草野 翔吾*; 松村 大樹; 石井 賢司*; 田中 裕久*; 水木 純一郎*
Nanomaterials (Internet), 9(4), p.642_1 - 642_14, 2019/04
The oxygen reduction reaction (ORR) on Pt/C in alkaline solution was studied by in situ high energy resolution X-ray absorption spectroscopy. To discuss the X-ray absorption near-edge structure (XANES), this paper introduced the rate of change of the (RCD), which is an analysis method that is sensitive to surface adsorption. The surface adsorptions as hydrogen (below 0.34 V), superoxide anion (from 0.34 V to 0.74 V), hydroxyl species (from 0.44 V to 0.74 V), atomic oxygen (above 0.74 V), and -PtO (above 0.94 V) were distinguished. It is clarified that the catalytic activity in an alkaline solution is enhanced by the stability of atomic oxygen and the low stability of superoxide anion/peroxide adsorption on the platinum surface.
浅野 駿*; 石井 賢司*; 松村 大樹; 辻 卓也; 伊奈 稔哲*; 鈴木 謙介*; 藤田 全基*
Journal of the Physical Society of Japan, 87(9), p.094710_1 - 094710_5, 2018/09
We investigated the Ce substitution and reduction annealing effects on the electronic states at copper sites by Cu -edge X-ray absorption near-edge structure measurements in PrCeCuO (PCCO) with varying and (amount of oxygen loss during annealing). Absorption near-edge spectra were modified by Ce substitution and reduction annealing similarly with increasing and . Considering electron doping by Ce substitution, this similarity indicates an increase in electron number at the copper sites due to annealing (). Furthermore, quantitative analyses of the spectra clarified that the number of Cu sites, corresponding to the induced electron number by Ce substitution increases linearly with in the as-sintered PCCO, whereas is not exactly equal to 2. For each -fixed sample, tends to exceed 2 with increasing , suggesting the emergence of two types of carrier due to annealing.
Cui, Y.-T.*; 原田 慈久*; 丹羽 秀治*; 尾嶋 正治*; 畑中 達也*; 中村 直樹*; 安藤 雅樹*; 吉田 利彦*; 石井 賢司*; 松村 大樹
NanotechJapan Bulletin (インターネット), 11(4), 6 Pages, 2018/08
浅野 駿*; 鈴木 謙介*; 松村 大樹; 石井 賢司*; 伊奈 稔哲*; 藤田 全基*
Journal of Physics; Conference Series, 969, p.012051_1 - 012051_5, 2018/04
Reduction and oxidation annealing effects on the electronic states around the copper sites for PrCeCuO and NdCeCuO with = 0 and = 0.15 were investigated by Cu -edge X-ray absorption measurements. Cu near-edge spectra were changed by the reduction annealing in a manner similar to the case of Ce substitution for both = 0 and = 0.15. This means an increase of electron density at the copper sites, indicating the aspect of electron doping in the reduction annealing. This reduction annealing effect on the near-edge spectra are reverted by the additional oxidation annealing. The amount of electron density around the copper sites is varied by the reduction and oxidation annealing, reversibly, corresponding to the reversible variation of the physical property from insulating to superconductivity.
石井 賢司*; 遠山 貴巳*; 浅野 駿*; 佐藤 研太朗*; 藤田 全基*; 脇本 秀一; 筒井 健二*; 曽田 繁利*; 宮脇 淳*; 丹羽 秀治*; et al.
Physical Review B, 96(11), p.115148_1 - 115148_8, 2017/09
We investigate electronic excitations in La(Br,Sr)CuO using resonant inelastic X-ray scattering (RIXS) at the oxygen edge. We observed momentum-dependent spectral weight below 1 eV, which is consistent with theoretical calculation of the dynamical charge structure factor on oxygen orbitals in a three-band Hubbard model. Our results confirm that the momentum-dependent charge excitations exist on the order of the transfer energy (), and the broad spectral line shape indicates damped and incoherent character of the charge excitations at the energy range in the doped Mott insulators.
Cui, Y.-T.*; 原田 慈久*; 丹羽 秀治*; 畑中 達也*; 中村 直樹*; 安藤 雅樹*; 吉田 稔彦*; 石井 賢司*; 松村 大樹; 陰地 宏*; et al.
Scientific Reports (Internet), 7(1), p.1482_1 - 1482_8, 2017/05
In situ high energy resolution fluorescence detection X-ray absorption spectroscopy (HERFD-XAS) was used to systematically evaluate interactions of HO and O adsorbed on Pt and PtCo nanoparticle catalysts in different particle sizes. The systematic increase in oxidation due to adsorption of different species (HO adsorption O adsorption O + HO coadsorption) suggests that cooperative behavior between O and HO adsorptions is responsible for the overpotential induced by hydrated species in fuel cells. From the alloying and particle size effects, it is found that both strength of O/HO adsorption and their cooperative effect upon coadsorption are responsible for the specific activity of Pt catalysts.
Cui, Y.*; 原田 慈久*; 畑中 達也*; 中村 直樹*; 安藤 雅樹*; 吉田 稔彦*; 池永 英司*; 石井 賢司*; 松村 大樹; Li, R.*; et al.
ECS Transactions, 72(8), p.131 - 136, 2016/10
The electronic structures of Pt and Pt-Co nanoparticles with O adsorption and O/HO co-adsorption were investigated by in situ hard X-ray photoelectron spectroscopy (HAXPES) and in situ high resolution fluorescence detection X-ray absorption spectroscopy (HERFD-XAS) to clarify the effects of water adsorption on fuel cell cathode catalysis surface. The experimental results suggest that under the pressure of 1 mbar, the adsorption of HO hinders the successive O adsorption on Pt surface, while under the pressure of 1 bar, the adsorption of HO enhances the adsorption of O on Pt surface. This water effect is found to be more significant on Pt surface than on Pt-Co surface. These results would be helpful to understand how the water affects the fuel cell performance and why Pt-Co nanoparticles show higher oxygen reduce reaction (ORR) activity than Pt nanoparticles.
野村 拓司*; 原田 慈久*; 丹羽 秀治*; 石井 賢司*; 石角 元志*; 社本 真一; Jarrige, I.*
Physical Review B, 94(3), p.035134_1 - 035134_9, 2016/07
吉田 雅洋*; 石井 賢司; 中 惇*; 石原 純夫*; Jarrige, I.*; 池内 和彦*; 村上 洋一*; 工藤 一貴*; 小池 洋二*; 永田 知子*; et al.
Scientific Reports (Internet), 6, p.23611_1 - 23611_8, 2016/03
In strongly correlated electron systems, enhanced fluctuations in the proximity of the ordered states of electronic degrees of freedom often induce anomalous electronic properties such as unconventional superconductivity. While spin fluctuations in the energy-momentum space have been studied widely using inelastic neutron scattering, other degrees of freedom, i.e., charge and orbital, have hardly been explored thus far. Here, we use resonant inelastic X-ray scattering to observe charge fluctuations proximate to the charge-order phase in transition metal oxides. In the two-leg ladder of SrCaCuO, charge fluctuations are enhanced at the propagation vector of the charge order () when the order is melted by raising the temperature or by doping holes. In contrast, charge fluctuations are observed not only at but also at other momenta in a geometrically frustrated triangular bilayer lattice of LuFeO. The observed charge fluctuations have a high energy ( 1 eV), suggesting that the Coulomb repulsion between electrons plays an important role in the formation of the charge order.
固体物理, 51(2), p.79 - 92, 2016/02
In the last decade, resonant inelastic X-ray scattering for the study of electronic excitations in strongly correlated electron systems has achieved significant progress utilizing brilliant synchrotron radiation X-rays. Some representative studies on cuprates and iridates are reviewed.
植松 大介*; 佐賀山 基*; 有馬 孝尚*; 石川 洵*; 中辻 知*; 高木 英典*; 吉田 雅洋*; 水木 純一郎; 石井 賢司
Physical Review B, 92(9), p.094405_1 - 094405_6, 2015/09
The half-filled topmost valence band of Ir in several iridates such as SrIrO, IrO, and CaIrO has been proposed to originate mainly from the spin-orbit coupled states. In pyrochlore iridates IrO (: rare earth), some exotic electronic states are theoretically proposed by assuming states. However, the octahedral coordination around Ir is trigonally distorted, which may affect the energy level scheme of Ir states. Here, we report spectra of resonant elastic and inelastic X-ray scattering in EuIrO at the Ir edges. A large suppression of the magnetic scattering signal at the Ir edge supports the picture rather than the one. The inelastic scattering spectrum indicates that the magnitude of the trigonal field on the Ir states is evaluated to be comparable to the spin-orbit interaction. The energy diagram of the state is proposed based on the simple cluster model.
松野 丈夫*; 井原 康太*; 山村 周玄*; 和達 大樹*; 石井 賢司; Shankar, V.*; Kee, H.-Y.*; 高木 英典*
Physical Review Letters, 114(24), p.247209_1 - 247209_5, 2015/06
In Ir oxides with interplay of spin-orbit coupling and electron correlations, we have tailored a spin-orbital magnetic insulator out of a semimetal SrIrO by tuning the structure through superlattices [(SrIrO), SrTiO] ( = 1, 2, 3, 4, and ). We observed the systematic decrease of the magnetic ordering temperature and the resistivity as a function of . The transition from the semimetal to the insulator is found to be closely linked to the appearance of magnetism at 3. Long range magnetic ordering was realized even in the = 1 single layer superlattice, implying that the design and realization of novel electronic phases is feasible at the level of a single atomic layer in complex Ir oxides.
Wray, L. A.*; Huang, S.-W.*; Jarrige, I.*; 池内 和彦*; 石井 賢司; Li, J.*; Qiu, Z. Q.*; Hussain, Z.*; Chuang, Y.-D.*
Frontiers in Physics (Internet), 3, p.32_1 - 32_11, 2015/05
In resonant inelastic X-ray scattering (RIXS), core hole resonance modes are used to enhance coupling between photons and low energy electronic degrees of freedom. Resonating with shallow core holes accessed in the extreme ultraviolet (EUV) can provide greatly improved energy resolution at standard resolving power, but has been found to often yield qualitatively different spectra than similar measurements performed with higher energy X-rays. This paper uses experimental data and multiplet-based numerical simulations for the M-edges of Co-, Ni-, and Cu-based Mott insulators to review the properties that distinguish EUV RIXS from more commonly performed higher energy measurements. Key factors such as the origin of the strong EUV elastic line and advantages of EUV spectral functions over soft X-ray RIXS for identifying intrinsic excitation line shapes are discussed.
脇本 秀一; 石井 賢司; 木村 宏之*; 藤田 全基*; Dellea, G.*; Kummer, K.*; Braicovich, L.*; Ghiringhelli, G.*; Debeer-Schmitt, L. M.*; Granroth, G.*
Physical Review B, 91(18), p.184513_1 - 184513_7, 2015/05
We have performed neutron inelastic scattering and resonant inelastic X-ray scattering (RIXS) at the Cu- edge to study high-energy magnetic excitations at energy transfers of more than 100 meV for overdoped LaSrCuO with = 0.25 ( = 15 K) and = 0.30 (nonsuperconducting) using identical single-crystal samples for the two techniques. Our results indicate consistency between neutron inelastic scattering and RIXS, and elucidate the entire magnetic excitation in the direction by the complementary use of two probes. The paramagnon along agrees well with the LCO spin-wave dispersion, while the paramagnon in the direction probed by RIXS appears to be less dispersive.
Jarrige, I.*; 小谷 章雄*; 山岡 人志*; 辻井 直人*; 石井 賢司; Upton, M.*; Casa, D.*; Kim, J. H.*; Gog, T.*; Hancock, J. N.*
Physical Review Letters, 114(12), p.126401_1 - 126401_5, 2015/03
We combine resonant inelastic X-ray scattering and model calculations in the Kondo lattice compound YbInCu, a system characterized by a dramatic increase in Kondo temperature and associated valence fluctuations below a first-order valence transition at T 42 K. The bulk-sensitive, element-specific, and valence-projected charge excitation spectra reveal an unusual quasigap in the Yb-derived state density which drives an instability of the electronic structure and renormalizes the low-energy effective Hamiltonian at the transition. Our results provide long-sought experimental evidence for a link between temperature-driven changes in the low-energy Kondo scale and the higher-energy electronic structure of this system.
Jarrige, I.*; 石井 賢司; 松村 大樹; 西畑 保雄; 吉田 雅洋*; 岸 浩史*; 谷口 昌司*; 上西 真里*; 田中 裕久*; 笠井 秀明*; et al.
ACS Catalysis, 5(2), p.1112 - 1118, 2015/02
Self-regenerating automotive catalysts owe their remarkable performance to the repeated motion of the precious metal atoms in and out of the perovskite lattice under fluctuating oxidizing and reducing conditions, preventing coalescence of the metal nanoparticles. Here we use resonant inelastic X-ray scattering to characterize the occupied and unoccupied Pt 5d states in two self-regenerating Pt-perovskite catalysts, CaTiPtO and CaZrPtO. Upon reduction, the element and symmetry-specific charge excitation spectra reveal a sizeable hybridization between the Pt 5d and the Ti 3d or Zr 4d states at the interface between the nanoparticles and the perovskite, which involves the occupied states and is thus invisible in X-ray absorption spectra. A correlation is found between the strength of this d-band hybridization and the proportion of Pt nanoparticles that remain buried below the surface during reduction, indicating that the motion of the Pt atoms towards the surface is hindered by this hybridization specifically, rather than by the Pt-O bonding. These results provide direct evidence that the strength of the metal-metal d-band hybridization plays a pivotal role in determining the efficiency of self-regeneration in perovskite catalysts.
藤田 全基*; 石井 賢司
波紋, 25(1), p.18 - 21, 2015/02
We introduce the inelastic neutron and synchrotron X-ray scattering studies on the magnetic excitation in the electron-doped copper oxide. The recent development of state-of-the-art spectrometers at large facilities such as J-PARC enables us to study composite dynamics in the energy-momentum space arising from the interacting degrees of freedom. High- copper oxide superconductor is exotic systems, in which the spin and charge degrees of freedom are coupled. We found the elongation of spin excitation by the electron-doping, which is quite different from the negligible doping effect in the hole-doped system. Therefore, there exists the electron-hole asymmetry in the observed spin excitation against the doping.
石井 賢司; 藤田 全基*
日本結晶学会誌, 57(1), p.20 - 26, 2015/02
We combine soft X-ray, hard X-ray, and neutron inelastic scattering measurements to study both spin and charge excitations in electron-doped copper oxide superconductors. Thanks to the recent development of beam sources and related experimental techniques, accessible energy range of the these inelastic scattering measurements overlaps each other and it enables us to investigate spin and charge dynamics in the important but unexplored energy-momentum space of the cuprate superconductors. Our study demonstrates that complementary use of X-ray and neutron has become effective in inelastic scattering for studying electron dynamics of materials.
石井 賢司; 藤田 全基*
Isotope News, (728), p.10 - 13, 2014/12
高山 知弘*; Yaresko, A.*; 松本 章代*; Nuss, J.*; 石井 賢司; 吉田 雅洋*; 水木 純一郎; 高木 英典*
Scientific Reports (Internet), 4, p.6818_1 - 6818_6, 2014/10
The complex iridium oxide NaIrO with a B-site ordered spinel structure was synthesized in single crystalline form, where the chiral hyper-kagome lattice of Irions, as observed in the spin-liquid candidate NaIrO, was identified. The average valence of Ir is 4.33+ and, therefore, NaIrO can be viewed as a doped analogue of the hyper-kagome spin liquid with Ir. The transport measurements, combined with the electronic structure calculations, indicate that the ground state of NaIrO is a low carrier density semi-metal. We argue that the semi-metallic state is produced by a competition of the molecular orbital splitting of orbitals on Ir triangles with strong spin-orbit coupling inherent to heavy Ir ions.