Ogawa, Shuichi*; Tsuda, Yasutaka; Sakamoto, Tetsuya*; Okigawa, Yuki*; Masuzawa, Tomoaki*; Yoshigoe, Akitaka; Abukawa, Tadashi*; Yamada, Takatoshi*
Applied Surface Science, 605, p.154748_1 - 154748_6, 2022/12
Immersion of graphene in KOH solution improves its mobility on SiO/Si wafers. This is thought to be due to electron doping by modification with K atoms, but the K atom concentration C in the graphene has not been clarified yet. In this study, the C was determined by XPS analysis using high-brilliance synchrotron radiation. The time evolution of C was determined by real-time observation, and the C before irradiation of synchrotron radiation was estimated to be 0.94%. The C 1s spectrum shifted to the low binding energy side with the desorption of K atoms. This indicates that the electron doping concentration into graphene is decreasing, and it is experimentally confirmed that K atoms inject electrons into graphene.
Tsuda, Yasutaka; Yoshigoe, Akitaka; Ogawa, Shuichi*; Sakamoto, Tetsuya*; Yamamoto, Yoshiki*; Yamamoto, Yukio*; Takakuwa, Yuji*
Journal of Chemical Physics, 157(23), p.234705_1 - 234705_21, 2022/12
Katsube, Daiki*; Ono, Shinya*; Inami, Eiichi*; Yoshigoe, Akitaka; Abe, Masayuki*
Vacuum and Surface Science, 65(11), p.526 - 530, 2022/11
The oxidation of oxygen vacancies at the surface of anatase TiO (001) was investigated by synchrotron radiation photoelectron spectroscopy and supersonic O beam (SSMB). The oxygen vacancies at the top surface and subsurface could be eliminated by the supply of hyperthermal oxygen molecules. Oxygen vacancies are present on the surface of anatase TiO(001) when it is untreated before transfer to a vacuum chamber. These vacancies, which are stable in the ambient condition, could also be effectively eliminated by using oxygen SSMB. This result is promising as a surface processing for various functional oxides.
Tsuda, Yasutaka; Yoshigoe, Akitaka; Ogawa, Shuichi*; Sakamoto, Tetsuya*; Takakuwa, Yuji*
e-Journal of Surface Science and Nanotechnology (Internet), 21(1), p.30 - 39, 2022/11
Mizobata, Hidetoshi*; Tomigahara, Kazuki*; Nozaki, Mikito*; Kobayashi, Takuma*; Yoshigoe, Akitaka; Hosoi, Takuji*; Shimura, Takayoshi*; Watanabe, Heiji*
Applied Physics Letters, 121(6), p.062104_1 - 062104_6, 2022/08
The interface properties and energy band alignment of SiO/GaN metal-oxide-semiconductor (MOS) structures fabricated on N-polar GaN(000) substrates were investigated by electrical measurements and synchrotron-radiation X-ray photoelectron spectroscopy. They were then compared with those of SiO/GaN MOS structures on Ga-polar GaN(0001). Although the SiO/GaN(000) structure was found to be more thermally unstable than that on the GaN(0001) substrate, excellent electrical properties were obtained for the SiO/GaN(000) structure by optimizing conditions for post-deposition annealing. However, the conduction band offset for SiO/GaN(000) was smaller than that for SiO/GaN(0001), leading to increased gate leakage current. Therefore, caution is needed when using N-polar GaN(000) substrates for MOS device fabrication.
Hosoi, Takuji*; Osako, Momoe*; Moges, K.*; Ito, Koji*; Kimoto, Tsunenobu*; Sometani, Mitsuru*; Okamoto, Mitsuo*; Yoshigoe, Akitaka; Shimura, Takayoshi*; Watanabe, Heiji*
Applied Physics Express, 15(6), p.061003_1 - 061003_5, 2022/06
The combination of NO annealing and subsequent post-nitridation annealing (PNA) in CO ambient for SiO/SiC structures has been demonstrated to be effective in obtaining both high channel mobility and superior threshold voltage stability in SiC-based metal-oxide-semiconductor field-effect transistors (MOSFETs). N atoms on the SiO side of the SiO/SiC interface incorporated by NO annealing, which are plausible cause of charge trapping sites, could be selectively removed by CO-PNA at 1300C without oxidizing the SiC. CO-PNA was also effective in compensating oxygen vacancies in SiO, resulting high immunity against both positive and negative bias-temperature stresses.
Tang, J.*; Seo, O.*; Rivera Rocabado, D. S.*; Koitaya, Takanori*; Yamamoto, Susumu*; Namba, Yusuke*; Song, C.*; Kim, J.*; Yoshigoe, Akitaka; Koyama, Michihisa*; et al.
Applied Surface Science, 587, p.152797_1 - 152797_8, 2022/06
The hydrogen absorption and diffusion mechanisms on cube-shaped Pd nanoparticles (NPs) which are important hydrogen-storage materials were studied using X-ray photoelectron spectroscopy and DFT calculations. In the surface region, hydrogen absorption showed almost similar behavior regardless of the NPs size. It was found that the octahedral sites are more favorable than the tetrahedral sites for hydrogen occupation. We also clarified that the hydrogen atoms absorbing on the smaller-sized Pd NPs diffuse to the subsurface more actively because of the weakened Pd-H bond by the surface disordering, which plays an important role in hydrogen adsorption at a low H pressure.
Nakanuma, Takato*; Iwakata, Yu*; Watanabe, Arisa*; Hosoi, Takuji*; Kobayashi, Takuma*; Sometani, Mitsuru*; Okamoto, Mitsuo*; Yoshigoe, Akitaka; Shimura, Takayoshi*; Watanabe, Heiji*
Japanese Journal of Applied Physics, 61(SC), p.SC1065_1 - SC1065_8, 2022/05
Nitridation of SiO/4H-SiC(110) interfaces with post-oxidation annealing in an NO ambient (NO-POA) and its impact on the electrical properties were investigated. Sub-nm-resolution nitrogen depth profiling at the interfaces was conducted by using a scanning X-ray photoelectron spectroscopy microprobe. The results showed that nitrogen atoms were incorporated just at the interface and that interface nitridation proceeded much faster than at SiO/SiC(0001) interfaces, resulting in a 2.3 times higher nitrogen concentration. Electrical characterizations of metal-oxide-semiconductor capacitors were conducted through capacitance-voltage () measurements in the dark and under illumination with ultraviolet light to evaluate the electrical defects near the conduction and valence band edges and those causing hysteresis and shifting of the curves. While all of these defects were passivated with the progress of the interface nitridation, excessive nitridation resulted in degradation of the MOS capacitors. The optimal conditions for NO-POA are discussed on the basis of these experimental findings.
Nakanuma, Takato*; Kobayashi, Takuma*; Hosoi, Takuji*; Sometani, Mitsuru*; Okamoto, Mitsuo*; Yoshigoe, Akitaka; Shimura, Takayoshi*; Watanabe, Heiji*
Applied Physics Express, 15(4), p.041002_1 - 041002_4, 2022/04
The leakage current and flat-band voltage (VFB) instability of NO-nitrided SiC (110) (a-face) MOS devices were systematically investigated. Although NO nitridation is effective in improving the interface properties, we found that it reduces the onset field of Fowler-Nordheim (F-N) current by about 1 MVcm, leading to pronounced leakage current. Synchrotron X-ray photoelectron spectroscopy revealed that the nitridation reduces the conduction band offset at the SiO/SiC interface, corroborating the above finding. Furthermore, systematical positive and negative bias stress tests clearly indicated the VFB instability of nitrided a-face MOS devices against electron and hole injection.
Kakiuchi, Takuhiro*; Matoba, Tomoki*; Koyama, Daisuke*; Yamamoto, Yuki*; Yoshigoe, Akitaka
Langmuir, 38(8), p.2642 - 2650, 2022/03
0xidation processes at the interface and the surface of Si(111) substrate with thin Hf films were studied using photoelectron spectroscopy in conjunction with supersonic oxygen molecular beams (SOMB). The oxidation starts at the outermost Hf layers and produces stoichiometric HfO. Hf silicates (Hf-O-Si configuration) were generated in the vicinity of the HfO/Si interface in the case of the irradiation of 2.2 eV SOMB. The oxidation of the Si substrate takes place to generate SiO compounds. Si atoms were emitted from the SiO/Si interface region underneath the HfO overlayers to release the stress generated within the strained Si layers. The emitted Si atoms can pass through the HfO overlayers and react with the impinging O gas.
Sumiya, Masatomo*; Sumita, Masato*; Tsuda, Yasutaka; Sakamoto, Tetsuya; Sang, L.*; Harada, Yoshitomo*; Yoshigoe, Akitaka
Science and Technology of Advanced Materials, 23(1), p.189 - 198, 2022/00
GaN is an attracting material for power-electronic devices. Understanding the oxidation at GaN surface is important for improving metal-oxide-semiconductor (MOS) devices. In this study, the oxidation at GaN surfaces depending on the GaN crystal planes (+c, -c, and m-plane) was investigated by real time XPS and DFT-MD simulation. We found that HO vapor has the highest reactivity due to the spin interaction between HO and GaN surfaces. The bond length between the Ga and N on the -c GaN surface was increased by OH attacking the back side of three-fold Ga atom. The chemisorption on the m-plane was dominant. The intense reactions of oxidation and AlGaN formation for p-GaN were observed at the interface of the AlO layer deposited by ALD using HO vapor. This study suggests that an oxidant gas other than HO and O should be used to avoid unintentional oxidation during AlGaN atomi layer deposition.
Hayashida, Koki*; Tsuda, Yasutaka; Yamada, Takashi*; Yoshigoe, Akitaka; Okada, Michio*
ACS Omega (Internet), 6(40), p.26814 - 26820, 2021/10
We report the X-ray photoemission spectroscopy (XPS) characterization of the bulk CuO(111) surface and 8-type and 29-type oxide structures on Cu(111) prepared by using 0.5 eV O supersonic molecular beam (SSMB) source. We propose a new structural model for the 8-type oxide structure and also confirmed the previously proposed model for the  oxide structure on Cu(111), based on the O1s XPS spectra. The detection-angle dependence of the O 1s spectra supports that the nanopyramidal model is more preferable for the (X)R30 CuO(111). We also report the electronic excitations which O1s electrons suffer.
Katsube, Daiki*; Ono, Shinya*; Takayanagi, Shuhei*; Ojima, Shoki*; Maeda, Motoyasu*; Origuchi, Naoki*; Ogawa, Arata*; Ikeda, Natsuki*; Aoyagi, Yoshihide*; Kabutoya, Yuito*; et al.
Langmuir, 37(42), p.12313 - 12317, 2021/10
We investigated the oxidation of oxygen vacancies at the surface of anatase TiO(001) using supersonic seeded molecular beam (SSMB) of oxygen. The oxygen vacancies at the top-surface and sub-surface could be eliminated by the supply of oxygen using an SSMB. These results indicate that the interstitial vacancies can be mostly assigned to oxygen vacancies, which can be effectively eliminated by using an oxygen SSMB. Oxygen vacancies are present on the surface of anatase TiO(001) when it is untreated before transfer to a vacuum chamber. These vacancies, which are stable in the as-grown condition, could also be effectively eliminated using the oxygen SSMB.
Ogawa, Shuichi*; Taga, Ryo*; Yoshigoe, Akitaka; Takakuwa, Yuji*
Journal of Vacuum Science and Technology A, 39(4), p.043207_1 - 043207_9, 2021/07
Nickel (Ni) is used as a catalyst for nitric oxide decomposition and ammonia production but it is easily oxidized and deactivated. Clarification of the reduction process of oxidized Ni is essential to promote more efficient use of Ni catalysts. In this study, the reduction processes were investigated by in situ time-resolved photoelectron spectroscopy. We propose a two-step reduction reaction model. The rate-limiting process for the first step is surface precipitation of O atoms and that of the second step is dissociation of H molecules.
Ogawa, Shuichi*; Zhang, B.*; Yoshigoe, Akitaka; Takakuwa, Yuji*
Vacuum and Surface Science, 64(5), p.218 - 223, 2021/05
The oxidation reaction kinetics on Ti(0001) and Ni(111) surfaces were observed by real-time photoelectron spectroscopy using synchrotron radiation to measure the oxidation state and oxide thickness. After the Ti(0001) surface was wholly covered by TiO with a thickness of 1.2 nm, the rapid growth of n-type TiO proceeded through the diffusion of Ti ions to the TiO surface at 400C. A saturation of oxygen uptake on the TiO surface indicates that the O sticking coefficient on the TiO surface is negligibly small and the segregation of Ti to the TiO surface is a trigger to initiate the TiO growth. On the Ni(111) surface at 350C, a thermally stable NiO proceeded preferentially and then the growth of p-type NiO was initiated. The time evolution of NiO thickness was represented by a logarithmic growth model, where the NiO growth is governed by the electron tunneling to the NiO surface.
Tsuda, Yasutaka; Gueriba, J. S.*; Makino, Takamasa*; Dio, W. A.*; Yoshigoe, Akitaka; Okada, Michio*
Scientific Reports (Internet), 11, p.3906_1 - 3906_8, 2021/02
Toyoda, Satoshi*; Yamamoto, Tomoki*; Yoshimura, Masashi*; Sumida, Hirosuke*; Mineoi, Susumu*; Machida, Masatake*; Yoshigoe, Akitaka; Suzuki, Satoru*; Yokoyama, Kazushi*; Ohashi, Yuji*; et al.
Vacuum and Surface Science, 64(2), p.86 - 91, 2021/02
We have developed measurement and analysis techniques in X-ray photoelectron spectroscopy. To begin with, time-division depth profiles of gate stacked film interfaces have been achieved by NAP-HARPES (Near Ambient Pressure Hard X-ray Angle-Resolved Photo Emission Spectroscopy) data. We then have promoted our methods to quickly perform peak fittings and depth profiling from time-division ARPES data, which enables us to realize 4D-XPS analysis. It is found that the traditional maximum entropy method (MEM) combined with Jackknife averaging of sparse modeling in NAP-HARPES data is effective to perform dynamic measurement of depth profiles with high precision.
Doi, Takashi*; Yoshigoe, Akitaka
Surface and Interface Analysis, 52(12), p.1117 - 1121, 2020/12
Ni-base alloys has been widely used for chemical plants because of their high strength and excellent oxidation resistance. In particular, the addition of Sn and Sb in Ni-base alloys significantly improves the metal dusting resistance. It is indicated that Sn and Sb are segregated on the alloy surface in the metal dusting environment; however, the details have not been clarified yet. The behavior of the Ni-Sn and Ni-Sb alloys under a high-temperature oxidation environment was investigated by in situ X-ray photoelectron spectroscopy. It was confirmed that Sn and Sb have been segregated at the surface of their alloys during oxidation in low oxygen potential environment. These results indicate that Sn and Sb segregation improves the metal dusting resistance.
Sumiya, Masatomo*; Sumita, Masato*; Asai, Yuya*; Tamura, Ryo*; Uedono, Akira*; Yoshigoe, Akitaka
Journal of Physical Chemistry C, 124(46), p.25282 - 25290, 2020/11
The initial oxidation of different GaN surfaces [the polar Ga-face (+c) and N-face (-c) and the nonpolar (100) ()plane] under O molecular beam irradiation was studied by real-time synchrotron radiation X-ray photoelectron spectroscopy and DFT molecular dynamics calculation. The results predict that triplet O either dissociates or chemisorbs at the bridge position on the +c-surface, while on N-terminated -c-surface the O2 molecule only undergoes dissociative chemisorption. On the -GaN surface, although the dissociation of O is dominant, the bond length and angle were found to fluctuate from those of O molecules adsorbed on the polar surfaces. The computational model including both the surface spin and polarity of GaN is useful for understanding the interface between GaN and oxide layers in metal-oxide electronic.
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
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.