Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
Initialising ...
鈴木 誠也; 勝部 大樹*; 矢野 雅大; 津田 泰孝; 寺澤 知潮; 小澤 孝拓*; 福谷 克之; Kim, Y.*; 朝岡 秀人; 柚原 淳司*; et al.
Small Methods, 9(3), p.2400863_1 - 2400863_9, 2025/03
被引用回数：1 パーセンタイル：30.18(Chemistry, Physical)For group 14 monoelemental two-dimensional materials, such as silicene, germanene, and stanene, oxidation is a severe problem that alters or degrades their physical properties. This study shows that the oxidized germanene on Ag(111)/Ge(111) can be reformed to germanene by simple heating around 500 
C in a vacuum. The key reaction in reforming germanene is the desorption of GeO and GeO
during heating around 350 C. After removing surface oxygen, Ge further segregates to the surface, resulting in germanene. The reformed germanene has the same crystal structure, a (7
7) R19.1 supercell with respect to Ag(111), and has equivalent high quality to that of as-grown germanene on Ag(111)/Ge(111). Even after air oxidation, germanene can be reformed by annealing in a vacuum. On the other hand, the desorption of GeO and GeO at high temperatures was not suppressed even in the O backfilling atmosphere. This instability of oxidized germanene/Ag(111)/Ge(111) at high temperatures contributes to the ease of germanene reformation without oxygen. In other words, the present germanene reformation, as well as the segregation of germanene on Ag(111)/Ge(111), is a highly robust process as a synthesis method of germanene.
Lim, G.-C.*; 福谷 克之; 他8名*
Journal of the American Chemical Society, 146(46), p.32013 - 32021, 2024/11
被引用回数：3 パーセンタイル：51.94(Chemistry, Multidisciplinary)We investigate ultrahigh concentration doping of hydrogen (H) into rutile-TiO(100) single crystals by low-energy (2.5 keV) hydrogen ion beam irradiation at low temperature (LT). While the hydrogen concentration was limited to H
TiO at 300 K, in situ nuclear reaction analysis (NRA) revealed ultrahigh concentration doping of hydrogen up to H
TiO by the LT irradiation at 50 K. The large (
8.2%) expansion of the out-of-plane lattice constant suggests that hydrogen occupies interstitial sites in rutile TiO. Hydrogens of early stage irradiation act as electron donors and induce a large increase in conductivity, which is consistent with theoretical studies in the dilute limit. The nature of excess H was investigated in situ by transport and photoemission measurements. After LT excess H doping and postannealing to room temperature, unusual electrical transport properties were observed while maintaining the ultrahigh H concentration. In situ photoemission measurements show that the excessively doped hydrogens by LT irradiation generate a deeper in-gap state (IGS) of metastable nature. Density functional theory predicts the formation of double neighboring interstitial hydrogens as a possible mechanism for the deeper IGS.
小澤 孝拓*; 福谷 克之; 他7名*
Nature Communications (Internet), 15, p.9558_1 - 9558_8, 2024/11
被引用回数：0 パーセンタイル：0.00(Multidisciplinary Sciences)Hydrogen, the smallest and lightest element, readily permeates a variety of materials and modulates their physical properties. Identification of the hydrogen lattice location and its amount in crystals is key to understanding and controlling the hydrogen-induced properties. Combining nuclear reaction analysis (NRA) with the ion channeling technique, we experimentally determined the locations of H and D in epitaxial nanofilms of titanium hydrides from the analysis of the two-dimensional angular mappings of NRA yields. Here we show that 11 at% of H are located at the octahedral site with the remaining H atoms in the tetrahedral site. Density functional theory calculations revealed that the structures with the partial octahedral site occupation are stabilized by the Fermi level shift and Jahn-Teller effect induced by hydrogen. In contrast, D was found to solely occupy the tetrahedral site owing to the mass effect on the zero-point vibrational energy. These findings suggest that site occupation of hydrogen can be controlled by changing the isotope mixture ratio, which leads to promising manifestation of novel hydrogen-related phenomena.
Kiliyankil, V. A.*; 福谷 克之; 他10名*
Journal of Materials Chemistry A, 12(42), p.28731 - 28743, 2024/10
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)The hydrogen evolution reaction (HER) on platinum (Pt) electrocatalysts involves the generation of hydrogen atoms and the formation of hydrogen molecules. It is commonly believed that the sites on the surfaces of the terrace (111, 110, and 100) domains are responsible for the formation of hydrogen molecules. However, the electrochemistry of the hydrogen atom generation is not well understood. We created edge-rich platinum electrocatalysts using nano-fabrics comprising entire single-walled carbon nanotubes (SWCNTs) as templates and supports. We then conducted the HER on the edge-rich Pt/SWCNT hybridized electrocatalysts and gained new insights into the electrochemical properties and functions of the edge sites. We propose that the edge sites are oxidized and serve two important functions: they act as atomic barriers, allowing electrons to accumulate within the terrace (111, 110, and 100) domains, and they transfer the electrons to the hydronium ions in the electrical double layer through discharge. Enhancing the discharge capability of the electrocatalysts is an efficient way to reduce the amount of platinum required, and this can be applied to various precious metal-based electrocatalysts to enhance their electrocatalytic activities and durability.
molecule generation from dissociatively adsorbed water on TiO through photoexcitation加藤 弘一*; 長塚 直樹*; 福谷 克之
Journal of Physical Chemistry C, 128(20), p.8188 - 8198, 2024/05
被引用回数：2 パーセンタイル：30.18(Chemistry, Physical)The dissociative adsorption of water, migration of hydrogen, and molecular hydrogen generation on anatase and rutile TiO surfaces were studied by first-principles calculations. Whereas dissociated H and OH are adsorbed strongly on both TiO surfaces, the adsorption energies were substantially decreased when H and OH were combined with polarons, which can be generated through photoexcitation. The H atom coupled with a polaron was found to undergo codiffusion. While a large polaron smoothly follows the H atom migration in anatase, a small polaron in rutile stochastically moves and abruptly jumps between neighboring Ti sites during the H atom migration, exerting strong retardation to the H atom migration. The favorable path for two H atoms coupled with polarons to form an H molecule was examined. It was found that the energy barrier is low when an H atom migrates to the H-adsorbed O site to form a 2H-coordinated O atom, followed by H desorption on both anatase and rutile surfaces. The atom of the oxazole forms a more stable 
electronic configuration by the adsorption of two H atoms. The two H atoms on the same O atom, coupled with polarons, possibly tunnel through the energy barrier to a desorbing H molecule. It is also shown that an HO molecule possibly desorbs from the same 2H=O configuration.
小澤 孝拓*; 福谷 克之; 他4名*
Journal of Vacuum Science and Technology A, 42(2), p.023402_1 - 023402_6, 2024/03
被引用回数：0 パーセンタイル：0.00(Materials Science, Coatings & Films)We synthesized an epitaxial film of high-entropy perovskite oxide (HEPO) consisting of three elements (Ca, Sr, Ba) in the A site and 12 elements (Si, Ti, Cr, Mn, Fe, Co, Ni, Ge, Zr, Sn, Ce, Hf) in the B site of ABO
, and investigated hydrogen absorption properties in the HEPO film. The hydrogen depth profile was measured by nuclear reaction analysis via the 
H(
N, 
)
C reaction, showing the hydrogen absorption in the HEPO film with a maximum atomic concentration of 0.3 in the ABO unit. The diffusion coefficient of H in the film was analyzed from the H depth profile, and the activation barrier for diffusion was estimated to be (0.54
0.13) eV. An absorption band was observed at 3290 cm 
in the infrared absorption spectrum, which corresponds to the O-H stretching vibration. Simultaneous measurements of nuclear reaction and resistance revealed that the HEPO film remained electrically insulating regardless of the hydrogen concentration. We demonstrated that hydrogen is incorporated in HEPO forming OH species while keeping HEPO electrically insulating.
Zhou, X.*; 福谷 克之; 他9名*
Applied Physics Letters, 124(8), p.082103_1 - 082103_7, 2024/02
被引用回数：6 パーセンタイル：87.23(Physics, Applied)Electron-doping Mottronics within correlated vanadium dioxide opens up a paradigm to abruptly regulate the Mottronic phase transitions via adjusting the 
-orbital occupancy and configuration. Nevertheless, the potential impact of high-valence elementary substitution in the hydrogen-associated Mottronic transitions of VO is yet unclear. Herein, we demonstrate the role of high-valence elementary substitution in regulating the hydrogen-triggered Mottronic transitions of VO, assisted by quantitative hydrogen analysis using the nuclear reaction analysis. Substituting vanadium with a high-valence transitional metal within doped-VO largely reduces the hydrogen incorporation compared to the intrinsic VO under the low temperature hydrogenation process. Therefore, in contrast to hydrogen-induced electron localization of intrinsic VO upon low-temperature hydrogenation, only the hydrogen-triggered metallic state is observed within the hydrogen-associated phase diagram of W
V
O, as further probed by the near-edge X-ray absorption fine structure analysis and X-ray photoelectron spectroscopy. The present work reveals the overlooked role associated with the donor substitutions that largely influences the competitive equilibrium between the two rival hydrogen-induced Mottronic transitions within VO toward either the metallic or the highly insulating phase.
小澤 孝拓*; 福谷 克之; 他4名*
Journal of Physics and Chemistry of Solids, 185, p.111741_1 - 111741_7, 2024/02
被引用回数：3 パーセンタイル：32.03(Chemistry, Multidisciplinary)Hydrogen (H), the lightest element, exhibits quantum nature. Because the quantum tunneling is almost independent of temperature, H diffusion shows a transition from thermal hopping to quantum tunneling at low temperature. The role of the nuclear quantum effects on H diffusion, however, has not been clarified around the crossover region. Hence, we elucidate the hopping mechanism at intermediate temperature by a combination of accurate experimental data on H hopping rates and theoretical calculations for quantum states of H. We derived H hopping rates in Pd from the resistance evolution due to the H ordering associated with the 50 K anomaly. A gradual transition from thermal hopping to quantum tunneling was observed around 65 K. Three-dimensional quantum-mechanical analysis for the H quantum states revealed that the gradual transition is attributed to the resonant tunneling between the discrete vibrational states in the octahedral site and the tetrahedral site via the thermal vibrational excitation. Based on the results at different H concentrations and deuterium, we demonstrated that the tunneling rate is tuned by energy level matching and the resonance nature is manifested as the abruptness of the transition from thermal to quantum hopping.
Mao, W.*; 福谷 克之; 他8名*
International Journal of Hydrogen Energy, 50(Part D), p.969 - 978, 2024/01
被引用回数：5 パーセンタイル：39.43(Chemistry, Physical)Cerium oxide (CeO) is well known to be reducible by hydrogen (H), yet the diffusion and solution properties of hydrogen in ceria at elevated temperatures have remained challenging to evaluate. We therefore fabricated nanometer-thin (100 nm) cerium oxide films on Si(111) substrates by pulsed laser deposition (PLD) and quantitatively investigated the H depth distributions therein by means of resonant H(N,)C nuclear reaction analysis (NRA) before and after annealing in H gas at 773-973 K. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) reveal that the as-deposited films exhibit single phase CeO structure and partially reduced stoichiometry (CeO
). H annealing does not largely change the H content of the as-deposited films; in all conditions several atomic percent of hydroxyl (OH) are found to exist in a thin (4 nm) surface layer, whereas stably bound hydrogen in the bulk of the films is almost uniformly distributed and of much smaller quantity (0.2 at.%) than the oxygen vacancy concentration in the partially reduced ceria. Its low concentration and high thermal stability identify this bulk H species as likely being strongly bound to defects in the polycrystalline films rather than as a hydride species that interacts weakly with O-vacancies. The H diffusion coefficient and activation energy in the ceria films are determined as 
10
m
s at 773-973 K and 
1.69 eV, respectively. The observed diffusion activation energy is somewhat larger than theoretical predictions for thermal diffusion of H in stoichiometric bulk CeO, suggesting that defects and oxygen vacancies in the PLD-fabricated ceria thin films possibly have an impact on the H mobility.
越田 裕之*; Wilde, M.*; 福谷 克之
Journal of Chemical Physics, 160(3), p.034703_1 - 034703_9, 2024/01
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)We have developed an experimental and analytical setup for thermal desorption spectroscopy of solid water films on surfaces. We obtain the coverage-dependent desorption kinetics of water molecules from a well-defined ultra-thin alumina/NiAl(110) surface in the coverage range of 0-2 monolayers. We use a novel deconvolution technique to eliminate the pumping delay of water vapor in the vacuum system, which has previously hindered the accurate estimation of desorption kinetic parameters, such as activation energy and pre-exponential factor. The coverage-dependent Arrhenius analysis reveals that the desorption activation energy decreases with increasing coverage in the submonolayer range, indicating that the water-water interaction is not attractive. We also find that the pre-exponential factor for the second layer is higher than that for the sub-monolayer. We explain this difference in terms of transition state theory and propose that entropic effects play a significant role in water desorption kinetics.
O
surfaces浅川 寛太*; 福谷 克之; 他3名*
Scientific Reports (Internet), 13, p.14965_1 - 14965_11, 2023/09
被引用回数：1 パーセンタイル：12.23(Multidisciplinary Sciences)Light-induced desorption of Rb atoms from a ferrimagnetic FeO(001) surface was studied using a spin-selective optical method, which provides information on the spin polarization, velocity distribution, and amount of the desorbed atoms. The results showed that the intensity of the desorption of Rb from FeO(001) induced by ultraviolet (UV) light irradiation was smaller than the detection limit at coverages lower than the threshold coverage at which the desorption rate began to increase. Moreover, the average magnetic quantum number of the desorbed atoms was smaller than that of electrons at the Fermi level of the FeO(001) surface. These indicate that the light-induced desorption of Rb from an FeO(001) surface occurs only in the high-coverage region in which the desorbing atoms are not in contact with the FeO surface, and that the desorption does not involve spin transfer.
保田 諭; Di
o, W. A.*; 福谷 克之
Vacuum and Surface Science, 66(9), p.514 - 519, 2023/09
原子層材料の代表である単層グラフェンは、近年、水素イオンと重水素イオンを透過するだけでなく、これら水素同位体イオンの高い選択透過性を有することが知られている。このため、シリコン半導体、光ファイバー、創薬、核融合といった分野における水素同位体ガス濃縮材料としてグラフェンが利用できることが期待されている。しかしながら、その重要性にもかかわらず、実験研究は依然として不足しており、分離メカニズムについては未だ議論が続いている。本研究では、ヒドロンの量子トンネリングがどのように起こるかについての最近の発見を紹介する。
植田 寛和; 福谷 克之*; 山川 紘一郎
Frontiers in Chemistry (Internet), 11, p.1258035_1 - 1258035_7, 2023/08
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)水素分子には、オルトとパラと呼ばれる2つの核スピン修飾がある。2つの陽子の順列に関する対称性の制約から、オルトとパラの異性体はそれぞれ回転量子数の奇数と偶数の値しかとらない。オルソからパラへの変換は凝縮系で促進され、余剰の回転エネルギーとスピン角運動量が移動する。われわれは、分子化学吸着系とマトリックス分離系における水素の高速オルソ-パラ変換に関する最近の研究をレビューし、その変換機構と回転緩和経路について議論する。
ortho-para conversion on a metal surface; Interplay between electron and phonon systems植田 寛和; 福谷 克之
Journal of Physical Chemistry Letters (Internet), 14(34), p.7591 - 7596, 2023/08
被引用回数：1 パーセンタイル：11.83(Chemistry, Physical)Clarifying energy transfer processes in molecular adsorption on solid surfaces is essential to understand gas-surface interaction. Unlike the vibrational-energy transfer processes, which are thought to be well understood in detail, the rotational-energy transfer process still remains unclear. Considering the interconversion between ortho and para states of H is accompanied by the nuclear spin flip and the rotational-energy transfer, the surface-temperature dependence of the ortho-to-para conversion of molecularly chemisorbed H on Pd(210) is studied. The conversion rate is accelerated with increasing surface temperature. Based on the conversion model proposed for metal surfaces, we analyze the temperature dependence of the conversion rate taking account of both electron and phonon systems of the substrate. The rotational-energy transfer is most likely mediated by surface electrons with an assistance of the substrate phonons.
松澤 郁也*; 福谷 克之; 他5名*
Physical Review Materials (Internet), 7(8), p.085003_1 - 085003_6, 2023/08
被引用回数：10 パーセンタイル：69.17(Materials Science, Multidisciplinary)Doping hydrogen in correlated oxides is a promising way to control the materials functionalities. With in situ measurements of the resistance and hydrogen concentration by a nuclear reaction analysis, we have derived the detailed relation between the resistance and hydrogen concentration (
) for 
NiOH ( = Sm, Nd, and La), which reveal a clear resistance jump at a certain concentration. Taking account of the spatial distribution of hydrogen in both in-plane and depth directions, we have clarified that an insulating state is realized at 
and another insulating state is formed at 
. The electronic mechanisms for the two states are proposed in terms of Mott phases.
矢野 雅大; 保田 諭; 福谷 克之; 朝岡 秀人
RSC Advances (Internet), 13(21), p.14089 - 14096, 2023/05
被引用回数：1 パーセンタイル：10.11(Chemistry, Multidisciplinary)金属表面でのボトムアップ合成により、原子レベルで精密な化学構造を持つグラフェンナノリボン(GNR)を作製し、新しい電子デバイスを実現することが注目されている。しかし、GNR合成時に表面上の長さや方向を制御することは困難であり、より長く、より整列したGNRの成長を実現することは重要な課題である。本発表では、GNRの長尺化・配向化を実現するために、Au結晶表面上の秩序的に配向した単分子層からGNRを合成することを報告する。走査型トンネル顕微鏡(STM)により、室温でAu(111)上に蒸着した10,10'-dibromo-9,9'-bianthracene (DBBA)が自己組織化し、秩序的に配向した単分子層を形成し、DBBAのBr原子が隣接する直線状の分子ワイヤ構造を形成した。この単分子層中のDBBAは、その後の加熱によって表面からほとんど脱離することなく、分子配列とともに効率よく重合し、従来の成長法に比べてより長く、より配向したGNRが成長することが確認された。この結果は、DBBAが高密度に充填されているため、重合中にAu表面でのDBBAのランダムな拡散や脱離が抑制されたことに起因すると考えられる。さらに、GNR成長におけるAu結晶面の影響を調べたところ、Au(100)ではAu(111)と比較してDBBAの相互作用が強いため、さらに異方的にGNRが成長することが明らかになった。これらの結果は、より長く、より配向したGNRを実現するために、秩序ある前駆体単層からのGNR成長を制御するための基礎的な知見を与える。
NH and CaNH thin films by reactive magnetron sputtering under hydrogen partial pressure controlChon, S.*; 福谷 克之; 他8名*
Journal of Physical Chemistry Letters (Internet), 13(43), p.10169 - 10174, 2022/11
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)Calcium compounds with N and H are promising catalysts for NH conversion, and their epitaxial thin films provide a platform to quantitatively understand the catalytic activities. Here we report the selective epitaxial growth of CaNH and CaNH thin films by controlling the hydrogen partial pressure (
) during reactive magnetron sputtering. We find that the hydrogen charge states can be tuned by : CaNH containing H
is formed at 
Pa, while CaNH containing H
is formed at 
Pa. In situ plasma emission spectroscopy reveals that the intensity of the Ca atomic emission (422 nm) decreases as increases, suggesting that Ca reacts with H and N to form CaNH at lower , whereas at higher , CaH is first formed on the target surface and then sputtered to produce CaNH. This study provides a novel route to control the hydrogen charge states in Ca-N-H epitaxial thin films.
O(111) surfaces浅川 寛太*; 河内 泰三*; 福谷 克之
Journal of Physics Communications, 6(10), p.105004_1 - 105004_6, 2022/10
The Verwey transition on FeO(111) surface was investigated using nuclear resonant X-ray scattering (NRS). Measurements were conducted below (85K) and above (297 and 500K) the Verwey transition temperature. The internal magnetic field estimated from the NRS frequency spectra agreed with that of bulk FeO at all measured temperatures. A clear change in the intensity ratio of the two peaks in the frequency spectra was observed across the Verwey transition. The results indicate that despite the presence of the peculiar surface electronic states which makes the changes in the electronic properties across the Verwey transition temperature blurred, the hyperfine parameters of the (111) surface show a clear change across the Verwey transition temperature.
保田 諭; 松島 永佳*; 原田 健児*; 谷井 理沙子*; 寺澤 知潮; 矢野 雅大; 朝岡 秀人; Gueriba, J. S.*; Dio, W. A.*; 福谷 克之
ACS Nano, 16(9), p.14362 - 14369, 2022/09
被引用回数：25 パーセンタイル：83.97(Chemistry, Multidisciplinary)水素同位体である重水素は、半導体産業や医薬品開発に必須な材料であることから、重水素の高効率かつ低コストでの濃縮分離技術の開発は重要である。本研究では、グラフェンとパラジウム薄膜からなるヘテロ電極触媒を開発し、固体高分子形電気化学水素ポンピング法に適用することで高い分離能をもつ重水素濃縮デバイスの開発を行った研究について報告する。その結果、印加電圧が大きくなるにつれ分離能の指標となるH/D値が小さくなる明瞭な電位依存性が観察された。観察されたH/Dの電圧依存性について理論計算により検証した結果、印加電圧が小さい場合、水素イオンと重水素イオンがグラフェン膜透過の活性化障壁を量子トンネル効果により透過することで大きなH/D分離能が発現すること、印加電圧が大きくなると活性化障壁を乗り越えて反応が進行するためH/D値が減少することが示された。以上、グラフェンの水素同位体イオンの量子トンネル効果を利用することで高いH/D分離能を有する水素同位体分離デバイス創製の設計指針を得た。
川村 隆明*; 深谷 有喜; 福谷 克之
Surface Science, 722, p.122098_1 - 122098_8, 2022/08
被引用回数：1 パーセンタイル：6.44(Chemistry, Physical)本研究では、多重散乱計算を用いて、Pd(100)表面上の水素の位置に敏感な反射高速電子回折(RHEED)条件を探査した。水素の散乱振幅はPdの7%以下でしかないため、水素の位置決定には、回折強度への水素からの散乱の寄与が最大化される条件を見出すことが重要となる。10keVの電子ビームでは、視射角が4以下、方位角が[011]軸から13オフのときにそのような条件が見出された。この条件では、水素の表面垂直・平行の両方向の原子変位に対して顕著な強度変化を示す。RHEED波動関数の解析から、この条件下では低次の回折波が支配的であること、またRHEED電子は新しいタイプの共鳴現象により表面近傍に局在化することがわかった。この条件でのロッキング曲線解析を用いると、水素の高さを0.2
以下の精度で決定することが可能となる。この結果は、RHEEDがPd表面上の水素位置の決定に極めて有用な手法であることを示している。
