, Akitaka

e-Journal of Surface Science and Nanotechnology (Internet), 16, p.370 - 374, 2018/08

https://doi.org/10.1380/ejssnt.2018.370

Physical and electrical characterizations of AlGaN/GaN MOS gate stacks with AlGaN surface oxidation treatment

Yamada, Takahiro*; Watanabe, Kenta*; Nozaki, Mikito*; Shih, H.-A.*; Nakazawa, Satoshi*; Anda, Yoshiharu*; Ueda, Tetsuzo*; Yoshigoe, Akitaka; Hosoi, Takuji*; Shimura, Takayoshi*; et al.

Japanese Journal of Applied Physics, 57(6S3), p.06KA07_1 - 06KA07_6, 2018/06

https://doi.org/10.7567/JJAP.57.06KA07

Thermal oxidation of AlGaN surface and its impact on the electrical properties of AlGaN/GaN MOS capacitors were investigated by means of synchrotron radiation photoelectron spectroscopy (SR-PES), atomic force microscopy (AFM) and C-V measurements. SR-PES analysis revealed that the AlGaN surface is oxidized even at low temperature of 400C, in contrast to no oxide formation on GaN surface. However, since no noticeable change in the surface morphology was observed at temperatures up to 800C, it can be concluded that an ultrathin oxide overlayer is formed on the AlGaN surface. On the other hand, for the oxidation treatments above 850C, the formation of small oxide grains was observed over the entire area of the AlGaN surface, and the growth of oxide grains significantly degraded the surface morphology. Therefore, the AlGaN/GaN MOS capacitors were fabricated on the AlGaN surface oxidized at moderate temperatures up to 800C. While we have confirmed that relatively good interface properties are obtained for direct AlON deposition without oxidation treatment, it was found that the oxidation treatment at 400C leads to further improvement of interface properties and reduction of C-V hysteresis.

Implementation of atomic layer deposition-based AlON gate dielectrics in AlGaN/GaN MOS structure and its physical and electrical properties

Nozaki, Mikito*; Watanabe, Kenta*; Yamada, Takahiro*; Shih, H.-A.*; Nakazawa, Satoshi*; Anda, Yoshiharu*; Ueda, Tetsuzo*; Yoshigoe, Akitaka; Hosoi, Takuji*; Shimura, Takayoshi*; et al.

Japanese Journal of Applied Physics, 57(6S3), p.06KA02_1 - 06KA02_7, 2018/06

https://doi.org/10.7567/JJAP.57.06KA02

We fabricated AlON dielectric films by repeating thin AlN deposition and in situ O oxidation for AlGaN/GaN MOS-HFETs. Uniform nitrogen distribution is achievable by the proposed ALD-based process and that nitrogen concentration can be precisely controlled by changing AlN thickness (ALD cycle number) in each step. It was found that AlON films grown by ALD system offers significant advantages in terms of practical application while keeping superior Vth stability and electrical properties at the insulator/AlGaN interface in AlGaN/GaN MOS-HFETs.

Nanoscale spatial analysis of clay minerals containing cesium by synchrotron radiation photoemission electron microscopy

Yoshigoe, Akitaka; Shiwaku, Hideaki; Kobayashi, Toru; Shimoyama, Iwao; Matsumura, Daiju; Tsuji, Takuya; Nishihata, Yasuo; Kogure, Toshihiro*; Okochi, Takuo*; Yasui, Akira*; et al.

Applied Physics Letters, 112(2), p.021603_1 - 021603_5, 2018/01

https://doi.org/10.1063/1.5005799

A synchrotron radiation photoemission electron microscope (SR-PEEM) was applied to demonstrate pinpoint analysis of micrometer-sized weathered biotite clay particles with artificially adsorbed cesium (Cs) atoms. Despite the insulating properties of the clay, we observed the spatial distributions of constituent elements (Si, Al, Cs, Mg, Fe) without charging issues. We found that Cs atoms were likely to be adsorbed evenly over the entire particle. Spatially-resolved X-ray absorption spectra (XAS) of the Cs M-edge region showed Cs to be present in a monocation state (Cs). Further pinpoint XAS measurements were also performed at the Fe L-edge to determine the chemical valence of the Fe atoms. Our results demonstrate the utility of SR-PEEM as a tool for spatially-resolved chemical analyses of various environmental substances, which is not limited by the poor conductivity of samples.

Comprehensive study on initial thermal oxidation of GaN(0001) surface and subsequent oxide growth in dry oxygen ambient

Yamada, Takahiro*; Ito, Joyo*; Asahara, Ryohei*; Watanabe, Kenta*; Nozaki, Mikito*; Nakazawa, Satoshi*; Anda, Yoshiharu*; Ishida, Masahiro*; Ueda, Tetsuzo*; Yoshigoe, Akitaka; et al.

Journal of Applied Physics, 121(3), p.035303_1 - 035303_9, 2017/01

https://doi.org/10.1063/1.4974458

Initial oxidation of GaN(0001) epilayers and subsequent growth of thermal oxides in dry oxygen ambient were investigated by means of X-ray photoelectron spectroscopy, spectroscopic ellipsometry, atomic force microscopy and X-ray diffraction measurements. It was found that, whereas initial oxide formation tends to saturate at temperatures below 800C, selective growth of small oxide grains proceeds at dislocations in the epilayers, followed by noticeable grain growth leading to rough surface morphology at higher oxidation temperatures. This indicates that oxide growth and its morphology are crucially dependent on the defect density in the GaN epilayers. Structural characterizations also revealed that polycrystalline - and -phase GaO grains in an epitaxial relation with the GaN substrate are formed from the initial stage of the oxide growth. On the basis of these experimental findings, we also developed a comprehensive model for GaN oxidation mediated by nitrogen removal and mass transport.

Effect of nitrogen incorporation into Al-based gate insulators in AlON/AlGaN/GaN metal-oxide-semiconductor structures

Asahara, Ryohei*; Nozaki, Mikito*; Yamada, Takahiro*; Ito, Joyo*; Nakazawa, Satoshi*; Ishida, Masahiro*; Ueda, Tetsuzo*; Yoshigoe, Akitaka; Hosoi, Takuji*; Shimura, Takayoshi*; et al.

Applied Physics Express, 9(10), p.101002_1 - 101002_4, 2016/10

https://doi.org/10.7567/APEX.9.101002

The superior physical and electrical properties of AlON gate dielectrics on AlGaN/GaN substrates in terms of thermal stability, reliability, and interface quality were demonstrated by direct AlON deposition and subsequent annealing. Nitrogen incorporation into alumina was proven to be beneficial both for suppressing intermixing at the insulator/AlGaN interface and reducing the number of electrical defects in AlO films. Consequently, we achieved high-quality AlON/AlGaN/GaN metal-oxide-semiconductor capacitors with improved stability against charge injection and a reduced interface state density as low as 1.210 cmeV. The impact of nitrogen incorporation into the insulator was discussed on the basis of experimental findings.