Nakajima, Atsushi



Faculty of Science and Technology, Department of Chemistry (Yagami)



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Career 【 Display / hide

  • 1989.04


  • 1994.04


  • 1997.04


  • 1999.04

    東京都立大学大学院 非常勤講師

  • 2001.04


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Academic Background 【 Display / hide

  • 1984.03

    The University of Tokyo, Faculty of Science, 化学科

    University, Graduated

  • 1986.03

    The University of Tokyo, Graduate School, Division of Natural Science, 化学専攻

    Graduate School, Completed, Master's course

  • 1989.03

    The University of Tokyo, Graduate School, Division of Natural Science

    Graduate School, Completed, Doctoral course

Academic Degrees 【 Display / hide

  • Dr. Sc., The University of Tokyo, Coursework, 1989.03


Research Areas 【 Display / hide

  • Basic chemistry (Physical Chemistry)

Research Themes 【 Display / hide

  • Nanocluster Assembled Material Science, 


  • 科学技術振興機構 戦略創造プログラム(CREST) 研究課題「次世代光磁気材料を指向したナノデザイン制御」, 


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Books 【 Display / hide

  • 最新 実用真空技術総覧 クラスタービーム生成

    NAKAJIMA ATSUSHI, ㈱産業技術サービスセンター, 2017

  • シリコンフラーレン

    NAKAJIMA ATSUSHI, 慶應義塾機関紙 三田評論, 2014

  • 現代界面コロイド科学の事典 10.4節「金属ナノクラスター」

    NAKAJIMA ATSUSHI, 丸善, 2010

    Scope: 240-241

  • 化学の考え方

    NAKAJIMA ATSUSHI, 岩波書店, 2008

  • ナノクラスター科学-機能ナノクラスターの創成と固定化-

    NAKAJIMA ATSUSHI, 三共出版, 2006

    Scope: 271-288

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Papers 【 Display / hide

  • Alkali-Like Superatom Chemistry of Group-5 Metal Encapsulating Si16 Cage; M@Si16 (M = V, Nb, Ta)

    Masahiro Shibuta, Toshiaki Kamoshida, Tsutomu Ohta, Hironori Tsunoyama, Atsushi Nakajima

    Communications Chemistry 1   50 2018.09

    Research paper (scientific journal), Joint Work, Accepted

  • Synthesis and Characterization of Metal-Encapsulating Si16 Cage Superatoms

    Tsunoyama Hironori, Shibuta Masahiro, Nakaya Masato, Eguchi Toyoaki, Nakajima Atsushi

    Accounts of Chemical Research 51 ( 8 ) 1735 - 1745 2018.08

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  0001-4842

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    <p>ConspectusNanoclusters, aggregates of several to hundreds of atoms, have been one of the central issues of nanomaterials sciences owing to their unique structures and properties, which could be found neither in nanoparticles with several nanometer diameters nor in organometallic complexes. Along with the chemical nature of each element, properties of nanoclusters change dramatically with size parameters, making nanoclusters strong potential candidates for future tailor-made materials; these nanoclusters are expected to have attractive properties such as redox activity, catalysis, and magnetism. Alloying of nanoclusters additionally gives designer functionality by fine control of their electronic structures in addition to size parameters. Among binary nanoclusters, binary cage superatoms (BCSs) composed of transition metal (M) encapsulating silicon cages, M@Si16, have unique cage structures of 16 silicon atoms, which have not been found in elemental silicon nanoclusters, organosilicon compounds, and silicon based clathrates. The unique composition of these BCSs originates from the simultaneous satisfaction of geometric and electronic shell-closings in terms of cage geometry and valence electron filling, where a total of 68 valence electrons occupy the superatomic orbitals of (1S)2(1P)6(1D)10(1F)14(2S)2(1G)18(2P)6(2D)10 for M = group 4 elements in neutral ground state. The most important issue for M@Si16 BCSs is fine-tuning of their characters by replacement of the central metal atoms, M, based on one-by-one adjustment of valence electron counts in the same structure framework of Si16 cage; the replacement of M yields a series of M@Si16 BCSs, based on their superatomic characteristics. So far, despite these unique features probed in the gas-phase molecular beam and predicted by quantum chemical calculations, M@Si16 have not yet been isolated.In this Account, we have focused on recent advances in synthesis and characterizations of M@Si16 BCSs (M = Ti and Ta). A series of M@Si16 BCSs (M = groups 3 to 5) was found in gas-phase molecular beam experiments by photoelectron spectroscopy and mass spectrometry: formation of halogen-, rare-gas-, and alkali-like superatoms was identified through one-by-one tuning of number of total valence electrons. Toward future functional materials in the solid state, we have developed an intensive, size-selected nanocluster source based on high-power impulse magnetron sputtering coupled with a mass spectrometer and a soft-landing apparatus. With scanning probe microscopy and photoelectron spectroscopy, the structure of surface-immobilized BCSs has been elucidated; BCSs can be dispersed in an isolated form using C60 fullerene decoration of the substrate. The intensive nanocluster source also enables the synthesis of BCSs in the 100-mg scale by coupling with a direct liquid-embedded trapping method into organic dispersants, enabling their structure characterization as a highly symmetric "metal-encapsulating tetrahedral silicon-cage" (METS) structure with Frank-Kasper geometry.</p>

  • Characterization of floating-gate memory device with thiolate-protected gold and gold-palladium nanoclusters

    Yokoyama Takaho, Hirata Naoyuki, Tsunoyama Hironori, Negishi Yuichi, Nakajima Atsushi

    AIP Advances 8 ( 6 ) 065002 2018.06

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  2158-3226

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    <p>The floating-gate memory characteristics of thiolate-protected gold (Au:SR) and palladium doped Au (AuPd:SR) nanoclusters, Au25(SR)18, Au24Pd(SR)18, and Au38(SR)24 (R = C12H25), were investigated by capacitance-voltage (C-V) measurements in vacuum. Monolayer films of Au:SR nanoclusters were formed as floating-gate memory layers on p-type Si substrates by the Langmuir-Schaefer method with surface pressure - area (π-A) isotherm measurements. A fluoropolymer (CYTOP, ∼15 nm thick) was spin-coated on top to form a hydrophobic insulating layer. Using an Au pad (∼40 nm thick) as the gate electrode, C-V measurements exhibit clockwise hysteresis curves originating from the Au:SR and AuPd:SR nanoclusters against the reference measured in each sample, and the hysteresis widths were dependent on the composition and sizes of the Au:SR nanoclusters. The positive and negative voltage shifts in the hysteresis can be explained in terms of electronic structures in Au:SR and AuPd:SR-based devices.</p>

  • Size-Effect on Electrochemical Hydrogen Evolution Reaction by Single-Size Platinum Nanocluster Catalysts Immobilized on Strontium Titanate

    Hironori Tsunoyama, Yohei Yamano, Chuhang Zhang, Masafumi Komori, Toyoaki Eguchi, and Atsushi Nakajima

    Topics in Catalysis (CSJ)  61 ( 1 ) 126 - 135 2018.01

    Research paper (scientific journal), Joint Work, Accepted

  • Energy Level Alignment of Organic Molecules with Chemically Modified Alkanethiolate Self-Assembled Monolayers

    Shibuta Masahiro, Ogura Munehisa, Eguchi Toyoaki, Nakajima Atsushi

    Journal of Physical Chemistry C 121 ( 49 ) 27399 - 27405 2017.12

    Research paper (scientific journal), Joint Work, Accepted,  ISSN  1932-7447

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    <p>We have employed two-photon photoemission spectroscopy to nondestructively resolve the unoccupied energy levels of fullerene C60 molecules deposited on alkanethiolate self-assembled monolayers (SAMs). By fluorine substitution of the hydrogen atoms in the alkyl chain, the work function (WF) increased from 4.3 eV for the alkanethiolate-SAM (H-SAM) to 5.7 eV for the fluorine-substituted SAM (F-SAM), owing to the formation of surface dipole layers. When C60 is deposited on the H-SAM and F-SAM, the energy positions of the unoccupied/occupied levels of C60 are pinned to the vacuum level (Fermi level (EF) + WF). As a result of the energy level alignment, on the F-SAM, the relative energy from EF of the highest occupied molecular orbital of C60 almost equals that of the lowest unoccupied molecular orbital, implying that the C60 film on the F-SAM exhibits both p- and n-type (ambipolar) charge transport properties, while C60 is known as a typical n-type semiconductor. The energetics are preserved even with multilayered C60 films at least up to ∼5 nm in thickness, showing that the dipole layers induced by SAMs are robust against molecular overlayers. Such a spectroscopic study on the energy levels for organic films will be of importance for further development of organic thin film devices.</p>

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Papers, etc., Registered in KOARA 【 Display / hide

Reviews, Commentaries, etc. 【 Display / hide

  • Fabrication method for nanocluster superatoms with high-power impulse magnetron sputtering

    Tsunoyama Hironori, Tona Masahide, Tsukamoto Keizo, Nakajima Atsushi

    Journal of the Vacuum Society of Japan 60 ( 9 ) 352 - 361 2017

    Introduction and explanation (scientific journal), Joint Work,  ISSN  1882-2398

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    <p>Intensive ion source for single-size nanoclusters was developed on the basis of high-power impulse magnetron sputtering (HiPIMS) technique combined with a low-pressure, low-temperature gas flow reactor. The nanocluster source exhibits superior characteristics originating from pulsed, high-power sputtering compared to conventional direct-current sputtering; (1) enhanced ion intensities, (2) fascicle tuning of nanocluster sizes, and (3) enhanced selectivity of stable, magic nanoclusters. The metallic (silver, platinum, and palladium) and binary (transition-metal and silicon) nanocluster ions in the size range of several to one hundred atoms can be generated with ion current of 100 pA to 10 nA (108 to 1011 nanoclusters/sec). The growth mechanism of nanoclusters in the source was also explained by the nucleation theory.</p>

Presentations 【 Display / hide

  • Monodispersed Immobilization and Island Formation of M@Si16 Superatom


    The Cluster Surface Interactions 2016 Workshop (Argonne National Laboratory) , 2016.06, Oral Presentation(guest/special)

  • Alkali-Like Binary Superatom of a Ta-Encapsulating Si16 Cage


    Symposium on Size Selected Clusters (S3C) 2016 (Davos, Switzerland) , 2016.03, Oral Presentation(key)

  • Nanocluster superatom formation using ion source based on high-power impulse magnetron sputtering


    Pacifichem 2015 (Honolulu, Hawaii, USA) , 2015.12, Oral Presentation(guest/special)

  • Formation of binary superatom nanocluster monolayer


    XXIV International Materials Research Congress (IMRC) on Clusters & Nanostructures (Cancun, Mexico) , 2015.08, Oral Presentation(guest/special)

  • Formation of Superatom Monolayer Using Nanocluster Ion Source Based on High-Power Impulse Magnetron Sputtering


    2015 Gordon Research Conference (GRC) “Clusters and Cluster Assembled Materials” (Girona, Spain) , 2015.07, Oral Presentation(guest/special)

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Research Projects of Competitive Funds, etc. 【 Display / hide

  • 次世代光磁気材料を指向したナノデザイン制御


    Keio University, Kobe University, Osaka University, Hiroshima University, University of Chicago, Argonne National Laboratory, -, Research grant

  • Development of Sub-nanosized Aggregates Having Novel Optical Properties


    Keio University, Kobe University, Tohoku University, Institute for Molecular Science, “Research for the Future (RFTF)” of the Japan Society for the Promotion of Science, Research grant

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    We have successfully established several new methodologies to generate sub-nanosized aggregates having novel optical properties, and revealed fundamental properties of their electronic and geometrical structures as well as molecular aggregates bridging between gas and liquid/solid phases. New areas of “gas-phase organometallic chemistry” have been developed to create and to design new optoelectronic materials with our proposed soft-landing method.

  • Study of Magnetic Bottle Electron Spectrometer and Their Application


    Keio University, Special Coordination Funds for the promotion of Science and Technology, Research grant

  • ナノ生体触媒の創成を指向したニトロゲナーゼ酵素の鉄-硫黄活性中心のデザイン制御


    慶應義塾大学, Grant-in-Aid for Scientific Research, Research grant

  • 気相多元系合金クラスターの基板担持による触媒機能と電子物性の研究


    Grant-in-Aid for Scientific Research, Research grant

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Intellectual Property Rights, etc. 【 Display / hide

  • ナノクラスター生成装置

    Application No.: 2013-112995  2013.05 

    Patent, Joint, National application

  • 多重レーザー照射による液滴試料の粉砕法

    Application No.: 2012-162131  2012.07 

    Patent, Joint, National application

  • “マイクロミキサー、マイクロミキサーエレメント及びその製造方法”

    Application No.: 2012-0989620  2012.04 

    Patent, Joint, National application

  • ナノクラスター分散液、ナノクラスター膜、ナノクラスター分散体の製造方法およびナノクラスター分散液の製造装置

    Application No.: 2015-160680   

    Patent, Joint

  • マイクロミキサー、マイクロミキサーエレメントおよびその製造方法

    Application No.: 2016-033117   

    Patent, Joint

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Awards 【 Display / hide

  • 分子科学会賞

    2018.08, 分子科学会, 複合ナノクラスター科学の開拓-気相化学からナノ機能表面化学へ

    Type of Award: Awards of National Conference, Council and Symposium

  • 田中貴金属研究財団 シルバー賞


    Type of Award: Awards of Publisher, Newspaper Company and Foundation

  • The Chemical Society of Japan Award for Creative Work for 2008

    NAKAJIMA ATSUSHI, 2009.03, 社団法人 日本化学会, 複合クラスターを用いたナノスケール物質群の創製とその電子物性の解明

    Type of Award: Awards of National Conference, Council and Symposium

  • Chemical Physics Letters Most Cited Paper 2003-2007 Award

    2008.10, Elsevier

    Type of Award: International Academic Awards

  • 分子科学研究奨励森野基金研究奨励


    Type of Award: Awards of Publisher, Newspaper Company and Foundation

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Courses Taught 【 Display / hide











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Memberships in Academic Societies 【 Display / hide

  • 分子科学研究会, 

  • ナノ学会, 

  • 日本物理学会, 

  • 日本化学会, 


Committee Experiences 【 Display / hide

  • 2008.09

    会長, 分子科学会

  • 2006.08

    連携会員, 日本学術会議

  • 2004.09

    Committee Chair, 分子科学研究会

  • 2004.05

    Director, ナノ学会

  • 1984.03

    Member, 日本物理学会

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