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Functional physical and chemical properties for precisely layered interfaces by superatomic periodicity

Research Project

Project/Area Number 19H00890
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Review Section Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
Research InstitutionKeio University

Principal Investigator

Nakajima Atsushi  慶應義塾大学, 理工学部(矢上), 教授 (30217715)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥46,540,000 (Direct Cost: ¥35,800,000、Indirect Cost: ¥10,740,000)
Fiscal Year 2021: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
Fiscal Year 2020: ¥9,490,000 (Direct Cost: ¥7,300,000、Indirect Cost: ¥2,190,000)
Fiscal Year 2019: ¥28,470,000 (Direct Cost: ¥21,900,000、Indirect Cost: ¥6,570,000)
Keywordsナノクラスター / 超原子 / 超原子周期律 / 超原子集積膜 / ヘテロ接合界面 / ナノクラスター薄膜 / 電磁気特性 / ヘテロ集積
Outline of Research at the Start

本研究では、HiPIMS法によるナノクラスターの精密気相合成法を基礎に、原子・分子単位の薄膜形成法の限界を超えて、精密に構造化させた金属内包シリコンケージナノクラスターM@Si16による超原子を、気相で予め選択的に生成させて、以下の3つの課題、①『超原子周期律』の化学、②均一組成かつ急峻な『超原子pn層界面』の機能物性、③『超原子層』の電磁気物性、に取り組み、新たなナノ機能物質科学を構築する。

Outline of Final Research Achievements

In this study, functional physical and chemical properties for precisely layered interfaces were explored by superatomic periodicity using a spherical superatom of a metal-atom encapsulating silicon cage nanocluster, M@Si16, in which accurate number of atomic aggregates is sharply layered beyond the limit of the conventional atomic/molecular vapor deposition method. With a magnetron sputtering nanocluster source, M@Si16 superatoms, containing group 3 to 9 metal atoms M, are monodispersively immobilized on an organic substrate such as C60, and the electronic properties were measured by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. The physical and chemical stabilities were systematically investigated in terms of the charge state and the chemical reactivity against oxygen exposures, revealing the periodicity of the M@Si16 superatom.

Academic Significance and Societal Importance of the Research Achievements

本研究ではこれまでのクラスター科学を、超原子を対象とするナノクラスターの合成化学へ展開して、表面科学との融合を図ることによって、超原子の集積で形成された精密層界面の機能について、新たな物理的、化学的な視点を拓いた。精密な層界面の構築には、基板上に予め有機分子を蒸着することで、超原子との局所的な電荷相互作用を誘起することが可能となることを明らかにするなど、クラスター科学における新たな分子論的な物質観を表面科学と融合できることを示した。金属原子数を少数とすることで、すべての構成原子を表面に露出させ、希少資源の金属原子でも、さらに少量の触媒で高活性を実現できることを明らかにした。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Comments on the Screening Results   Annual Research Report
  • Research Products

    (44 results)

All 2022 2021 2020 2019 Other

All Int'l Joint Research (1 results) Journal Article (11 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 11 results,  Open Access: 5 results) Presentation (23 results) (of which Int'l Joint Research: 10 results,  Invited: 5 results) Book (2 results) Remarks (5 results) Patent(Industrial Property Rights) (2 results)

  • [Int'l Joint Research] カイザースラウテルン工科大学(ドイツ)

    • Related Report
      2021 Annual Research Report
  • [Journal Article] Enhanced oxygen reduction activity of size-selected platinum subnanocluster catalysts: Ptn (n = 3-9)2022

    • Author(s)
      Ohnuma Akira、Takahashi Koki、Tsunoyama Hironori、Inoue Tomoya、Zhao Pei、Velloth Archana、Ehara Masahiro、Ichikuni Nobuyuki、Tabuchi Masao、Nakajima Atsushi
    • Journal Title

      Catalysis Science and Technology

      Volume: 12 Issue: 5 Pages: 1400-1407

    • DOI

      10.1039/d1cy00573a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Size-Dependent Oxidative Stability of Silicon Nanoclusters Mixed with a Tantalum Atom2022

    • Author(s)
      Shibuta Masahiro、Huber Maximilian、Kamoshida Toshiaki、Terasaka Kazuya、Hatanaka Miho、Niedner-Schatteburg Gereon、Nakajima Atsushi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 126 Issue: 9 Pages: 4423-4432

    • DOI

      10.1021/acs.jpcc.1c10895

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Al13- and B@Al12- superatoms on a molecularly decorated substrate2022

    • Author(s)
      Shibuta Masahiro、Inoue Tomoya、Kamoshida Toshiaki、Eguchi Toyoaki、Nakajima Atsushi
    • Journal Title

      Nature Communications

      Volume: 13 Issue: 1 Pages: 1336-1336

    • DOI

      10.1038/s41467-022-29034-9

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electrical Conduction of Superatom Thin Films Composed of Group-V-Metal-Encapsulating Silicon-Cage Nanoclusters2021

    • Author(s)
      Yokoyama Takaho、Chiba Tatsuya、Hirata Naoyuki、Shibuta Masahiro、Nakajima Atsushi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 125 Issue: 33 Pages: 18420-18428

    • DOI

      10.1021/acs.jpcc.1c03591

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Platinum nanocluster catalysts supported on Marimo carbon via scalable dry deposition synthesis2021

    • Author(s)
      Hirata Naoyuki、Katsura Yui、Gunji Hiroyuki、Tona Masahide、Tsukamoto Keizo、Eguchi Mika、Ando Toshihiro、Nakajima Atsushi
    • Journal Title

      RSC Advances

      Volume: 11 Issue: 62 Pages: 39216-39222

    • DOI

      10.1039/d1ra07717a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Confined Hot Electron Relaxation at the Molecular Heterointerface of the Size-Selected Plasmonic Noble Metal Nanocluster and Layered C602021

    • Author(s)
      Shibuta Masahiro、Yamamoto Kazuo、Ohta Tsutomu、Inoue Tomoya、Mizoguchi Kaito、Nakaya Masato、Eguchi Toyoaki、Nakajima Atsushi
    • Journal Title

      ACS Nano

      Volume: 15 Issue: 1 Pages: 1199-1209

    • DOI

      10.1021/acsnano.0c08248

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Occupied and Unoccupied Levels of Half-Fluorinated and Perfluorinated Rubrene Thin Films Probed by One- and Two-Photon Photoemission2020

    • Author(s)
      Inoue Tomoya、Shibuta Masahiro、Suzuki Toshiyasu、Nakajima Atsushi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 23 Pages: 12409-12416

    • DOI

      10.1021/acs.jpcc.0c01162

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visualization of Surface Plasmons Propagating at the Buried Organic/Metal Interface with Silver Nanocluster Sensitizers2020

    • Author(s)
      Yamagiwa Kana、Shibuta Masahiro、Nakajima Atsushi
    • Journal Title

      ACS Nano

      Volume: 14 Issue: 2 Pages: 2044-2052

    • DOI

      10.1021/acsnano.9b08653

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Enhanced oxygen reduction activity of platinum subnanocluster catalysts through charge redistribution2019

    • Author(s)
      Tsunoyama Hironori、Ohnuma Akira、Takahashi Koki、Velloth Archana、Ehara Masahiro、Ichikuni Nobuyuki、Tabuchi Masao、Nakajima Atsushi
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 84 Pages: 12603-12606

    • DOI

      10.1039/c9cc06327g

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Highly Dispersive Nearly Free Electron Bands at a 2D-Assembled C60 Monolayer2019

    • Author(s)
      Shibuta Masahiro、Yamamoto Kazuo、Guo Hongli、Zhao Jin、Nakajima Atsushi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 1 Pages: 734-741

    • DOI

      10.1021/acs.jpcc.9b10006

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Vibrational Spectra of Thiolate-Protected Gold Nanocluster with Infrared Reflection Absorption Spectroscopy: Size- and Temperature-Dependent Ordering Behavior of Organic Monolayer2019

    • Author(s)
      Yokoyama Takaho、Hirata Naoyuki、Tsunoyama Hironori、Eguchi Toyoaki、Negishi Yuichi、Nakajima Atsushi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 1 Pages: 363-371

    • DOI

      10.1021/acs.jpcc.9b07550

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] 有機表面上に担持された13族超原子の化学的反応性2022

    • Author(s)
      井上朋也、中嶋 敦
    • Organizer
      日本化学会 第102 春季年会(2022)
    • Related Report
      2021 Annual Research Report
  • [Presentation] 金属内包シリコンケージ超原子集積薄膜における電気伝導特性と電子状態2021

    • Author(s)
      横山 高穂,千葉 竜弥,中嶋 敦
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 有機基板とサイズによる表面担持されたアルミニウムナノクラスターの反応性制御2021

    • Author(s)
      井上 朋也,渋田 昌弘,中嶋 敦
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 有機分子基板上に担持したパラジウムナノクラスターの電荷状態と反応性2021

    • Author(s)
      四ノ宮 康,井上 朋也,中嶋 敦
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 有機基板上にソフトランディングさせた単一サイズ銀ナノクラスターの局在表面プラズモン共鳴2021

    • Author(s)
      溝口 凱斗,井上 朋也,渋田 昌弘,中嶋 敦
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Superatom Chemistry of Metal-Encapsulating Silicon Cage Nanoclusters2021

    • Author(s)
      Atsushi Nakajima
    • Organizer
      The International Chemical Congress of Pacific Basin Societies 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 気相精密大量合成とソフトランディング法による超原子ナノクラスター集積膜の作製とその電気特性評価2021

    • Author(s)
      横山高穂, 千葉竜弥, 平田直之, 渋田昌弘, 中嶋 敦
    • Organizer
      日本化学会 第101 春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Occupied and Unoccupied Levels of Half- and Per- Fluorinated Rubrene Thin Films Probed by One- and Two- Photon Photoemission2020

    • Author(s)
      Tomoya Inoue, Masahiro Shibuta, Toshiyasu Suzuki, Atsushi Nakajima
    • Organizer
      第14回 表面・界面スペクトロスコピー 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] Localized surface plasmonic resonances of size-selected silver nanoclusters (Agn) soft-landed on an organic substrate2020

    • Author(s)
      Kaito Mizoguchi, Tomoya Inoue, Masahiro Shibuta, Atsushi Nakajima
    • Organizer
      第14回 表面・界面スペクトロスコピー 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] 前期5d遷移金属内包シリコンケージナノクラスターの有機表面上における化学的特性の比較2020

    • Author(s)
      寺坂一也, 渋田昌弘, 中嶋敦
    • Organizer
      第14回 表面・界面スペクトロスコピー 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] Silver Nanocluster Sensitizers to Visualize Surface Plasmons Propagating at the Buried Organic-Metal Interface2020

    • Author(s)
      Atsushi Nakajima
    • Organizer
      Symposium on Size Selected Clusters (S3C)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Fabrication and Electrical Characterization of Metal-Encapsulating Si16 Cage Nanocluster Assembled Thin Films2020

    • Author(s)
      Takaho Yokoyama, Tatsuya Chiba, Naoyuki Hirata, Hironori Tsunoyama, Masahiro Shibuta, Atsushi Nakajima
    • Organizer
      Symposium on Size Selected Clusters
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Chemical Stabilities of Aluminum Superatoms on Organic Substrates2020

    • Author(s)
      Tomoya Inoue, Masahiro Shibuta, and Atsushi Nakajima
    • Organizer
      Symposium on Size Selected Clusters
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Size-selected platinum nanocluster catalysts: catalytic activity for oxygen reduction reaction and structure characterization2020

    • Author(s)
      Koki Takahashi, Hironori Tsunoyama, Akira Ohnuma, Archana Velloth, Masahiro Ehara, Nobuyuki Ichikuni, Masao Tabuchi, Atsushi Nakajima
    • Organizer
      Symposium on Size Selected Clusters
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 有機基板上にソフトランディングした単一サイズ銀ナノクラスター(Agn)の電子物性評価2020

    • Author(s)
      溝口凱斗, 井上朋也, 渋田昌弘, 中嶋敦
    • Organizer
      日本化学会 第100 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 超微細マイクロリアクターを用いたポリマー保護金合金ナノクラスターの精密合成2020

    • Author(s)
      竹本英成, 家壽英里子, 田中克敏, 中嶋敦
    • Organizer
      日本化学会 第100 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Nucleation and growth of small atom clusters into superatom for functional units2019

    • Author(s)
      Atsushi Nakajima
    • Organizer
      Nucleation & Growth Research Conference (NGRC2019)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Creating Assemblies of Size Selected Clusters on Surfaces by Cluster Beam Deposition2019

    • Author(s)
      Atsushi Nakajima
    • Organizer
      2019 Gordon Research Conference (GRC) “Clusters & Nanostructures”
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Formation and characterization of metal-encapsulating silicon cage2019

    • Author(s)
      Atsushi Nakajima
    • Organizer
      The 7th Asian Silicon Symposium (ASiS-7)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Optimizing cluster-surface interaction with organic substrates2019

    • Author(s)
      Atsushi Nakajima
    • Organizer
      “Advances in Cluster Beam Deposition” workshop
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 赤外反射吸収分光による金ナノクラスターに配位したチオール誘導体分子の構造評価: 配向秩序の空間次元・温度依存性2019

    • Author(s)
      横山高穂,平田直之,角山寛規,江口豊明,根岸雄一,中嶋敦
    • Organizer
      ナノ学会第17回大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Structural characterization of organic thiolate ligands on gold nanoclusters with infrared reflection absorption spectroscopy2019

    • Author(s)
      Takaho Yokoyama, Naoyuki Hirata, Hironori Tsunoyama, Toyoaki Eguchi Yuichi Negishi and Atsushi Nakajima
    • Organizer
      Gordon Research Conference: Clusters and Nanostructures
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 赤外反射吸収分光によるAu(111)表面に修飾した自己組織化単分子膜及び配位子保護金ナノクラスターの構造評価2019

    • Author(s)
      横山高穂、平田直之、角山 寛規、江口豊明、根岸雄一、中嶋 敦
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Annual Research Report
  • [Book] Electronic properties of transition metal-benzene sandwich clusters2020

    • Author(s)
      Tsugunosuke Masubuchi and Atsushi Nakajima
    • Total Pages
      561
    • Publisher
      Springer Nature
    • ISBN
      9789811500060
    • Related Report
      2020 Annual Research Report
  • [Book] Superatomic nanoclusters comprising silicon or aluminum cages2019

    • Author(s)
      Atsushi Nakajima
    • Total Pages
      404
    • Publisher
      Springer Nature
    • ISBN
      9789811393716
    • Related Report
      2019 Annual Research Report
  • [Remarks] 研究室ホームページ

    • URL

      http://chem.keio.ac.jp/nakajima-lab/index.html

    • Related Report
      2021 Annual Research Report
  • [Remarks] 中嶋研究室ホームページ

    • URL

      http://chem.keio.ac.jp/nakajima-lab/index.html

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
  • [Remarks] プレスリリース「プラズモン現象の最小単位を銀ナノクラスター9量体と決定」

    • URL

      https://www.k2.keio.ac.jp/press/press20210115.html

    • Related Report
      2020 Annual Research Report
  • [Remarks] プレスリリース「銀ナノクラスターの光増感を用いて「埋れた界面」の光伝播の観測に成功」

    • URL

      https://www.keio.ac.jp/ja/press-releases/2020/1/31/28-67151/

    • Related Report
      2019 Annual Research Report
  • [Remarks] プレスリリース「高活性な白金サブナノクラスター触媒の創製と構造決定に成功」

    • URL

      https://www.keio.ac.jp/ja/press-releases/2019/10/17/28-63895/

    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] 担持体、担持体の製造装置及び担持体の製造方法2020

    • Inventor(s)
      中嶋敦、角山寛規、江口美佳、郡司浩之、安藤寿浩、他3名
    • Industrial Property Rights Holder
      中嶋敦、角山寛規、江口美佳、郡司浩之、安藤寿浩、他3名
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2020-099669
    • Filing Date
      2020
    • Related Report
      2020 Annual Research Report
  • [Patent(Industrial Property Rights)] 担持体、及び担持体の製造方法2019

    • Inventor(s)
      大沼 明、中嶋 敦、角山寛規
    • Industrial Property Rights Holder
      大沼 明、中嶋 敦、角山寛規
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report

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Published: 2019-04-18   Modified: 2023-01-30  

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