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Shimoyama, Iwao; Baba, Yuji; Hirao, Norie*
Advances in Engineering (Internet), 1 Pages, 2018/02
The performance of organic devices largely depends on molecular orientation in organic films. Whereas micro-orientation control of organic molecules is an indispensable technology for integration of organic devices, the method has not been established. We attempted to control micro-orientation of polydimethylsilane (PDMS) thin films by deposition of PDMS on graphite substrates modified by hetero atom doping using ion beam. Polarization dependence measurements of X-ray absorption spectroscopy and molecular orbital calculations clarified that PDMS films have lying, standing, and random orientations on the non irradiated, N
-irradiated, and Ar-irradiated graphite surfaces, respectively. Furthermore, photoemission microscopy observation clarified that a PDMS film showed micro-patterns on a graphite surface with a microstructure on the order of 
m by separating N-irradiated and non irradiated areas. These results demonstrate our method is promising for micro-orientation of organic molecules.
Shimoyama, Iwao; Baba, Yuji; Hirao, Norie*
Applied Surface Science, 405, p.255 - 266, 2017/05
Times Cited Count：1 Percentile：5.94(Chemistry, Physical)NEXAFS spectroscopy is applied to study orientation structures of polydimethylsilane (PDMS) films deposited on heteroatom-doped graphite substrates prepared by ion beam doping. The Si 
-edge NEXAFS spectra of PDMS show opposite trends of polarization dependence for non irradiated and N-irradiated substrates, and show no polarization dependence for an Ar-irradiated substrate. Based on a theoretical interpretation of the NEXAFS spectra via first-principles calculations, we clarify that PDMS films have lying, standing, and random orientations on the non irradiated, N-irradiated, and Ar-irradiated substrates, respectively. Furthermore, photoemission electron microscopy indicates that the orientation of a PDMS film can be controlled with microstructures on the order of m by separating irradiated and non irradiated areas on the graphite surface. These results suggest that surface modification of graphite using ion beam doping is useful for micro-orientation control of organic thin films.
Shimoyama, Iwao; Honda, Mitsunori; Kogure, Toshihiro*; Baba, Yuji; Hirao, Norie*; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi
Photon Factory News, 35(1), p.17 - 22, 2017/05
We introduce Cs-free mineralization (CFM) for Cs removal and reuse of radioactive-contaminated soil in Fukushima and report recent work conducted in the BL27A beamline in Photon Factory. In this work, we investigated compositional and structural changes of Cs-sorbed weathered biotite (WB) before and after heating treatment with addition of NaCl-CaCl salts under low-pressure condition, to study Cs desorption mechanism from clay minerals. X-ray fluorescence spectroscopy clarified that almost all Cs and K were removed with the salts at 700 
C. On the other hand, Ca increased with heating temperature. X-ray diffraction and transmission electron microscopy analysis clarified that phase transitions from WB to some Ca-rich silicate minerals, e.g., augite, were caused by the heating treatment with the salt. Based on these results, CFM is proposed for Cs removal utilizing the mechanism in which large monovalent cations are discharged with accompanying the phase transition. We also discuss the role of Cl in this reaction showing chemical bonding change of Cl observed using X-ray absorption spectroscopy in the early stage of the chemical reaction.
Baba, Yuji; Shimoyama, Iwao; Hirao, Norie*
Applied Surface Science, 384, p.511 - 516, 2016/10
Times Cited Count：5 Percentile：25.9(Chemistry, Physical)Chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by total reflection X-ray photoelectron spectroscopy (TR-XPS). For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg/cm
can be detected by TR-XPS. This amount corresponds to about 200 Bq of 
Cs (t
= 30.2y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.
Hirao, Norie; Shimoyama, Iwao; Baba, Yuji; Izumi, Toshinori; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi
Bunseki Kagaku, 65(5), p.259 - 266, 2016/05
Times Cited Count：4 Percentile：14.35(Chemistry, Analytical)After the Fukushima nuclear plant accident, radiocesium was strongly fixed to clay minerals in the soil. Some dry methods with heating are being developed to remove radiocesium from the soil. In this work, we propose a new dry method that combines heat treatment in vacuum and molten salts to reduce the processing temperature in dry methods. Vermiculite saturated with non-radioactive Cs was heated in vacuum, and Cs contents in the vermiculite were compared before and after heating using X-ray photoelectron spectroscopy. Approximately 40% of cesium were removed by heating at 800C for three minutes when only vermiculite was heated. Approximately 70% of cesium were removed by heating at 450C for three minutes when vermiculite was heated with NaCl/CaCl mixed salts. Based on these results, this method is expected to reduce temperature and increase efficiency on dry methods for cesium removal from clay minerals.
Sekiguchi, Tetsuhiro; Baba, Yuji; Hirao, Norie; Honda, Mitsunori; Izumi, Toshinori; Ikeura, Hiromi*
Molecular Crystals and Liquid Crystals, 622(1), p.44 - 49, 2015/12
Times Cited Count：0 Percentile：0.01(Chemistry, Multidisciplinary)The molecular orientation is one of the important factors for controlling various properties in organic semiconductor materials. Films are usually heterogeneous. Thus they exist as a mixture of microscopic domains which have a variety of orientation directions. Therefore, it is essential to observe selectively microscopic domains with different orientation direction. In this work, we have developed the photoelectron emission microscopy (PEEM) system combined with the linearly polarized vacuum ultraviolet (VUV) light or synchrotron radiation (SR) X-rays. PEEM images (FOV = ca.50 micro m) for poly(3-hexylthiophene), P3HT thin films were observed under the UV irradiation with various polarization angles, including in-plain and out-of-plain polarization. Morphologies at some bright parts are different each other. The resultant observation suggests that it enables us to distinguish oriented micro-domains with specific directions of polymer chain axis from other amorphous parts.
Baba, Yuji; Shimoyama, Iwao; Hirao, Norie; Izumi, Toshinori
e-Journal of Surface Science and Nanotechnology (Internet), 13, p.417 - 421, 2015/09
Times Cited Count：1The interaction between alkali metals and oxides has attracted much attention as heterogeneous catalysis, chemical reaction promoters, and high intensity electron emitter. Also the interaction of cesium and oxides has become important subject, because radioactive cesium trapped in minerals such as clay and soil may cause health risks. In the present study, we analyzed chemical states of ultra-trace amount of cesium on oxide surfaces by total reflection X-ray photoelectron spectroscopy (TR-XPS) exited by synchrotron radiation. For the adsorbed cesium thicker than 0.01 layer, cesium is weakly bound with oxide through Van-der-Waals force. On the other hand, for ultra-thin layer about 0.002 layer, the chemical bond changes to covalent bond. It is suggested that this change in the chemical bonding state is one of the reasons why radioactive cesium is hard to be released from minerals.
Entani, Shiro; Antipina, L. Y.*; Avramov, P.*; Otomo, Manabu*; Matsumoto, Yoshihiro*; Hirao, Norie; Shimoyama, Iwao; Naramoto, Hiroshi*; Baba, Yuji; Sorokin, P. B.*; et al.
Nano Research, 8(5), p.1535 - 1545, 2015/05
Times Cited Count：26 Percentile：71.65(Chemistry, Physical)Baba, Yuji; Shimoyama, Iwao; Hirao, Norie; Sekiguchi, Tetsuhiro
Chemical Physics, 444, p.1 - 6, 2014/09
Times Cited Count：2 Percentile：6.3(Chemistry, Physical)Silicon thin films were deposited on a sapphire and a highly oriented pyrolytic graphite (HOPG), which have atomically flat and chemically inert surfaces. The electronic and geometrical structures of the films were analyzed by polarization-dependent X-ray absorption fine structure (XAFS). It was found that the silicon K-edge XAFS spectra for ultra-thin silicon films thinner than 0.2 monolayer exhibited two distinct resonance peaks which were not observed for bulk silicon. The peaks were assigned to the resonance excitations from the Si 1s into the valence unoccupied orbitals with 
and 
characters. The average tilted angle of the orbitals was determined by the polarization dependencies of the peak intensities. It was demonstrated that direction of a part of the orbitals in silicon film is perpendicular to the surface. These results support the existence of quasi-freestanding single-layered silicon films with sp2 configuration.
Shimoyama, Iwao; Hirao, Norie; Baba, Yuji; Izumi, Toshinori; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi
Clay Science, 18(3), p.71 - 77, 2014/09
no abstracts in English
Honda, Mitsunori; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie
Thin Solid Films, 556, p.307 - 310, 2014/04
Times Cited Count：5 Percentile：23.98(Materials Science, Multidisciplinary)Baba, Yuji; Shimoyama, Iwao; Hirao, Norie; Sekiguchi, Tetsuhiro
Chemical Physics Letters, 594, p.64 - 68, 2014/02
Times Cited Count：3 Percentile：10.21(Chemistry, Physical)Structures of mono-layered silicon on a highly oriented pyrolytic graphite (HOPG) have been investigated by X-ray photoelectron spectroscopy and X-ray absorption near edge structure (XANES). For the Si K-edge XANES spectrum of the 0.15 mono-layered film, two distinct peaks were observed, which were assigned to the resonant excitations from the Si 1s into the valence unoccupied orbitals with 
and 
characters. On the basis of the polarization dependences of the peak intensities, it was concluded that a part of the Si film lies flat on the HOPG surface, which supports the existence of two-dimensional graphene-like structure in mono-layered silicon.
Hirao, Norie; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao
Bunseki Kagaku, 63(1), p.53 - 58, 2014/01
Times Cited Count：0 Percentile：0(Chemistry, Analytical)A method for quick and real-time observations of a solid surface at nanometer scale is described. The principle of the method is as follows. Soft X-rays from a synchrotron light source are irradiated on a solid surface and the total photoelectrons are expanded and focused on a screen using electrostatic lenses. When the energy of X-rays is scanned and the brightness is plotted, we can obtain micro X-ray absorption (micro-XAFS) spectra in all regions of the image. The spacial resolution of the method was 40 nm. In order to more quickly observe a microscopic image and measure micro-XAFS spectra, the soft X-rays from the bending magnet were focused using a newly developed poly-capillary. As a result, the photon flux of 3 keV X-rays was increased about 60 time higher than that before the focusing. Using focused X-rays, we succeeded in observing one image at 10 ms for a bulk sample. We have also tried to shorten the measuring time of the micro-XAFS spectrum. For a Si-SiO sample, it has been demonstrated that micro-XAFS spectra in all regions of an image can be obtained within 1 min. It is concluded that real-time observations of chemical-states at nanometer scale are possible by the present method.
Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Hirao, Norie; Honda, Mitsunori; Izumi, Toshinori; Ikeura, Hiromi*
Photon Factory Activity Report 2013, Part B, P. 546, 2014/00
The molecular orientation is one of the important factors for controlling various properties in organic semiconductor materials. Films are usually heterogeneous. Thus they exist as a mixture of microscopic domains which have a variety of orientation directions. Therefore, it is essential to observe selectively microscopic domains with different orientation direction. In this work, we have developed the photoelectron emission microscope (PEEM) system combined with the linearly polarized vacuum ultraviolet (VUV) light or synchrotron radiation (SR) X-rays. PEEM images for poly(3-hexylthiophene), P3HT thin films were observed under synchrotron X-ray irradiation with linearly polarization. In conclusion, it was found that PEEM with polarized synchrotron can be a powerful tool that gives information of molecular orientation in nano-meter scale.
Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie
Surface Science, 612, p.77 - 81, 2013/06
Times Cited Count：9 Percentile：40.37(Chemistry, Physical)Electronic structures of thin films of silicon monoxides (SiO) deposited on a solid surface have been in-situ investigated by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS). For thin films with less than monolayer on highly oriented pyrolytic graphite (HOPG), it was elucidated that the stable divalent silicon surely exists in the deposited SiO layer. For the Si K-edge XAFS spectrum of the SiO thin film, the energy of the core-to-valence resonance peak is located between those of the elemental silicon (Si
) and SiO (Si
). The polarization dependence of the Si K-edge XAFS spectra revealed that the SiO molecules are well-ordered and almost perpendicularly oriented on HOPG surface. The obtained well-ordered SiO films with divalent silicon will become an excellent starting material for the synthesis of low-dimensional SiO
films.
Mn
)O
Shinoda, Ryoichi*; Ito, Masayoshi*; Sakurai, Yoshiharu*; Yamamoto, Hiroyuki; Hirao, Norie; Baba, Yuji; Iwase, Akihiro*; Matsui, Toshiyuki*
Journal of Applied Physics, 113(17), p.17E307_1 - 17E307_3, 2013/05
Times Cited Count：9 Percentile：37.98(Physics, Applied)We revealed that the Ba(CoMn)O (BCMO) ceramic samples exhibited ferromagnetic-dielectric behavior below the magnetic transition temperature of about 35 K. The origin of their magnetic ordering was expected to super-exchange coupling of Co(
)-O
-Mn (
) with bonding angle of 180. and/or Mn()-O-Mn () with bonding angle of 90. The magnetic spin momentum estimated by the magnetic Compton profiles (MCP) of the samples had similar temperature dependence as that determined by the SQUID measurement, which meant that the observed magnetic moments could be ascribed to the spin moment. The shapes of the MCPs of the samples were completely same regardless of the temperature measured. This result indicates that there are no changes of the momentum space distribution of spin density between ferromagnetic and paramagnetic states. So, this magnetic transition is simply caused by a thermal fluctuation of the spin.
Mannan, M. A.*; Baba, Yuji; Hirao, Norie; Kida, Tetsuya*; Nagano, Masamitsu*; Noguchi, Hideyuki*
Materials Sciences and Applications, 4(5A), p.11 - 19, 2013/05
Hexagonal nano-crystalline boron carbonitride (h-BCN) films grown on Si (100) substrate have been investigated. The films were synthesized by radio frequency plasma enhanced chemical vapor deposition using tris-dimethylamino borane as a precursor. Formation of the nano-crystalline h-BCN compound has been confirmed by X-ray diffraction analysis. The films composed of B, C, and N atoms with different B-N, B-C, C-N chemical bonds in forming the sp2-BCN atomic configuration studied by X-ray photoelectron spectroscopy. Orientation and local structures of the h-BCN hybrid were studied by near-edge X-ray absorption fine structure (NEXAFS) measurements. The dominant presence of and resonance peaks of the sp2-hybrid orbitals in the B K-edge NEXAFS spectra revealed the formation of the flat sp2-BCN configuration around B atoms which are bound with three nitrogen atoms.
Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Hirao, Norie; Honda, Mitsunori; Deng, J.*
Photon Factory Activity Report 2012, Part B, P. 68, 2013/00
The orientation of organic semiconducting molecules on surfaces plays a crucial role in improving the properties of electronic devices. We prepared thin films of silicon phthalocyanine dichroride (SiPcCl) on graphite spin-cast followed by heating to 350C at ambient condition. We investigate the molecular orientation of the films using angle-dependent near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. Si 1s NEXAFS spectra for the thin films after annealing are very different each other, indicating that the corresponding reactions thus the structures of final products are different. The structures of the reaction products are estimated with the help of ab initio molecular orbital calculations that fit the observed NEXAFS spectra.
Narita, Ayumi; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie; Yaita, Tsuyoshi
e-Journal of Surface Science and Nanotechnology (Internet), 10, p.367 - 373, 2012/07
To apply organic thin films as new devices, it is important to immobilize organic molecules on oxide surfaces. In this study, we investigated the formation of organic self-assembled monolayer on the oxide surface. Decyl phosphonic acid (DPA) molecules were used as the adsorbed molecule on the surface. The DPA film was prepared by immersing the sapphire substrate in DPA ethanol solution. The sample was measured by XPS using synchrotron soft X-ray. For the P 1s XPS spectra of the DPA powder and the DPA film on the sapphire surface, a single peak was observed and the binding energies of the two samples were almost the same. And we measured the sample by the total reflection (TR) XPS, which is highly surface sensitive method. Compared with the normal XPS, the intensity of the C 1s peak in TR-XPS was enhanced. As a result, it was elucidated that the phosphonic acid of the DPA molecule was located at the lower side, while the alkyl chain was located at the upper side on the surface.
Baba, Yuji; Narita, Ayumi; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie; Entani, Shiro; Sakai, Seiji
e-Journal of Surface Science and Nanotechnology (Internet), 10, p.69 - 73, 2012/04
We report on the first results for the geometrical determination of adsorbed atoms on an oxide by a soft-X-ray sanding wave method. The samples investigated were alkyl phosphonic acid (C10) adsorbed on a sapphire surface, which is one of the candidate systems for organic self-assembled monolayer (SAM) on oxides. The surface was irradiated by synchrotron soft X-rays from the surface normal. The intensity of photoelectrons was plotted as a function of the photon energy. We observed clear profiles of the photoelectron intensity due to the standing wave from the substrate. Compared with the simulation using the crystal parameters, it was found that the phosphorus atoms are located at 0.11 nm from the surface, while the constant height was not observed for carbon atoms. The results are in consistent with the results by XPS and NEXAFS; the molecules form SAM on the sapphire surface with phosphonic acids and alkyl chains are located at the upper side.
