Basic research for the development of coupled reactivity of electrons and ions by nano-space design of oxide hetero-composites

通过氧化物异质复合材料的纳米空间设计开发电子和离子耦合反应性的基础研究

• 批准号: 16206074
• 负责人: YAMAGUCHI Shu
• 金额: $ 31.7万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16206074/
• 关键词: Nanoionics; Solid state ionics; Space charge layer; Schottky barrier; Soft X-ray spectroscopy; Molecular dynamics; Electrode reaction; Mixed potential

The objectives of the present study is to pursue an experimental approach to understand and discuss the correlation between electronic structure, electrochemical and ionic transport properties of heterogeneous interface composed of either ionic or mixed ionic-and-electronic oxide materials fabricated based on various nano-scaled designs, in order to establish the directions of nano-space design to realize novel functionality of heterogeneous interface. With small alteration of the initial experimental plan, various oxides and sulfide systems have been extensively examined for its electrochemical properties in correlation of electronic band structure. The achievement throughout whole term is summarized as follows:1. Using various electron spectroscopy measurements, the band bending behavior has been examined and concluded that the band cramp behavior is determined by the nature and density of state (DOS) of the corresponding level. In case of oxide with d-and f-electrons, the charge transfer reaction from O2p to Mmd/nf govern the surface level and possibly the interfacial one. d2. A novel concept of Nonstoichiometry-Induced Carrier Modification has been proposed for the asymmetric cell with blocking and reversible electrode. The change in the conductivity in the vicinity of blocking electrode region is experimentally observed and is attributed for the anti-Schottky type rectification in dc I-V properties. The concept is extended to oxide systems with the experimental confirmations and is concluded to be applicable to compounds with a certain level of ionic transference number.3. A dynamic structural and electronic relaxation of interface and resultant modification of surface reactivity of hydrogen and water at the tri-phase region of metal oxide, proton conductor, and gas phase are simulated using ab-initio molecular dynamics technique.

本研究的目的是寻求一种实验方法来理解和讨论基于各种纳米级制造的离子或混合离子电子氧化物材料组成的异质界面的电子结构、电化学和离子传输特性之间的相关性设计，以建立纳米空间设计的方向，以实现异构接口的新颖功能。通过对最初的实验计划进行微小的改变，各种氧化物和硫化物系统的电化学性质与电子能带结构的相关性得到了广泛的研究。整个学期的工作成果概括如下： 1．使用各种电子能谱测量，对能带弯曲行为进行了检查，并得出结论：能带钳行为是由相应能级的性质和态密度（DOS）决定的。对于具有 d 电子和 f 电子的氧化物，从 O2p 到 Mmd/nf 的电荷转移反应控制表面能级，也可能控制界面能级。 d2。针对具有阻断和可逆电极的不对称电池，提出了非化学计量诱导的载流子修饰的新概念。通过实验观察到阻挡电极区域附近电导率的变化，并将其归因于直流 I-V 特性中的反肖特基型整流。经实验证实，这一概念扩展到氧化物体系，适用于具有一定离子迁移数的化合物。 3．使用从头算分子动力学技术模拟了金属氧化物、质子导体和气相三相区域中氢和水的表面反应性的动态结构和电子弛豫以及由此产生的改性。

项目成果

Electronic Structure of Proton Conducting BaCe_<0.90>Y_<0.10>O<3-σ>

质子传导BaCe_<0.90>Y_<0.10>O<3-σ>的电子结构

• 发表时间: 2005
• 期刊: Solid State Ionics 176
• 作者: T. Higuchi;T. Tsukamoto;H. Matsumoto;T. Shimura;K. Yashiro;T. Kawada;J. Mizusaki;S. Shin;T. Hattori
• 通讯作者: T. Hattori

Electronic Structure of Protonic Conductor SrCeO_3-SrZrO_3 Mixed Thin Film

质子导体SrCeO_3-SrZrO_3混合薄膜的电子结构

• 发表时间: 2005
• 期刊: Solid State Ionics 176
• 作者: T. Higuchi;T. Tsukamoto;N. Sata;S. Yamaguchi;S. Shin;T. Hattori
• 通讯作者: T. Hattori

Effect of TiO_2 Anatase Layer for Bi_4Ti_3O_<12> Thin Film Prepared on La_<0.05>Sr_<0.95>TiO_3 Substrate

La_<0.05>Sr_<0.95>TiO_3基底上TiO_2锐钛矿层对Bi_4Ti_3O_<12>薄膜的影响

• 发表时间: 2007
• 期刊: Trans. Mater. Res. Soc. Jpn. 32
• 作者: M. Konishi;T. Higuchi;T. Hattori;T. Tsukamoto
• 通讯作者: T. Tsukamoto

Ab initio study of proton dynamics on perovskite oxide surfaces

钙钛矿氧化物表面质子动力学的从头算研究

• 发表时间: 2007
• 期刊: Science and Technology of Advanced Materials 8・6
• 作者: J.C.Rao;M.Song;K.Furuya;S.Yoshimoto;M.Yamasaki;Y.Kawamura;Hiroshi Yoshino;阿部 浩也;F. Shimojo
• 通讯作者: F. Shimojo

Electronic Structure in the Band-Gap Region of Protonic Conductor SrZr_<0.90>Y_<0.10>O_<3-σ>

质子导体带隙区电子结构SrZr_<0.90>Y_<0.10>O_<3-σ>

• 发表时间: 2004
• 期刊: Jpn. J. Appl. Phys. 43(8A)
• 作者: T. Higuchi;H. Matsumoto;T. Shimura;K. Yashiro;T. Kawada;J. Mizusaki;S. Shin;T. Tsukamoto
• 通讯作者: T. Tsukamoto