京都大学化学研究所 平成 30 年度
国際共同利用・共同研究拠点 成果報告書
化学関連分野の深化・連携を基軸とする
先端・学際グローバル研究拠点

京都大学化学研究所

国際共同利用・共同研究拠点

化学関連分野の深化・連携を基軸とする
先端・学際グローバル研究拠点

平成 30 年度

成果報告書

まえがき京都大学化学研究所は、平成２２年度から「化学関連分野の深化・連携を基軸とす
る先端・学際研究拠点」（平成２８年度から第二期）として国内外の共同利用・共同研究を推し進め、それを新たな糧としてより多様でグローバルな化学研究の展開と若手研究者の育成・輩出を図って参りました。特に本拠点では、化学関連コミュニティの研究者の皆様からの要請を踏まえながら、化学研究所の研究分野の広がりと深さに加えて、これまでの様々な連携実績を活かし、国内外の研究機関の相互協力を担保す
るハブ環境も提供しています。先端・学際的分野深耕にあたっては、関連コミュニテ
ィの研究者の皆様と化学研究所の教員が推進する分野選択型、課題提案型、施設・機器利用型、連携・融合促進型等の多彩な共同研究と、拠点として主催・共催する各種
国際会議、シンポジウム、研究会等を通じて、多様性と先進性を担保し、さらに、国際的視点に基づいて次代の化学関連分野を担う若手研究者の育成にも注力しています。また、拠点運営では、所外、学外の関連分野有識者と化学研究所の教員を委員とする共同研究委員会および運営評議会を核として、共同研究課題の公募・採択などを戦略的に遂行しております。
第二期拠点活動の三年目にあたる平成３０年度には、化学研究所教員が一丸となって、１５５件の応募の中から採択された１１５件の共同研究を遂行し、５件の国際シンポジウム・研究会を主催・共催致しました。また、グローバルな化学研究の展開と人材育成のため、平成３０年度の国際共同研究枠を平成２９年度の１１件から２０件に増やしました。このようなグローバルな拠点活動が評価され、化学研究所は、平成
３０年１１月１３日文部科学大臣から国際共同利用・共同研究拠点に認定され、「化学関連分野の深化・連携を基軸とする先端・学際グローバル研究拠点」として活動を強化しています。今後とも、国際的ハブ機能を活用し、国際共同利用・共同研究の一層の促進、国際学術ネットワークの充実、国際的・先進的視野をもつ若手研究者の育成に取り組むことで、化学を中心とする研究分野の深化と国際的な境界学術分野の新規開拓を推進して参ります。皆様にはさらなるご支援・ご協力のほどよろしくお願い申し上げます。
本報告書は、平成３０年度の本拠点における研究成果をとりまとめたものです。本
報告書をご一読頂き、今後の本拠点の目指すべき方向や活動の推進方法などに関する忌憚のないご意見・ご提案などをお聞かせ下されば幸甚に存じます。
化学研究所所長 辻井 敬亘平成30年度 共同利用・共同研究報告書 目次
１．共同研究成果報告
分野選択型共同研究
ビーム科学分野
キラルな金属ナノ結晶の作製とその光学特性の解明
2018-1
2018-2

2018-3※2018-42018-5

2018-62018-7
2018-8
2018-92018-10
2018-112018-122018-132018-14

東京理科大学 河合 武司
Directional neutron generation via laser-driven-photonuclear reaction byusing a spin polarized deuterium target
Osaka University Yasunobu Arikawa
マルチピコ秒の相対論的放射圧で駆動される臨界面の超高速運動の観測
大阪大学 藤岡 慎介
X-Ray Structural Studies on Reaction Mechanism of Maleylacetate Reductase
Kansai University Tadao Oikawa
X-ray Crystallographic Studies on Thermostability and Substrate
Specificity of L-Asparaginase
Kagawa University Shiro Kato
レーザー吸収制御による半導体の微細加工に関する基礎研究
大阪産業大学 草場 光博
高輝度テラヘルツ波による材料表面への新規機能性付与
摂南大学
長島 健
レーザー駆動高強度テラヘルツ表面波の研究
大阪大学 時田 茂樹
超高強度レーザー生成重陽子ビームの大強度化：リチウムイオン電池計
測、小型中性子源開発を目指して
光産業創成大学院大学 藤田 和久
加速器ビーム制御コンポーネントの永久磁石化の検討
高エネルギー加速器研究機構 照沼 信浩
化学反応の量子制御を目指したCEP安定化自由電子レーザのための省電力型超伝導加速空洞の製作方法の研究
量子科学技術研究開発機構 羽島 良一
中性子速度濃縮法の開発
名古屋大学 北口 雅暁
超伝導空洞の内面処理による高性能化とコスト削減の研究
高エネルギー加速器研究機構 佐伯 学行
リチウムイオン二次電池の電極材内の充放電反応可視化を目的とした、六極磁石によるパルス中性子透過イメージ拡大の研究
産業技術総合研究所 木野 幸一

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元素科学分野Construction of metal-substituted carbenium ion and silyl cation and their
2018-15
applications for Lewis acid catalysts
2018-16

Hirosaki University Masaaki Okazaki
Synthesis of Transition Metal Complexes Bearing a Low-coordinate
Phosphorus Ligand and Their Application to Catalytic Reactions

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Kindai University Tsukasa Matsuo

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2018-17

窒化炭素構造体の結晶構造決定のための基礎研究

2018-18

物質・材料研究機構
ペロブスカイト半導体を用いた新規冷却デバイスの実現可能性検討
長岡技術科学大学※ 国際共同利用・共同研究

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坂牛 健

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山田 昇

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2018-19

新規レーザー顕微分光技術を活用したナノ発光材料の量子物性の研究
情報通信研究機構 井原 章之
Optical properties of Pb perovskite solar cells by heterodyne interference
2018-20
spectroscopy
Joetsu University of Education Yoshihiro Ogawa
2018-21※ Discovery of novel functional transition-metal oxides with ultra-highpressure condition
國立臺灣大學陳 威廷
Synthesis of Low-coordinated Heavier Group 14 Species bearing Stable2018-22
Redox Behavior and Elucidation of Their Structures
Nagoya City University Takahiro Sasamori
Base Metal Catalysis for Creation of Functional Materials
2018-23
RIKEN Laurean Ilies
Developmentof
first-row
latetransition-metal
complexes
withconstrained
2018-24geometry using tridentate anionic ligands
Yokohama National University Yoshitaka Yamaguchi
シクロパラフェニレンにおける面内芳香族性の解明
2018-25
理化学研究所 村中 厚哉
Study of the reaction mechanisms of radical polymerization utilizing the
2018-26
reactivity of organotellurium compounds
National Institute for Materials Science Yasuyuki Nakamura
バイオ情報学分野
次数相関のある複雑ネットワークの解析
2018-27
九州工業大学 竹本 和広
2018-28※ Novel approaches to prediction of caspase cleavage sites
Monash University Jiangning SongControl and Analysis of Complex Networks via Minimum Dominating Sets
2018-29
Toho University Jose C. Nacher
Development of prediction method for growth conditions based on
2018-30
microbial genome information
Research Organization of Information and Systems Susumu Goto
赤潮発生後の生態遷移における巨大ウイルスの生態学的役割の解明
2018-31高知大学 長崎 慶三
日本の水環境からの新規巨大ウイルスの単離とゲノム解析研究
2018-32
東京理科大学 武村 政春
2018-33※ Machine Learning based Integration of Diverse Biological Data with Network
Nagoya Institute of Technology Masayuki Karasuyama
統計的機械学習による分子ネットワークの差分解析法
2018-34
帯広畜産大学 茅野 光範
物質合成分野
ブレスピロールの全合成
2018-35
京都府立大学 今吉 亜由美
Studies on the reactivities between curved pi-conjugated molecules and2018-36transition metal complexes and their applications
2018-37
2018-38
2018-39

Osaka University Sensuke Ogoshi
有機機能性材料を指向した新規非交互複素環化合物の創製
久留米工業高等専門学校
黒飛 敬
新規な有機半導体材料で構成される有機太陽電池
大阪大学
家 裕隆
非鉛ペロブスカイト太陽電池の電子準位と光電気物性
大阪大学 佐伯 昭紀※ 国際共同利用・共同研究

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2018-41

2018-42Development of small-molecule n-type organic semiconductors that canbe processed via precursor approaches
Nara Institute of Science and Technology Mitsuharu Suzuki
Synthesis and Thermoelectric Performance of π-Conjugated Coordination
Polymers
Osaka Institute of Technology Michihisa Murata
付加脱離反応と縮環反応を駆使した新規チエノアセン分子の合成とその物性評価
岡山大学
菅 誠治

現象解析分野Biogeochemical study of bioactive trace metals in the aerosols over
2018-43
northern North Pacific Ocean
Kindai University Yuzuru Nakaguchi
In vivo detection of temperature change using optical spectroscopic
2018-44
characterization of metal nanoparticle
National Defense Medical College Miya Ishihara
π共役系ユニット含有単分子膜集積体のpMAIRS法を用いた精密構造解析
2018-45
東北大学 山本 俊介
2018-46※ Correlated molecular motion in polymeric liquids
Yamagata University Sathish K. Sukumaran
Relationshipbetweenhydrogenbondingandrheological properties of
2018-47
polyurethanes having several chemical structures
Osaka University Osamu Urakawa
Analysis of molecular condensation in temperature gradient field created2018-48through plasmonic heating
Japan Women's University Ryoko Shimada
液膜輸送における金属イオンの輸送効率の向上に関する研究
2018-49
京都教育大学
向井 浩
The study on density fluctuations of polycarbonate by using time-resolved
2018-50
scattering method
Yamagata University Shotaro Nishitsuji
Depth-resolved Structure Analysis of Organic Thin Films by Energy
2018-51
Dispersive GISAXS utilizing Tender X-rays
Nagoya Institute of Technology Katsuhiro Yamamoto
形状制御されたPdナノ粒子の広温度領域における水素吸蔵特性の解明
2018-52
九州大学 山内 美穂
新規部分フッ素化リン脂質分子群の合成と膜物性・構造の解析
2018-53
群馬大学 園山 正史
フラボノイド系色素混合物を用いた色素増感太陽電池の作製と特性評価、
2018-54
並びに効率向上を目指した計算化学研究
名古屋大学 吉田 久美
課題提案型共同研究
2018-55※ Regulatory Network of Gene Expression for Plant Cell Morphogenesis
Peking University QU, Li-Jia
Dynamics of the transcription factor ARR1 on plant chromosomal DNA
2018-56
RIKEN Jong-Myong Kim
ビタミンＤの新機能の調節
2018-57
東京農工大学 長澤 和夫※ 国際共同利用・共同研究

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2018-58※
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2018-60
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2018-63
2018-64※
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2018-66
2018-67※
2018-68※

2018-69

2018-70
2018-71
2018-72

2018-73
2018-74
2018-75

2018-76

2018-77※

2018-78

Discovery and Use of Bioactive Self-Assembling Molecules
Fudan University
Zhou Lu
合成細胞接着分子を利用した移植細胞延命化による損傷治癒の促進
東京理科大学 西川 元也
スピネルフェライト/非磁性重金属系における界面構造とスピン流現象の解明
北海道大学 長浜 太郎
Observation of Current-Driven Domain Wall Motions in the Ni nanowire
Gifu University Keisuke Yamada
Study of spin-filtering effect of the magnetic insulator films withperpendicular magnetic anisotropy
Nagoya Institute of Technology Masaaki Tanaka
誘導磁気モーメントを有する系における磁壁移動速度に対する電界効果
東京大学 千葉 大地
Real time observation of topological Hall effectKorea Advanced Institute of Science and Technology KIM, Kab-Jin
電界によるスカーミオンの高速移動電気通信大学 仲谷 栄伸
熱活性遅延蛍光分子のスピン動力学研究
新潟大学 生駒 忠昭
Mechanism study of heterogeneous catalysis on zeolites by DNP-NMR
Chinese Academy of Sciences
Jun XuDetermination of high-order structure of organic device molecules using
dynamic nuclear polarization solid-state NMR
U.S. Department of Energy, Ames National Laboratory Takeshi Kobayashi
Characteristics of membrane vesicles produced by intestinal bacteria andfermented food-derived bacteria and their biogenesis
Kindai University Atsushi Kurata
Functional study of metal-induced proteins in microbial metal respiration
Ritsumeikan University Hisaaki Mihara
合成ペプチドを用いた結合態D-アミノ酸の生成機構の解析
大阪工業大学 大森 勇門
植物の多環性芳香族二次代謝産物の生合成に関与する環形成酵素の同定および機能解析
信州大学 高梨 功次郎
植物におけるヒト型ステロイドホルモンの生合成および機能の解明
静岡大学 大西 利幸
レアメタルに対して高選択的な認識・分離系の開発
奈良教育大学 山崎 祥子
再生医療を指向した二次元配列された微粒子により誘導される間葉系幹細胞の分化挙動解析
東北大学 山本 雅哉
Intramolecular photoinduced charge separation in D-A
cycloparaphenylenes
ISIR, Osaka University Mamoru Fujitsuka
Reptation Relaxation of Entangled Polymer Chains Undergoing Head-toHead Association and Dissociation.
Sungkyunkwan University Youngdon Kwon
アンチセンス核酸によるグアニン四重鎖構造を介したRNA構造・機能制御
弘前大学 萩原 正規※ 国際共同利用・共同研究

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新規π共役系ポリマーの開発と有機薄膜太陽電池への応用

広島大学
尾坂 格 79
4-ピロリジン-ピリジン型分子触媒による化学選択的アシル化反応の理論的解析
立教大学 山中 正浩 80
位置及び立体選択的酸化触媒の開発
2018-81
岐阜薬科大学 伊藤 彰近 81
Development of organocatalytic site-selective phosphorylation and2018-82
sulfation reactions of carbohydrate and its application to drug delivery
Gifu Pharmaceutical University Hideko Nagasawa 82
2018-83※ Search for four wave-mixing in the vacuum
Hiroshima University Kensuke Homma 83
電界誘起電気化学的エッチングを利用した遷移金属酸化物における機能開発
2018-84
名古屋大学 畑野 敬史 84
抽出剤含浸樹脂を用いた固相抽出における界面活性剤の協同効果
2018-85
大阪府立大学工業高等専門学校 倉橋 健介 85
高分子／アゾベンゼン混合液晶系における上限臨界溶液温度の異常な2018-86
光応答に関する研究
産業技術総合研究所 山本 貴広 86
2018-87※ Interfacial structure control and photo-induced charge transfer dynamics
of semiconductor nanocrystal based hybrid materials
RMIT University Yasuhiro Tachibana 87
Room temperature operation of Au25 cluster single-electron transistor
2018-88
Tokyo Institute of Technology Yutaka Majima 88
Vibrational spectroscopy study on ozonolysis of Kalanchoe pinnata leaf surface
2018-89
Hokkaido University Tetsuya Hama 89
ダイヤモンド中のNV中心量子ビットの電気的制御と電気的検出2018-90
産業技術総合研究所 牧野 俊晴 90
ダイヤモンド中のNV中心のスピンコヒーレンス時間の長時間化
2018-91
金沢大学 徳田 規夫 91
超高感度磁気センサのためのダイヤモンドNV中心の研究
2018-92
東京工業大学 波多野 睦子 92
超分子マルチブロック共重合体の合成と機能創製
2018-93
広島大学 灰野 岳晴 93
様々なブロック長を有する2成分多元ブロック共重合体のシークエンス長と2018-94
セグメントサイズの関係
名古屋大学 高野 敦志 94
トリフェニルアミンユニットを組み込んだ大環状分子を基盤とした有機機能
2018-95
性材料の創製岡山理科大学 岩永 哲夫 95
連携・融合促進型共同研究
2018-96※ 次世代材料の創製に向けたジョイントセミナー
東京理科大学 藤本 憲次郎 96
Facileintracellulardeliverybythestructural
alterationofoligoarginines
2018-97※
National Taiwan University Richard Cheng 100
2018-98※ Novel drug-delivery system using albumin as a reservoir
CNRS Sandrine Sagan 101
2018-99※ Functional design for drag delivery into brain
University of Barcelona Ernest Giralt 102
2018-80※ 国際共同利用・共同研究－v－

2018-100※ Modification of cell-penetrating peptides for the effective delivery ofmolecules into the cells
Eotvos L. University Ferenc Hudecz 103
2018-101※ The 14th International Workshop for East Asian Young Rheologists
Osaka University Tadashi Inoue 104
2018-102※ Study on emergent spin-orbit phenomena in artificial superlattices without
structural inversion symmetry
University of Ulsan Sanghoon Kim 106
2018-103 第3回 「固体化学フォーラム」研究会
東北大学
宮坂 等 108
施設・機器利用型共同研究
2018-104 核融合プラズマ対向材中の水素・ヘリウム挙動に関する電子分光学的研究
島根大学 宮本 光貴 110
2018-105 単結晶X線構造解析を用いた、含フッ素共役分子の結晶構造におけるフルオラス相互作用の解明
茨城大学 吾郷 友宏 111
2018-106 トリプチシルメチル基を速度論的安定化に用いるに高反応性典型元素化
学種の合成と構造
立教大学 箕浦 真生 112
フラットで完璧なπ共役二次元シート「シリセン」の理論設計とその物性探索
2018-107東北大学 高橋 まさえ 113
2018-108 電子エネルギー損失分光によるギャッププラズモンモードの分析
九州大学
斉藤 光 114
2018-109 Synthesis and Elucidation of Properties of Unsymmetrically-Substituted
Disilyne and Related π-Electron Systems
Tohoku University Takeaki Iwamoto 116
2018-110 Synthesis and Structural Characterization of Low-Coordinate Compoundsof Group 14 Elements
Kindai University Tsukasa Matsuo 117
2018-111 Synthesis and structures of phosphorus-containing aromatics bearing anamine moiety
Fukuoka University Noriyoshi Nagahora 118
2018-112 超高感度FT-MSを活用したポルフィリンへテロ多量体の観測―分子認識、
高次化、及び、不斉誘起における動的挙動の精密解析
福井大学 徳永 雄次 119
2018-113 質量分析イメージング法を用いたステロイドホルモン産生機構の研究
奈良県立医科大学
秦野 修 1202018-114 Determination of compositions of protected novel metal clusters with
precise mass analysis
The University of Tokyo Kiichirou Koyasu 121
2018-115 親水性チオラート保護金属クラスターの合成とLC/MSによる精密分離及び評価
東京理科大学 根岸 雄一 122※ 国際共同利用・共同研究－vi－２．国際学会、シンポジウム・研究報告会
国際会議
・第 15 回無機環状化合物国際シンポジウム
・第 10 回国際ペプチドシンポジウム
・第 24 回ペプチドフォーラム

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シンポジウム・研究会
・第 3 回 pMAIRS ワークショップ

129

３．成果発表論文

131（平成 31 年 2 月までに刊行された論文で、平成 22－29 年度の成果報告書に掲載されていないもの）

紙数の都合により、*を付けた論文のみについて、別刷りを本報告書に記載する。

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Acetylacetonato-based pincer-type nickel(II) complexes: synthesis and catalysis incrosscouplings of aryl chlorides with aryl Grignard reagents, Dalton Trans., 47, 8003–8012(2018).
1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion tohalogermylenoids, Eur. J. Inorg. Chem., 47, 814–822 (2018).
Synthesis and Structure of Lewis Base-coordinated Phosphanylalumanes Bearing P–H and
Al–Br Moieties, Eur. J. Inorg. Chem., 2018, 1984–1987 (2018).
Chalcogenation Reaction of Cyclic Digermenes, Cｐhem. Lett., 47, 719–722 (2018).
Heavy Phenyllithium and -sodium: Synthesis and Characterization of Germanium Analogues of
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Synthesis of a New Highly-fluorinated cis-1,2-Cyclopentanediol and Its Application for
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Ru-Complexes of an Anionic Germabenzenyl Ligand, Chem. Commun., 54, 8044–8047 (2018).
Syntheses and Structures of d(10) Coinage Metal Complexes of Electron-accepting Phosphine
Ligands Featuring a 3,3,4,4,5,5-Hexafluorocyclopentene Framework, Inorg. Chem., 57,
9105–9114 (2018).
Facile Transformation of 2H,3H-Decafluoropentane (HFC-4310mee) into (Z)-2HNonafluoropent-2-ene and Its Application to the Synthesis of Polyfluorinated Homoallylic
Ketones by Claisen Rearrangement, J. Fluor. Chem., 213, 74–79 (2018).
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Synthesis of Dodecaallylhexasilacyclohexane and Its Convertibility, Z. Anorg. Allg. Chem., 644,
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The Selective Formation of a 1,2-Disilabenzene from the Reaction of a Disilyne with
Phenylacetylene, Dalton Trans., 47, 13318–13322 (2018).
Generation of Stannabenzenes and Their Monomer-dimer Equilibration, Dalton Trans., 47,
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Stannabenzenylpotassium: The First Isolable Tin-containing Benzene Derivative, Chem. Eur. J.,
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A Straightforward Synthesis of Polyfluorinated Furan Derivatives and Their Property, Asian J.
Org. Chem., 7, 2484–2489 (2018).
Efficient Synthesis and Properties of [1]Benzothieno[3,2-b]thieno[2,3-d]furans and[1]Benzothieno[3,2-b]thieno[2,3-d]thiophenes, Asian J. Org. Chem., 7, 1635–1641 (2018).
Construction of a Metal-Free Electron Spin System by Encapsulation of an NO Molecule inside
an Open-Cage Fullerene C60 Derivative, Angew. Chem. Int. Ed., 57, 12804–12808 (2018).
USAXS Analysis of Concentration-Dependent Self-Assembling of Polymer-Brush-Modified
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Flocculation of Cells by Cellulose Nanofibers Modified with Concentrated Polymer Brushes,ACS Appl. Nano Mater., 1, 1450–1455 (2018).
Strain-Induced Double Carbon-Carbon Bond Activations of Cycloparaphenylenes (CPPs) by a
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Synthesis and Inhibitory Activity of Mechanism-Based 4-Coumaroyl-CoA Ligase Inhibitors,
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Generation of α-Solanine-Free Hairy Roots of Potato by CRISPR/Cas9 Mediated Genome
Editing of the St16DOX Gene, Plant Physiol. Biochem., 131, 70–77 (2018).
Superflexible Multifunctional Polyvinylpolydimethylsiloxane-Based Aerogels as Efficient
Absorbents, Thermal Superinsulators, and Strain Sensors , Angew. Chem. Int. Ed., 57,
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Superheated Melting Kinetics of Metastable Chain-Folded Polymer Crystals, Cryst. GrowthDes., 18, 2602–2608 (2018).
Kinetics of "Melting" of Sucrose Crystals, Cryst. Growth Des., 18, 3637–3643 (2018).
Versatile Double-Cross-Linking Approach to Transparent, Machinable, Supercompressible,
Highly Bendable Aerogel Thermal Superinsulators, Chem. Mater., 30, 2759–2770 (2018).
Adamantyl Substitution Strategy for Realizing Solution-Processable Thermally Stable
Deep-Blue Thermally Activated Delayed Fluorescence Materials, Adv. Mater., 30,[1705641-1]–[1705641-8] (2018).
Transparent, Superflexible Doubly Cross-Linked Polyvinylpolymethylsiloxane Aerogel
Superinsulators via Ambient Pressure Drying, ACS Nano, 12, 521–532 (2018).
Iscoelastic and Dielectric Relaxation of Reptating Type-A Chains Affected by Reversible
Head-to-Head Association and Dissociation, Macromolecules, 51, 6476–6496 (2018).
Synthesis and Properties of Dithieno-Fused 1,4-Azaborine Derivatives, Org. Lett., 20,
7336–7340 (2018).

－viii－

Half-cycle terahertz surface waves with MV/cm field strengths generated on metal wires, Appl.
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Robust Surface Plasmon Resonance Chips for Repetitive and Accurate Analysis of
Lignin–Peptide Interactions, ACS Omega, 3, 7483–7493 (2018).
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Highly Efficient Catalysts for Direct Arylation Polymerization (DArP), Asian J. Org. Chem., 7,
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Taxon richness of “Megaviridae” exceeds those of Bacteria and Archaea in the ocean, Microbes
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Locality and diel cycling of viral production revealed by a 24 h time course cross-omics
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Analysis of critical and redundant vertices in controlling directed complex networks using
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４．参考資料
141
146

4-1.平成３０年度公募要領
4-2.平成３０年度採択課題一覧－ix－

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2018-26
Study of the reaction mechanisms of radical polymerization utilizing thereactivity of organotellurium compounds
Yasuyuki Nakamura

National Institute for Materials Science

Objective and Results of This Work. The mechanism of termination reaction in the radical
polymerization, i.e. the selectivity of a disproportionation and a combination, and the factors affecting them,has not been unclear and controversial. In this research with Prof. Shigeru Yamago supported by the
Collaborative Research Program of the ICR, we carried out the model study of the termination reaction toclarify the effect of solvent viscosity, especially “microviscosity”, on the diffusion of radical and thetermination mechanism focusing on the solvent cage effect.
Azo compound V-601 (1) and organotellurium compound (2) were used as the sources of radicals underphotoirradiation at various temperature and solvents with different viscosity (Scheme 1). The diffusion
efficiency (Fd) of the generated radical from the initial solvent cage was determined by the reaction in thepresence or absence of PhSD as a radical scavenger. The reactions revealed the Fd of radicals from 1 and theselectivity of a disproportionation and a combination (D/C) of encountered diffused radicals (D(d)/C(d)) arestrongly affected by the solvent viscosity, and Fd and D(d)/C(d) showed respective good correlations withmicroviscosity (ηmicro) calculated from Einstein-Stokes equation and DOSY NMR measurements (Figure 1).
In contrast, the selectivity of caged radical pair (D(c)/C(c)) was rather insensitive. On the other hand, thephotolysis of 2 showed the diffusion of all radical generated and the determined D/C was well matched with
D(d)/C(d) of 1. The difference in viscosity dependence between D(c)/C(c) and D(d)/C(d) is explained by the spinstate of the radical pair inside and outside the cage and the spin state dependent configurational changes of
the radical pair upon their collision. As the configurational change of the radicals associates the displacement
and reorganization of solvents around the radicals, the termination outside the cage which requires largerchange than that inside the cage is highly viscosity dependent.
Publications. 1) Li, X.; Ogihara, T.; Abe, M.; Nakamura, Y.; Yamago, S. Manuscript Submitted. 2) Li, X.;
Nakamura, Y.; Yamago, S. 67th Symposium on Macromolecules (SPSJ), 2018, 2B12.

3ln(D/C)

2
1
0
-2.5

-2.0

C6D6
D(c)/C(c)D(d)/C(d)
8d

－26－

-1.5
-1.0
lnmicroDMSO-d6
D(c)/C(c)D(d)/C(d)8d-0.5
PEG400D(c)/C(c)D(d)/C(d)8d0.02018-27－27－

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2018-102（国際）Study on emergent spin-orbit phenomena in artificial superlattices
without structural inversion symmetry
Sanghoon Kim University of Ulsan

Due to the disadvantage of the hard-disk drive which is highly energy-consuming andslow, scientists are recently focusing on the racetrack type magnetic storage technique.
The racetrack type memory uses an electrode as the memory itself. When the thin-film
electrode is made from magnetic material, we can make the magnetic object such as amagnetic domain wall or Skyrmions as shown in Fig. 1 (a) and (b), then, move themagnetic object flowing current into the electrode. To control the magnetic object
efficiently, the electrode should have a special energy term, which is called
Dzyaloshinskii-Moriya interaction (DMI). Once an electrode has DMI, successivechange of magnetization direction shows chirality as shown in Fig 1(c), thereby
magnetic objects can be topologically stable even with only a few-nanometer scale.
These chiral objects find the potential for applications in ultra-high density, low-energy,
and high-speed memory devices because they are stable due to topological protectionand easy to move with high efficiency. However, clear microscopic origin of DMI has
not been reported yet while there are, currently, so many element-by-element casestudies.

Figure 1. (a) Magnetic domain wall in a ferromagnetic nanostrip. (b) A skyrmion. (b) 1
dimensional chiral spin structure. D is the DMI energy vector. The spin alignment showschirality (mirror symmetry).

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Reprinted from Bull. Chem. Soc. Jpn., 92, 661–663 (2019)with permission from The Chemical Society of Japan.

Document type: Article

Short Article

Systematic Synthesis and Crystal
Structures of Tetraaryltellurium
Compounds Ar4TeIV #Sho Kobayashi, Koh Sugamata,and Mao Minoura*
Department of Chemistry, College of Science,
Rikkyo University, 3-34-1 Nishi-Ikebukuro,
Toshima-ku, Tokyo 171-8501, Japan

Figure 1. 1­4 and related organochalcogen(IV) compounds.
washed withhexaneM. Minoura

ArX+ n-BuLi(X = Br or I)

E-mail: minoura@rikkyo.ac.jp
Received: December 4, 2018; Accepted: December 8, 2018;
Web Released: December 15, 2018

4.5 ArLi +

TeCl4

ArLi
white solid

hexanerecryst. with
Et2O
Et2O

Ar4Te
yellow solid

Scheme 1. Synthesis of 1­4.

Abstract
Hypervalent tetraaryltellurium(IV) compounds of thetype Ar4TeIV (1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar =p-t-BuC6H4; 4: Ar = p-F3CC6H4) were prepared via a convenient
one-pot reaction between the isolated corresponding ArLi reagent and TeCl4. X-ray crystallographic analyses of 1­4 revealed
distorted pseudo-trigonal-bipyramidal (TBP) structures for Ar4Te
and the TBP character was analyzed by the dihedral angle
method.
Keywords: Hypervalent j Tellurium j Berry pseudorotation

1. Introduction
Organotellurium compounds have attracted interest as potential
precursors for organic synthesis1 and tellurium-containing nanomaterials.2 Moreover, the structural chemistry of organotellurium
compounds has also received substantial attention due to thevariable oxidation states of tellurium.3 Given that divalent organotellurium compounds have been characterized extensively by
X-ray crystallography (>1000 examples), it is rather surprisingthat only four examples of structurally deﬁned tetraorganotellurium(IV) compounds have been reported,4 especially consideringthat signiﬁcant attention has been focused on the structural properties of the so-called hypervalent bonds in chalcogen(IV) compounds.5 In 1982, Ziolo et al. reported a distorted pseudo-trigonalbipyramidal (TBP) crystal structure for Ph4Te with long apical andshort equatorial C­Te bonds.4a It should be noted that this ﬁrst
characterization of the solid-state structure of such a tetraorganotellurium(IV) compound was only achieved 30 years after the ﬁrst
isolation of Ph4Te by Wittig in 1952.6 The lack of systematic
structural studies to examine hypervalent bonds in detail is mainly
due to the instability of tetraorganotellurium(IV) compounds.4,5For example, Ph4Te easily decomposes in the presence of atmospheric moisture and/or oxygen, halogen-containing solvents, andupon heating.7 As for the isolation of Ph4Te, the only method
suitable for its puriﬁcation is recrystallization.4­7 Hellwinkel et al.
have developed a stabilization method that is based on the formation of ﬁve-membered rings containing a chalcogen(IV) atom,
using a biphenylene ligand instead of two phenyl groups.8 Anothereﬀective and powerful stabilization method for hypervalent compounds has been established by Martin et al.; the bidentate Martin
ligand can stabilize hypervalent chalcogen(IV) molecules by theconstruction of ﬁve-membered rings containing the hypervalentatom and the strong electron-withdrawing properties of the ligand,although oxygen atom(s) are bound to the chalcogen(IV) atomin the ring system (Figure 1).9 The paucity of bonding parameters
on hypervalent tetraorganotellurium(IV) compounds in which thetellurium atom is bound to carbon substituents stimulated us tosynthesize tetraaryltellurium compounds of the type Ar4TeIV(1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar = p-t-BuC6H4; 4: Ar =p-F3CC6H4) in order to elucidate their crystal structures andexamine their hypervalent bonds.
2. Results and Discussion
During the course of our study of hypervalent compounds, wehave found that impurities such as alkyl halides or excess Li
reagent accelerate the deterioration of Ar4TeIV; therefore, we used
the isolated ArLi reagent instead of the in-situ-generated ArLi
reagent for the isolation of 1­4.10 The ArLi reagents were preparedby treatment of the corresponding ArX (X = Br or I) with n-BuLi
in hexane for 1 h at 0 °C. The thus obtained white ArLi reagentswere collected by ﬁltration and subsequently extracted into Et2O.
Then, LiX was removed by ﬁltration to aﬀord ArLi as white solids
after the removal of the solvent in vacuo. 1­4 were obtained fromthe reaction of TeCl4 with the corresponding ArLi in Et2O at¹78 °C. This one-pot reaction aﬀorded 1­4 in moderate yield as
pale yellow crystalline solids after recrystallization from Et2O
(Scheme 1).
The 125Te NMR resonances of 1­4 were observed at 512, 500,
515, and 504 ppm, respectively. In the 1H and 13C spectra of 1­4(and the 19F NMR spectrum of 4), only one set of aryl groups wasobserved at room temperature in C6D6 (Figure 2), suggesting rapid
Berry pseudorotation (BPR)11 in solution between TBP structures
via square pyramidal (SP) transition structures (Figure 3), which iscommon for pentaorgano-element compounds.12 In this sense, eachof the spectra reﬂects an averaged structure in the BPR and the
dynamic nature of such tetraorganotellurium(IV) compounds.

Bull. Chem. Soc. Jpn. 2019, 92, 661–663 | doi:10.1246/bcsj.20180380© 2019 The Chemical Society of Japan | 661－131－

The unambiguous identiﬁcation of 1­4 was accomplished by
X-ray crystallographic analysis (Figure 4).13 For 1­4, pseudo-TBP
structures with elongated Capical­Te bonds and Cequatorial­Te bonds
were observed (vide infra). Although the previously reported
crystal structure of Ph4Te¢1/8C6H6 revealed four independent
molecules per P-1 unit cell with half a molecule of benzene,
crystals of 1 contain only one independent molecule of Ph4Te in a
lattice of higher symmetry (P21/n), even when the single crystals
were obtained from a benzene solution.
In the unit cells of 1­4, the tellurium centers exhibit weakintermolecular contacts in the crystalline state, evident from theshortest Te-Te and Te-element distances (1: 4.181 ¡ (Te), 3.202(H); 2: 4.639 (Te), 3.231 (H); 3: 5.735 (Te), 3.858 (H); 4: 9.081(Te), 3.633 (F)). The corresponding sums of the van der Waals
radii (¡) are 4.12 (Te£Te), 3.26 (Te£H), and 3.53 (Te£F).14 All
Capical­Te bonds in 1­4 are signiﬁcantly longer than the Cequatorial­
Te bonds and the substituents at the para-positions of the aryl rings
induce only small diﬀerences among 1­4 and a clear trend in the
C­Te bond lengths was not observed. In an ideal TBP structure, theCapical­Te­Capical bond angle should be 180°; yet, narrower bondangles were observed around the Te atom in 1­4 due to repulsion
between the C­Te bonding electrons and the corresponding lonepair of electrons (Table 1).
The TBP character (%) of 1­4 and that of previously reported
Ph4Te¢1/8C6H6 were calculated by the dihedral angle method15
based on the observed bond angles around the Te atoms.
It is noteworthy that the tellurium environment of 1 showed low
TBP character (55%), while those in 2 (84%), 3 (93%), 4 (87%),
and Ph4Te¢1/8C6H6 (93%) exhibit high TBP character. This may
be rationalized considering the diﬀerences in the packing latticeenergy of the crystalline state of Ph4Te (P21/n vs. P-1).16
3. Conclusions

Figure 2.

1

H NMR spectrum of 2.

a: apical

b: basal

e: equatorial

e
e

pivot
a
TBP

e
a

b

b

pivot

b
SP
(Transision structure)

a

e
pivot

We have developed a convenient one-pot route to hypervalenttetraorganotellurium compounds 1­4. The results of NMR spectroscopy measurements and X-ray crystallographic analyses indicatethat 1­4 exhibit a dynamic behavior and Berry pseudorotation insolution. Diﬀerent trigonal bipyramidal character values were calculated for 1­4 in the solid state and attributed to diﬀerent packing
arrangements.
We are currently carrying out further structural characterizationsof these reactive hypervalent molecules and the corresponding
results will be reported elsewhere in due course.
4. Experimentale
TBP

Preparation of Ph4Te (1). A solution of PhI (10.0 g, 5.46 mL,
49.0 mmol) in hexane (100 mL) was treated with n-BuLi (31.2 mL,
49.0 mmol, 1.57 M) at 0 °C. After the mixture was stirred for 30
min at 0 °C and 1 h at room temperature, the reaction mixture wasﬁltered and extracted with Et2O. After removal of all volatiles, theresidue was washed with hexane and ﬁltered to give PhLi as awhite solid. A solution of PhLi (3.34 g, 37.0 mmol) in Et2O (40mL) was added to a solution of TeCl4 (2.38 g, 8.82 mmol) in Et2O(100 mL) at ¹78 °C. After stirring for 2 h at room temperature, themixture was ﬁltered and recrystallized from Et2O at ¹35 °C togive Ph4Te (2.21 g, 5.0 mmol, 57.5%) as a pale yellow solid: mp
118 °C; 1H NMR (400 MHz, C6D6, 298 K) δ 6.97­7.01(m, 12H),
7.42­7.47 (m, 8H); 13C NMR (100 MHz, C6D6, 298 K) δ 128.8,
133.5, 149.8; signals for the para-carbon atom could not be identiﬁed due to overlap with solvent signals; 13C NMR (100 MHz,
CD3CN, 298 K) δ 128.6, 129.4, 133.7, 150.6; 125Te NMR (126MHz, C6D6, 298 K) δ 512.3.
X-ray Crystal Structure Analysis. Pale yellow single crystalsof 1­4 suitable for X-ray diﬀraction measurements were obtained

Figure 3. Schematic view of the Berry pseudorotation interconversion between two trigonal bipyramidal (TBP) structures
via a square pyramidal (SP) transition structure.

Figure 4. ORTEP drawings of 1­4 with thermal ellipsoids at
50% probability.

Table 1. Selected bond lengths (¡) and angles (°) of 1­4 and (C6H5)4Te¢1/8C6H6
C1ap-Te C2ap-Te C3eq-Te C4eq-Te C1ap-Te-C2ap C3eq-Te-C4eq R-factor Space Gp. Z Z'
Compound
4 1(C6H5)4Te (1)2.245(3) 2.239(3) 2.162(3) 2.161(3)157.3(1)129.3(2)
2.22
P21/n
2 1
(p-H3CC6H4)4Te (2) 2.279(2) 2.303(2) 2.123(3) 2.132(3)172.26(8)104.85(9)
3.07
P1
4 2
(p-t-BuC6H4)4Te (3) 2.281(2) 2.296(2) 2.134(2) 2.130(2)166.10(8)110.96(9)
2.94
P1
2 1
(p-F3CC6H4)4Te (4) 2.271(2) 2.291(2) 2.135(2) 2.143(2)161.78(8)114.41(8)
2.38
P1
8 4
(C6H5)4Te·1/8C6H64a 2.27(1) 2.30(1) 2.13(1) 2.16(1)168.3(4)110.0(4)6.5
P1662 | Bull. Chem. Soc. Jpn. 2019, 92, 661–663 | doi:10.1246/bcsj.20180380－132－© 2019 The Chemical Society of Japan

from recrystallization from benzene or Et2O. Diﬀraction data
were collected at ¹173 °C using a Bruker APEX II diﬀractometerequipped with an APEX II CCD detector with MoKα radiation.
A wavelength of ­ = 0.71069 ¡ and single crystals of 0.10 ©
0.10 © 0.10 mm3 were selected in order to reduce absorption. Data
reduction was performed using Bruker SAINT. Structures weresolved by direct methods (SHELXT-2014)17a and reﬁned against F 2
by weighted full-matrix least-squares (SHELXL-2014).17b
The crystal data, data correction, and reﬁnement details are
summarized in Table S1.
This work was supported by the Japanese Ministry of Education,
Culture, Sports, Science, and Technology (MEXT) via a Grant-inAid for Science Research on Innovative Areas (15H00962; StimuliResponsive Chemical Species), by the MEXT-supported Program
for the Strategic Research Foundation at Private Universities(2013­2017), the Japan Society for the Promotion of Science(JSPS) via KAKENHI grants JP24550063 and JP15K05439, and by
the Collaborative Research Program of the Institute for Chemical
Research, Kyoto University (grants 2017-102 and 2018-106).
M. M. is grateful for ﬁnancial support from the Rikkyo University
Special Fund for Research.
Supporting Information
General experimental procedures and materials, as well as
X-ray crystallographic and spectroscopic data (1H, 13C, 19F, and125
Te NMR spectra) are available in the Supporting Information. This material is available on https://doi.org/10.1246/bcsj.
20180380.
References# This paper is dedicated to Emeritus Professor Naomichi
Furukawa on the occasion of his 82nd birthday.
1 N. Petragnani, Tellurium in Organic Synthesis, 2nd ed.,Academic Press, New York, 2007. doi:10.1016/B978-0-08-0453101.X5000-X; R. A. Zingaro, K. Irgolic, in Tellurium, ed. by W. C.
Cooper, Von Nostrand Reinhold, New York, 1971, pp. 184­279; K. Y.
Irgolic, in Houben-Weyl, Methods of Organic Chemistry, ed. by D.
Klamann, Georg Thieme, Stuttgart, 1990, Vol. E 12b; F. S. Guziec, Jr.,
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Pattenden, Pergamon, Oxford, 1995, Vol. 3, pp. 381­401. doi:10.
1016/b0-08-044705-8/00253-3.
2 A. Redaelli, in Phase Change Memory: Device Physics,
Reliability and Application, 1st ed., Springer, 2018. doi:10.1007/9783-319-69053-7; A. V. Kolobov, J. Tominaga, Chalcogenides: Metastability and Phase Change Phenomena, in Springer Series inMaterials Science, 2012. doi:10.1007/978-3-642-28705-3.
3 W. Nakanishi, S. Hayashi, M. Hashimoto, M. Arca, M. C.
Aragoni, V. Lippolis, in Organic Selenium and Tellurium Compounds, in PATAI’S Chemistry of Functional Groups, ed. by Z.
Rappoport, Wiley, 2014, Vol. 4, Part 2, pp. 885­972. doi:10.1002/
9780470682531.pat0701.
4 Compounds containing C­Te bonds were analyzed in
Cambridge Structural Database (CSD); Ver. 5.39, May, 2018.

a) Ph4Te¢0.125C6H6: C. S. Smith, J. S. Lee, D. D. Titus, R. F.
Ziolo, Organometallics 1982, 1, 350. b) Bis(2,2¤-Biphenylylene)Te: S.
Sato, N. Kondo, N. Furukawa, Organometallics 1994, 13, 3393.
c) Me4Te: A. J. Blake, C. R. Pulham, T. M. Greene, A. J. Downs, A.
Haaland, H. P. Verne, H. V. Volden, C. J. Marsden, B. A. Smart, J. Am.
Chem. Soc. 1994, 116, 6043. d) (C6F5)4Te: D. Naumann, W. Tyrra,
H. T. M. Fischer, S. Kremer, Z. Anorg. Allg. Chem. 2007, 633, 527.
5 Chemistry of Hypervalent Compounds, ed. by K.-y. Akiba,
Wiley-VCH, 1999; J. I. Musher, Ann. N.Y. Acad. Sci. 1972, 192, 52; D.
Hellwinkel, Ann. N.Y. Acad. Sci. 1972, 192, 158; L. Lunazzi, J. C.
Martin, in Organic Sulfur Chemistry, ed. by F. Bernardi, I. G.
Csizmadia, A. Mangini, Elsevier, Amsterdam, 1985, pp. 408­483; J.
Bergman, L. Engman, L. Sidén, in The Chemistry of Organic Selenium
and Tellurium Compounds, ed. by S. Patai, Z. Rappoport, John Wiley& Sons, New York, 1986, Vol. 1, pp. 517­558. doi:10.1002/
9780470771761.ch14; M. R. Detty, M. B. O’Regan, in TelluriumContaining Heterocycles, ed. by E. C. Taylor, John Wiley and Sons,
New York, 1994, pp. 425­490.
6 G. Wittig, H. Fritz, Justus Liebigs Ann. Chem. 1952, 577, 39.
7 D. H. R. Barton, S. A. Glover, S. V. Ley, J. Chem. Soc., Chem.
Commun. 1977, 266; S. A. Glover, J. Chem. Soc., Perkin Trans. 1
1980, 1338.
8 D. Hellwinkel, G. Fahrbach, Tetrahedron Lett. 1965, 6, 1823;
D. Hellwinkel, G. Fahrbach, Chem. Ber. 1968, 101, 574; D.
Hellwinkel, G. Fahrbach, Justus Liebigs Ann. Chem. 1968, 715, 68;
S. Ogawa, Y. Matsunaga, S. Sato, I. Iida, N. Furukawa, J. Chem. Soc.,
Chem. Commun. 1992, 1141; S. Ogawa, S. Sato, T. Erata, N.
Furukawa, Tetrahedron Lett. 1992, 33, 1915.
9 E. F. Perozzi, J. C. Martin, J. Am. Chem. Soc. 1979, 101, 1591;
R. S. Michalak, S. R. Wilson, J. C. Martin, J. Am. Chem. Soc. 1984,
106, 7529.
10 All manipulations were carried out in an argon-ﬁlled glovebox
with heavy-walled Schlenk ﬂasks. CAUTION: Solid ArLi compounds
may be explosive, especially those that contain ﬂuorine.
11 R. S. Berry, J. Chem. Phys. 1960, 32, 933.
12 P. Gillespie, P. Hoﬀman, H. Klusacek, D. Marquarding, S.
Pfohl, F. Ramirez, E. A. Tsolis, I. Ugi, Angew. Chem., Int. Ed. Engl.
1971, 10, 687; M. Minoura, T. Mukuda, T. Sagami, K.-y. Akiba, J. Am.
Chem. Soc. 1999, 121, 10852; M. Saito, S. Imaizumi, T. Tajima, K.
Ishimura, S. Nagase, J. Am. Chem. Soc. 2007, 129, 10974.
13 Crystallographic data for 1­4 have been deposited at The
Cambridge Crystallographic Data Centre (CCDC) under reference
numbers CCDC 1881325-1881328. These can be obtained free ofcharge from the CCDC via www.ccdc.cam.ac.uk/structures.
14 A. Bondi, J. Phys. Chem. 1964, 68, 441.
15 R. Hoﬀmann, J. M. Howell, E. L. Muetterties, J. Am. Chem.
Soc. 1972, 94, 3047; R. R. Holmes, Prog. Inorg. Chem. 1984, 32, 119.
16 To gain further insight into the molecular structure of Ph4Te(1), DFT calculations were performed using Gaussian 09 program. The
geometry of 1 was fully optimized at the M062X level using the
LANL2DZ for Te and 6-31G* for the others.
The optimized structure of 1 (NIMAG = 0, SCF = verytight,
Grid = ultraﬁne) is a TBP structure: C1ap-Te: 2.2450; C2ap-Te:
2.2568; C3eq-Te: 2.1358; C4eq-Te: 2.1358 ¡; C1ap-Te-C2ap: 168.4;
C3eq-Te-C4eq: 108.4 (°). The atom cooridinates were shown in
Table S2.
17 a) G. M. Sheldrick, Acta Crystallogr., Sect. C 2015, 71, 3.
b) G. M. Sheldrick, Acta Crystallogr., Sect. A 2015, 71, 3.

Bull. Chem. Soc. Jpn. 2019, 92, 661–663 | doi:10.1246/bcsj.20180380© 2019 The Chemical Society of Japan | 663－133－

Reprinted from J. Magn. Magn. Mater., 475, 721–726 (2019)with permission from Elsevier.

Journal of Magnetism and Magnetic Materials 475 (2019) 721–726

Contents lists available at ScienceDirect

Journal of Magnetism and Magnetic Materials
journal homepage: www.elsevier.com/locate/jmmm

Research articles

Perpendicular magnetic anisotropy and tunneling conductivity of epitaxial
cobalt-ferrite (0 0 1) films grown on nonmagnetic metal films
Katsuyoshi Narusea, Masaaki Tanakaa, , Kosuke Nomuraa, Takuya Taniguchib,c, Syuta Hondad,e,Teruo Onob,e, Ko Mibua⁎a

Graduate School of Engineering, Nagoya Institute of Technology, Nagoya, Aichi 466-8555, Japan
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japanc
Department of Physics, Technical University of Munich, Garching 85749, GermanydDepartment of Pure and Applied Physics, Kansai University, Suita, Osaka 564-8680, Japane
Center for Spintronics Research Network, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japanb

A RT IC LE IN F O
Keywords:
Spintronics
Cobalt ferrite
Perpendicular magnetic anisotropy

A BS TR A C T

We successfully fabricated perpendicularly magnetized cobalt-ferrite Cox Fe3 x O4 + (0 0 1) films on nonmagnetic
metal TiN (0 0 1) films. We found that the in-plane lattice constant of the Cox Fe3 x O4 + (0 0 1) films was larger
than the out-of-plane lattice constant. This lattice strain induced perpendicular magnetic anisotropy, and squarehysteresis curves were observed in out-of-plane magnetic fields for the Cox Fe3 x O4 + (x = 0.4 ∼ 0.6) films. With
the decrease of the Co composition from x = 1 to x = 0, the Cox Fe3 x O4 + films approached not to conductive
Fe3O4 but to insulating -Fe2 O3 accompanying cation vacancies in the cubic spinel structure. The good tunnelingconductivity character was observed for the Cox Fe3 x O4 + tunnel junctions. The results open up a possibility that
insulating Cox Fe3 x O4 + films can be applied to elements of perpendicularly magnetized spintronics devices.

1. Introduction
Cobalt-ferrite (CoFe2 O4 ) has an inverse spinel AB2 O4 structure inwhich Fe3 + ions occupy the tetragonal site (A-site) and a half of theoctagonal site (B-site) and Co2 + ions occupy the rest of the B site. The
cobalt-ferrite exhibits good insulating character, high magnetocrystalline anisotropy [1], and large magneto-elastic constants [2]. Its film
forms also show high magnetic anisotropy and high coercivity [3–7].
Such magnetic insulator films can be used for the application to thespin-current source via the tunneling spin filter effect [8–11] and to thecurrent-less spintronics devices using spin waves [12].
It has been reported that cobalt-ferrite (0 0 1) films grown epitaxially on MgO (0 0 1) substrates show especially large perpendicularmagnetic anisotropy (PMA) [5–7]. Because the lattice constant of cubic
CoFe2 O4 (8.38 Å ) is slightly smaller than twice the lattice constant of
cubic MgO (4.21 Å ), in-plane tensile strain is induced to the epitaxial
CoFe2 O4 (0 0 1) films. The PMA of the CoFe2 O4 (0 0 1) films is thought tooriginate from the lattice-strain-induced magneto-elastic effect [13,14].
Niizeki et al. have reported that the squareness of out-of-plane hysteresis curves of the cobalt-ferrite films can be improved by tuning the CoFe composition [15,16]. However, there have been no reports of perpendicularly magnetized cobalt-ferrite films prepared on conductive⁎

underlayers. If perpendicularly magnetized cobalt-ferrite films withhigh squareness in the perpendicular hysteresis curves can be grown on
conductive underlayers, they would be applicable to perpendicularly
magnetized spintronics devices.
In this paper, we report successful growth of perpendicularly magnetized cobalt-ferrite (Cox Fe3 x O4 + (0 < x < 1)) (0 0 1) films on
nonmagnetic cubic metal TiN (001), whose lattice constant is 4.24 Å .
Here, the possibility of cation vacancies in the spinel structure is expressed with the correction coefficient of excess oxygen . The crystal
structure of Cox Fe3 x O4 + films was investigated to evaluate the lattice
distortion. The valency of Fe ions in the Cox Fe3 x O4 + films was examined to estimate the cation vacancies. First principles calculation was
performed to confirm insulating character for the off-stoichiometric
Cox Fe3 x O4 + . The tunneling conductivity of the Co0.54 Fe2.46 O4 + thinfilms was examined to see the applicability to perpendicularly magnetized spintronics devices.
2. Experimental

Cox Fe3 x O4 + (x = 1.00, 0.90, 0.75, 0.60, 0.54, 0.34, 0.24, 0.12,
and 0.00) films of 20 nm in thickness were grown on TiN films of 15 nm
in thickness on MgO (0 0 1) substrates by a pulsed laser deposition

Corresponding author.
E-mail address: mtanaka@nitech.ac.jp (M. Tanaka).

https://doi.org/10.1016/j.jmmm.2018.12.025
Received 28 September 2018; Received in revised form 2 December 2018; Accepted 7 December 2018
Available online 08 December 20180304-8853/ © 2018 Elsevier B.V. All rights reserved.

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a shadow mask was placed between the target material and the substrates, was used in order to reduce the formation of droplets andparticulates [17]. The typical deposition rate was 0.03 nm/s.
The compositional ratio of Co and Fe of the prepared Cox Fe3 x O4 +films was calibrated using an electron probe micro analyzer. The film
thickness was measured using a small angle X-ray reflection technique.
The crystal structures and out-of-plane lattice constants of theCox Fe3 x O4 + films were characterized by an X-ray diffraction (XRD)
technique with Cu K radiation. In order to investigate the in-plane andout-of-plane strains, the reciprocal space map of X-ray diffraction intensity was obtained for the Co0.54 Fe2.46 O4 + (60 nm) film. Magnetic
hysteresis loops were measured using a superconducting quantum interference device magnetometer at 300 K. To examine the valency of Fe
ions in the Cox Fe3 x O4 + films, 57Fe Mössbauer spectroscopy was performed by means of conversion electron Mössbauer spectroscopy at
300 K.
In order to investigate the tunneling conductivity of theCox Fe3 x O4 + films, Au (100 nm)/Cr (2 nm)/Co0.54 Fe2.46 O4 + (3 nm)/TiN (20 nm) layered structures were prepared on MgO (0 0 1) substrates, and fabricated into tunnel junctions comprising circle-shaped
pillars with the in-plane size of several µ m using photolithography andAr ion etching. The current-voltage measurements were carried out
using a standard dc four-probe method.

Fig. 1. -2 XRD patterns for the Cox Fe3 x O4 + (x = 1.00, 0.90, 0.75, 0.60,
0.54, 0.34, 0.24, 0.12, and 0.00) films grown on TiN films.

3. Results
Fig. 1 shows the -2 XRD patterns of the Cox Fe3 x O4 + /TiN films.
The XRD patterns exhibit clear Cox Fe3 x O4 + (004) and Cox Fe3 x O4 +(0 0 8) diffraction peaks with satellite peaks. No peaks related to theother planes of Cox Fe3 x O4 + were detected, which means that theCox Fe3 x O4 + films are highly oriented along the [0 0 1] directions on
the MgO (0 0 1) substrates. The satellite peaks observed in the XRD
patterns indicate that the atomic layers of the Cox Fe3 x O4 + films arehighly oriented and the interfaces are flat. The Cox Fe3 x O4 + (0 0 4) andCox Fe3 x O4 + (0 0 8) diffraction peaks shift to higher angles with decreasing the Co composition.
Fig. 2(a) shows the Co composition dependence of the out-of-planelattice constants a of the Cox Fe3 x O4 + films estimated from the -2
XRD patterns. It was shown that the lattice constant of theCox Fe3 x O4 + films decreases with the decrease of the Co composition.
Fig. 2(b) shows the reciprocal space map around the Cox Fe3 x O4 +(115) peak in the horizontal Q(1 1 0) and vertical Q(0 0 1) directions for
the Co0.54 Fe2.46 O4 + (60 nm)/TiN film. The in-plane a// and out-of-planea lattice constants are estimated to be 8.42 Å and 8.31 Å , respectively.
This means that the in-plane tensile strain is induced in the
Cox Fe3 x O4 + film by the lattice mismatch. The unit cell volume ofCox Fe3 x O4 + decreases with decreasing the Co composition. This implies that the Cox Fe3 x O4 + approaches not to conductive Fe3 O4(8.39 Å ) but to insulating -Fe2 O3 (8.33 Å ) as x decreases. These results
are consistent with a previous report on Co0.8 Fe2.2 O4 films grown on Pt(1 1 1) films [18].
Fig. 3 shows the typical magnetic hysteresis loops at 300 K with theout-of-plane and in-plane directions for the Cox Fe3 x O4 + (x = 1.00,
0.54, 0.34, and 0.12) films. The hysteresis loops clearly show that theCox Fe3 x O4 + films have PMA and sharp switching of the magnetizationis realized in the out-of-plane hysteresis of the x = 0.54, 0.34, and 0.12
films. Fig. 4(a) shows the Co composition dependence of the squarenessratio, the ratio of remanence magnetization Mr with respect to the saturation magnetization Ms , of out-of-plane hysteresis loops. The
squareness ratio increases with the decrease of the Co composition andhigh squareness ratios of more than 0.8 are realized for the

Fig. 2. (a) Vertical lattice constants a of the Cox Fe3 x O4 + films as a function of
the Co composition. The blue cross is a of the Co0.54 Fe2.46 O4 + (60 nm) film. (b)Reciprocal space map around the (1 1 5) peak in the horizontal Q(1 1 0) andvertical Q(0 0 1) directions for the Co0.54 Fe2.46 O4 + (60 nm) film.

(PLD) technique. The TiN films were grown at the substrate temperature of 500 °C under the background nitrogen pressure of 5.0 Pa using
commercial TiN targets (Kojundo Chemical Laboratory Co. Ltd.). The
Cox Fe3 x O4 + films were grown at the substrate temperature of 300° C
under the background oxygen pressure of 6.0 Pa using homemade
Cox Fe3 x O4 + targets, which were prepared from powder mixtures of
CoO and Fe3 O4 by a conventional ceramic fabrication technique. A
neodymium-doped yttrium-aluminum-garnet laser at the double frequency ( = 532 nm) with the pulse width of 6 ns and the repetition
rate of 30 Hz was used. The energy density of the laser beam wascontrolled to 1 J/cm2 by an optical lens. The eclipse PLD method, where

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Fig. 3. In-plane and out-of-plane hysteresis loops of the Cox Fe3 x O4 + films at 300 K. (a) x = 1.00, (b) x = 0.54, (c) x = 0.34, and (d) x = 0.12.

Co0.54 Fe2.46 O4 + /TiN tunnel junction with a junction diameter of 12 µ m
at 40 K and 300 K. A nonlinear tunnel-like I-V curve was obtained.
Fig. 6(b) shows the temperature dependence of the resistance of thetunnel junction at 500 mV bias voltage. The resistance increased dramatically with decreasing temperature, which indicates that the conductivity of the junction is governed by the tunneling current.

Cox Fe3 x O4 + (x = 0.1 ∼ 0.6) films. A similar tendency is also observedfor Cox Fe3 x O4 + films on MgO (001) substrates [15,16]. The squareness ratio dramatically decreases for the Fe3 O4 + (x = 0.00) film.
Fig. 4(b) shows the saturation magnetization Ms as a function of the Cocomposition. The red and green dashed lines are the saturation magnetization of bulk CoFe2 O4 (370 emu/cm3) and -Fe2 O3 (430 emu/cm3),
respectively. The saturation magnetization of the Cox Fe3 x O4 + films
varied unsystematically with respect to the Co composition. Fig. 4(c)shows the coercive field Hc as a function of Co composition. The
coercive field Hc decreases with the decrease of the Co composition.
Fig. 4(d) shows the PMA energy density Ku of the Cox Fe3 x O4 + films
estimated from the out-of-plane and in-plane hysteresis loops as afunction of the Co composition. The PMA energy density of about
4 × 106 erg/cm3 is obtained for the Cox Fe3 x O4 + (x = 0.4 ∼ 0.9)
films.
Fig. 5 shows the 57Fe Mössbauer spectrum of the Co0.54 Fe2.46 O4 +film together with the spectra of Fe3 O4 and -Fe2 O3 films [19]. The
spectrum shows a magnetically split sextet pattern. The second and fifthlines are very weak, indicating that the alignment of the magnetic
moments in this sample is perpendicular to the film plane, that is, theCo0.54 Fe2.46 O4 + film has PMA [20]. The red solid line is a fitting line.
Unlike the spectrum for Fe3 O4 , which is composed of two sextet, one
from Fe3 + at the A-site, the other from Fe2.5 + at the B-site, the spectrum
for Co0.54 Fe2.46 O4 + has a symmetric feature as the spectrum for -Fe2 O3.
Fig. 6(a) shows the current–voltage curves of the Au/Cr/

4. Discussion
It is evident from the XRD patterns that the Cox Fe3 x O4 + films aregrown epitaxially on the TiN (001) films and tetragonally distorted. The
in-plane and out-of-plane lattice strain for the Co0.54 Fe2.46 O4 + film area 0)/ a 0) = 0.60%(=(aandestimatedtobe// (=(a//a0)/ a0) = 0.72%, respectively. Here, a0 (8.36 Å ) is the bulk lattice
constant of Co0.54 Fe2.46 O4 + obtained from Vegard’s law on bulk endmaterials. Poisson ratio of the Co0.54 Fe2.46 O4 + film is estimated as1) [5]. In comparison with the
0.29 from the equation // / = 2 /(lattice strain for the Co0.75Fe2.25 O4 + /MgO film which was grown by amagnetron sputtering method ( // = 0.405% , = 1.108% ) [15], the inplane lattice strain of the Co0.54 Fe2.46 O4 + /TiN film is larger.
As in the case of the CoFe2 O4 /MgO films [13,14], the PMA of theCox Fe3 x O4 + /TiN films is thought to originate from the lattice-straininduced magneto-elastic effect. The squareness ratio of our
Cox Fe3 x O4 + /TiN films is higher than that of the Co0.75Fe2.25 O4 + /MgO
film [15]. Nevertheless, the estimated PMA energy density of our

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Fig. 4. Composition x of Cox Fe3 x O4 + dependence of (a) squareness Mr / Ms , (b) saturation magnetization Ms , (c) coercive field Hc , and (d) perpendicular magnetic
anisotropy energy density Ku .

zero. Because the large PMA of the Cox Fe3 x O4 + films is attributed to
the large magneto-elastic constants of Cox Fe3 x O4 + [14], the -Fe2 O3film, which has no Co2 + at the B-site and whose magneto-elastic effect issmall, cannot have large PMA.
The saturation magnetization Ms of the Cox Fe3 x O4 + films varied
unsystematically with respect to the Co composition. In previous researches about the cobalt ferrite film grown on the MgO substrates, thedecrease of Ms was attributed to the antiphase boundaries [21] and thecation vacancies [15]. It is speculated that unsystematic change in theexistence of antiphase boundaries and cation vacancies occurs in thepresent samples.
Because the Cox Fe3 x O4 + films have the spinel structure which isstabilized by the oxygen ions, oxygen (anion) vacancies would not be
predominant. The 57Fe Mössbauer spectrum in Fig. 5 indicates that Fe2 +ions, which cause B-site electron hopping conductivity [22], do notexist in the present Co0.54 Fe2.46 O4 + film, and that the Cox Fe3 x O4 +films
becomeclosertoferromagnetic
insulator3+, 1/3]O4) not to conductive Fe3 O4 (Fe3 + [Fe2 +,-Fe2 O3 (Fe3 + [Fe5/3
Fe3 +]O4) as the Co composition decreases from x = 1. Thus, there must
be vacancies at the cation site in order to preserve the electrical neutrality. This situation would make the sample structure deviated from
ideal inverse spinel structure, causing the unsystematic change in Ms
with respect to the Co composition.
In order to investigate the tunneling properties of off-stoichiometricFig. 5. Mössbauer spectra at 300 K for Fe3O4 , -Fe2 O3 , and Co0.54 Fe2.46 O4 + ,films. The spectra for Fe3O4 and -Fe2 O3 films are cited from Ref. 19.

Cox Fe3 x O4 + /TiN films is smaller than that of the Co0.75Fe2.25 O4 + /MgO
film. This is because the magnetization Ms of our Cox Fe3 x O4 + films islower than that of the Co0.75Fe2.25 O4 + /MgO films. The squareness ratioof the pure iron oxide (x = 0.00) film on the TiN (0 0 1) film is almost

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Cox Fe3 x O4 + films, we calculate the electronic structure for an optimized Co12 Fe56O96 super-cell structure shown in Fig. 7(a), which corresponds to Co0.53Fe2.47 O4.24 . The lattice structure is based on the-Fe2 O3 structure of previous study [23]. A- and B-sites have 24 and 48
cations, respectively. There are 24 Fe3 + ions at the A-site, and 32 Fe3 +ions, 12 Co2 + ions, and 4 vacancies at the B-site. The calculation is
performed using the VASP code with the PAW potentials [24] in the
GGA-PBE [25,26]. A correction of the Coulomb interaction U [27] of
4.5 eV is assumed for the Fe and Co ions [23]. The 400 eV cutoff energy
and the k sampling mesh of (k x , k y, k z ) = (9, 9, 3) were set. The calculated Ms is 403 emu/cm3 and the optimized lattice parameter a is
8.35 Å . The calculated Ms is larger than the experimental value of
280 emu/cm3. The lattice parameter a is similar than the values estimated by Vegard’s law. Fig. 7(b) shows the calculated spin-dependent
density of state for Co12 Fe56O96 . The band gaps of 2.06 eV and 1.87 eV
are open for spin-up state (majority spin state) and spin-down state(minority spin state), respectively. Hence, a spin-filtering effect is expected to occur when the electrons pass through this Co0.53Fe2.47 O4.24
film.
The I-V curves at 40 K were fitted using the Simmons’ equation [28]assuming a single tunnel barrier with the width of d and the height of .
In this equation, the tunneling current J is described by
J = A V + 0.0115

d2

0.03155

d

3/2

V3 ,

(1)

where V is the applied bias and A is an adjustable parameter. Thisequation leaves the barrier width d and the barrier height as freeparameters. The red line in Fig. 6(a) is a fitting curve. When the barrierheight is assumed to be 0.94 eV, the value of d is estimated to be
1.4 nm. The estimated barrier width is smaller than the designed barrier
width because the barrier width in the junctions is governed by regions
where the barrier is thinner. Nevertheless, the Cox Fe3 x O4 + film shows
good tunneling properties.
5. Conclusion
We have succeeded in fabricating perpendicularly magnetized
Cox Fe3 x O4 + films on nonmagnetic metal TiN films. The Cox Fe3 x O4 +films grown on the TiN (0 0 1) films were tetragonally distorted andshowed the lattice strain induced PMA. The Co2 + ions were replaced by
Fe3 + ions and vacancies and the Cox Fe3 x O4 + films were in the intermediate structure between ferromagnetic insulator CoFe2 O4 and-Fe2 O3. First principles calculation predicted that the Cox Fe3 x O4 +films have a good insulating character and the different barrier height
depending on the spin direction of tunneling electrons. The good tunneling conductivity was observed for the Cox Fe3 x O4 + junctions.
Additionally, the Cox Fe3 x O4 + is not expensive and has high Curie
temperature. It is expected that the Cox Fe3 x O4 + films can be applied
to the spin filtering of perpendicularly magnetized spintronics devices.
Acknowledgements
Fig. 6. (a) Current-voltage curve of the Au (100 nm)/ Cr (2 nm)/Co0.54 Fe2.46 O4 +(3.0 nm)/TiN (20 nm) tunnel junction at 40 K. Red line is a Simmons’s fitting
line. (b) Temperature dependence of resistance of the tunnel junction at 500 mV
bias voltage.

This work was supported by JSPS KAKENHI (Grant No: 25287086)
and by the Kazuchika Okura Memorial Foundation and Toukai
Foundation for Technology. The work was also supported by the
Collaborative Research Program of Institute for Chemical Research,
Kyoto University (grant Nos: 2016-60, 2017-58, and 2018-62).

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Journal of Magnetism and Magnetic Materials 475 (2019) 721–726

K. Naruse et al.

Fig. 7. (a) Crystal structure of the Co12 Fe56 O96 used in first principals calculation. The white, green, and purple spheres are O, Fe, and Co atoms, respectively. (b) The
local density of Co12 Fe56 O96 of spin up and spin down states as a function of energy E. The orange, green, and blue lines are the local density at the Fe(A), Fe(B), andCo sites, respectively. Fermi energy EF is located at E = 0.

References

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高エネルギー加速器研究機構加速器研究施設

量子科学技術研究開発機構

名古屋大学現象解析研究センター

高エネルギー加速器研究機構加速器研究施設

産業技術総合研究所

弘前大学大学院理工学研究科

近畿大学理工学部

2018-11 羽島 良一

2018-12 北口 雅暁

2018-13 佐伯 学行

2018-14 木野 幸一

2018-15 岡崎 雅明

2018-16 松尾 司

摂南大学基礎理工学機構

2018-7 長島 健

2018-10 照沼 信浩

大阪産業大学工学部電子情報通信工学科

2018-6 草場 光博

光産業創成大学院大学

香川大学国際希少糖研究教育機構

2018-5 加藤 志郎

2018-9 藤田 和久

関西大学化学生命工学部

2018-4 老川 典夫

大阪大学レーザーエネルギー学研究センター

大阪大学レーザー科学研究所

2018-3 藤岡 慎介

2018-8 時田 茂樹

大阪大学レーザー科学研究所

2018-2 有川 安信

研究代表者所属

東京理科大学工学部

研究代表者

2018-1 河合 武司

課題番号

小澤 文幸

小澤 文幸

岩下 芳久

岩下 芳久

岩下 芳久

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

2 萌芽的

2 発展的

1 発展的

1 発展的

1 萌芽的

1 発展的

分野選択型

岩下 芳久

1 発展的

分野選択型

岩下 芳久

1 発展的

1 発展的

1 発展的

1 発展的

1 発展的

1 発展的

1 萌芽的 国際

1 発展的

1 萌芽的

選択 実施
国際
分野 状況

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

型

阪部 周二

阪部 周二

橋田 昌樹

橋田 昌樹

藤井 知実

藤井 知実

井上 峻介

井上 峻介

倉田 博基

化研内
研究協力者

化学研究所共同利用・共同研究拠点 H30年度採択課題（応募155件、採択 115件）

Synthesis of Transition Metal Complexes Bearing a Low-coordinate Phosphorus Ligand and Their Application to Catalytic Reactions

低配位リン化合物を配位子とする遷移金属錯体の合成と触媒反応への応用

Construction of metal-substituted carbenium ion and silyl cation and their applications for Lewis acid catalysts

金属置換カルベニウムイオンおよびシリルカチオンの創製とルイス酸触媒への応用

Study on magnification of the pulsed-neutron transmission image using the sextupole magnet, aimed at visualization of charge anddischarge in the electrode materials of Li-ion batteries

リチウムイオン二次電池の電極材内の充放電反応可視化を目的とした、六極磁石によるパルス中性子透過イメージ拡大の研究

Research on the high-performance superconducting cavity and the cost reduction by noble inner-surface processes

超伝導空洞の内面処理による高性能化とコスト削減の研究

Development of neutron velocity concentrator

中性子速度濃縮法の開発

Fabrication Process of a Superconducting Electron Accelerating Cavity Operated by Small Electricity Power for a CEP-stabilized
Free-Electron Laser

化学反応の量子制御を目指したCEP安定化自由電子レーザのための省電力型超伝導加速空洞の製作方法の研究

Investigation of accelerator beam component using permanent magnets

加速器ビーム制御コンポーネントの永久磁石化の検討

Intense deuteron beam generation by ultra-intense laser irradiation for development of Li-battery diagnostics and laser-driven compact
neutron source

超高強度レーザー生成重陽子ビームの大強度化：リチウムイオン電池計測、小型中性子源開発を目指して

A study of laser driven high-intensity terahertz surface wave

レーザー駆動高強度テラヘルツ表面波の研究

Advanced functionality on materials induced by Intense THz interaction

高輝度テラヘルツ波による材料表面への新規機能性付与

Fundamental study on micro-fabrication of metal with controlling laser absorption

レーザー吸収制御による半導体の微細加工に関する基礎研究

X-ray Crystallographic Studies on Thermostability and Substrate Specificity of L-Asparaginase

X線結晶解析によるL-アスパラギナーゼの耐熱性及び基質特異性の研究

X-Ray Structural Studies on Reaction Mechanism of Maleylacetate Reductase

X 線構造解析によるマレイル酢酸還元酵素の反応機構研究

Probing ultrafast motion of critical surface pushed by multi-pico-second relativistic radiation pressure

マルチピコ秒の相対論的放射圧で駆動される臨界面の超高速運動の観測

Directional neutron generation via laser-driven-photonuclear reaction by using a spin polarized deuterium target

スピン偏極重水素ターゲットのレーザー駆動光核反応による高指向性中性子発生

Fabrication of chiral metal nanocrystals and clarification of their optical property

キラルな金属ナノ結晶の作製とその光学特性の解明

課題名（和文・英文）

－147－
緒方 博之

緒方 博之

情報通信研究機構未来ICT 研究所

上越教育大学学校教育研究科

國立臺灣大學名古屋市立大学大学院システム自然科学研究科

理化学研究所環境資源科学研究センター

横浜国立大学大学院工学研究院

理化学研究所

物質・材料研究機構構造材料拠点

九州工業大学大学院情報工学研究院

Monash University

東邦大学理学部情報科学科

情報・システム研究機構

高知大学農林海洋科学部

東京理科大学理学部

名古屋工業大学

帯広畜産大学2018-19 井原 章之

2018-20 小川 佳宏

2018-21 陳 威廷

2018-22 笹森 貴裕

2018-23 ILIES Laurean

2018-24 山口 佳隆

2018-25 村中 厚哉

2018-26 中村 泰之

2018-27 竹本 和広

2018-28 Jiangning Song2018-29 ホセ ナチェル

2018-30 五斗 進

2018-31 長崎 慶三

2018-32 武村 政春

2018-33 烏山 昌幸

2018-34 茅野 光範

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

馬見塚 拓

馬見塚 拓

緒方 博之

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

阿久津 達也 分野選択型

阿久津 達也 分野選択型

阿久津 達也 分野選択型

山子 茂

山子 茂

中村 正治

中村 正治

時任 宣博

島川 祐一

金光 義彦

金光 義彦

金光 義彦

長岡技術科学大学

2018-18 山田 昇

梶 弘典

物質・材料研究機構

2018-17 坂牛 健

3 発展的

3 萌芽的 国際

3 萌芽的

3 萌芽的

3 萌芽的

3 萌芽的

3 萌芽的 国際

3 萌芽的

2 発展的

2 発展的

2 萌芽的

2 発展的

2 発展的

2 発展的 国際

2 萌芽的

2 発展的

2 萌芽的

2 発展的

Differential molecular network analysis through statistical machine learning

統計的機械学習による分子ネットワークの差分解析法

Machine Learning based Integration of Diverse Biological Data with Network

多様な生物データとネットワクの統合的解析ため機械学習基盤技術開発

Isolation and genome analysis of new giant viruses from Japanese aquatic environments

日本の水環境からの新規巨大ウイルスの単離とゲノム解析研究

Ecological roles of giant viruses during the succession after red tide blooms

赤潮発生後の生態遷移における巨大ウイルスの生態学的役割の解明

Development of prediction method for growth conditions based on microbial genome information

既知微生物ゲノム情報に基づく培養条件の予測法開発

Control and Analysis of Complex Networks via Minimum Dominating Sets

最小支配集合による複雑ネットワークの制御と解析

Novel approaches to prediction of caspase cleavage sites

Caspase酵素による切断部位予測のための新手法の開発

Analysis of Complex Networks with Degree Correlations

次数相関のある複雑ネットワークの解析

Study of the reaction mechanisms of radical polymerization utilizing the reactivity of organotellurium compounds

有機テルル化合物の反応性を利用したラジカル重合反応の機構解析

Unraveling in-plane aromaticity in cycloparaphenylenes

シクロパラフェニレンにおける面内芳香族性の解明

Development of first-row late transition-metal complexes with constrained geometry using tridentate anionic ligands

3座アニオン性配位子を用いた幾何拘束型第一列後周期遷移金属錯体の開発

Base Metal Catalysis for Creation of Functional Materials

機能性分子の創製を指向した普遍金属触媒反応の開発

Synthesis of Low-coordinated Heavier Group 14 Species bearing Stable Redox Behavior and Elucidation of Their Structures

安定な酸化還元特性を示す高周期14族元素低配位化合物の合成と分子構造の解明

Discovery of novel functional transition-metal oxides with ultra-high-pressure condition

Optical properties of Pb perovskite solar cells by heterodyne interference spectroscopy

ヘテロダイン干渉分光法を用いた鉛ペロブスカイト太陽電池の光物性の研究

Investigation on quantum properties of luminescent nanomaterials using novel techniques of laser microscopic spectroscopy

新規レーザー顕微分光技術を活用したナノ発光材料の量子物性の研究

Feasibility study of novel cooling devices with perovskite semiconductors

ペロブスカイト半導体を用いた新規冷却デバイスの実現可能性検討

Basic Study for Unveiling Crystal Structure of Carbon-, Nitrogen-based Frameworks

窒化炭素構造体の結晶構造決定のための基礎研究

－148－

名古屋工業大学大学院工学研究科

九州大学ｶｰﾎﾞﾝﾆｭｰﾄﾗﾙ･ｴﾈﾙｷﾞｰ国際研究所

2018-52 山内 美穂

寺西 利治

竹中 幹人

竹中 幹人

宗林 由樹

渡辺 宏

2018-51 山本 勝宏

長谷川 健

山形大学大学院有機材料システム研究科

東北大学多元物質科学研究所

2018-45 山本 俊介

寺西 利治

2018-50 西辻 祥太郎

防衛医科大学校

2018-44 石原 美弥

宗林 由樹

京都教育大学教育学部理学科

近畿大学理工学部

2018-43 中口 譲

分野選択型

分野選択型

5 萌芽的

5 発展的

5 発展的

5 萌芽的

分野選択型

分野選択型

5 萌芽的

5 萌芽的

5 発展的 国際

5 萌芽的

5 萌芽的

5 発展的

4 萌芽的

4 萌芽的

4 萌芽的

4 発展的

4 発展的

4 萌芽的

4 発展的

4 萌芽的

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

分野選択型

村田 靖次郎 分野選択型

2018-49 向井 浩

岡山大学大学院

2018-42 菅 誠治

村田 靖次郎 分野選択型

日本女子大学理学部数物科学科

大阪工業大学工学部応用化学科

2018-41 村田 理尚

分野選択型

分野選択型

村田 靖次郎 分野選択型

2018-48 島田 良子

奈良先端科学技術大学院大学

2018-40 鈴木 充朗

若宮 淳志

松宮 由実

大阪大学大学院工学研究科

2018-39 佐伯 昭紀

若宮 淳志

大阪大学大学院理学研究科

大阪大学産業科学研究所

2018-38 家 裕隆

分野選択型

分野選択型

村田 靖次郎 分野選択型

2018-47 浦川 理

久留米工業高等専門学校

2018-37 黒飛 敬

山子 茂

渡辺 宏

大阪大学大学院工学研究科

2018-36 生越 専介

川端 猛夫

2018-46 Sathish K. Sukumaran 山形大学大学院有機材料システム研究科

京都府立大学2018-35 今吉 亜由美

Hydrogen absorption properties for shape controlled Pd nanoparticles in wide temperature region

形状制御されたPdナノ粒子の広温度領域における水素吸蔵特性の解明

Depth-resolved Structure Analysis of Organic Thin Films by Energy Dispersive GISAXS utilizing Tender X-rays

テンダーX線領域のエネルギー分散斜入射小角X線散乱法による有機薄膜構造解析

The study on density fluctuations of polycarbonate by using time-resolved scattering method

時分割散乱法を用いたポリカーボネートの密度揺らぎに関する研究

Study on improvement of transportation efficiency of metal ions through a liquid membrane

液膜輸送における金属イオンの輸送効率の向上に関する研究

Analysis of molecular condensation in temperature gradient field created through plasmonic heating

プラズモン発熱による温度勾配形成を利用した分子凝縮の解析

Relationship between hydrogen bonding and rheological properties of polyurethanes having several chemical structures

様々な化学構造を持つポリウレタンの水素結合とレオロジー特性の関係

Correlated molecular motion in polymeric liquids

高分子融液における分子運動の相関

Structure Analysis of Monolayer Assembly with π-Conjugated Units Studied by pMAIRS

π共役系ユニット含有単分子膜集積体のpMAIRS法を用いた精密構造解析

In vivo detection of temperature change using optical spectroscopic characterization of metal nanoparticle

金属ナノ粒子の分光特性を利用する生体内温度変化の検出

Biogeochemical study of bioactive trace metals in the aerosols over northern North Pacific Ocean

北部北太平洋洋上大気エアロゾル中の生体活性微量金属の生物地球化学的研究

Synthesis and Properties of Novel Tehinoacenes Synthesized by Addition–Elimination Reaction and Following Cyclization

付加脱離反応と縮環反応を駆使した新規チエノアセン分子の合成とその物性評価

Synthesis and Thermoelectric Performance of π-Conjugated Coordination Polymers

π共役配位高分子の合成と熱電変換特性

Development of small-molecule n-type organic semiconductors that can be processed via precursor approaches

熱前駆体法により成膜可能な低分子n型有機半導体の創製

Electronic landscape and optoelectronics of non-lead perovskite solar cell transfer layer

非鉛ペロブスカイト太陽電池の電子準位と光電気物性

Organic Photovoltaic Devices Composed of Novel Organic Semiconductors

新規な有機半導体材料で構成される有機太陽電池

Synthesis of Novel Non-alternant Heterocycles toward Organic Functional Material

有機機能性材料を指向した新規非交互複素環化合物の創製

Studies on the reactivities between curved pi-conjugated molecules and transition metal complexes and their applications

曲面パイ共役分子と遷移金属錯体との反応性の解明とその応用

Total Synthesis of Blespirol

ブレスピロールの全合成

－149－

Korea Advanced Institute of Science and Technology

電気通信大学情報理工学研究科

新潟大学大学院

Chinese Academy of Sciences

U.S. Department of Energy, Ames National Laboratory

近畿大学農学部

立命館大学生命科学部

2018-65 仲谷 栄伸

2018-66 生駒 忠昭

2018-67 Jun Xu

2018-68 小林 武史

2018-69 倉田 敦志

2018-70 三原 久明

北海道大学工学研究院

2018-60 長浜 太郎

2018-64 KIM, Kab-Jin

東京理科大学薬学部

2018-59 西川 元也

東京大学大学院工学系研究科

Fudan University

2018-58 Zhou Lu

2018-63 千葉 大地

東京農工大学工学部生命工学科

2018-57 長澤 和夫

名古屋工業大学物理工学科

理化学研究所環境資源科学研究センター

2018-56 Jong-Myong Kim

2018-62 田中 雅章

北京大学生命科学院

2018-55 QU, Li-Jia

岐阜大学工学部

名古屋大学大学院情報学研究科

2018-54 吉田 久美

2018-61 山田 啓介

群馬大学大学院理工学府

2018-53 園山 正史

課題提案型

栗原 達夫

栗原 達夫

梶 弘典

梶 弘典

梶 弘典

小野 輝男

小野 輝男

小野 輝男

小野 輝男

小野 輝男

小野 輝男

課題提案型

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発展的

萌芽的

発展的 国際

発展的 国際

萌芽的

萌芽的

萌芽的 国際

発展的

萌芽的

発展的

発展的

課題提案型

課題提案型

萌芽的

課題提案型

上杉 志成

上杉 志成

萌芽的 国際

課題提案型

上杉 志成

発展的

萌芽的

課題提案型

青山 卓史

発展的 国際

課題提案型

青山 卓史

5 萌芽的

5 発展的

分野選択型

分野選択型

若宮 淳志

長谷川 健

Functional study of metal-induced proteins in microbial metal respiration

微生物の金属呼吸における金属誘導性タンパク質の機能解析

Characteristics of membrane vesicles produced by intestinal bacteria and fermented food-derived bacteria and their biogenesis

腸内細菌および発酵食品由来細菌が生産する膜小胞の特性と形成機構

Determination of high-order structure of organic device molecules using dynamic nuclear polarization solid-state NMR

動的核分極固体NMRによる有機デバイス分子の局所構造解析

Mechanism study of heterogeneous catalysis on zeolites by DNP-NMR

Studies on Spin Dynamics of TADF Molecules

熱活性遅延蛍光分子のスピン動力学研究

Electric field induced Skyrmion motion

電界によるスカーミオンの高速移動Real time observation of topological Hall effect

トポロジカルホール効果の実時間観測

Electric field effect on magnetic domain wall velocity in a system with an induced magnetic moment

誘導磁気モーメントを有する系における磁壁移動速度に対する電界効果

Study of spin-filtering effect of the magnetic insulator films with perpendicular magnetic anisotropy

強磁性絶縁体垂直磁化膜によるトンネル型スピンフィルター効果に関する研究

Observation of Current-Driven Domain Wall Motions in the Ni nanowire

単一Niナノワイヤーにおける磁壁電流駆動の観測

Interface structure and spin current phenomena of spinel ferrite/heavy metal systems.

スピネルフェライト/非磁性重金属系における界面構造とスピン流現象の解明

Promotion of wound healing by a synthetic cell-adhesion molecule

合成細胞接着分子を利用した移植細胞延命化による損傷治癒の促進

Discovery and Use of Bioactive Self-Assembling Molecules

生理活性自己集合性化合物の発見と利用

Modulation of New Cellular Functions of Vitamin D

ビタミンＤの新機能の調節

Dynamics of the transcription factor ARR1 on plant chromosomal DNA

転写因子 ARR1の植物染色体DNA上における動態の研究

Regulatory Network of Gene Expression for Plant Cell Morphogenesis

植物細胞形態形成における遺伝子発現制御ネットワーク

Fabrication and evaluation of dye-sensitized solar cells using mixture of flavonoid compounds, and their theoretical studies toward
improvement of the efficiency

フラボノイド系色素混合物を用いた色素増感太陽電池の作製と特性評価、並びに効率向上を目指した計算化学研究

Analysis of physical properties and structure of partially fluorinated phospholipid bilayer

新規部分フッ素化リン脂質分子群の合成と膜物性・構造の解析

－150－

岐阜薬科大学薬学部

広島大学大学院理学研究科

名古屋大学大学院工学研究科物質科学専攻

大阪府立大学工業高等専門学校

産業技術総合研究所機能化学研究部門

RMIT 大学工学研究科

東京工業大学フロンティア材料研究所

2018-83 本間 謙輔

2018-84 畑野 敬史

2018-85 倉橋 健介

2018-86 山本 貴広

2018-87 橘 泰宏

2018-88 真島 豊

弘前大学大学院理工学研究科

2018-78 萩原 正規

2018-82 永澤 秀子

Sungkyunkwan University

2018-77 Youngdon Kwon

岐阜薬科大学薬学部

大阪大学産業科学研究所

2018-76 藤塚 守

2018-81 伊藤 彰近東北大学大学院工学研究科

2018-75 山本 雅哉

立教大学理学部化学科

奈良教育大学教育学部

2018-74 山崎 祥子

2018-80 山中 正浩

静岡大学学術院農学領域

2018-73 大西 利幸

広島大学大学院工学研究科

信州大学山岳科学研究所

2018-72 高梨 功次郎

2018-79 尾坂 格

大阪工業大学工学部

2018-71 大森 勇門

寺西 利治

寺西 利治

大野 工司

宗林 由樹

菅 大介

阪部 周二

川端 猛夫

川端 猛夫

川端 猛夫

脇岡 正幸

佐藤 慎一

松宮 由実

山子 茂

大野 工司

梅谷 重夫

渡辺 文太

渡辺 文太

栗原 達夫

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

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課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

萌芽的

発展的 国際

発展的

萌芽的

発展的

発展的 国際

萌芽的

萌芽的

発展的

発展的

萌芽的

萌芽的 国際

発展的

発展的

萌芽的

発展的

萌芽的

発展的

Room temperature operation of Au25 cluster single-electron transistor

Au25クラスター常温動作単電子トランジスタ

Interfacial structure control and photo-induced charge transfer dynamics of semiconductor nanocrystal based hybrid materials

半導体ナノ結晶複合材料の界面構造制御と光誘起電荷移動ダイナミクスの評価

Study on unusual photoresponses of upper critical solution temperature of polymer solutions using an azobenzene-doped
liquid-crystalline solvent particle/photoresponsive liquid crystals

高分子／アゾベンゼン混合液晶系における上限臨界溶液温度の異常な光応答に関する研究

Synergistic effect of surfactant for solid phase extraction using solvent impregnated resin

抽出剤含浸樹脂を用いた固相抽出における界面活性剤の協同効果

Exploring functional properties transition metal oxides by electric-field-induced electrochemical etching

電界誘起電気化学的エッチングを利用した遷移金属酸化物における機能開発

Search for four wave-mixing in the vacuum

真空内四光波混合の探索

Development of organocatalytic site-selective phosphorylation and sulfation reactions of carbohydrate and its application to drug delivery

有機触媒による無保護糖類の位置選択的リン酸化、硫酸化法の開発と薬物送達への応用

Development of Catalysts for Regio- and Stereoselective Oxidation

位置及び立体選択的酸化触媒の開発

Theoretical Study on Chemoselective Acylation Catalyzed by 4-Pyrrolidinopyridine Derivatives

4-ピロリジン-ピリジン型分子触媒による化学選択的アシル化反応の理論的解析

Development of novel π-conjugated polymers and their application to organic photovoltaics

新規π共役系ポリマーの開発と有機薄膜太陽電池への応用

Antisense-Induced Guanine Quadruplex Formation in mRNAs

アンチセンス核酸によるグアニン四重鎖構造を介したRNA構造・機能制御

Reptation Relaxation of Entangled Polymer Chains Undergoing Head-to-Head Association and Dissociation.

末端会合/解離平衡下における絡み合い鎖のreptation緩和

Intramolecular photoinduced charge separation in D-A cycloparaphenylenes

D-Aシクロパラフェニレン内光誘起電荷分離過程

Studies on mesenchymal stem cells differentiation induced by two-dimensional ordered arrays of monodisperse microparticles with apolymer brush for regenerative medicine

再生医療を指向した二次元配列された微粒子により誘導される間葉系幹細胞の分化挙動解析

Development of recognition and separation system highly selective for rare metals

レアメタルに対して高選択的な認識・分離系の開発

Studies on the biosynthesis and physiological functions of human steroidal hormones in plant.

植物におけるヒト型ステロイドホルモンの生合成および機能の解明

Determination and functional analyses of cyclization enzymes in the biosynthesis of plant polycyclic aromatic compounds

植物の多環性芳香族二次代謝産物の生合成に関与する環形成酵素の同定および機能解析

Studies on the formation mechanism of the bound D-amino acids using the synthetic peptides

合成ペプチドを用いた結合態D-アミノ酸の生成機構の解析

－151－

島根大学大学院総合理工学研究科

茨城大学工学部生体分子機能工学科

立教大学理学部

2018-105 吾郷 友宏

2018-106 箕浦 真生

バルセロナ大学バルセロナ生物医薬研究所

2018-99 Ernest Giralt

2018-104 宮本 光貴

フランス国立科学研究センター

2018-98 Sandrine SAGAN

東北大学金属材料研究所

国立台湾大学化学系

2018-97 Richard Cheng

2018-103 宮坂 等

東京理科大学理工学部先端化学科

2018-96 藤本 憲次郎

University of Ulsan

岡山理科大学理学部化学科

2018-95 岩永 哲夫

2018-102 Sanghoon Kim

名古屋大学大学院工学研究科

2018-94 高野 敦志

大阪大学大学院理学研究科

広島大学大学院理学研究科

2018-93 灰野 岳晴

2018-101 井上 正志

東京工業大学大学院理工学研究科工学院電気電子系 水落 憲和

2018-92 波多野 睦子

ハンガリー科学アカデミー

金沢大学理工研究域電子情報学系

2018-91 徳田 規夫

2018-100 Ferenc HUDECZ

水落 憲和

産業技術総合研究所
先進パワーエレクトロニクス研究センター

2018-90 牧野 俊晴

時任 宣博

時任 宣博

倉田 博基

島川 祐一

小野 輝男

渡辺 宏

二木 史朗

二木 史朗

二木 史朗

施設・機器利用型

施設・機器利用型

施設・機器利用型

連携・融合促進型

連携・融合促進型

連携・融合促進型

連携・融合促進型

連携・融合促進型

連携・融合促進型

連携・融合促進型

連携・融合促進型

菅 大介

二木 史朗

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

課題提案型

若宮 淳志

渡辺 宏

山子 茂

水落 憲和

長谷川 健

北海道大学低温科学研究所

2018-89 羽馬 哲也

萌芽的

発展的

発展的

発展的

発展的

発展的

萌芽的

国際

国際

国際

国際

国際

国際

国際

Synthesis and Structure of Kinetically Stabilized Main Group Element Compounds using Triptycylmethyl Groups

トリプチシルメチル基を速度論的安定化に用いるに高反応性典型元素化学種の合成と構造

Elucidation of the fluorous interactions in the crystal structures of fluorine-containing conjugated molecules by the single-crystal X-ray
structural analysis

単結晶X線構造解析を用いた、含フッ素共役分子の結晶構造におけるフルオラス相互作用の解明

Nano-electron spectroscopic study on hydrogen and helium behavior in plasma facing materials for nuclear fusion devices

核融合プラズマ対向材中の水素・ヘリウム挙動に関する電子分光学的研究

3rd Solid-State Chemistry Forum第3回 「固体化学フォーラム」研究会

Study on emergent spin-orbit phenomena in artificial superlattices without structural inversion symmetry

The 14th International Workshop for East Asian Young Rheologists

東アジア圏の若手レオロジストのための第14回ワークショップ

Modification of cell-penetrating peptides for the effective delivery of molecules into the cells

効果的な細胞内分子送達を目指した細胞透過ペプチドの改変

Functional design for drag delivery into brain

脳への薬物送達を目指した機能設計

Novel drug-delivery system using albumin as a reservoir

アルブミンを血中保持担体に用いた薬物送達

Facile intracellular delivery by the structural alteration of oligoarginines

アルギニンペプチドの構造改変と細胞内移送能の向上

Joint seminar 2018 on next generation materials

次世代材料の創製に向けたジョイントセミナー

Creation of Organic Functional Materials Based on Macrocycles Incorporating Triphenylamine Units

トリフェニルアミンユニットを組み込んだ大環状分子を基盤とした有機機能性材料の創製

Investigation of relationship between sequence length and segment size of various kinds of two-component multiblock copolymers

様々なブロック長を有する2成分多元ブロック共重合体のシークエンス長とセグメントサイズの関係

Development of Functional Supramolecular Multiblock Copolymer

超分子マルチブロック共重合体の合成と機能創製

Research toward ultra-high sensitivity sensor by using diamond

超高感度磁気センサのためのダイヤモンドNV中心の研究

Toward long spin coherence time of NV center in diamond

ダイヤモンド中のNV中心のスピンコヒーレンス時間の長時間化

Electrical control and detection of qubit of NV center

ダイヤモンド中のNV中心量子ビットの電気的制御と電気的検出

Vibrational spectroscopy study on ozonolysis of Kalanchoe pinnata leaf surface

振動分光法を用いたセイロンベンケイの葉の表面のオゾン酸化過程の解明

－152－

福岡大学理学部化学科

福井大学学術研究院工学系部門

奈良県立医科大学医学部

東京大学大学院理学系研究科化学専攻

2018-111 長洞 記嘉2018-112 徳永 雄次

2018-113 秦野 修

2018-114 小安 喜一郎

東京理科大学理学部応用化学科

時任 宣博

近畿大学理工学部

2018-110 松尾 司

2018-115 根岸 雄一

時任 宣博

東北大学大学院理学研究科

2018-109 岩本 武明

磯﨑 勝弘

磯﨑 勝弘

磯﨑 勝弘

中村 正治

時任 宣博

倉田 博基

九州大学大学院総合理工学研究院

2018-108 斉藤 光

時任 宣博

東北大学大学院農学研究科

2018-107 高橋 まさえ

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

施設・機器利用型

Synthesis of Metal Clusters Protected by Hydrophilic Thiolate, and Precise Separation and Evaluation by LC/MS

親水性チオラート保護金属クラスターの合成とLC/MSによる精密分離及び評価

Determination of compositions of protected novel metal clusters with precise mass analysis

精密質量分析を用いる新規配位子保護金属クラスターの組成決定

Study of the mechanism of steroid hormone production using imaging mass spectrometry

質量分析イメージング法を用いたステロイドホルモン産生機構の研究

Studies of porphyrin hetero-dimer formation by using high-resolution FT-MS spectroscopic monitoring. Precise analysis of its molecular
recognition, oligomerization, and dynamic chirality

超高感度FT-MSを活用したポルフィリンへテロ多量体の観測―分子認識、高次化、及び、不斉誘起における動的挙動の精密解析

Synthesis and structures of phosphorus-containing aromatics bearing an amine moiety

アミノ基を有する含リン芳香族化合物の合成と構造解析

Synthesis and Structural Characterization of Low-Coordinate Compounds of Group 14 Elements

14族元素低配位化合物の合成と分子構造の解明

Synthesis and Elucidation of Properties of Unsymmetrically-Substituted Disilyne and Relatedπ-Electron Systems

非対称型ジシリンおよび関連π電子系の合成と物性解明

Analysis of gap plasmon modes by electron energy-loss spectroscopy

電子エネルギー損失分光によるギャッププラズモンモードの分析

Theoretical design of flat and perfect two-dimensional・-conjugated “silicene” and the search of their solid-state properties

フラットで完璧なπ共役二次元シート「シリセン」の理論設計とその物性探索