Nano-NEMCA phenomena investigated by means of electron spectroscopy

2008 Fiscal Year Final Research Report

• Project/Area Number: 16079205
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: YAMAGUCHI Shu The University of Tokyo, 大学院・工学系研究科, 教授 (10182437)
• Co-Investigator(Kenkyū-buntansha): SHIN Shoku 東京大学, 物性研究所, 教授 (00162785) ; HIGUCHI Touru 東京理科大学, 理学部, 助教 (80328559) ; OYAMA Yukiko 東京大学, 大学院・工学系研究科, 助教 (00345373) ; TANAKA Kazuhiko 東京大学, 大学院・工学系研究科, 技術職員 (20456156) ; KOBAYASHI Kiyoshi 物材機構, 燃料電池センター, 主任研究員 (90357020) ; MIYOSHI Shogo 東京大学, 大学院・工学系研究科, 助教 (30398094)
• Project Period (FY): 2004 – 2008
• Keywords: ナノイオニクス / 固体イオ二クス / 空間電荷層 / ショットキー障壁 / 軟X線分光法 / NEMCA / 電極反応 / 混成電位

Research Abstract

電子分光を用いた物理的手法と電気化学的測定を織り交ぜて,ヘテロ界面近傍における電子構造の変調と電気化学的特性,特に速度論的性質に現れる化学特性の変化を検討した.正逆光電子分光,軟X線分光,共鳴電子分光の各種方法を組み合わせて酸化物表面でのバンド屈曲および表面準位形成による電子状態の変化を明らかにした.これらの手法と電気化学的測定で得られる特性との相関を検討した.BaPr_<1-x>Yb_xO_3の伝導特性は電子-ホールペアの強い相互作用による特異な電子構造に起因し,Pt微粒子を粒界に分散させたCe_<1-x>Gd_xO_2における伝導度の向上は界面への酸素空孔注入メカニズムで説明した.さらに,電気化学的に分極した状態下での硬X 線光電子分光の測定手法を確立し,電子-イオン混合伝導体の不定比性変化に伴う変化を観察した.

Research Products

• [Journal Article] Powder neutron diffraction of La-apatite under low temperature (2009)
  • Author(s): Y. Matsushita, F. Izumi, K. Kobayashi, N. Igawa, H. Kitazawa, Y. Oyama, S. Miyoshi and S, Yamaguchi
  • Journal Title: Nuclear Instruments and Methods in Physics Research Section A : Accelerators, Spectrometers, Detectors and Associated Equipment 600 Pages: 319-321
  • Peer Reviewed
• [Journal Article] Nonstoichiometry induced carrier modification in gapless type atomic switch device using Cu_2S mixed conductor (2009)
  • Author(s): T. Tsuchiya, Y. Oyama, S. Miyoshi, and S. Yamaguchi
  • Journal Title: Applied Physics Express 2 Pages: 055002
  • Peer Reviewed
• [Journal Article] Water-based sol-gel synthesis and crystal structure refinement of lanthanum silicate apatite (2008)
  • Author(s): K. Kobayashi, Y. Matsushita, N. Igawa, F. Izumi, C. Nishimura, S. Miyoshi, Y. Oyama, S. Yamaguchi
  • Journal Title: Solid State Ionics 179 Pages: 2209-2215
  • Peer Reviewed
• [Journal Article] Structural study and proton transport of bulk nanograined Y-doped BaZrO_3 oxide protonics materials (2008)
  • Author(s): R. B. Cervera, Y. Oyama, S. Miyoshi, K. Kobayashi, T. Yagi, S. Yamaguchi
  • Journal Title: Solid State Ionics 179 Pages: 236-242
  • Peer Reviewed
• [Journal Article] Main group oxides : making the transition (2008)
  • Author(s): Shu Yamaguchi
  • Journal Title: Nature Materials 7 Pages: 353-354
  • Peer Reviewed
• [Journal Article] Low temperature synthesis of nanocrystalline proton conducting BaZr_<0.8>Y_<0.2>O_3-・by sol gel method (2007)
  • Author(s): R. B. Cervela, Y. Oyama, and S. Yamaguchi
  • Journal Title: Solid State Ionics 178 Pages: 569-574
  • Peer Reviewed
• [Journal Article] Proton incorporation and defect chemistry of Yb-doped BaPrO_3 (2007)
  • Author(s): S. Mimuro, S. Shibako, Y. Oyama, K. Kobayashi, T. Higuchi, S. Shin, and S. Yamaguchi
  • Journal Title: Solid State Ionics 178 Pages: 641-647
  • Peer Reviewed
• [Journal Article] Phase stability of cerium species in aqueous solutions effected by water activity (2006)
  • Author(s): Y. Oyama, S. Hirooka, K. Kobayashi, and S. Yamaguchi
  • Journal Title: Proceedings of the 16th Iketani Conference, Masuko Symposium Pages: 815-820
• [Journal Article] Nanoceramics and thin films of proton conducting BaZr_<0.8>Y_<0.2>O_<3->・ synthesized via sol-gel method (2006)
  • Author(s): R. B. Cervela, Y. Oyama, and S. Yamaguchi
  • Journal Title: Proceedings of the 16th Iketani Conference, Masuko Symposium Pages: 883-888
• [Journal Article] Electrochemical analysis and SPM investigations of Solid Electrochemical Reaction in atomic switch using Cu_2S ion/hole mixed conductor (2006)
  • Author(s): T. Tsuchiya, Y. Oyama, K. Terabe, and S. Yamaguchi
  • Journal Title: Proceedings of the 16th Iketani Conference, Masuko Symposium Pages: 889-894
• [Journal Article] Defect chemistry of proton-hole mixed conducting oxides Yb-doped BaPrO_3 (2006)
  • Author(s): S. Mimuro, S. Shibako, K. Kobayashi, Y. Oyama, and S. Yamaguchi
  • Journal Title: Proceedings of the 16th Iketani Conference, Masuko Symposium Pages: 889-894
• [Journal Article] Electronic Structure of Protonic Conductor BaCe_<0.90>Y_<0.10>O_<3-δ> (2005)
  • Author(s): T. Higuchi, T. Tsukamoto, H. Matsumoto, T. Shimura, K. Yashiro, T. Kawada, J. Mizusaki, S. Shin, S. Yamaguchi, T. Hattori
  • Journal Title: Solid State Ionics 176 Pages: 2967-2970
  • Peer Reviewed
• [Journal Article] Electronic Structure of Protonic Conductor SrCeO_3-SrZrO_3 Mixed Thin Film (2005)
  • Author(s): T. Higuchi, T. Tsukamoto, N. Sata, S. Yamaguchi, S. Shin, T. Hattori
  • Journal Title: Solid State Ionics 176 Pages: 2963-2966
  • Peer Reviewed
• [Journal Article] Electronic Structure of Protonic Conductor SrZr_<0.90>M_<0.10>O_3 (M=Y^<3+>, Sc^<3+>) Probed by Soft-X-Ray Spectroscopy (2005)
  • Author(s): T. Higuchi, T. Tsukamoto, H. Matsumoto, T. Shimura, K. Yashiro, T. Kawada, J. Mizusaki, S. Shin, T. Hattori
  • Journal Title: Solid State Ionics 176 Pages: 2435-2438
  • Peer Reviewed
• [Journal Article] Electronic Structure of Protonic Conductor SrTi_<0.98>Sc_<0.02>O_3 Probed by Soft-X-ray Spectroscopy (2005)
  • Author(s): T. Higuchi, S. Yamaguchi, S. Shin, T. Hattori, T. Tsukamoto
  • Journal Title: Jpn. J. Appl. Phys. 43 Pages: 285-286
  • Peer Reviewed
• [Journal Article] Protonic-Electronic Mixed Conduction and Hydrogen Permeation in BaCe_<0.9-x>Y_<0.1>Ru_xO_<3-δ> (2005)
  • Author(s): H. Matsumoto, T. Shimura, T. Higuchi, H. Tanaka, H. Iwahara, K. Katahira, T. Otake, T. Kudo, K. Yashiro, A. Kaimai, T. Kawada, J. Mizusaki
  • Journal Title: J. Elctrochemical Society 152 Pages: A488-492
  • Peer Reviewed
• [Journal Article] Unoccupied Electronic State of SrTi_<1-x>Nb_xO_3 Observed by Inverse-Photoemission Spectroscopy (2004)
  • Author(s): T. Higuchi, Y. Tezuka, T. Hattori, S. Yamaguchi, S. Shin, T. Tsukamoto
  • Journal Title: Jpn. J. Appl. Phys. 43 Pages: 7623-7624
  • Peer Reviewed
• [Journal Article] Electronic Structure of Ce_<1-x>Nd_xO_<2-σ> Probed by Soft-X-Ray Spectroscopy (2004)
  • Author(s): T. Higuchi, S. Yamaguchi, K. Kobayashi, T. Hattori, A. Fukushima, S. Shin, T. Tsukamoto
  • Journal Title: Jpn. J. Appl. Phys. 43 Pages: L1463-L1465
  • Peer Reviewed
• [Journal Article] Fabrication of CeO_2 Thin Film on Quartz Glass and MgO (100) by Electron Beam Evaporation (2004)
  • Author(s): N. Yamada, Y. Oyama, T. Higuchi, S. Yamaguchi
  • Journal Title: Solid State Ionics 172 Pages: 293-297
  • Peer Reviewed
• [Presentation] アクセプターおよびドナーをドープしたBaPrO_3の電気輸送特性 (2009)
  • Author(s): 菊池健夫, 三好正悟, 三室伸, 尾山由紀子, 樋口透, 山口周
  • Organizer: 固体化学の新しい指針を探る研究会 若手研究者による研究発表会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2009-03-18
• [Presentation] Ba(Pr,M)O_3 (M=Yb, Zr)におけるイオン・電子伝導特性と欠陥・電子構造 (2008)
  • Author(s): 田丸奏, 菊池健夫, 三室伸, 三好正悟, 樋口透, 小林清, 尾山由紀子, 辛埴, 山口周
  • Organizer: 第34回固体イオニクス討論会
  • Place of Presentation: 東京大学生産技術研究所
  • Year and Date: 2008-12-04
• [Presentation] Chemical Thermodynamics of Pt-(Ce,Gd)O_2 Mixed System (2008)
  • Author(s): K. Yoshimura, S. Miyoshi, Y. Oyama, S. Yamaguchi
  • Organizer: PRiME 2008 (2008年電気化学日米合同大会) 214th ECS Meeting
  • Place of Presentation: Honolulu, Hawaii
  • Year and Date: 2008-10-13
• [Presentation] A possible proton conduction in nanograined Y-doped ZrO_2 and Yb-doped CeO_2 (2008)
  • Author(s): Y. Akao, T. Fukuda, R. B. Cervera, S. Miyoshi, Y. Oyama, T. Yagi, S. Yamaguchi
  • Organizer: The 2008 Korea-Japan-China SOFC Symposium
  • Place of Presentation: Pohang, Korea
  • Year and Date: 2008-09-18
• [Presentation] Defect Chemical, Electronic and Transport Properties of Doped BaPrO_3 (2008)
  • Author(s): S. Miyoshi, T. Kikuchi, S. Mimuro, T. Higuchi, K. Kobayashi, Y. Oyama, S. Shin, S. Yamaguchi
  • Organizer: The 14th International Conference on Solid State Protonic Conductors (SSPC-14)
  • Place of Presentation: Kyoto
  • Year and Date: 2008-09-08
• [Presentation] 抵抗変化型不揮発メモリ(ReRAM)の動作メカニズムに関する固体電気化学的解析 (2008)
  • Author(s): 土屋敬志, 三好正悟, 尾山由紀子, 山口周
  • Organizer: 電気化学75回大会
  • Place of Presentation: 山梨
  • Year and Date: 2008-03-30
• [Presentation] YbをドープしたBaPrO_3の電子輸送特性と欠陥・電子構造 (2007)
  • Author(s): 三室伸, 樋口透, 小林清, 尾山由紀子, 辛埴, 三好正悟, 山口周
  • Organizer: 第33回固体イオニクス討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2007-12-08
• [Presentation] YbをドープしたBaPrO_3の電子輸送特性と電子構造 (2007)
  • Author(s): 三室伸, 樋口透, 小林清, 尾山由紀子, 辛埴, 三好正悟, 山口周
  • Organizer: 2007年電気化学会秋季大会
  • Place of Presentation: 東京
  • Year and Date: 2007-09-20
• [Presentation] Development of Nonstoichiometry-Induced Carrier Modification Device Based on Nanoionics Principle (2007)
  • Author(s): S. Yamaguchi, T. Tsuchiya, Y. Oyama, K. Terabe, T. Hasegawa
  • Organizer: Materials Science & Technology 2007 (MS&T'07)
  • Place of Presentation: Detroit
  • Year and Date: 2007-09-20
• [Presentation] Simultaneous Measurements of Electrical Conductivity and Seebeck Coefficient in YB3+ -Doped BaPrO_3 (2007)
  • Author(s): S. Mimuro, K. Tanaka, Y. Oyama, K. Kobayashi, S. Yamaguchi
  • Organizer: Materials Science & Technology 2007 (MS&T'07)
  • Place of Presentation: Detroit
  • Year and Date: 2007-09-17
• [Presentation] Anti-Schottky Type Rectification at Metal/Mixed Conductor Hetero-Interface Based on Nonstoichiometry Induced Carrier Doping (2007)
  • Author(s): T. Tsuchiya, Y. Oyama, S. Yamaguchi
  • Organizer: 16th International conference on Solid State Ionics (SSI-16)
  • Place of Presentation: Shanhai
  • Year and Date: 2007-07-05
• [Presentation] Synthesis and characterization of Y-doped BaZrO_3 oxide protonic nanoceramics and thin films by sol-gel method (2006)
  • Author(s): R. B. Cervera, Y. Oyama, K. Kobayashi, S. Yamaguchi
  • Organizer: The 5th Petite Workshop on Defect Chemical Nature of Advanced Materials
  • Place of Presentation: Kyoto
  • Year and Date: 2006-11-18
• [Presentation] Defect Chemistry of Proton-hole Mixed Conducting Oxides Yb-doped BaPrO_3 (2006)
  • Author(s): S. Mimuro, S. Shibako, K. Kobayashi, Y. Oyama, S. Yamaguchi
  • Organizer: The 5th Petite Workshop on Defect Chemical Nature of Advanced Materials
  • Place of Presentation: Kyoto
  • Year and Date: 2006-11-18
• [Presentation] Phase stability of cerium species in aqueous solutions effected by water activity (2006)
  • Author(s): Y. Oyama, S. Hirooka, K. Kobayashi, S. Yamaguchi
  • Organizer: The 16th Iketani Conference, Masuko Symposium
  • Place of Presentation: Tokyo
  • Year and Date: 2006-11-13
• [Presentation] Nanoceramics and thin films of proton conducting BaZr_<0.8>Y_<0.2>O_<3->・synthesized via sol-gel method (2006)
  • Author(s): R. B. Cervera, Y. Oyama, S. Yamaguchi
  • Organizer: The 16th Iketani Conference, Masuko Symposium
  • Place of Presentation: Tokyo
  • Year and Date: 2006-11-13
• [Presentation] Hole-proton mixes conductivity in Yb^<3+> doped BaPrO_3 (2006)
  • Author(s): S. Shibako, S. Mimuro, K. Tanaka, Y. Oyama, S. Yamaguchi
  • Organizer: Materials Science & Technology 2006 Conference and Exhibition (MS&T '06)
  • Place of Presentation: Cincinnati, USA
  • Year and Date: 2006-10-16
• [Presentation] Sol-gel synthesis of BaZr_<0.8>Y_<0.2>O_<3-δ> proton conducting ceramics and thin films (2006)
  • Author(s): R. B. Cervera, Y. Oyama, S. Yamaguchi
  • Organizer: 13th Solid state proton conductors conference (SSPC-13)
  • Place of Presentation: St Andrews, Scotland, UK
  • Year and Date: 2006-09-05
• [Presentation] Mixed Valence State in the surface of Ce_<1-x>Nd_xO_<2-δ> probed by soft-X-ray spectroscopy (2006)
  • Author(s): T. Higuchi, T. Tsukamoto, T. Hattori, S. Shin, Y. Oyama, S. Yamaguchi
  • Organizer: 13th Solid state proton conductors conference (SSPC-13)
  • Place of Presentation: St Andrews, Scotland, UK
  • Year and Date: 2006-09-05
• [Presentation] Phase relation in BaO-ZrO_2-LnO_<1.5> (Ln=Y, Sc) system and chemical stability of doped BaZrO_3 (2006)
  • Author(s): Y. Oyama, A. Kojima, K. Tanaka, S. Yamaguchi
  • Organizer: 13th Solid state proton conductors conference (SSPC-13)
  • Place of Presentation: St Andrews, Scotland, UK
  • Year and Date: 2006-09-05
• [Presentation] Proton conduction of SrZr_<1-x>Y_xO_3 thin film on SrTiO_3 substrate prepared by pulsed laser deposition (2006)
  • Author(s): T. Higuchi, S. Okada, S. Shimizu, T. Hattori, T. Tsukamoto, S. Yamaguchi
  • Organizer: 13th Solid state proton conductors conference (SSPC-13)
  • Place of Presentation: St Andrews, Scotland, UK
  • Year and Date: 2006-09-05
• [Presentation] Electronic Structure in the Surface State of Ce_<1-x>Nd_xO_<2-δ> Probed by Resonant-Photoemission Spectroscopy (2005)
  • Author(s): T. Higuchi, S. Yamaguchi, K. Kobayashi, T. Hattori, S. Shin, T. Tsukamoto
  • Organizer: SSI-15
  • Place of Presentation: Barden-Barden, Germany
  • Year and Date: 2005-07-10
• [Book] 「高温ナノイオニクスが描く夢の技術」, ナノイオニクス-最新技術とその展望 (2008)
  • Author(s): 山口周
  • Total Pages: 1-8
  • Publisher: シーエムシー出版
• [Book] 「電子分光法によるnano-NEMCA現象の追及」, ナノイオニクス-最新技術とその展望- (2008)
  • Author(s): 山口周, 樋口透, 尾山由紀子, 三好正悟
  • Total Pages: 144-155
  • Publisher: シーエムシー出版
• [Book] ペロブスカイト型プロトン導電体の分光学的解析 (2005)
  • Author(s): 樋口透, 塚本桓世, 山口周, 辛埴, 服部武志
  • Total Pages: 7, 18, 28-36
  • Publisher: マテリアルインテグレーション
• [Remarks]
  • URL: http://www.ionics.t.u-tokyo.ac.jp/tokutei/