ISSN 2-

KUR16-EKR- ４

平成 30 年度
「短寿命 RI を用いた核分光と核物性研究 V」

Proceedings of the Specialists' Meeting on"Nuclear Spectroscopy and Condensed Matter Physics
Using Short-Lived Nuclei V"

平成 30 年 12 月 18 - 19 日 開催
(December 18 - 19, 2018)

編集：小林義男、柴田理尋、大久保嘉高
Edited by : Y. Kobayashi, M. Shibata, and Y. Ohkubo

京 都 大 学 複 合 原 子 力 科 学 研 究 所
Institute for Integrated Radiation and Nuclear Science, Kyoto Universityࡣ ࡌ ࡵ ࡟ி㒔኱Ꮫ」ྜཎᏊຊ⛉Ꮫ◊✲ᡤࡢ◊✲⏝ཎᏊ⅔ࡣ୰ᛶᏊࢆⓎ⏕ࡍࡿࡓࡵࡢ⿦⨨࡛࠶ࡿࡀࠊࡇࡢ୰ᛶᏊࢆཎᏊ᰾࡟↷ᑕࡍࡿࡇ࡜࡟ࡼࡾࠊ୰ᛶᏊ㐣๫ࡢ୙Ᏻᐃ࡞ཎᏊ᰾ࢆᥦ
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ᐑṊᏱஓࠊ.,660572)WHDP

ȧࣃࣝࢫ࡟ࡼࡿ +2 ୰ 1ࡢ⢭ᐦ 105 ࢫ࣌ࢡࢺࣝ ᐃyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy 㜰኱㝔⌮ ࠊ⌮◊ோ⛉ࢭ ࠊ᪂₲኱◊✲᥎㐍ᶵᵓ ࠊ᪂₲኱⌮ ࠊᮾி㒔ᕷ኱ ࠊ㧗▱ᕤ⛉኱ ࠊ⟃Ἴ኱ ࠊ㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓ ୕ཎᇶႹ ࠊᯇከ೺⟇ ࠊ⚟⏣ග㡰 ࠊ༡ᅬᛅ๎ ࠊ⏣୰⪷⮧ ࠊⱝᯘㄹ ࠊᰗཎ㝣ᩯ ࠊ
ᮡཎ㈗ಙ ࠊ኱すᗣ௓ ࠊඵᮌ⩧୍ ࠊす⏿Ὧᕼ ࠊ㛗཭ഔ ࠊἨᕝ༟ྖ ࠊᮏ㛫ᙲ ࠊ኱ᆤ㝯 ࠊすᮧኴᶞ ࠊⓒ⏣బከ⏕ ࠊᑠἑ㢧 ࠊ໭ᕝᩔᚿ ࠊబ⸨┾஧ ㈇࣑ࣗ࢜ࣥࡢP65yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy ᅜ㝿ᇶ╩ᩍ኱Ꮫ
ஂಖㅬဢ࣓ࢱࣥ㞺ᅖẼୗࡢ㕲࣮ࣞࢨ࣮⵨╔࡟ࡼࡾ⏕ᡂࡋࡓ‽Ᏻᐃ┦ࡢⅣ໬㕲ⷧ⭷yyyyyyyyyyyyyyyyyyyy ᮾ⌮኱ ࠊ㟁㏻኱ ࠊ⌮◊ ⯚ᶫᣅᕫ ࠊす⏣┤ᶞ ࠊᑠᯘ⩏⏨ ࠊᒣ⏣ᗣὒ ❅⣲㞺ᅖẼୗࡢ㕲࢔࣮ࢡ⵨╔࡟ࡼࡗ࡚⏕ᡂࡋࡓ❅໬㕲ⷧ⭷yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy ᮾ⌮኱ ࠊ㟁㏻኱ ࠊ⌮◊ ℈ᓮ୍㈗ ࠊす⏣┤ᶞ ࠊᑠᯘ⩏⏨ ࠊᒣ⏣ᗣὒ ⅳ

CONTENTS
1) Present Status of Mössbauer Spectroscopy at Institute for Integrated Rdiation and Nuclear Science,
Kyoto University ······································································································ (1)S. Kitao1, Y. Kobayashi1, T. Kubota1, M. Saito1, R. Masuda1, M. Kurokuzu1,S.Hosokawa2, H. Tajima 2,
S. Yazaki2, and M. Seto1
1
Research Reactor Institute, Kyoto Univ.
2
Graduate School of Science, Kyoto Univ.
2) The effect of bis(pyridyl) type ligand using aromatic rings for Spin-Crossover phenomenon of iron(II)assembled complex ····································································································· (4)S. Iwai1 and S. Nakashima1, 2
1
Graduate School of Science, Hiroshima Univ.
2
Natural Science Center for Basic Research and Development, Hiroshima Univ.
3) Study on the dynamical spin equilibrium and its induced successive magnetic phase transition for assembled metal
complexes ·············································································································· (8)N. Kojima
Toyota Physical and Chemical Research Institute4) Spin-Crossover Coordination Polymer with 4-methylpyrimidine ··················································· (15)
Kosuke KITASE1, Masashi TAKAHASHI1,2 and Takafumi KITAZAWA1,2
1
Faculty of Science, Toho University.
2
Research Centre for Materials with Integrated Properties, Toho University.
5) Evolution for Spin Crossover 2D Hofmann-like Coordination Polymers ·········································· (21)Takafumi Kitazawa1,2, Hitomi Shiina1, and Masashi Takahashi1,21Department of Chemistry, Faculty of Science, Toho University
2
Research Center for Materials with Integrated Properties, Toho University
6) Mössbauer Spectra of Frozen Solutions Containing Fe2+ and Glutathione;
One Aspect of Researches of Biological Function of Glutathione ················································· (26)Haruto Arima1, Yui Ohno1, Kasane Sugano1, Kazuho Ozaki1, Tatsuki Kawagoe1, Shinya Kimata1, Tomonori
Suzuki1, Youichi Niimura1, Tadahiro Nakamoto2, Tsutomu Takayama 3, Yoichi Sakai3
1
Tokyo University of Agriculture
2
Toray Research Center
3
Daido Univesity7) Production of iron oxyhydroxide nanoparticles by a wet chemical method········································ (26)
N. Nishida1, S. Amagasa1, H. Ito1, Y. Kobayashi2, 3 and Y. Yamada1
1
Faculty of Science, Tokyo University of Science
2
The University of Electro-Communications
3
RIKEN
8) Production of iron oxyhydroxide nanoparticles by a wet chemical method········································ (30)
K. Nishimura1䠈 S.Amagasa1䠈 H.Ito1䠈Y.Kobayashi2,3䠈T. Matsizaki2䠈and Y. Yamada1
1
Faculty of Science, Tokyo University of Science
2
The University of Electro-Communications
3
RIKEN

ϼ

9) Precise Magnetic Field for Neutron Electric Dipole Moment Search using Ultra-cold Neutrons ··············· (38)
K. Matsuta1㸪Y. Matsuda2㸪M. Mihira1
1Department of Physics2None10) PSR Study of Hydrogen Atoms in Al Alloys········································································· (41)
K. Nishimura1㸪 K. Matsuda1㸪 N. Nunomura1㸪I. Watanabe2㸪W. Higemoto3, Y. Miyake4
1
Graduate School of Science and Engineering, University of Toyama
2
RIKEN Nishina Center for Accelerator Based Science
3
Advanced Science Research Center, Japan Atomic Energy Agency
4High Energy Accelerator Research Organization, Institute of Materials Structure Science11) Local Structure of Hydrogen in Pd during Hydrogen Absorption-Desorption Process Studied by muon ····· (43)
M. Mihara1, H. Araki2, K. Shimomura3, W. Higemoto4, M. Mizuno2, K. Sugita2, A. Kobayashi2,
M. Kondo2, Y. Tanaka2, Y. Kitayama2, D. Tomono5, E. Torikai6, W. Sato7, K. Ohkubo2, R. Murakami2,
N. Matsuoka2, I. Watanabe8, T. Matsuzaki8, R. Kadono3, T. Nakano9, and T. Fukuda2
1
Department of Physics, Osaka University
2
Division of Materials and Manufacturing Science, Osaka University
3
High Energy Accelerator Research Organization (KEK)4Japan Atomic Energy Agency (JAEA)
5
Research Center for Nuclear Physics (RCNP), Osaka University
6
Faculty of Engineering, University of Yamanashi
7
Institute of Science and Engineering, Kanazawa University
8
RIKEN Nishina Center for Accelerator-Based Science9
Graduate School of Science and Engineering, Ibaraki University12) Dynamic Motion of Impurity Indium Ions in Magnetite ···························································· (47)
W. Sato1,3, S. Komatsuda2, T. Fujisawa3, S. Takanaka3, T. Sugimoto3, and Y. Ohkubo4
1
Institute of Science and Engineering, Kanazawa Univ.
2
Graduate School of Natural Science and Technology, Kanazawa Univ.
3
National Institute of Technology, Ichinoseki College
4
Institute for Integrated Radiation and Nuclear Science, Kyoto Univ.
13) Precise NMR Spectrum of 17N in H2O Measured with a ʌpulse ·················································· (54)
M. Mihara1, K. Matsuta1, M. Fukuda1, T. Minaisono1, M. Tanaka1, R. Wakabayashi1, R. Yanagihara1,
T. Sugihara1, K. Ohnishi1, S. Yagi1, H. Nishibata2, T. Nagatomo2, T. Izumikawa3, A. Honma4,
T. Ohtsubo4, D. Nishimura5, S.Momota6, A. Ozawa7, A. Kitagawa8, and S. Sato81
Department of Physics, Osaka University
2
RIKEN Nishina Center for Accelerator-Based Science
3
Institute for Research Promotion, Niigata University
4
Department of Physics, Niigata University
5
Tokyo City University
6
Kochi University of Technology
7
University of Tsukuba
8
National Institute for Quantum and Radiological Science and Technology (QST)
14) PSR with negative muon ······························································································· (57)
M. K. Kubo
International Christian UniversityϽ15) Metastable iron carbide thin films produced by pulsed laser deposition of iron in the methane atmosphere · (60)
T. Funabashi1, N. Nishida1, Y. Kobayashi2,3, and Y. Yamada1
1
Tokyo University of Science
2
The University of Electro-Communications
3
RIKEN
16) Iron nitride thin films produced by arc deposition of iron in the nitrogen atmosphere ·························· (66)
K. Hamazaki1, N. Nishida1, Y. Kobayashi2,3 and, Y. Yamada1
1
Tokyo Univ. of Science
2
The University of Electro-Communications
3
RIKEN

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9HORFLW\ PPVࢢࣝࣆ࣮ࢡࡢ྾཰య࡜ࡋ࡚ '\) ࢆ⏝࠸࡚'\ ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓ )LJ  '\0|VVEDXHU VSHFWUXP RI '\) DW URRP㸦)LJ㸧ࠋ ᐃ ᗘࡣᐊ ࡛࠶ࡿࠋࡑࡢ⤖
WHPSHUDWXUHXVLQJ7EVRXUFHLQ'\*G)LUUDGLDWHG
ᯝࠊⰋዲ࡞ࢩࣥࢢࣝࣆ࣮ࢡࡢࢫ࣌ࢡࢺࣝࡀ
DW.85ᚓࡽࢀࠊ⥺※࡜ࡋ࡚ᐇ⏝ྍ⬟࡛࠶ࡿࡇ࡜ࡀ
☜ㄆ࡛ࡁࡓࠋ

2 7P ࣓ࢫࣂ࢘࢔࣮ศග
 7P ࡢ࣓ࢫࣂ࢘࢔࣮‽఩ࡣ 7P ࡢ NH9 ࡢ‽఩ࡀ⏝࠸ࡽࢀ࡚࠾ࡾ>@ࠊ࣐࢞ࣥ⥺ࡢ࢚ࢿࣝࢠ࣮ࡀ
ప࠸࡜࠸࠺≉ᚩࡀ࠶ࡿࠋࡑࡢࡓࡵࠊᐊ ࡟࠾࠸࡚ࡶ↓཯㊴ศ⋡ࡀ኱ࡁ࠸ࡀࠊヨᩱࢆ㏱㐣ࡋ࡚ ᐃࡍࡿሙྜࠊⷧ࠸ヨᩱࢆసᡂࡍࡿᚲせࡀ࠶ࡿࠋ
7P ࡣኳ↛Ꮡᅾẚ ࡢࡓࡵࠊヨᩱࡣኳ↛ࡢ 7P ࢆ౑⏝ࡋ࡚ࠊຠ⋡ࡢࡼ࠸ ᐃࡀྍ⬟࡛࠶ࡿࠋ⥺※࡜ࡋ࡚ࡣ (U ༙ῶᮇ  ᪥ ࢆ⏝࠸ࡿࡇ࡜ࡀ࡛ࡁࠊኳ↛(U ࢆ⏝࠸ࡓሙྜࠊ(U  ࡢ࡯࠿࡟(U  ࡀྵࡲࢀࡿࡀࠊ๪⏕ᡂ≀ࡢ(U ࡣ  ᫬㛫ࡢ༙ῶᮇࡢࡓࡵࠊᩘ᪥
ᚅࡘࡇ࡜࡛ῶ⾶ࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡿࠋ⥺※≀㉁࡜ࡋ࡚ࡣࠊ࠸ࡃࡘ࠿▱ࡽࢀ࡚࠸ࡿ
ࡀࠊࡇࡇ࡛ࡣࠊ(U$O ྜ㔠㸦(U㹼ZW㸧ࡢ⥺※ࡢసᡂࢆヨ⾜ࡋࡓ>@ࠋ⥺※ࡣ (U)LJ7P0|VVEDXHU VSHFWUXP RI 7P$O DW URRP࡜ $O ࢆ࢔࣮ࢡ⁐ゎ࡟࡚ྜ㔠໬ࡋࠊ⁐య໬ࡋࡓᚋࠊᅽᘏࡋ࡚ⷧ⭷࡜ࡋ࡚సᡂࡋࡓࠋ
 WHPSHUDWXUHXVLQJ (UVRXUFHLQ(U$ODOOR\LUUDGLDWHGDW.85୰ᛶᏊ↷ᑕࡣ㛗ᮇ↷ᑕ࡟࠾࠸࡚  㐌㛫ࡢ↷ᑕࢆ⾜ࡗࡓࠋNH9 ࡢ࣐࢞ࣥ⥺ࡣ;H ẚ౛ィᩘ⟶࡟ࡼࡾ ᐃࢆ⾜ࡗࡓࡀࠊ(U ࡢ⺯ග /; ⥺ࡀ NH9 ࡢ࢚ࢿࣝࢠ࣮࡟Ꮡᅾࡋ࡚ࣆ࣮
ࢡࡀ㔜࡞ࡿࡓࡵࠊ㔜࡞ࡗࡓࣆ࣮ࢡࡢྑഃࢆ ᐃࡍࡿࡇ࡜࡛ᐇ㦂ࢆ⾜ࡗࡓࠋ྾཰యࡣ 7P$O ࢆ⏝࠸࡚ᐊ ࡟࡚ 7P ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓ )LJ ࠋࡑࡢ⤖ᯝࠊࢩࣥࢢࣝࣆ࣮ࢡࡢ࣓ࢫࣂ࢘࢔
࣮ࢫ࣌ࢡࢺࣝࡀほ ࡉࢀࠊ7P ࣓ࢫࣂ࢘࢔࣮ศගࡢᐇ⏝ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀᐇドࡉࢀࡓࠋ ࡲ࡜ࡵ ᮏ◊✲࡛ࡣࠊ'\ ࠾ࡼࡧ 7P ࡢ࣓ࢫࣂ࢘࢔࣮ศගࡢࡓࡵࡢࠊࢩࣥࢢࣝࣆ࣮ࢡ⥺※≀㉁ࡢసᡂࢆ
⾜࠸ࠊ◊✲⅔↷ᑕ࡟ࡼࡾྛ࣓ࢫࣂ࢘࢔࣮ศගࡀᐇ᪋ྍ⬟࡛࠶ࡿࡇ࡜ࡀᐇドࡉࢀࡓࠋ⌧≧࡟࠾࠸࡚ࠊ
༑ศᛂ⏝ᐇ㦂ࡀྍ⬟࡛࠶ࡾࠊ௒ᚋࠊᛂ⏝ᐇ㦂ࢆᒎ㛤ࡋ࡚ࡃࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋࡑࡢ࡯࠿ࠊ◊✲⅔
࡜ࣛ࢖ࢼࢵࢡࡢ┦⿵ⓗ࡞฼⏝࡟ࡼࡾࠊ1L(U ࡢ࣓ࢫࣂ࢘࢔࣮ศග࡟ࡘ࠸࡚ࡶࠊ⥺※⏕ᡂࡀྍ⬟࡛࠶ࡾࠊᛂ⏝ᐇ㦂ࢆ㛤ጞࡋ࡚࠸ࡿࠋࡲࡓࠊ<E ࡢ࣓ࢫࣂ࢘࢔࣮ศග࡟ࡘ࠸࡚ࡶࠊᐇ㦂ྍ⬟࡛࠶ࡿࡇ࡜ࡢᐇドࢆ⾜ࡗ࡚࠸ࡿࠋ௒ᚋࠊࡉࡽ࡟௚ࡢ᰾✀࡬ࡢᒎ㛤࡟ࡘ࠸࡚ࡶヨ⾜ᐇ㦂ࢆ⾜࠸ࠊᐇ㦂ྍ⬟࡞᰾✀ࡢᣑ኱ࢆ㐍ࡵ࡚࠸ࡃ࡯࠿ࠊࡇࢀࡽࡢᐇ⏝ྍ⬟ᛶࡢ࠶ࡿ᰾✀࡟ࡘ࠸࡚ࠊ⥺※≀㉁ࡢ㑅ᐃࡸᐇ㦂ᡭἲࡢຠ⋡໬࡞࡝࡟ࡼࡾࠊᐇ㝿ⓗ࡟ᛂ⏝ᐇ㦂ࢆྍ⬟࡟ࡍࡿࡓࡵࡢᨵၿࢆ㐍ࡵ࡚࠸ࡃணᐃ࡛࠶ࡿࠋཧ⪃ᩥ⊩>@ ³7DEOHRI,VRWRSHV´WKHGXSGDWH5%)LUHVWRQH :LOH\9&+ >@ ³0|VVEDXHU6SHFWURVFRS\´11*UHHQZRRGDQG7&*LEE &KDSPDQDQG+DOO/RQGRQ 
>@ *-%RZGHQ'6W3%XQEXU\-0:LOOLDPV3URF3K\V6RF  
>@ 5/&RKHQDQG+-*XJJHQKHLP1XFO,QVWU0HWKRGV  
>@ *.DOYLXV):DJQHU:3RW]HO-3K\V&ROORT &   3ⰾ㤶⎔ࢆ᭷ࡍࡿࣅࢫ㸦ࣆࣜࢪࣝ㸧ᆺᯫᶫ㓄఩Ꮚࡀ୚࠼ࡿ
㕲஧౯㞟✚ᆺ㘒యࡢࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟࡬ࡢᙳ㡪The effect of bis(pyridyl) type ligand using aromatic rings
for Spin-Crossover phenomenon of iron(II) assembled complexᗈᓥ኱㝔⌮ 1ࠊᗈᓥ኱ N-BARD2ᒾ஭ဏᶞ 1ࠊ୰ᓥぬ 1, 2
S. Iwai1 and S. Nakashima1, 2
1

Graduate School of Science, Hiroshima Univ.

2

Natural Science Center for Basic Research and Development, Hiroshima Univ.

1. ࡣࡌࡵ࡟
ṇඵ㠃యᆺࢆ࡜ࡿࣅࢫ(ࣆࣜࢪࣝ)ᆺ㕲஧౯㞟✚ᆺ㘒యࡣࠊᗘ࣭ᅽຊ࣭ග࡜࠸ࡗࡓእ㒊ᅉᏊࡢኚ໬

࡟ࡼࡗ࡚పࢫࣆࣥ≧ែ(S = 0)࡜㧗ࢫࣆࣥ≧ែ(S = 2)ࢆ⾜ࡁ᮶ࡍࡿࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮(SCO)⌧㇟ࢆⓎ⌧ࡍࡿࡇ࡜ࡀ࠶ࡿࠋ[1]-[3]SCO ⌧㇟࡟ᙳ㡪ࢆ୚࠼ࡿせᅉ࡜ࡋ࡚ࠊࢤࢫࢺศᏊࡢ᭷↓[4][5]ࠊ㕲ࡢ㓄఩⎔ቃ[6][7]ࠊ⨨᥮ᇶ[8]ࠊศᏊ㛫┦஫స⏝[9]࡞࡝ࡀᣲࡆࡽࢀࡿࠋ౛࠼ࡤᯫᶫ㓄఩Ꮚ bpanth = 9,10-bis(4pyridyl)anthracene ࢆ⏝࠸ࡓ㞟✚ᆺ㕲஧౯㘒య[Fe(NCS)2(bpanth)2]nࡣࠊᒙ㛫ࡢ CH-ʌ ┦஫స⏝ࡀ㕲࿘ࡾࡢᵓ㐀ࢆ SCO ࡀ㉳ࡁ࡟ࡃ࠸ᵓ
㐀࡟ᅛᐃࡍࡿࡓࡵࠊSCO ⌧㇟ࡀⓎ⌧ࡋ࡞࠸ࠋ[10]ࡔࡀࡇࡢࡼ࠺࡟ศ
Ꮚ㛫┦஫స⏝ࡀࢫࣆࣥ㌿⛣ᣲື࡟୚࠼ࡿᙳ㡪ࡣᮍࡔヲࡋࡃゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣȧ㟁Ꮚࢆ௓ࡍࡿศᏊ㛫┦஫స⏝ࡀ
SCO ⌧㇟࡬୚࠼ࡿᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋbpanthࢆ⏝࠸ࡓ㘒యࡣศᏊ㛫┦஫స⏝ࡢᙉࡉࡢࡓࡵ࡟ SCO-off ࢆ࡜ࡗࡓࡇ࡜ࢆ㋃ࡲ࠼ࠊbpanth ࠿ࡽ࣋ࣥࢮࣥ⎔ࢆ୍ࡘῶࡽࡋࡓࢼࣇࢱࣞࣥ
ࢆ᭷ࡍࡿᯫᶫ㓄఩Ꮚ m, n-bpna = m, n-bis(4-pyridyl)naphthalene ; (m,n) = (1, 4), (1, 5), (2, 7)ࢆタィࡋࡓࠋࡇࡇ࡛ࡇࢀࡽࡢᯫᶫ㓄఩Ꮚࢆ 1,
2 ࠾ࡼࡧ 3 ࡜ᐃ⩏ࡍࡿࠋࡑࡋ࡚ 1, 2 ࠾ࡼࡧ 3 ࡜࢔ࢽ࢜ࣥᛶ㓄఩Ꮚ
࡜ࡋ࡚ KNCS, KNCSe, NaNCBH3 ࢆ⏝࠸ࡓ㕲㘒య 1a~1c, 2a~2c,
Fig. 1 Bridging ligand 1,2 and 3

3a~3c ࡢ㟁Ꮚ≧ែࡸᵓ㐀ࢆㄪ࡭ࡓࠋ

2. ᐇ㦂
㕥ᮌ-ᐑᾆ࢝ࢵࣉࣜࣥࢢ཯ᛂࢆ⏝࠸࡚ᯫᶫ㓄఩Ꮚ m, n-bpna ࢆྜᡂࡋࠊ1H NMR ࡜ඖ⣲ศᯒࢆ⏝࠸࡚ྠᐃࢆ⾜ࡗࡓࠋ཰⋡ࡣࡑࢀࡒࢀ 1 = 63.2%, 2 = 58.5%, 3 = 75.4%࡛࠶ࡗࡓࠋࡑࡋ࡚ࢪࢡ࣓ࣟࣟࢱࣥࡲ
ࡓࡣ࢚ࢱࣀ࣮ࣝ࡟ᯫᶫ㓄఩Ꮚࢆ⁐࠿ࡋࡓ⁐ᾮ࡟ࠊ◲㓟㕲୐Ỉ࿴≀࡜࢔ࢫࢥࣝࣅࣥ㓟ࠊࡉࡽ࡟࢔ࢽ

4࢜ࣥᛶ㓄఩Ꮚ࡜ࡋ࡚ KNCS, KNCSe, NaNCBH3 ࢆࡑࢀࡒࢀ࢚ࢱࣀ࣮ࣝ࡟ࡲࡓࡣỈ࡟⁐࠿ࡋࡓ⁐ᾮࢆຍ࠼ࠊ┤᥋ΰྜἲ࡟ࡼࡗ࡚⢊ᮎ≧ࡢ㕲஧౯㘒యࢆィ 9 ✀㢮ྜᡂࡋࡓࠋྜᡂࡋࡓ㘒య࡟ࡘ࠸࡚ඖ⣲ศᯒ࡛ྠᐃࡋࠊ78K ࡜ᐊ ୗ࡛ 57Fe ࣓ࢫࣂ࢘࢔࣮ ᐃࢆ⾜ࡗࡓࠋࡲࡓ⢊ᮎ X ⥺ᅇᢡࡣࠊ2ȟ=5r~50rࡢ⠊ᅖ࡛ ᐃࡋࡓࠋ☢໬⋡ࡣ 5K~300K ࡢ⠊ᅖ࡛᪼ Ѝ㝆 ࡢ㡰࡟㸯ࢧ࢖ࢡ࡛ࣝ ᐃࡋࠊᚓࡽࢀࡓ☢໬⋡࡟ࡘ࠸࡚཯☢ᛶ⿵ṇࢆ⾜ࡗࡓࠋࡲࡓࡇࢀࡽࡢ᮲௳ࡢୗࠊᣑᩓἲ࡟ࡼࡗ࡚༢⤖ᬗࢆ⫱ᡂࡋ XRDᐃࢆ⾜ࡗࡓࠋ

3. ⤖ᯝ࡜⪃ᐹ☢໬⋡ ᐃࡢ⤖ᯝࠊᯫᶫ㓄఩Ꮚ 1 ࡜ 2 ࢆ⏝࠸ࡓ 6✀㢮ࡢ㘒యࡣࢫࣆࣥ㌿⛣ࡀほ㢮ࡢ㘒యࡣࡉࢀࡓࡀࠊ3 ࡢ 3 ✀ᗘ࡟ࡼࡗ࡚ࢫࣆࣥࡢኚ໬ࡣࡳࡽࢀ࡞࠿

ࡗࡓࠋ1a, 1b ࠾ࡼࡧ 1cࠊࡉࡽ࡟ 2a, 2b ࠾ࡼࡧ 2c ࡢ㌿⛣ᗘࡣࡑࢀࡒࢀ 103K, 202(up), 198(down)K ࠾ࡼࡧ 218(up), 221(down)Kࠊࡉࡽ࡟ 100K, 111K ࠾ࡼࡧ
174K ࡛࠶ࡗࡓࠋFig.2 ࡟♧ࡋࡓ 1a ࡢ࣓ࢫࣂ࢘࢔࣮ࢫ
࣌ࢡࢺࣝࡢࡼ࠺࡟ࠊࡇࢀࡽࡢ㘒యࡣ࣓ࢫࣂ࢘࢔࣮
ᐃ࠿ࡽࡶࠊ஧౯ࡢ㕲ࡢపࢫࣆࣥ≧ែ࡜㧗ࢫࣆࣥ≧ែࡢ๭ྜࡢኚ໬ࡀぢࡽࢀࡓࠋ(Fig.2 ࡢ஧౯㧗ࢫࣆࣥ㸸஧౯పࢫࣆࣥ = 61% : 39% )ࡋࡓࡀࡗ࡚ 1a, 1b ࠾ࡼ)LJ 0ØVVEDXHUVSHFWUDRI
D

ࡧ 1cࠊ2a, 2b ࠾ࡼࡧ 2c ࡣ SCO ⌧㇟ࢆⓎ⌧ࡍࡿࡇ࡜[Fe(NCS)2(1,4-bpna)2]nࡀุ᫂ࡋࡓࠋ୍᪉ࠊ3a, 3b ࠾ࡼࡧ 3c ࡣ࣓ࢫࣂ࢘࢔࣮
ᐃ࡟࠾࠸࡚ࡶ ᗘኚ໬࡟కࡗࡓࢫࣆࣥ㌿⛣ࡀ☜ㄆ࡛ࡁ࡞࠿ࡗࡓࡓࡵࠊSCO ⌧㇟ࢆⓎ⌧ࡋ࡞࠸࡜⪃ᐹࡋࡓࠋᣑᩓἲࡼࡾ 3a ࡜ࢺ࢚ࣝࣥࢆໟ᥋ࡋࡓ 2a ࡢ༢⤖ᬗ 2a_t ࡀᚓࡽࢀࠊࡑࡢゎᯒ࡟ᡂຌࡋࡓࠋࡲࡎ
2a_t ࡟ࡘ࠸࡚ࡣࠊ⢊ᮎྜᡂ࡜ྠࡌ᮲௳࡛⤖ᬗࡀᚓࡽࢀ࡞࠿ࡗࡓࡓࡵࠊࢺ࢚ࣝࣥࢆ⁐፹࡜ࡋ࡚⏝࠸ࡿࡇ࡜࡛༢⤖ᬗࢆᚓࡓࠋᵓ㐀ゎᯒࡢ⤖ᯝࠊ⤌ᡂࡣ[Fe(NCS)2(1,5-bpna)2]n࣭1Toluene ࡛࠶ࡾࠊ 2 ḟඖࢢࣜࢵࢻࢆᙧᡂࡋ࡚✚ᒙࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ㕲࡟㓄఩ࡋ࡚࠸ࡿྥ࠿࠸ྜ࠺ࣆࣜࢪࣥࡢ஧㠃ゅࢆ☜ㄆࡍࡿ࡜ࠊ஫࠸࡟ᖹ⾜࡟㓄఩ࡍࡿࣃࣛࣞࣝᆺ㓄఩࡛࠶ࡗࡓࠋ[6][7]ࡲࡓศᏊ㛫┦஫స⏝ࡣ☜ㄆ࡛ࡁ࡞࠿ࡗࡓࠋ⢊ᮎ㘒య࡜ࡢ㐪࠸ࢆ☜ㄆࡍࡿࡓࡵ࡟☢໬⋡ࢆᐃࡍࡿ࡜ࠊ ᗘ࡟ࡼࡗ࡚ࢫࣆࣥ㌿⛣ࡀ㉳ࡁ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓᵓ㐀࠿ࡽィ⟬ࡋࡓ⢊ᮎ X ⥺ᅇᢡࡢࣃࢱ࣮ࣥࡣ 2a ࡜ 2a_t ࡛ࣆ࣮ࢡࡢ఩⨨ࡀ␗࡞ࡗ࡚࠸ࡓࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ2a ࡣ SCO ࢆ㉳ࡇࡍࡀࢺ࢚ࣝࣥࢆໟ᥋ࡋࡓ 2a_t
ࡣ SCO ࢆ㉳ࡇࡉ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ2a_t ࡀ SCO-off ࡜࡞ࡿ⌮⏤ࡣࠊ᱁Ꮚ୰ࡢࢺ࢚ࣝࣥࡢᏑᅾ
࡜ࠊ㕲࿘ࡾࡢྥ࠿࠸ྜ࠺ࣆࣜࢪࣥࡀᖹ⾜࡟㓄఩ࡋ࡚࠸ࡿࡇ࡜ࡀ❧య㞀ᐖ࡜࡞ࡾࠊࢫࣆࣥ㌿⛣࡟క5࠺ᵓ㐀ኚ໬ࡀ㜼ࡲࢀࡿࡓࡵ࡛࠶ࡿ࡜⪃ᐹࡋࡓࠋḟ࡟ 3a ࡢ X ⥺ᵓ㐀ゎᯒࡢ⤖ᯝࠊ⤌ᡂࡣ
[Fe(NCS)2(2,7-bpna)2]n ࡛࠶ࡾࠊ୕ḟඖ᱁Ꮚࢆᙧᡂ
ࡋࡑࢀࡀ㸳ࡘ┦஫㈏ධࡋ࡚࠸ࡿ㞟✚ᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋFig.3 ࡟ࡣ୕ḟඖ᱁Ꮚࢆࡦ࡜ࡘษࡾྲྀࡾࠊc ㍈᪉ྥ࠿ࡽࡢᵝᏊࢆ♧ࡍࠋ᱁
ᏊࡣࠊFig.3 ࡢ⣬㠃ࡢዟ࡟ྥࡅ࡚ࠊࡘࡲࡾ c ㍈᪉ྥ࡟⼺᪕ࢆᕳࡁ࡞ࡀࡽ୕ḟඖ᱁Ꮚࢆᙧᡂࡋ࡚࠸
ࡓࠋࡉࡽ࡟ Fig.3 ࡢୗ㒊ࡢᅗࡢ㏻ࡾࠊR ࡜♧ࡋࡓ࡜ࡇࢁࡣྑᕳࡁࠊL ࡜♧ࡋࡓ࡜ࡇࢁࡣᕥᕳࡁࢆ࡜
ࡗ࡚࠸ࡿࡓࡵࠊ㘒య࡜ࡋ࡚ࡣࣛࢭ࣑య࡛࠶ࡿࡇ
࡜ࡀࢃ࠿ࡗࡓࠋḟ࡟ྥ࠿࠸ྜ࠺ࣆࣜࢪࣥࡢ㓄఩
ゅࢆ☜ㄆࡋࡓ࡜ࡇࢁࠊFig.4 ࡢࡼ࠺࡟ᖹ⾜࡟㓄఩ࡍࡿࣃࣛࣞࣝᆺ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟
ศᏊ㛫┦஫స⏝࡟㛵ࡋ࡚ࡣࠊ␗࡞ࡿ᱁Ꮚ㛫࡟࠾࠸࡚ࢼࣇࢱࣞࣥ㒊ࡢⅣ⣲ཎᏊ㛫ࡀ 3.481ύ࡛࠶ࡿࡓࡵࠊࡇࡇ࡟ȧ-ȧࢫࢱࢵ࢟ࣥࢢࡢᏑᅾࡀ♧၀ࡉࢀࡓࠋ௨ୖࢆࡲ࡜ࡵࡿ࡜ࠊ3a ࡣࣆࣜࢪࣥࡀᖹ⾜࡟㓄఩ࡍࡿࣃࣛࣞࣝᆺࢆ࡜ࡗ࡚࠸ࡿࡓࡵࠊࢫࣆ

D
)LJ5DFHPLFVWUXFWXUHRI

ࣥ㌿⛣࡟క࠺ᵓ㐀ኚ໬ࢆ㉳ࡇࡋ࡟ࡃࡃࠊSCO-off࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊ᱁Ꮚ㛫ࡢȧ-ȧࢫࢱࢵ࢟ࣥࢢࡀ SCO-off ࡜࡞ࡿࣃࣛࣞࣝᆺ㓄఩ࡢࡲࡲᵓ㐀ࢆᅛᐃࡍࡿᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿ࡜⪃ᐹࡋࡓࠋ

4. ࡲ࡜ࡵ
ᮏ◊✲࡛ࡣ㞟✚ᆺ㕲஧౯㘒య࡟࠾࠸࡚ࠊᒙ㛫ࡢศᏊ㛫┦஫స⏝ࡣᵓ㐀ኚ໬ࢆጉࡆࡿせᅉ࡜ࡋ࡚ࡣࡓ
ࡽ࠸࡚࠸ࡓࠋࡋࡓࡀࡗ࡚㞟✚ᆺ㘒య࡟࠾ࡅࡿศᏊ
㛫┦஫స⏝ࡢᏑᅾࡣ SCO ࡢⓎ⌧ࢆጉࡆࡿᏑᅾ࡟࡞


)LJ7KHSDUDOOHOFRRUGLQDWLRQRIS\ULGLQHVࡾࡸࡍ࠸ࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ

6㸺ཧ⪃ᩥ⊩㸼[1] Real, J., et al., Science, 268, 265-267, 1995.
[2] Halder, G.J., et al., Science, 298, 1762-1765, 2002.
[3] Banerjee, H., et al., Inorganics, 5, 47, 2017.
[4] T. Morita, Y. Asada, T. Okuda and S. Nakashima, Bull. Chem. Soc. Jpn., 79, 5, 738-744, 2006.
[5] M. Atsuchi, et al., Chem. Lett., 36, 8, 1064-1065, 2007.
[6] M. Kaneko, S. Tokinobu and S. Nakashima, Chem. Lett., 42, 1432-1434, 2013.
[7] M. Kaneko and S. Nakashima, Bull. Chem. Soc. Jpn., 88, 1164-1170, 2015.
[8] K. Yoshinami, et al., Radioisotopes, 66, 625-632, 2017.
[9] H. Hagiwara and S. Okada, Chem. Commun., 52, 815-818, 2016.
[10] S. Iwai, K. Yoshinami and S. Nakashima, Inorganics, 5(3), 61, 2017.

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14PHWK\OS\ULPLGLQH ࢆ㓄఩Ꮚ࡜ࡍࡿࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮㧗ศᏊ㘒య
Spin-Crossover Coordination Polymer with 4-methylpyrimidineᮾ㑥኱⌮ ࠊᮾ㑥኱」ྜ≀ᛶࢭࣥࢱ࣮
໭Ύ⯟㍜ ࠊ㧗ᶫṇ ࠊ໭⃝Ꮥྐ 
Kosuke KITASE1, Masashi TAKAHASHI1,2 and Takafumi KITAZAWA1,2
1

Faculty of Science, Toho University.

2

Research Centre for Materials with Integrated Properties, Toho University.

1.ࡣࡌࡵ࡟
ᙜ◊✲ᐊ࡛ࡣࠊHofmann ᆺᵓ㐀ࢆᣢࡘࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮(SCO)㘒య࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ
SCO ⌧㇟࡜ࡣࠊ ᗘࡸᅽຊ࣭ග࡞࡝ࡢせᅉ࡟ࡼࡾࠊ୰ᚰ㔠ᒓࡢࢫࣆࣥ≧ែࡀྍ㏫ⓗ࡟ኚ໬ࡍࡿ⌧㇟ࡢࡇ࡜ࢆᣦࡍࠋSCO ⌧㇟ࢆ♧ࡍ㘒య࡟㛵ࡍࡿ◊✲ࡣྛᆅ࡛⾜ࢃࢀ࡚࠸ࡿࡀࠊ≉࡟㕲(II)࡞࡝ࡢ d6 㔠ᒓ࢖࢜ࣥࡢሙྜࠊ㧗ࢫࣆࣥ≧ែ࡛ࡣᖖ☢ᛶࠊపࢫࣆࣥ≧ែ࡛ࡣ཯☢ᛶࢆ♧ࡍࡓࡵ࡟ࠊศᏊࢭࣥࢧ࣮ࡸศᏊࢫ࢖ࢵ
ࢳ࡞࡝ࡢᶵ⬟ᛶᮦᩱ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡑࡢࡓࡵࠊ≉࡟┒ࢇ࡟◊✲ࡀ࠾ࡇ࡞ࢃࢀ࡚࠸ࡿࠋ
Hofmann ᆺ㘒య࡜ࡣࠊඵ㠃యභ㓄఩ࡢ 2 ౯ࡢ୰ᚰ㔠ᒓ MII (M = Fe, Co, Cd etc.)ࡢ࢚ࢡ࢔ࢺࣜ࢔ࣝ఩࡟
┤⥺ 2 㓄఩[M’I(CN)2]㸫 (M’I = Cu, Ag, Au) ࡲࡓࡣᖹ㠃 4 㓄఩[M’II(CN)4]2㸫 (M’II = Ni, Pd, Pt) ࡀࠊ࢔࢟ࢩࣕࣝ఩࡟ࣆࣜࢪࣥ⣔㓄఩Ꮚࡀ㓄఩ࡋࡓᵓ㐀ࡢ㧗ศᏊ㘒యࡢࡇ࡜࡛࠶ࡿࠋFig. 1 ࡟ࡣࠊᖹ㠃 4 㓄఩ࡢ[Ni(CN)4]2㸫ࡀ࢚ࢡ࢔ࢺࣜ࢔ࣝ఩࡟ࠊ࢔࢟ࢩࣕࣝ఩࡟ pyridine ࡀ㓄఩ࡋࡓ㘒య Fe (pyridine)2 [Ni(CN)4]ࡢᵓ㐀ࢆ♧ࡋࡓࠋࡇࡢ㘒యࡣࠊHofmann ᆺᵓ㐀ࢆᣢࡘ SCO 㘒యࡢ᭱ึࡢሗ࿌౛࡛࠶ࡿ[1]ࠋFig. 2 ࡟ࡣ Fe (pyridine)2 [Ni(CN)4]ࡢ☢Ẽᣲື࣭ᵓ㐀ࢆ♧ࡋࡓࠋࡉࡽ࡟ࠊ┤⥺ 2 㓄఩ࡢ[M’I(CN)2]㸫ࡀ㓄఩ࡍࡿሙྜࡣࠊ୰ᚰ㕲 1 ཎᏊ࡟ᑐࡋ[M’I(CN)2]㸫2 ศᏊࡀ㓄఩ࡋࠊᯫᶫ㓄఩Ꮚࡢ඲㛗ࢆ୍㎶࡜ࡍࡿ஧ḟඖ㓄఩㧗ศᏊᒙࢆᙧᡂࡍࡿࠊ⤌ᡂFe(pyridine)2[M’I(CN)2]2 ࡢ SCO 㘒య࡜࡞ࡿ[2]ࠋࡲࡓࠊ57Fe
Mössbauerᐃࡣ㕲ཎᏊࡢࢫࣆࣥ≧ែ࣭౯ᩘ࡞࡝ࡢ㟁Ꮚ≧ែศᯒ࡟࠾࠸࡚㠀ᖖ࡟᭷ຊ࡞ᡭἲ࡛࠶ࡾࠊ㕲(II)ࡢሙྜࡣࢫࣆࣥ㌿⛣࡟ࡼࡾࣆ࣮ࢡࡀᅄᴟᏊศ⿣ࡢ኱ࡁ࠸஧㔜⥺࠿ࡽᅄᴟᏊศ⿣ࡢᑠࡉ࠸஧㔜⥺࡟

Fig 1
Fi
1. C
Crystalt l structurett
off
Fe(pyridine)2[Ni(CN)4]

ኚ໬ࡍࡿࠋከࡃࡢ Hofmann ᆺ SCO 㘒యཬࡧ㛵㐃㘒య࡟࠾࠸࡚ࡶᙜ
◊✲ᐊ࡟ࡼࡾሗ࿌ࡉࢀ࡚࠾ࡾ [1-11]ࠊࡑࢀࡽࡢ໬ྜ≀ࡢ Mössbauerࢫ࣌ࢡࢺࣝࡢ

ᗘ౫Ꮡᛶ࡟ࡘ࠸࡚ࡶሗ࿌ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊ௚ࡢ◊✲ᐊ࡟ࡼࡗ࡚ࡶ㛵㐃 SCO 㘒యࡢ◊✲౛ࡶከࡃሗ࿌ࡉࢀ࡚࠸ࡿࠋ
[12-18]ࠋᙜ◊✲ᐊ࡛㐣ཤ࡟ሗ࿌ࡉࢀࡓ Hofmann ᆺ SCO 㘒యࡢ 1
ࡘ࡟ࠊFe(4-methylpyridine)2 [Au(CN)2]2 ࡀ࠶ࡿࠋࡇࡢ㘒యࡣࠊ3 ẁ㝵ࡢࢫࣆࣥ㌿⛣ࢆ♧ࡍ⯆࿡῝࠸ SCO ᣲືࡀሗ࿌ࡉࢀ࡚࠸ࡿ (Tc1 =216, TcŅ =192, TcŃ = 193, TcŅ =171, TcŃ = 174 K)[19] ࠋ௒ᅇࠊࡇ

15

Fig 2. Magnetic susceptibility ofFe(pyridine)2[Ni(CN)4]ࡢ㘒యࡢ㓄఩Ꮚࢆ 4-methylpyridine ࠿ࡽ 4-methylpyrimidine ࡟ኚ࠼ࡓ᪂つ Hofmann ᆺ SCO 㘒య࡛࠶ࡿ Fe(4-methylpyrimidine)2[Ag(CN)2]2 (௨ୗ㘒య1)ཬࡧ Fe(4-methylpyrimidine)2 [Au(CN)2]2(௨ୗ㘒య 2)ࢆྜᡂࡋࠊࡑࡢ≀ᛶࢆホ౯ࡋࡓࠋ2.ᐇ㦂㘒య 1 ࡜㘒య 2 ࡢ⢊ᮎ⤖ᬗࡣ௨ୗࡢ᪉ἲ࡟ࡼࡾྜᡂࡋࡓࠋ
㘒య 1:ࢧࣥࣉࣝ⎼࡟ Fe(NH4)2(SO4)2㺃6H2O(Mohr ሷ)ࠊK[Ag(CN)2]2 ࢆࣔࣝẚ 1:2 ࡢ๭ྜ࡛ຍ࠼ࠊࡇ
ࢀࢆỈ࡟⁐ゎࡋࠊࡑࡇ࡟㉸㡢Ἴ᧠ᢾࢆࡋ࡞ࡀࡽ 4-methylpyrimidine ࢆ⁲ୗࡋࡓࠋ2-3 ᪥ᚋ⏕ࡌࡓỿ⃦
ࢆℐ㐣ࡋࡓࠋ
㘒య 2:ࢧࣥࣉࣝ⎼࡟ Fe(NH4)2(SO4)2㺃6H2O(Mohr ሷ)ࠊL-࢔ࢫࢥࣝࣅࣥ㓟ࠊK[Au(CN)2]2 ࢆࣔࣝẚ 1:1:2
ࡢ๭ྜ࡛ຍ࠼ࠊࡇࢀࢆỈ࡟⁐ゎࡋࠊࡑࡇ࡟㉸㡢Ἴ᧠ᢾࢆࡋ࡞ࡀࡽ 4-methylpyrimidine ࢆ⁲ୗࡋࡓࠋ2-3
᪥ᚋ⏕ࡌࡓỿ⃦ࢆℐ㐣ࡋࡓࠋ㘒య 1 ࡜㘒య 2 ࡢ༢⤖ᬗࡣ௨ୗࡢ᪉ἲ࡟ࡼࡾྜᡂࡋࡓࠋ
㘒య 1:ࢧࣥࣉࣝ⎼࡟࣮ࣔࣝሷࠊࢩ࢔ࣥ໬㖟࣒࢝ࣜ࢘ࢆࣔࣝẚ 1:2 ࡢ๭ྜ࡛ຍ࠼ࠊࡇࢀࢆỈ࡟⁐ゎࡉࡏࡓࠋ⁐ᾮࡢධࡗࡓࢧࣥࣉࣝ⎼ࢆ 4-methylpyrimidine ࢆຍ࠼ࡓࡼࡾ኱ࡁ࡞ࢧࣥࣉࣝ⎼ࡢ୰࡟ධࢀ⵹ࢆࡋࠊ
3 ᪥-1 㐌㛫ᚋ⏕ࡌࡓ⤖ᬗࢆℐ㐣ࡋࡓࠋ࡞࠾ࠊ༢⤖ᬗヨᩱ࡜⢊ᮎ⤖ᬗヨᩱࡣྠᙧ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ
㘒య 2:ࢧࣥࣉࣝ⎼࡟࣮ࣔࣝሷࠊL-࢔ࢫࢥࣝࣅࣥ㓟ࠊࢩ࢔ࣥ໬㔠࣒࢝ࣜ࢘ࢆࣔࣝẚ 1:1:2 ࡢ๭ྜ࡛ຍ࠼ࠊ
ࡇࢀࢆỈ࡟⁐ゎࡉࡏࡓࠋ⁐ᾮࡢධࡗࡓࢧࣥࣉࣝ⎼ࢆ
4-methylpyrimidine ࢆຍ࠼ࡓࡼࡾ኱ࡁ࡞ࢧࣥࣉࣝ⎼ࡢ୰࡟ධࢀ
⵹ࢆࡋࠊ3 ᪥-1 㐌㛫ᚋ⏕ࡌࡓ⤖ᬗࢆℐ㐣ࡋࡓࠋྜᡂࡋࡓ༢⤖ᬗࢆ⏝࠸࡚༢⤖ᬗ X ⥺ᵓ㐀ゎᯒࢆࠊ⢊ᮎ⤖ᬗࢆ⏝࠸࡚☢໬⋡ ᐃࠊ
㘒య 1:࡟ࡘ࠸࡚ࡣ 57Fe Mössbauerᐃࢆ⾜ࡗࡓࠋ

㘒య 2:࡟ࡘ࠸࡚ࡣࠊ㘒య୰ࡢ Au ཎᏊࡢ L1 ྾཰➃ࡢ࢚ࢿࣝࢠ࣮
(14.353 keV)࡜ 57Fe Mössbauerᐃ࡟౑⏝ࡍࡿ Ǆ ⥺ࡢ࢚ࢿࣝࢠ࣮

(14.4 keV)ࡢ࢚ࢿࣝࢠ࣮ࡀᴟࡵ࡚㏆࠸ࡓࡵ࡟ࠊࡇࡢ Ǆ ⥺ࡀ྾཰ࡉࢀࠊᐃࡢጉᐖ࡜࡞ࡗ࡚ࡋࡲ࠺ࡓࡵ ᐃࢆ⾜ࢃ࡞࠿ࡗࡓࠋ࡞࠾ࠊ

Fig 3. Magnetic susceptibility of྾཰యࢆⷧࡃࡍࡿࡇ࡜࡟ࡼࡾࡇࡢጉᐖࢆ㍍ῶࡍࡿࡇ࡜ࡀ࡛ࡁ[20]ࠊ
Fe(4-methylpyrimidine)2[Ag(CN)2]2
ᐇ㝿࡟ Au ࢆྵࡴ㕲㘒య࡛ 57Fe Mössbauer ᐃࢆ⾜ࡗࡓ౛ࡣᏑ
ᅾࡍࡿࡀ[21]ࠊࡇࡢሙྜ࡛ࡶᙳ㡪ࢆཷࡅ࡞࠸ Ag 㘒య࡜ẚ㍑ࡋ࡚
ࢫ࣌ࢡࢺࣝ୰ࡢ Ǆ ⥺ࡢᙉᗘࡣ኱ࡁࡃపୗࡋ࡚࠸ࡿࠋ

3.⤖ᯝ࡜⪃ᐹ
3.1. ☢໬⋡ᐃ

Fig.3, 4 ࡟㘒య 1 ཬࡧ㘒య 2 ࡢ☢໬⋡ᐃࡢࢹ࣮ࢱࢆ♧ࡍࠋ㘒య 1 ࡣ 130 – 140
ᐃࡣ 4 K – 300 K ࡲ࡛ 1 K min-1 ࡛⾜ࡗࡓࠋK ࡢ㛫࡛ 6 K ࡢࣄࢫࢸࣜࢩࢫࢆᣢࡗࡓ 1 ẁ㝵ࡢࢫࣆࣥ㌿⛣ࢆ(TcŃ= 138 K, TcŅ = 132 K)ࠊ㘒య 2 ࡟ࡘ࠸࡚ࡣ 180 – 200 K ࡢ㛫࡛

Fig 4. Magnetic susceptibility of2 ẁ㝵┠࡟ 1 K ࡢࣄࢫࢸࣜࢩࢫࢆ♧ࡍ 2 ẁ㝵ࡢࢫࣆࣥ㌿⛣ࢆFe(4-methylpyrimidine)2[Au(CN)2]2

1㻢

♧ࡋࡓࠋ(Tc1 = 202 K, TcŃ = 187 K, TcŅ = 186 K) 㘒య 2 ࡢ 190 K ࡟Ꮡᅾࡍࡿ୰㛫≧ែ࡛ࡣࠊ☢໬⋡ࡀ
ᐊ

࡛ࡢ್࡜ప

࡛ࡢ್ࡢ୰㛫⛬ᗘࡢ್ࢆ࡜ࡗ࡚࠸ࡓࠋࡲࡓࠊ㘒య 2 ࡟ࡘ࠸࡚ࠊ㐣ཤ࡟ሗ࿌ࡉࢀ࡚࠸ࡿ

㘒య࡛࠶ࡿ Fe (4-methylpyridine)2[Au(CN)2]2[19]࡜㌿⛣ᗘࢆẚ㍑ࡍࡿ࡜ࠊ㌿⛣ ᗘࡀ 10 – 15 K 㧗ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡓࠋࡇࢀࡽ 2 ࡘࡢࣆ࣑ࣜࢪࣥ㘒యࡢ㛫࡛ࡣࠊࣄࢫࢸࣜࢩࢫࡢ᭷↓ࡸ㌿⛣ࡢẁᩘ➼ࡢࢫࣆࣥᣲື࡟኱ࡁ࡞ᕪࡀ࠶ࡗࡓࠋࡇࡢせᅉ࡜ࡋ࡚ࡣࠊ㘒య 1 ࡣ༢ᒙᵓ㐀࡛࠶ࡿࡢ࡟ᑐࡋࠊ㘒య 2 ࡣ஧ᒙᵓ㐀࡛࠶ࡿࡇ࡜࡟ࡼࡾ༙ศࡢ㕲ཎᏊࡀࢫࣆࣥ㌿⛣ࡋࡓ≧ែࡶྲྀࢀࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋ
3.2. ⤖ᬗᵓ㐀㘒య 1 ཬࡧ㘒య 2 ࡢ 298 K ཬࡧ᏶඲࡟ࢫࣆࣥ㌿⛣ࡋࡓప (㘒య 1 ࡢሙྜ 150 Kࠊ
㘒య 2 ࡢሙྜ 100 K)࡛ࡢ⤖ᬗᵓ㐀ࢆẚ㍑ࡋࡓࠋᐊ ࡛ࡢ୧㘒యࡢᵓ㐀ࢆẚ㍑ࡍࡿ࡜ࠊ㘒య 1 ࡣ༢ᒙࡢ Hofmann ᆺ㦵᱁ࢆᣢࡕ✵㛫⩌ࡀ Pccn ࡛࠶ࡾࠊࣆ࣑ࣜࢪࣥ⎔ࡢ㕲࡟㓄఩ࡋ࡚࠸࡞࠸❅⣲ཎᏊࡀ㖟ཎᏊ࡜᥋㏆ࡋ࡚࠸ࡓࠋࡇࢀ
࡟ᑐࡋࠊ㘒య 2 ࡣぶ㔠┦஫స⏝࡟ࡼࡿ஧ᒙᵓ㐀ࢆᣢࡕ✵㛫⩌ࡀ Pbcm ࡛࠶ࡾࠊࣆ࣑ࣜࢪࣥ⎔ࡢ㕲࡟㓄఩ࡋ࡚࠸࡞࠸㕲ཎᏊࡣ 2 ࡘࡢ᪉ྥࡢ㛫࡛ࢹ࢕ࢫ࣮࢜ࢲ࣮ࢆ㉳ࡇࡋ࡚࠸ࡓࠋࡲࡓࠊ㘒య 1 ࡟ࡘ࠸࡚ࡣ 296 K
ཬࡧ 100 K ࡛ࡢᵓ㐀ࢆẚ㍑ࡍࡿ࡜✵㛫⩌ࡣྠࡌ Pccn ࡛࠶ࡿࡀࠊFe – N(CN)㛫ࡢ⤖ྜࡀ 2.148(6) Å ࠿
ࡽ 1.945(7) Å ࡜▷ࡃ࡞ࡾࠊ༢఩⬊ࡀ 1969.9(4) Å3 ࠿ࡽ 1826(2) Å3 ࡬⦰ᑠࡋࡓࠋࡇࢀࡣ☢໬⋡ ᐃ࡛ࡢᣲືࢆᨭᣢࡍࡿࠋ୍᪉ࠊ㘒య 2 ࡟ࡘ࠸࡚ࡣ 298 K ཬࡧ 150 K ࡛ࡢᵓ㐀ࢆẚ㍑ࡍࡿ࡜✵㛫⩌ࡣྠࡌ Pbcm
࡛࠶ࡿࡀࠊFe – N(CN)㛫ࡢ⤖ྜࡀ 2.151(4) Å ࠿ࡽ 1.949(4) Å ࡜▷ࡃ࡞ࡾࠊ༢఩⬊ࡀ 2059.0(3) Å3 ࠿ࡽ 1911.4(3) Å3 ࡬⦰ᑠࡋࡓࠋ
ࡲࡓࠊ190 K ࡛ࡣ༢఩⬊ࡢᑐ⛠ᛶࡀ P21/m ࡟పୗࡋࠊ㕲ࡀ 2 ࢧ࢖ࢺᏑᅾࡋ࡚࠸ࡓࠋࡇࡢ᫬ࡢ㕲ࢧ࢖ࢺࡣ Fe – N(CN)㛫ࡢ⤖ྜ㛗ࡀ
2.14(3) Å ࡜ 1.98(2) Å ࡢ 2 ✀㢮࠶ࡾࠊ㧗ࢫࣆࣥ≧ែ࡛ࡢ㊥㞳࡜పࢫࣆࣥ≧ែ࡛ࡢ㊥㞳ࡢࡶࡢࡢ 2 ✀㢮ࡀ஺஫࡟Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀ
ศ࠿ࡗࡓࠋࡇࢀࡣࡇࡢ㘒యࡀ 2 ẁ㝵ࡢࢫࣆࣥ㌿⛣ࢆ♧ࡍ࡜࠸࠺☢
໬⋡ᐃࡢᣲືࢆᨭᣢࡍࡿࠋࡍ࡞ࢃࡕࠊ୰㛫≧ែ࡛ᑐ⛠ᛶపୗࡀ㉳ࡁ࡚࠸ࡿࠋ
3.3. Mössbauerᐃ

Fig.5 ࡟㘒య 1 ࡢ 57Fe Mössbauer༷᫬࣭᪼ᐃࡢࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ෭᫬࡜ࡶ࡟ 㻝㻠㻜㻌㻷 ࠿ࡽ 㻝㻟㻜㻌㻷 ࡢ㛫࡛㧗ࢫࣆࣥ≧ែ㕲㻔㻵㻵㻕ཎᏊࡢᅄᴟศ⿣ࡀ኱ࡁ࠸ࢲࣈࣞࢵࢺ࠿ࡽపࢫࣆࣥ≧ែ㕲㻔㻵㻵㻕ཎᏊࡢᅄᴟศ⿣ࡀᑠࡉ࠸ࢲࣈࣞࢵࢺ࡬ࡢኚ໬ࡀ࠶ࡾࠊ␗ᛶయࢩࣇࢺࡀኚ
໬ࡋࡓࠋ295 K ཬࡧ 78 K ࡛ࡢ್ࡣୗࡢ Table 1 ࡢ࡜࠾ࡾ࡛࠶ࡿࠋ
Table 1. IS , QS and ƥ of complex 1
T/K

Spin state

IS / mm s-1

QS / mm s-1

ƥ / mm s-1

295

HS

1.078

1.178

0.266

Fig 5. 57Fe Mössbauer spectra of

78

LS

0.479

0.284

0.285

Fe(4-methylpyrimidine)2[Ag(CN)2]2

1㻣

295 K ཬࡧ 78 K ࡛ࡢࢫ࣌ࢡࢺࣝࡢ㉸ᚤ⣽ᵓ㐀ࣃ࣓࣮ࣛࢱ࣮ࡣࡑࢀࡒࢀ㧗ࢫࣆࣥ≧ែ㕲(II)ࡢࢫ࣌ࢡࢺࣝ
࠾ࡼࡧపࢫࣆࣥ≧ែ㕲(II)ࡢඵ㠃య 6 㓄఩ᵓ㐀ࡢ㉸ᚤ⣽ᵓ㐀ࣃ࣓࣮ࣛࢱ࣮ࡢ⠊ᅖ࡟࠶ࡿࠋ࣓ࢫࣂ࢘࢔࣮
ࢫ࣌ࢡࢺࣝࡼࡾࠊヨᩱ୰ࡢ㕲ཎᏊࡣࡍ࡭࡚㕲(II)࡜ࡋ࡚Ꮡᅾࡋࠊ௚ࡢ౯ᩘࡢ㕲ཎᏊࡣྵࡲࢀ࡚࠾ࡽࡎࠊ
Ỉࡀ㓄఩ࡋࡓ㘒యࡶྵࡲࢀ࡚࠸࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋࡇࡢ⤖ᯝࡣ☢໬⋡ ᐃࡢ⤖ᯝࢆᨭᣢࡍࡿࡶࡢ࡛࠶ࡿ
ࡀࠊ☢໬⋡ᐃ࡟࠾࠸࡚ほ ࡉࢀࡓࣄࢫࢸࣜࢩࢫࡣ㠀ᖖ࡟ᑠࡉ࡞ࡶࡢ࡜࡞ࡗ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞⤖ᯝ࡜࡞ࡗࡓせᅉ࡜ࡋ࡚ࠊ☢໬⋡ ᐃ࡛ࡣ 1 K min-1 ࡢ㏿ᗘ࡛㝆࡛ࠊMössbauerᐃ࡛ࡣ 1 ࡘࡢヨᩱ࡟ᑐࡋᩘ᪥࠿ࡅ࡚

࣭᪼ࢆ⾜࠸ࡑࡢ᫬ࡢࢹ࣮ࢱࢆ࡜ࡗࡓ୍᪉

ᐃࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ⇕ᖹ⾮ࡢ≧ែ࡛ᐃࢆ⾜ࡗࡓ࡜࠸࠺㐪࠸ࡀ࠶ࡾࠊࡇࢀ࡟ࡼࡾࣄࢫࢸࣜࢩࢫࡢᣲືࡀኚ໬ࡋࡓࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋ☢໬⋡ ᐃ࡟࠾࠸࡚ࠊ ᗘኚ໬ࡢ㏿ᗘࢆኚ࠼ࡿࡇ࡜࡟ࡼࡾࣄࢫࢸࣜࢩࢫࡀኚ໬ࡍࡿ⌧㇟ࡣሗ࿌౛ࡀ࠶ࡾ[22-26]ࠊࡇࢀࡽ
ࡢከࡃࡀ ᗘࡢኚ໬㏿ᗘࢆ㐜ࡃࡍࡿ࡜ࣄࢫࢸࣜࢩࢫࡀ⊃ࡃ࡞ࡗ࡚࠸ࡿࠋ௒ᅇࡢ㘒య࡛ࡶࠊࡇࡢࡼ࠺࡞⌧㇟࡟ࡼࡾࡺࡗࡃࡾ࡜ ᗘኚ໬ࢆ⾜ࡗࡓ Mössbauerᐃ࡛ࡣࣄࢫࢸࣜࢩࢫࡀ㠀ᖖ࡟ᑠࡉࡃ࡞ࡗࡓ࡜⪃࠼

ࡽࢀࡿࠋ

4.ࡲ
ࡲ࡜ࡵ
௒ᅇࠊ㘒య 1 ཬࡧ㘒య 2 ࢆྜᡂࡋࠊࡑࡢ≀ᛶࢆホ౯ࡋࡓࠋࡲࡎࠊ୧㘒యࡢ⤖ᬗᵓ㐀ࢆẚ㍑ࡍࡿ࡜ࠊ㘒య 1 ࡣ༢ᒙᵓ㐀࡛࠶ࡿࡢ࡟ᑐࡋࠊ㘒య 2 ࡣぶ㔠┦஫స⏝࡟ࡼࡿ஧ᒙᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿ࡜࠸࠺㐪࠸ࡀぢࡽࢀࡓࠋ㻌ḟ࡟ࠊ୧㘒యࡣඹ࡟ SCO ᣲືࢆ♧ࡍࡀࠊ୧⪅ࡣࡑࡢᣲືࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ㘒య 1 ࡣ
1 ẁ㝵ࡢ SCO ࡛࠶ࡾࠊ㘒య 2 ࡣ 2 ẁ㝵 SCO ࡛࠶ࡾࠊ኱ࡁࡃ㌿⛣ᗘࡶ␗࡞ࡗ࡚࠸ࡿࠋࡇࢀࡣࠊ㘒య 1ࡣ༢ᒙᵓ㐀࡛࠶ࡿࡢ࡟ᑐࡋࠊ㘒య 2 ࡣ஧ᒙᵓ㐀࡛࠶ࡿࡇ࡜࡟ࡼࡿࡶࡢ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㘒య
2 ࡟ࡘ࠸࡚ࠊ㐣ཤ࡟ሗ࿌ࡉࢀࡓ㘒య࡛࠶ࡿ Fe (4-methylpyridine)2[Au(CN)2]2 ࡜㌿⛣ ᗘࢆẚ㍑ࡍࡿ࡜ࠊ㌿⛣ᗘࡀ 10 – 15 K 㧗ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡓࠋ

ࡲࡓࠊ㘒య 1 ࡢ 57Fe Mössbauerᐃ࡛ࡣࠊ෭༷᫬࣭᪼

᫬࡜ࡶ࡟ 㻝㻠㻜㻌㻷 ࠿ࡽ 㻝㻟㻜㻌㻷 ࡢ㛫࡛㧗ࢫࣆࣥ≧ែ㕲㻔㻵㻵㻕ཎᏊࡢᅄᴟศ⿣ࡀ኱ࡁ࠸ࢲࣈࣞࢵࢺ࠿ࡽపࢫࣆࣥ≧ែ㕲㻔㻵㻵㻕ཎᏊࡢᅄᴟศ⿣ࡀᑠࡉ࠸ࢲࣈࣞࢵ
ࢺ࡬ࡢኚ໬ࡀぢࡽࢀࠊ☢໬⋡ ᐃ࡜ྠᵝࡢ 㻿㻯㻻 ⌧㇟ࡀほࡉࢀࡓࠋࣄࢫࢸࣜࢩࢫࡢᖜࡀ㠀ᖖ࡟ᑠࡉࡃ࡞ࡗࡓせᅉ࡜ࡋ࡚ࡣࠊ☢໬⋡ ᐃ࡜ࡣ␗࡞ࡾ⇕ᖹ⾮ࡢ≧ែ࡛ ᐃࢆ⾜ࡗࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ㻌
௒ᅇࠊ57Fe Mössbauerᐃࢆࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓ 㘒య 2 ࡟ࡘ࠸࡚ࡣࠊ᭱㏆㌾ X ⥺࡟ࡼࡿ㧗ࢫࣆࣥ≧ែࡢᤕᤊ(SOXIESST)ࡀほ
Mössbauerࡉࢀ࡚࠾ࡾ[27]ࠊ57Co ࢆ⏝࠸ࡓ Co(pyridine)2[Ni(CN)4]ࡢⓎගᐃ࡟ࡼࡾ᰾ᔂቯ࡟ࡼࡿపࢫࣆࣥ≧ែ࠿ࡽ㧗ࢫࣆࣥ≧ែࡢᤕᤊ(NIESST) [28] ࡀほ࡚࠸ࡿࡢ࡛ࠊྠᵝ࡞ࡇ࡜ࡀ Co(4-methylpyrimidine)2[Au(CN)2 ࡛ほࡉࢀࡉࢀࡿ࠿ࢆ᳨ウࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓ Fe(pyridine)2[Ni(CN)4]࡟࠾࠸࡚ࡶ SOXIESST ⌧㇟ࡀほ ࡉࢀ࡚࠾ࡾࠊ
[27]NIEEST ⌧㇟࡜ SOXIESST ⌧㇟ࡢ㛵㐃ᛶࢆ᳨ウࡋ࡚࠸ࡃࡇ࡜ࡶ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
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T. Sato, F. Ambe, T. Kitazawa, H. Sano, M. Takeda, Chem. Lett., 26, 1287 (1997)㻞㻜ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮ᣲືࢆ♧ࡍ +RIPDQQOLNH' 㘒య໬ྜ≀ࡢ≉ᛶホ౯(YROXWLRQIRU6SLQ&URVVRYHU'+RIPDQQOLNH&RRUGLQDWLRQ3RO\PHUVᮾ㑥኱⌮  ᮾ㑥኱」ྜ≀ᛶࢭࣥࢱ࣮

ᮾ㑥኱⌮  ᮾ㑥኱」ྜ≀ᛶࢭࣥࢱ࣮
໭⃝Ꮥྐ ࠊ᳝ྡ▖ ࠊ㧗ᶫṇ 
7DNDIXPL .LWD]DZD  +LWRPL6KLLQD DQG0DVDVKL7DNDKDVKL'HSDUWPHQWRI&KHPLVWU\)DFXOW\RI6FLHQFH7RKR8QLYHUVLW\
5HVHDUFK&HQWHUIRU0DWHULDOVZLWK,QWHJUDWHG3URSHUWLHV 7RKR8QLYHUVLW\㸬ࡣࡌࡵ࡟ 㧗ࢫࣆࣥ≧ែ࡜పࢫࣆࣥ≧ែࡢ཮Ᏻᐃ≧ែࢆ ᗘࠊᅽຊࠊගࠊ☢ሙࠊࢤࢫࢺศᏊ⬺╔➼ࡢእ㒊่⃭࡟ࡼࡾ ᮶ࡍࡿࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮㻔6&2㻕ᣲືࡣ 㼐㻢 ࡛࠶ࡿ )H,, 㘒య࡟ࡘ࠸࡚ከࡃ◊✲ࡉࢀ࡚࠾ࡾࠊ㓄఩㧗ศᏊ㘒య࡟ࡘ࠸࡚ࡶᯫᶫ㓄఩Ꮚ࡟ࡼࡿ༠ྠຠᯝࡀᮇᚅࡉࢀࡿࡇ࡜࠿ࡽ⢭ຊⓗ࡟◊✲ࡉࢀ࡚࠸ࡿ>@ࠋ≉࡟ࢩ࢔ࢽࢻᇶࡣࠊ༢ᗙ㓄఩Ꮚ࡜୧ᗙ㓄఩Ꮚࡢ୧᪉ࡢᣲືࢆࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
.>0 &1 @ 0 1L,,3G,,3W,, ࡛ࡣࢩ࢔ࢽࢻᇶࡀ༢ᗙ㓄఩Ꮚ࡜ࡋ࡚ᣲືࡍࡿⅭࠊᖹ㠃ᅄ㓄఩༢᰾㘒య࡜࡞ࡿࠋࡲࡓ .>0 &1 @ 0  1L,, 3G,, 3W,, ࢆ౑⏝ࡋࡓ࣍ࣇ࣐ࣥᆺ㓄఩㧗ศᏊ 6&2 㘒య)H / 0 &1  / /LJDQG0 1L,,3G,,3W,, ࡛ࡣࢩ࢔ࢽࢻᇶࡀᯫᶫ㓄఩Ꮚ࡜࡞ࡾࠊඵ㠃యභ㓄఩ᵓ㐀ࢆྲྀࡿ )H,, ࡜ᅄ㠃యᅄ㓄఩ᵓ㐀ࢆྲྀࡿ 0 ࢆ㐃⤖ࡋ࡚࠸ࡿࠋࡼࡗ࡚ )H / 0 &1  ࡣ  ḟඖᒙ≧ᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿ㓄఩㧗ศᏊ㘒య࡛࠶ࡾࠊ/ ࢆኚ໬ࡉࡏࡿࡇ࡜࡟ࡼࡾᵓ㐀ไᚚࡀྍ⬟࡛࠶ࡿ>@ࠋ㓄఩㧗ศᏊࢆ࣍ࢫࢺ㦵᱁࡟᭷ࡍࡿ࣍ࣇ࣐ࣥᆺ 6&2 㘒యࡣࠊ஧ḟඖ࣍ࢫࢺࡢᵓᡂ㔠ᒓ࢖࢜ࣥࠊ࣍
ࢫࢺ㠃ࢆᨭ࠼ࡿ㓄఩Ꮚࠊᒙ㛫ࡢ✵Ꮝ࡟ໟ᥋ࡉࢀࡓ᭷ᶵࢤࢫࢺศᏊ➼࠿ࡽ࡞ࡗ࡚࠾ࡾࠊࡑࡢ☢Ẽᣲືࡀࡇࢀࡽࡢᵓᡂせ⣲ࡢከᵝ࡞⤌ࡳྜࢃࡏ࡛⯆࿡῝࠸᭷┈࡞ᣲືࢆ♧ࡍࡇ࡜ࡀぢฟࡉࢀ࡚࠸ࡿ
>@ࠋᙜࢢ࣮ࣝࣉ࡛ࡣࠊ ᖺ࡟࣍ࣇ࣐ࣥᆺໟ᥋య㘒యࡢ⣔⤫ⓗ◊✲㐣⛬࡟࠾࠸࡚ࠊ⌧ᅾࡢ 6&2◊ ✲ ࡟ ࠾ ࠸ ࡚ ከ ኱ ࡞ ࣄ ࣥ ࢺ ࢆ ୚ ࠼ ࡚ ࠸ ࡿ  ḟ ඖ ᵓ 㐀 ࢆ ᭷ ࡍ ࡿ ㉸ ศ Ꮚ 6&2 ໬ ྜ ≀)H S\ULGLQH >1L &1 @ࢆぢฟࡋ࡚࠾ࡾࠊࡇࡢ໬ྜ≀ࡣప ࡛☢Ẽ㌿⛣ࢆ♧ࡍࡇ࡜ࡀ 648,' ࡜࣓ࢫࣂ࢘࢔࣮ศගἲࢆ⏝࠸࡚ド᫂ࡉࢀࡓ>D@ࠋࡉࡽ࡟༢⤖ᬗᵓ㐀ゎᯒ࠿ࡽ☢Ẽ㌿⛣ࢆ )H,, ࢖࢜ࣥ࿘ࡾࡢ
㓄఩ᵓ㐀ኚ໬ࢆ㧗ࢫࣆࣥ +6 ࡜పࢫࣆࣥ /6 㛫ࡢྍ㏫ⓗኚ᥮࡟㛵㐃௜ࡅࡿࡇ࡜ࡀ࡛ࡁࡓࠋ୍᪉㸪ࢫ࣌࢖ࣥࡢ 5HDO ᩍᤵࡽࡢࢢ࣮ࣝࣉࡣࠊඵ㠃య  㓄఩㕲 ,, ࢖࢜ࣥ࡟㓄఩ࡋ࡚࠸ࡿ S\ULGLQH ࢆᯫᶫ㓄఩Ꮚ࡜࡞ࡾᚓࡿ S\UD]LQH ࡟ኚ࠼ࡓ  ḟඖᵓ㐀㘒య>)H S\UD]LQH 0 &1 @Q+2 ࢆྜᡂࡋࠊᐊ ௜㏆࡛ࡢࢫࣆࣥ㌿⛣ ᗘࢆᐇ⌧ࡋࡓ>E@ࠋࡇࡢ⤖ᯝࡣ㸪ḟඖᛶࢆ㧗ࡵࡿࡇ࡜࡛᱁Ꮚෆࡢ㔠ᒓ࢖࢜ࣥ㛫ࡢ༠ྠຠᯝࡀ㧗ࡵࡽࢀ㸪ࡑࢀ࡟௜㝶ࡋ࡚㧗࠸ࢫࣆࣥ㌿⛣ ᗘ࡜኱ࡁ࡞ࣄࢫࢸࣜࢩࢫࢆᐇ⌧ࡍࡿࡇ࡜ࡀྍ⬟࡞ࡇ࡜ࢆ♧ࡋࡓࠋࡇࢀࡽࡢ◊✲࡟ゐⓎࡉࢀࠊ᭱㏆࡛ࡣᅜෆࠊᅜእࡢከࡃࡢ◊✲ࢢ࣮ࣝࣉࡀࡇࡢ✀ࡢ㉸ศᏊࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮㘒య࡟ࡘ࠸࡚ࡢ◊✲࡟╔ᡭࡋ࡚࠸ࡿ>@ࠋࡍ࡞ࢃࡕࠊ
ࣉࣟࢺࢱ࢖ࣉ࡛࠶ࡿ>)H S\ULGLQH 1L &1 @ࡣከᙬ࡞ᵓ㐀ᒎ㛤ࡀྍ⬟࡛࠶ࡾࠊࡑࡢᵓ㐀ᒎ㛤࡟ࡼࡾ
6&2 ᣲືࡢไᚚ࡬ࡢࣇ࢕࣮ࢻࣂࢵࢡࡀ⾜࠼ࡿྍ⬟ᛶࡀ኱ࡁ࠸⣔࡛࠶ࡿࠋࢃࢀࢃࢀࡢࢢ࣮ࣝࣉࡶࡑ
ࡢᚋࡢ◊✲࡛ࠊ⤖ᬗᏛⓗ࡟ྠᆺ࡞ࣇ࣮࣒࣮ࣞ࣡ࢡ୰࡟❧య໬Ꮫⓗぢᆅ࠿ࡽ⣔⤫ⓗ࡟㑅ࢇࡔ୍㐃ࡢࢤࢫࢺ✀ࢆໟ᥋ࡉࡏࠊᚓࡽࢀࡓ໬ྜ≀࡟ࡘ࠸࡚ᗈ࠸ ᗘ⠊ᅖࡢ༢⤖ᬗᵓ㐀ゎᯒ࡜☢Ẽ ᐃࢆ ᐃ21ࡋࡓࠋࡑࡢ⤖ᯝࠊ᱁Ꮚ࡜ࢤࢫࢺ࠾ࡼࡧࢤࢫ
ࢺྠኈࡢ༠ྠⓗ┦஫స⏝ Ỉ⣲⤖ྜࡸ ʌ㸫ʌࢫࢱࢵ࢟ࣥࢢ࡞࡝ ࡀࠊ☢Ẽ㌿⛣ᣲືࢆᚤጁ
࡟ᙳ㡪ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚ࡁ࡚
࠸ࡿࠋࡲࡓࠊ㏆ᖺࢤࢫࢺศᏊࡢ࣍ࢫࢺ┦࡟࠾ࡅࡿࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮ᣲື࡬ࡢᙳ㡪࡟㛵ࡍࡿ◊✲ࡶ┒ࢇ࡟࡞ࡗ࡚࠸ࡿ>@ࠋ௒ᅇࡣ㟁Ẽ㝜ᛶᗘࡀẚ㍑ⓗ㧗࠸ 2 ཎᏊࢆྵࡳ࠿ࡘച㧗࠸ S\ULGLQH ⣔㓄఩Ꮚࡀ࡝ࡢࡼ
࠺࡟ 6&2 ᣲື࡟ᙳ㡪ࢆ୚࠼ࡿ࠿ࡢほⅬ࠿ࡽࠊ(WK\O,VRQLFRWLQDWH ࢆ㓄఩Ꮚ࡜ࡋࡲࡓᖹ
㠃ᅄ㓄఩ᆺࣘࢽࢵࢺ࡟>3W &1 @ࢆ᭷ࡍࡿ㸰ḟඖ㓄఩㧗ศᏊ࣍ࣇ࣐ࣥᆺࢫࣆࣥࢡࣟࢫ࢜
࣮ࣂ࣮㘒య )H (WK\O ,VRQLFRWLQDWH >3W &1 @࡟ࡘ࠸࡚ࠊ⤖ᬗᏛⓗほⅬ࠾ࡼࡧ࣓ࢫࣂ࢘࢔
࣮ศගᏛⓗ࡟◊✲ࡋࡓࠋࡲࡓࠊ>3W &1 @㒊఩ࡀ࡝ࡢࡼ࠺࡟ 6&2 ᣲື࡟ᙳ㡪ࢆ୚࠼ࡿ
Fig. 1 Crystal structure of࠿᳨ウࡋࡓࠋ
Fe(Ethyl Isonicotinate)2[Pt(CN)4]
ࡲࡓࠊ1L 3G ࠾ࡼࡧ 3W ࡣ࡜ࡶ࡟  ᪘ඖ⣲࡛࠶ࡿࡀ࿘ᮇࡢ㐪࠸ࡀ࡝ࡢࡼ࠺࡟ 6&2
࡟ᙳ㡪ࡍࡿ࠿ࡶ᳨ウࡋࡓࠋ㸬ᐇ㦂 ྜᡂࡣࠊ⮬ᕫ㞟✚໬ᶵ⬟ࢆ⏝࠸ࡓࢫࢵ࣏ࢺྜᡂ࡛⾜ࡗࡓࠋ┤᥋ἲ࡛ࡣ⢊ᮎ⤖ᬗࡢྜᡂࢆ⾜࠸ࠊ⵨Ẽᣑᩓἲ࡛༢⤖ᬗࡢྜᡂࢆ⾜ࡗࡓࠋ)H 1+  62 ࣭+2ࠊ.>0 &1 @ 0  3W ࠊ⦆⾪⁐ᾮ࡜ࡋ࡚ࢡ
࢚ࣥ㓟࡜ GLDPLQRSURSDQH ࢆỈ࡟⁐࠿ࡋࠊ(WK\O,VRQLFRWLDQWH ࢆ཯ᛂࡉࡏࡓࠋྜᡂࡋࡓ⢊ᮎ⤖ᬗ࡛ 57Fe
࣓ࢫࣂ࢘࢔࣮ศග ᐃࢆ⾜ࡗࡓࠋ༢⤖ᬗヨᩱ࠾ࡼࡧ⢊ᮎヨᩱ࡜ࡶ࡟ࠊྠᙧᵓ㐀ࢆ᭷ࡋ࡚࠸
ࡿࡇ࡜ࢆ⤖ᬗᏛⓗᐇ㦂ࡼࡾ☜ㄆࡋࡓࠋ࡞࠾ࠊ
⣔࡟ࡼࡗ࡚ࡣࠊ⢊ᮎ⤖ᬗ࡜༢⤖ᬗࡀ␗࡞ࡿ☢
Ẽᣲືࢆ♧ࡍከᙧ࡜࡞ࡿࡇ࡜ࡀ࠶ࡿࡀࠊ௒ᅇ
ࡢ㸰ḟඖࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮㘒య
Fe(Ethyl Isonicotinate)2[Pt(CN)4]࡟ࡘ࡚ࡣࠊ
ࡑࡢࡼ࠺࡞ࡇ࡜ࡣ㉳ࡁ࡚࠸࡞࠸ࠋ ⤖ᯝ࡜⪃ᐹ⵨Ẽᣑᩓἲ࡛ ᚓࡽࢀࡓⰋዲ࡞༢⤖ᬗࢆ⏝࠸࡚ Fe(Ethyl Isonicotinate)2[Pt(CN)4]ࡢᵓ
㐀ࢆ X ⥺ᵓ㐀ゎᯒࡼࡾỴᐃࡋࠊFigure 1 ࡟♧ࡍࠋඵ㠃య㸴㓄఩ᵓ㐀ࢆᣢࡘ Fe(II)ࢆ୰ᚰ࡟
Ethyl Isonicotinate ࡢ N ཎᏊࡀ 2 ࡘ㓄఩ࡋ࡚࠾ࡾࠊ࢚ࢡ࢔ࢺࣜ࢔ࣝ఩࡟ 4 ࡘࡢ[Pd(CN)4]2ࡀ↓㝈࡟ᯫᶫࡋࡓ஧ḟඖᵓ㐀ࢆࡋ࡚࠸ࡿࠋ
Fe-N ࡢᖹᆒ⤖ྜ㊥㞳ࡣᐊ ࡛ 2.1785 ύࠊప࡛ 1.966 ύ࡜ࡑࢀࡒࢀ㧗ࢫࣆࣥ≧ែ࠾ࡼࡧపࢫࣆࣥ≧ែ࡟┦ᙜࡋࠊSCO ⌧㇟ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࡀᨭᣢࡉࢀࠊࡇࢀࡣᐊ ࡛㯤Ⰽࠊ  Fig.2 Mössbauer spectra ofFe(Ethyl Isonicotinate)2[Pt(CN)4]22

77 K ࡛㉥Ⰽࡢ໬ྜ≀ࡢⰍࡢኚ໬࡟ࡶ㛵㐃ࡋ࡚࠸ࡿࠋ
Fe(Ethyl Isonicotinate)2[Pt(CN)4]ࡣࠊᖹ㠃ᅄ㓄఩ࣘࢽࢵࢺࢆࡶࡘ㸰ḟඖ㧗ศᏊ㘒య࡛࠶ࡿࡀࠊ┤⥺஧㓄఩ࣘࢽࢵࢺࢆ᭷ࡍࡿ࣍ࣇ࣐ࣥᆺ SCO 㓄఩㧗ศᏊ Fe(L)2[M(CN)2]2 (M = Ag(I), Au(I)) ࡣ Fe2+
࡜ [M(CN)2]㸫 ࡢࣘࢽࢵࢺࡀࢩ࢔ࢽࢻᇶࢆ௓ࡋ࡚㐃⤖ࡋࡓ஧ḟඖࢩ࣮ࢺᵓ㐀࡛࠶ࡾࠊࡇࡢࢩ࣮ࢺࡀ✚ᒙࡋࡓ⤖ᬗᵓ㐀࡜࡞ࡿⅬ࡟࠾࠸࡚ࡣඹ㏻Ⅼࢆᣢࡘ[15-21]ࠋ L ࡣࣆࣜࢪࣥ⣔㓄఩Ꮚ࡛࠶ࡾࠊࢩ࣮ࢺ࡟
ᑐࡋ࡚ᆶ┤᪉ྥ࡟㓄఩ࡋ࡚࠾ࡾࠊ୍ᐃࡢ⨨᥮ᇶࢧ࢖ࢬࡢ㓄఩Ꮚ࡟࠾࠸࡚ࠊࢩ࣮ࢺᵓ㐀ࢆᣢࡗࡓ SCO≀㉁⩌ࢆ㛤Ⓨ࡛ࡁࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡇࡢ≀㉁⣔ࡣᩘከࡃⓎぢࡉࢀ࡚࠸ࡿ࣍ࣇ࣐ࣥᆺ໬ྜ≀ࡢ୰࡛ࡶࠊ㓄఩Ꮚ L ࡢ㑅ᢥࡢᖜࡀᗈࡃࠊ⨨᥮ᇶࡢᴟᛶࡸᔞ㧗ࡉ࡟ࡼࡗ࡚ࣇ࣮࣒࣮ࣞ࣡ࢡᵓ㐀ࡢ◚ቯࢆ㉳ࡇࡋ࡙ࡽ࠸⛥᭷࡞≉ᚩࢆᣢࡘࠋ
Figure 2 ࡢ 57Fe ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࡼࡾࠊ㧗 ࡛ࡣ㧗ࢫࣆࣥ≧ែࡢẚ㍑ⓗ኱ࡁ࡞ᅄᴟศ⿣ࢆ
ࡶࡘࢲࣉࣞࢵࢺࢆ♧ࡋࠊప ࡛ࡣపࢫࣆࣥ≧ែࡢẚ㍑ⓗᑠࡉ࡞ᅄᴟศ⿣ࢆᣢࡘࢲࣈࣞࢵࢺࢆ♧ࡋࠊ
SCO ㌿⛣ࡀ᫂☜࡟♧ࡉࢀ࡚࠸ࡿ 292 K ࡛ࡣ␗ᛶయࢩࣇࢺ(IS) = 1.058 mm s–1ࠊᅄᴟᏊศ⿣(QS) =0.917 mm s–1 ࡛ HS ≧ែࡣ 100 %ࡔࡗࡓࠋ࡞࠾ࠊFe(III)࡜ᛮࢃࢀࡿ୙⣧≀ࡢࣆ࣮ࢡࡀぢࡽࢀࡿࠋ୍᪉
77 K ࡛ࡣ IS = 0.458 mm s–1ࠊQS = 0.302 mm s–1 ࡛ HS ≧ែࡣ 0 %࡜᏶඲࡟ LS ≧ែ࡛࠶ࡗࡓࠋࡲࡓ
292 K ࡛ࡢ IS ࡜ QS ್ࡣ S = 2 ࡢ᫬ࡢ Fe(II)ࡢ⠊ᅖෆ࡟࠶ࡾࠊ77 K ࡛ࡢ IS ࡜ QS ್ࡣ S = 0 ࡢ᫬ࡢ
Fe(II)ࡢ⠊ᅖෆ࡟࠶ࡿⅭࠊࡇࡢ㘒యࡢ Fe ࡣ 2 ౯࡛ࢫࣆࣥ㌿⛣ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ࡞࠾ Pt ࡀ
14 keV ࡢȚ⥺ࢆ㠀ඹ㬆྾཰ࡍࡿࡓࡵȚ⥺ࡢ྾཰ࡀ኱ࡁࡃࠊFe(Ethyl Isonicotinate)2Pd(CN)4 ࡜ẚ࡭ࡿ࡜ࡇࡢ⣔ࡢ࣓ࢫࣂ࢘࢔࣮ࡢ ᐃࡣ㞴ࡋ࠸ࡀࠊヨᩱཌࡳࢆⷧࡃࡋ࡚᫬㛫ࢆ࠿ࡅ࡚ ᐃࡋ࡚ゎᯒྍ⬟࡞ࢫ࣌ࢡࢺࣝࢆᚓࡓࠋ
ࡲࡓࠊ࣓ࢫࣂ࢘࢔࣮ࡢࢹ࣮ࢱࡣࠊSQUID ࡢ ᐃ࡟࠾࠸࡚㝆 ᫬ 214 K ࠿ࡽ 212 K ௜㏆࡟࠿ࡅ࡚ᛴ
⃭࡞ 1 ẁ㝵ࢫࣆࣥ㌿⛣ࡀ㉳ࡇࡾࠊ᪼ ᫬࡟ࡣ 236 K ࠿ࡽ 238 K ௜㏆࡟࠿ࡅ࡚ᛴ⃭࡞ 1 ẁ㝵ࢫࣆࣥ㌿⛣ࡀ㉳ࡇࡾࠊࡑࡢࣄࢫࢸࣜࢩࢫࡀ 24 K ࡛࠶ࡿࡇ࡜࡜୍⮴ࡋ࡚࠸ࡿࠋ
ࡲࡓࠊFe(Ethyl Isonicotinate)2[Pt(CN)4]ࡣࠊFe(Ethyl Isonicotinate)2Pd(CN)4 ࡜ࢫࣆࣥࢡࣟࢫ࣮࢜
ࣂ࣮ᣲືࡀ኱ࡁࡃኚࢃࡽ࡞࠸ࡢࡣࠊPt(II)࡜ Pt(II)ࡢ࢖༙࢜ࣥᚄࡀ࡯࡜ࢇ࡝ྠࡌ࡛࠶ࡿࡇ࡜࡟㛵㐃ࡋ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ໬Ꮫᅽຊຠᯝࡀྠࡌ࡛࠶ࡿࡢ࡛ࠊࢫࣆࣥ㌿⛣ ᗘࡀྠࡌ࡛࠶ࡿ࡜ࡶ⪃࠼ࡽࢀࡿ[22]ࠋ
ࡲࡓࠊFe(Ethyl Isonicotinate)2[Pt(CN)4]࡟ࡘ࠸࡚ࡶࠊa soft X-ray–induced excited spin state
trapping (SOXEISST) effect ࡀࠊFe(py)2[Ni(CN)4]࡜ྠᵝ࡟㉳ࡇࡿ[23]ྍ⬟ᛶࡀ࠶ࡿࡢ࡛ࠊᐇ㦂ࢆ㐍ࡵࡓ࠸࡜⪃࠼࡚࠸ࡿࠋࡉࡽ࡟ࠊྜᡂ᮲௳࡟ࡼࡾࠊ4-CN-pyridine ࢆ⏝࠸ࡓ⣔[24]ࡢࡼ࠺࡟ࠊ␗࡞ࡿࢫ
ࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮㘒యࡀ࡛ࡁࡿ࠿ࡢ᳨ウࡶ㐍ࡵ࡚࠸ࡁࡓ࠸ࠋMn2+ࡣࠊd5 ࡢ㟁Ꮚ㓄⨨ࢆᣢࡘࡇ࡜࠿ࡽࠊ
Fe2+ࡢࢧ࢖ࢺ࡟ Mn2+ࢆࢻ࣮ࣉࡍࡿ࡜☢Ẽᣲືࡀ࠸࠿ࡼ࠺࡟ኚ໬ࡍࡿ࠿ࡢ᳨ウࡶ㐍ࡵ࡚࠸ࡁࡓ࠸[25]ࠋ

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24

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2QH$VSHFWRI5HVHDUFKHVRI%LRORJLFDO)XQFWLRQRI*OXWDWKLRQH㸦ᮾி㎰ᴗ኱Ꮫ㸧᭷㤿἞ேࠊ኱㔝⏤౫ࠊⳢ㔝࠿ࡉࡡࠊᑿᓮ࿴ᕹࠊᕝ㉺ ᶞࠊᮌಛ┿ᘺࠊ㕥ᮌᬛ඾ࠊ᪂ᮧὒ୍  㸦ᮾࣞࣜࢧ࣮ࢳࢭࣥࢱ࣮㸧୰ᮏᛅᏹ  㸦኱ྠ኱Ꮫ㸧㧘ᒣ ດࠊ㓇஭㝧୍
7RN\R8QLYHUVLW\RI$JULFXOWXUH +DUXWR$ULPD<XL2KQR.DVDQH6XJDQR.D]XKR2]DNL
7DWVXNL.DZDJRH6KLQ\D.LPDWD7RPRQRUL6X]XNL<RXLFKL1LLPXUD  
7RUD\5HVHDUFK&HQWHU 7DGDKLUR1DNDPRWR 'DLGR8QLYHVLW\ 7VXWRPX7DND\DPD<RLFKL6DNDL㸯㸬ࡣࡌࡵ࡟
  ㏆ᖺࠊ⏕యෆࡢάᛶ㓟⣲✀㸦2+࣭ࠊ2㸫࣭ࠊ+2࡞࡝㸧ࡢ཯ᛂࡀὀ┠ࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚ࡁࡓࡀࠊ
ࡉࡲࡊࡲ࡞⑌ᝈ࡟㛵୚ࡍࡿ࡜ࡉࢀࡿ࠿ࡽ࡛࠶ࡿࠋάᛶ㓟⣲✀ࡢ࡞࠿࡛ࡶࣄࢻࣟ࢟ࢩࣛࢪ࢝ࣝ㸦2+࣭㸧ࡢጾຊࡣ኱ࡁ࠸ࠋ㐣㓟໬Ỉ⣲㸦+2㸧ࡣࠊ㐟㞳ࡢ)H࡜཯ᛂࡋ࡚ࠊࣄࢻࣟ࢟ࢩࣛࢪ࢝ࣝࢆ⏕ᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ )H 㸩 +2 Ѝ )H 㸩 2+࣭ 㸩 2+㸫ࡇࢀࡣࣇ࢙ࣥࢺࣥ཯ᛂ࡜ࡼࡤࢀ࡚࠸ࡿࠋ
ᮾி㎰ᴗ኱Ꮫ࣭᪂ᮧ◊✲ᐊ࡟࠾࠸࡚ࡣࠊin vitroᐇ㦂࡛ࠊୖグࡢࣇ࢙ࣥࢺࣥ཯ᛂࡀ'1$ࢆᦆയ㸦ศゎ㸧ࡍࡿࡇ࡜ࢆ♧ࡋࡓࠋࡇࡢᐇ㦂⣔࡟ࠊࡉࡽ࡟ࢢࣝࢱ
ࢳ࢜ࣥࢆῧຍࡍࡿࡇ࡜࡟ࡼࡾࠊ'1$ᦆയࠊࡍ࡞ࢃࡕ
ࣇ࢙ࣥࢺࣥ཯ᛂࢆࠊ኱ࡁࡃᢚไ࡛ࡁࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡿ >@ࠋࢢࣝࢱࢳ࢜ࣥ࡜ࡣࠊࢢࣝࢱ࣑ࣥ㓟ࠊࢩࢫࢸ࢕ࣥࠊࢢࣜࢩࣥࡢࡘࡢᚲ㡲࢔࣑ࣀ㓟ࡀ࢔࣑ࢻ⤖ྜࡋࡓࢺࣜ࣌ࣉࢳࢻ㸦Ț*OX&\V*O\㸧࡛࠶ࡿࠋᅗ࡟ศ
Ꮚᵓ㐀ࢆ♧ࡍࠋ
+LGHU࡜.RQJ>@࡟ࡼࢀࡤࠊື᳜≀ࡢ⣽⬊㉁࡟࠾ࡅࡿࢢࣝࢱࢳ࢜ࣥ⃰ᗘࡣ㠀ᖖ࡟㧗ࡃࠊaP0࡛࠶ࡿ࡜࠸࠺ࠋࢢࣝࢱࢳ࢜ࣥࡢ㜵ᚚᶵ⬟࡜㛵ಀࡋ࡚࠸ࡿࡢ࠿ࡶࡋࢀ࡞࠸ࠋ୍᪉ࠊ⣽⬊࡛ࡢ㐟㞳ࡢ)Hࡣࠊ㕲㈓ⶶࢱࣥࣃࢡ࡛࠶ࡿࣇ࢙ࣜࢳࣥ࡟ᤕᤊࡉࢀ࡚࠸ࡿ)Hࡀࠊࢫ࣮ࣃ࣮࢜࢟ࢩࢻ࢔ࢽ࢜ࣥࣛࢪ࢝
ࣝ㸦2㸫࣭㸧࡟ࡼࡾ㑏ඖࡉࢀࠊ⣽⬊㉁࡟౪⤥ࡉࢀࡿ>@ࠋάᛶ㓟⣲✀࡟ࡼࡿ⑌ᝈࡣࠊ௨ୖࡢࡼ࠺࡟ࠊ㕲ࠊࢢࣝࢱࢳ࢜ࣥࡀࣂ࢖ࣉ࣮࣮ࣞࣖ࡜ࡋ࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࡇ࡜ࡣ☜࠿࡟࡞ࡾࡘࡘ࠶ࡿࡀࠊලయⓗ࡞㕲࢖࢜ࣥࡢ໬Ꮫ✀ࠊ཯ᛂࣉࣟࢭࢫࡣࡼࡃࢃ
࠿ࡽ࡞࠸Ⅼࡀከ࠸ࠋ
ࡇࢀࡽࡢࡇ࡜ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊᡃࠎࡣࠊ)H࣓ࢫࣂ࢘࢔࣮ศගἲࢆ⏝࠸ࠊin vitroᐇ㦂㸦෾⤖⁐ᾮ⣔㸧࠾ࡼࡧin vivoᐇ㦂㸦ࣂࢡࢸࣜ࢔ᇵ㣴⣔㸧࡟ࡼࡾㄪ〇ࡋࡓヨᩱ୰ࡢ㕲ࡢ໬Ꮫ≧ែ㸦౯ᩘࠊ⤖ྜ≧ែ࡞࡝㸧ࢆ㏣㊧ࡋ࡚࠸ࡿࠋ௒ᅇࡣࠊ)H࡜ࢢࣝࢱࢳ࢜ࣥࢆྵࡴ෾⤖Ỉ⁐ᾮ୰࡛ࡢ㕲ࡢ໬Ꮫ≧ែࢆㄪ࡭ࡓࡢ࡛ሗ࿌ࡍࡿࠋ

26㸰㸬ᐇ㦂$ )HỈ⁐ᾮࡢㄪ〇ᕷ㈍ࡢ)H⃰⦰  㔠ᒓ㕲ࢆࠊ⃰ሷ㓟࡟ຍࡋ࡞ࡀࡽ⁐࠿ࡋ)Hሷ㓟Ỉ⁐ᾮࢆㄪ〇ࡋࡓࠋ)H࡛࠶ࡿࡇ࡜ࡣࠊᚋ࡟♧ࡍ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝ࠿ࡽ☜ㄆࡋࡓࠋ㹀 ෾⤖Ỉ⁐ᾮࡢㄪ〇
)Hࡢ⃰ᗘࠊࢢࣝࢱࢳ࢜ࣥࡢ⃰ᗘࢆࠊࡑࢀࡒࢀࠊP0ࠊP0࡜࡞ࡿࡼ࠺ࠊ+(3(6⦆⾪Ỉᐜᾮࢆࡘࡃࡗࡓࠋᅇࡢㄪ〇ࢆ⾜࠸ࠊ᭱⤊ⓗ࡞S+ࡣࠊࡑࢀࡒࢀࠊࠊ࡜ࡋࡓࠋ
᎘Ẽࢢ࣮ࣟࣈ࣎ࢵࢡࢫ୰࡛ࠊP/ࡢ⁐ᾮࢆᾮయ❅⣲࡟ᾐࡅ࡚ᛴ෭෾⤖ࡋࡓࠋ෾⤖ࡢ๓࡟ࠊ௨ୗࡢ㏻ࡾࡢฎ⌮ࢆࡋࡓࠋ
㸦㸧 ᎘Ẽ㸦✵Ẽ᏶඲㐽᩿㸧ୗ࡛ࠊ෾⤖ࡋࡓࠋ⁐ᾮࡣ࡯࡜ࢇ࡝↓Ⰽ࡛࠶ࡗࡓࠋ
㸦㸧 ▷᫬㛫✵Ẽ࡟᭚ࡋࡓࡢࡕ㸦⁐ᾮࡣⷧ࠸ࣆࣥࢡⰍ࡜࡞ࡗࡓ㸧ࠊ෾⤖ࡋࡓࠋ㸦㸧 ༑ศ࡟㸦୍᫨ኪ㸧✵Ẽ࡟᭚ࡋࡓࡢࡕ㸦⁐ᾮࡣ㯤ኚࡋࡓ㸧ࠊ෾⤖ࡋࡓࠋ㹁 ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࡢ ᐃ  㸿㸪㹀࡛ㄪ〇ࡉࢀࡓ෾⤖ヨᩱࢆࠊ㏻ᖖࡢ྾཰ἲ࣓ࢫࣂ࢘࢔࣮ศගἲ࡛ࠊ㹉࡛ᐃࡋࡓࠋࢫ࣌

ࢡࢺࣝࡢᶓ㍈࡛࠶ࡿࢻࢵࣉ࣮ࣛ㏿ᗘࡣࠊᐊ ࡢ㔠ᒓ㕲ࡢࢫ࣌ࢡࢺࣝࡢࢭࢡࢸࢵࢺ྾཰఩⨨࡟ࡼࡗ࡚ᰯṇࡋࡓࠋ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࡢゎᯒ㸦ࣇ࢕ࢵࢸ࢕ࣥࢢ㸧ࡣࠊᕷ㈍ࡢࣉࣟࢢ࣒࡛ࣛ࠶ࡿ0RVV:LQQ
L3UHࢆ౑ࡗ࡚⾜ࡗࡓࠋ㸱㸬⤖ᯝ࡜⪃ᐹ ᅗࠊᅗ࡟ࠊࡑࢀࡒࢀࠊS+ࠊ࡛ㄪ〇ࡋࡓ.࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᅗ  ࠊᅗ  ࠊᅗ  ࡣ⤌ࡢࢲࣈࣞࢵࢺ࡜ࡋ࡚ࠊᅗ  ࠊᅗ  ࠊᅗ  ࡣ⤌ࡢࢲࣈࣞࢵࢺ࡜ࡋ࡚ࠊࣇ࢕ࢵࢸ
࢕ࣥࢢ࡛ࡁࡓࠋ27

⾲ ࠊ ࡟ࡣࠊᚓࡽࢀࡓ࣓ࢫࣂ࢘࢔࣮ࣃ࣓࣮ࣛࢱ㸦␗ᛶయࢩࣇࢺ ,6 ࠊᅄᴟศ⿣ 46 ࠊ⥺ᖜ /: ࠊ┦ᑐ㠃✚ᙉᗘ $UHD 㸧ࢆ♧ࡋࡓࠋ⾲㸬)Hࢢࣝࢱࢳ࢜ࣥࡢ෾⤖Ỉ⁐ᾮ S+ ࡢ࣓ࢫࣂ࢘࢔࣮ࣃ࣓࣮ࣛࢱ㸦.   ᎘Ẽㄪ〇  ▷᫬㛫✵Ẽ᭚ࡋ  ୍᫨ኪ✵Ẽ᭚ࡋ

,6PPV

46PPV

/6PPV$UHD ≧ែ㸦㸯㸧       㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘ࠊ❅⣲ 㓄఩㸧㸦㸰㸧         㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘ ❅⣲ 㓄఩㸧        㧗ࢫࣆࣥᆺ)H㸰㸦㓟⣲ 㓄఩㸧㸦㸱㸧       㧗ࢫࣆࣥᆺ)H㸱㸦㓟⣲ 㓄఩㸧⾲㸬)Hࢢࣝࢱࢳ࢜ࣥࡢ෾⤖Ỉ⁐ᾮ S+ ࡢ࣓ࢫࣂ࢘࢔࣮ࣃ࣓࣮ࣛࢱ㸦.   ᎘Ẽㄪ〇  ▷᫬㛫✵Ẽ᭚ࡋ  ୍᫨ኪ✵Ẽ᭚ࡋ

,6PPV

46PPV

/6PPV$UHD ≧ែ㸦㸯㸧         㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘ࠊ❅⣲ 㓄఩㸧        㧗ࢫࣆࣥᆺ)H㸰㸦㓟⣲ 㓄఩㸧㸦㸰㸧         㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘ࠊ❅⣲ 㓄఩㸧        㧗ࢫࣆࣥᆺ)H㸰㸦㓟⣲ 㓄఩㸧㸦㸱㸧       㧗ࢫࣆࣥᆺ)H㸱㸦㓟⣲ 㓄఩㸧⾲ࠊ࡟♧ࡉࢀࡓ௒ᅇ ᐃࡉࢀࡓࡘ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࡢࣃ࣓࣮ࣛࢱ್ࢆ⢭ᰝࡍࡿ࡜ࠊ㕲໬Ꮫ✀࡟኱ู࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡍ࡞ࢃࡕࠊ
࣭㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘❅⣲ 㓄఩㸧࣭㧗ࢫࣆࣥᆺ)H㸰㸦㓟⣲ 㓄఩㸧࣭㧗ࢫࣆࣥᆺ)H㸱㸦㓟⣲ 㓄఩㸧 ࡛࠶ࡿࠋ
ࡇࡢ࡞࠿࡛⯆࿡῝࠸໬Ꮫ✀ࡣࠊ㧗ࢫࣆࣥᆺ)H㸰㸦࢖࢜࢘ࠊ❅⣲ 㓄఩㸧࡛࠶ࢁ࠺ࠋ,6 ੈVࠊ46 ੈVࡣࠊ㧗ࢫࣆࣥ)H࡛࠶ࡿࡀࠊࡇࡢ≧ែ࡜ࡋ࡚ࡣ,6್ࡀᑠࡉࡵ࡛࠶ࡿࡇ࡜࠿ࡽࠊඹ᭷⤖ྜᛶࡢᙉ࠸
ཎᏊࠊࡓ࡜࠼ࡤ࢖࢜࢘ࡀ)H࡟㓄఩ࡋ࡚࠸ࡿࡇ࡜ࡀ᥎ᐃࡉࢀࡿࠋ+DPHGࡽ>@ࡣඛ⾜◊✲࡛ࠊ࡯ࡰྠ
ࡌࡃࡽ࠸,6ࠊ46್ࢆࠊ࢖࢜࢘ࠊ❅⣲ࢆ㓄఩ཎᏊ࡜ࡋ࡚ྵࡳ㓄఩࡛࠶ࡿ໬Ꮫ✀>@ࡢࡶࡢ࡜᥎ ࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡶࠊࢢࣝࢱࢳ࢜ࣥࡀ㓄఩Ꮚ࡜ࡋࡓ㧗ࢫࣆࣥᆺ)H໬Ꮫ✀ࡀ⏕ᡂࡋࡓࡇ࡜ࡣ☜࠿࡛࠶ࢁ࠺ࠋ
S+ࡢ෾⤖Ỉ⁐ᾮ㸭᎘Ẽ≧ែ࡜ࡋ࡚ㄪ〇ࡋࡓヨᩱ㸦ᅗ  ࠾ࡼࡧ⾲  㸧࡛ࡣࠊ⤌ࡢࢲࣈࣞࢵࢺ
㸦,6 ੈVࠊ46 ੈV㸧࡜ࡋ࡚ࢫ࣌ࢡࢺࣝゎᯒࡉࢀࡓࠋ㕲໬Ꮫ✀ࡀࠊࢢࣝࢱࢳ࢜ࣥ࡜⤖ࡧࡘ࠸ࡓ)H≧ែࢆࠊ࡯ࡰ㸣࡜ࡗ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡇࡢ≧ែࡣ㓟⣲᭚ࡋࠊ࠶ࡿ࠸ࡣS+್ࡢపῶ࡟ᑐࡋᏳᐃ࡛ࡣ࡞ࡃࠊࢢࣝࢱࢳ࢜ࣥࢆ㓄఩Ꮚ࡜ࡋ࡚ࡣኻࡗࡓ㧗ࢫࣆࣥᆺ)H㸰㸦㓟⣲ 㓄఩㸧໬Ꮫ✀࡟ࠊ㏿ࡸ࠿࡟ኚ໬ࡋ࡚࠸ࡃࡇ࡜ࡶᮏ◊✲࡛᫂ࡽ࠿࡜࡞ࡗࡓࠋ
ᡃࠎࡣࠊࡇࡇ࡛ሗ࿌ࡋࡓin vitroᐇ㦂ࡔࡅ࡛࡞ࡃࠊ኱⭠⳦ࠊ$PSKLEDFLOOXV[\ODQXV⳦࡟)Hࢆྲྀࡾ㎸

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ࣜ☢ᛶࢆ♧ࡍ࡞࡝㠀ᖖ࡟⯆࿡῝࠸≀㉁࡛࠶ࡿ>@ࠋ୍᪉ࠊ☢ᛶࢼࣀ⢏Ꮚࡢ◊✲ࡣゐ፹ࡸ 05,ࠊࢻࣛࢵ
ࢢࢹࣜࣂ࣮ࣜࢩࢫࢸ࣒࡞࡝ࡢᛂ⏝࡬ࡢᮇᚅ࠿ࡽ┒ࢇ࡟◊✲ࡉࢀ࡚࠸ࡿࠋ㏆ᖺࠊG)H22+ ࢼࣀ⢏Ꮚ࡟㛵ࡋ࡚ࡶ࠸ࡃࡘ࠿ࡢࢢ࣮ࣝࣉࡀ◊✲ࢆ㛤ጞࡋ࡚࠾ࡾࠊ㉸ᖖ☢ᛶࢆ♧ࡍࡇ࡜ࡸගゐ፹࡬ࡢᛂ⏝ࡢྍ⬟ᛶࢆ♧၀ࡋ࡚࠸ࡿ>@ࠋࡉࡽ࡟ࠊ㕲ࢼࣀ⢏Ꮚ࡟௚ࡢ㔠ᒓࢆ」ྜࡉࡏࡓ」ྜࢼࣀ⢏Ꮚࡶ௨๓ࡼࡾ◊✲ࡀ࡞ࡉࢀ࡚࠸ࡿࠋ౛࠼
ࡤඛ㏙ࡢG)H22+ ࡟ࢽࢵࢣࣝ࡞࡝ࡢඖ⣲ࢆ」ྜࡉࡏࡿࡇ࡜࡟ࡼࡗ࡚ࠊගゐ፹άᛶࡀ኱ࡁࡃྥୖࡍࡿ
ࡇ࡜ࡶሗ࿌ࡉࢀ࡚࠸ࡿ>@ࠋࡋ࠿ࡋࠊG)H22+ ࢼࣀ⢏Ꮚࡣࡑࡢࡲࡲ࡛ࡣ୙Ᏻᐃ࡛࠶ࡿࡢ࡛ಖㆤ๣ࡢ
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」ྜG)H22+ ࡣࡇࢀࡲ࡛࡯࡜ࢇ࡝ྜᡂ࡟ᡂຌࡋࡓ౛ࡀ࡞࠿ࡗࡓࡓࡵ࡟ሗ࿌౛⮬యࡀᑡ࡞ࡃࠊ␗ඖ⣲ࡀ࡝ࡢࢧ࢖ࢺ࡟ධࡿ࠿࡞࡝ࡢᵓ㐀࡟㛵ࡍࡿ㆟ㄽࡶࡉࢀ࡚ࡇ࡞࠿ࡗࡓࠋࡉࡽ࡟ࠊ」ྜࡋࡓ㔠ᒓࡢ✀㢮࡟ࡼࡿ☢Ẽᵓ㐀࡟㛵ࡍࡿ▱ぢࡶ㔜せ࡛ࡣ࠶ࡿࡀ㆟ㄽࡉࢀ࡚࠸࡞࠸ࠋࡑࡢࡓࡵࠊ኱ẼᏳᐃ໬ࡉࢀࡓ」ྜG)H22+ ࡢ⣔⤫ⓗ࡞ྜᡂ࡜☢Ẽᵓ㐀ࡢゎ᫂ࡀㄢ㢟࡛࠶ࡗࡓࠋ
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㑏ඖ๣࡛࠶ࡿࣄࢻࣛࢪࣥỈ⁐ᾮࢆ  ศ㛫࠿ࡅ࡚⁲ୗࡋࡓࠋࡑࡢᚋࠊ㉸㡢Ἴ↷ᑕࢆ  ศ㛫⾜࠸  ᫬㛫㟼⨨ࡍࡿࡇ࡜࡛ỿẊ≀ࢆᚓࡓࠋᚓࡽࢀࡓỿẊ≀ࢆ㐲ᚰศ㞳ࡋࡓᚋࠊỈ࡜࢚ࢱࣀ࣮ࣝ࡟࡚Ὑίࡋᚤ⢏Ꮚࢆᚓࡓࠋ⃰ᗘẚ &X )H&X ࢆ ࠊࠊࠊ ࡛ᚓࡽࢀࡓ
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࠸ࢧࣥࣉ࡛ࣝࡣ⢏ᚄࡀⱝᖸ኱ࡁࡃ࡞ࡗࡓࠋࡉࡽ࡟ࠊ('6 )LJ ࡟ࡼࡗ࡚ࠊ㖡࡜㕲ࡀࢧࣥࣉࣝ୰࡟Ꮡ
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ࡢ್༙ᖜࡀᗈ࠸ࡇ࡜࠿ࡽࠊ⢏ᚄࡀᑠࡉ࡞ࡇ࡜ࡀ᥎ᐹࡉࢀࡿࠋࡲࡓࠊ㔜㔞ẚࢆ 5,5 ἲ࡛ồࡵࡓ⤖ᯝࠊ

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ࡢ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊ㉸ᖖ☢ᛶࡢຠᯝࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ప
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ࡉࢀࡓࠋࡇࡢ  ᡂศࡢࣃ࣓࣮ࣛࢱ࣮ࡣ௨๓

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
7DEOH0|VVEDXHUSDUDPHWHUVRI6

33)LJ  ࡟స〇┤ᚋࡢ 6&X ࡜  ࢝᭶㛫✵Ẽ୰࡛ಖ⟶ࡋࡓࢧࣥࣉࣝࡢ ;5'ᐃࡢ⤖ᯝࢆ♧ࡍࠋG)H22+ ⏤᮶ࡢࣆ࣮ࢡࡣࠊ࡯࡜ࢇ࡝ኚ໬ࡀぢࡽࢀ࡞࠿ࡗࡓࠋ௨๓ࡢᡃࠎࡢ◊✲࡛ࡣࠊ
G)H22+ ࢼࣀ⢏Ꮚࡣ✵Ẽ୰࡛ಖ⟶ࡍࡿ࡜኱ࡁࡃᡂ㛗ࡍࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿ>@ࠋࡋ࠿ࡋࠊ
㖡ࢆ」ྜࡉࡏࡿࡇ࡜࡟ࡼࡾࠊG)H22+ ࢼࣀ⢏ᏊࡀᏳᐃ໬ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
௨๓ࡢᡃࠎࡢ◊✲࡛ࡣࠊį࢜࢟ࢩỈ㓟໬㕲ࡢ⏕ᡂᶵᵓࡣ )H2 ࡢ㓟໬࡟ࡼࡿࡶࡢ࡛࠶ࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡿ>@ࠋࡘࡲࡾࠊ)H,,)H,,,2࡟࠾ࡅࡿ  ౯ࡢ㕲ࡀ  ౯࡟ኚ໬ࡍࡿ㝿࡟ į࢜࢟ࢩỈ㓟໬㕲࡟ኚ໬ࡍࡿ࡜࠸࠼ࡿࠋ୍᪉ࠊ㖡ࡢ๭ྜࡀ኱ࡁࡃ࡞ࡿ࡜ࠊ ౯ࡢ㕲ࡀ㖡࡜ධࢀ᭰ࢃࡿࡇ࡜࡟ࡼࡾ &X)H,,,2 ࡜࡞ࡿࠋ ౯ࡢ㕲

)LJ  7KH ;UD\ GLIIUDFWLRQ SDWWHUQV REWDLQHG IURP VDPSOHVࡀᏑᅾࡋ࡞࠸ࡢ࡛ į࢜࢟ࢩỈ㓟໬㕲ࡀ⏕ᡂࡉ

LPPHGLDWHO\DIWHUSUHSDUDWLRQ DQGDIWHUVWRUDJHLQWKHODERUDWRU\XQGHUࢀ࡞࠸ࠋ㖡ࡢ๭ྜࡀᑡ࡞࠸ሙྜࡣࠊ

DLUIRURQHPRQWK&X[)H,,[)H,,,2 ࡜࡞ࡾࠊ ౯ࡢ㕲ࡀὙί๓࡟
Ꮡᅾࡍࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ  ౯ࡢ㕲ࡀᛴ⃭࡟㓟໬ࡍࡿࡇ࡜࡟ࡼࡾ㖡ࡀ」ྜࡉࢀࡓ į࢜࢟ࢩỈ㓟໬㕲ࡀ⏕ᡂࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ
 ࣐ࣥ࢞ࣥ」ྜG)H22+ ࢼࣀ⢏Ꮚ
)LJ ࡟ 60Qࠊ60Qࠊ60Qࠊ60Q ࡢ
7(0 ീࢆ♧ࡍࠋࡍ࡭࡚ࡢࢧࣥࣉ࡛ࣝ࢘ࢽᆺᵓ
㐀ࢆ♧ࡋࡓࠋࡲࡓࠊ┤ᚄࡀ QP ⛬ᗘࡢ㔪≧⢏Ꮚࡀ㞟ࡲࡗࡓᵓ㐀࡛࠶ࡗࡓࠋ
)LJ ࡟ 60Qࠊ60Qࠊ60Qࠊ60Q ࡢ;5'ᐃࡢ⤖ᯝࢆ♧ࡍࠋࡍ࡭࡚ࡢࢧࣥࣉ࡛ࣝ

G)H22+ ࡢࣆ࣮ࢡࢆほ ࡋࡓ -&3'6&DUG1R
 ࠋࡲࡓࠊ㔠ᒓ࣐ࣥ࢞ࣥࠊ࣐ࣥ࢞ࣥ㓟໬≀ࡣほࡉࢀ࡞࠿ࡗࡓࠋ

)LJ  ࡟ ,&3ᐃࡢ⤖ᯝࢆ♧ࡍࠋᚓࡽࢀࡓ

0Q ࡜ )H ࡢẚࡣฟⓎ≀㉁ࡢẚ࡜▩┪ࡋ࡞࠸್࡛࠶ࡗࡓࠋ;5' ࡛ࡣG)H22+ ࡢࣆ࣮ࢡࡢࡳほࡉࢀࡓࡇ࡜࠿ࡽࠊG)H22+ ࡟࣐ࣥ࢞ࣥࡀࢻ
࣮ࣉࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊࡑࢀࡒ
ࢀࡢ⤌ᡂࡣ 60Q㸻G)H0Q22+ࠊ60Q

)LJ7(0LPDJHVRI 60Q60Q60QDQG60Q

34)LJ;UD\GLIIUDFWLRQSDWWHUQVRI60Q60Q60Q

)LJ5HODWLRQVKLSEHWZHHQ0Q )H0Q PRODUUDWLRIRUPDQJDQHVH

DQG60QGRSHGQDQRSDUWLFOHVPHDVXUHGE\,&3DQGWKHVWDUWLQJPDWHULDO SMn50 SMn70
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㸻G)H0Q22+ࠊ60Q㸻G)H0Q22+ࠊ60Q㸻G)H0Q22+ ࡜ぢ✚ࡶࡽࢀࡓࠋ

35

7DEOH0|VVEDXHUSDUDPHWHUVRIPDQJDQHVHGRSHGVDPSOHV
60Qࠊ60Qࠊ60Qࠊ60Q ࡢ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࢆ )LJ  ࡟♧ࡍࠋࡲࡓࠊᚓࡽࢀࡓ
ࣃ࣓࣮ࣛࢱ࣮ࡣ 7DEOH  ࡟♧ࡍࠋᐊ࡛ࡣࠊࢲࣈࣞࢵࢺࡀほࡼࡿ㉸ᖖ☢ᛶ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊప

ࡉࢀࡓࠋࡇࡢࢲࣈࣞࢵࢺࡣᚤ⢏Ꮚ࡟ . ࡛࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࡢ ᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊෆ㒊☢ሙศᕸࡀほ ࡉࢀࡓࠋࡉࡽ࡟࣐ࣥ࢞
)LJ ࡟ෆ㒊☢ሙࡢᖹᆒ್࡜ ,&3 ࡛ồࡵࡓ࣐ࣥ࢞ࣥ࡜
㕲ࡢẚ࡜ࡢࣉࣟࢵࢺࢆ♧ࡍࠋෆ㒊☢ሙࡢෆ㒊☢ሙࡢῶᑡࡣ┤⥺ⓗ࡛ࡣ࡞࠸ࡇ࡜ࡀぢ࡚࡜ࢀࡿࠋࡶࡋࠊ࣐ࣥ࢞ࣥࡀ
ࣛࣥࢲ࣒࡟ࢻ࣮ࣉࡋ࡚࠸ࡓࡽࠊෆ㒊☢ሙࡢ್ࡣ  ࡟㏆࡙ࡃࡣࡎ࡛࠶ࡿࠋࡇࡢ⤖ᯝࡼࡾࠊ࣐ࣥ࢞ࣥࡣG)H22+ ࡟ᑐࡋ࡚ࠊᒁᡤⓗ࡟ࢻ࣮ࣉࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
࣐ࣥ࢞ࣥࡣࠊ ౯࡜  ౯ࢆ࡜ࡾ࠺ࡿࠋ)H࡜ )Hࡀ 0Q

࡜ 0Q ࡜ධࢀ᭰ࢃࡿࡇ࡜ࡀ࡛ࡁࡿࠋ ౯ࡢ㕲࡜࣐ࣥ࢞ࣥ
ࡀᛴ⃭࡟㓟໬ࡍࡿࡇ࡜࡟ࡼࡾ࣐ࣥ࢞ࣥࡀ」ྜࡉࢀࡓ



7KHDYHUDJHRIK\SHUILQHPDJQHWLFILHOGV7ࣥࡢࢻ࣮ࣉ㔞࡟ᑐࡋ࡚ෆ㒊☢ሙࡢ್ࡣᑠࡉࡃ࡞ࡗࡓࠋ


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

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0RODUUDWLR 0Q )H0Q

G)H22+ ࡀ⏕ᡂࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ

)LJ  5HODWLRQVKLS EHWZHHQ WKH 0Q )H0Q  PRODUUDWLRVRIWKHQDQRSDUWLFOHVPHDVXUHGXVLQJ,&3$(6DQG

4. ⤖ㄽ

WKHDYHUDJHK\SHUILQHPDJQHWLFILHOGV‵ᘧἲ࡟ࡼࡾ㖡࠾ࡼࡧ࣐ࣥ࢞ࣥࡀ」ྜࡉࢀࡓ
G)H22+ ࢼࣀ⢏Ꮚࢆస〇ࡋࡓࠋ㖡ࡢሙྜࡣࠊ㖡ࡢ๭ྜࢆኚ໬ࡉࡏࡿࡇ࡜࡛ࠊ㖡」ྜ࣐ࢢ࣐࣊࢖ࢺ࠿

36

ࡽ㖡」ྜG)H22+ ࢆᚓࡓࠋᚓࡽࢀࡓࢼࣀ⢏Ꮚࡣ⌫≧࡛ QP ⛬ᗘࡢࢧ࢖ࢬ࡛࠶ࡾࠊ㉸ᖖ☢ᛶࢆ♧ࡋࡓࠋࡲࡓᚓࡽࢀࡓࢼࣀ⢏Ꮚࡣ኱Ẽୗ࡛ࡶᏳᐃ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ㖡」ྜG)H22+ ࡣ  ౯ࡢ㕲ࡀᛴ⃭࡟㓟໬ࡍࡿࡇ࡜࡟ࡼࡾ⏕ᡂࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉࣐ࣥ࢞ࣥࡢሙྜࡣࠊ࣐ࣥ࢞ࣥࡢ๭ྜ࡟ࡼ
ࡽࡎࠊࡍ࡭࡚G)H22+ ࡜࡞ࡗࡓࠋᚓࡽࢀࡓࢼࣀ⢏Ꮚࡣ࢘ࢽᆺᵓ㐀࡛࠶ࡗࡓࠋ࣐ࣥ࢞ࣥࡢࢻ࣮ࣉ㔞࡟ᑐࡋ࡚ෆ㒊☢ሙࡢ್ࡣᑠࡉࡃ࡞ࡗࡓࠋ࣐ࣥ࢞ࣥࡣG)H22+ ࡟ᑐࡋ࡚ࠊᒁᡤⓗ࡟ࢻ࣮ࣉࡋ࡚࠸ࡿࡇ࡜
ࡀ♧၀ࡉࢀࡓࠋ

5. ཧ⪃ᩥ⊩>@ 8 6FKZHUWPDQQ 50 &RUQHOO ,URQ 2[LGHV LQ WKH /DERUDWRU\ 3UHSDUDWLRQ DQG &KDUDFWHUL]DWLRQ
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 䛿䛨䜑䛻
Ᏹᐂ䛻䛚䛡䜛≀㉁๰ᡂ䛻䛿䚸&3 ᑐ⛠ᛶ䛾◚䜜䚸༶䛱᫬㛫཯㌿ᑐ⛠ᛶ䛾◚䜜䛜ᚲせ䛸䛥䜜䜛䛜䚸⣲⢏Ꮚ≀⌮Ꮫ䛾ᶆ‽ᶍᆺ䠄60䠅䛜ෆໟ䛩䜛 &3 䛾◚䜜䛷䛿䚸≀㉁๰ᡂ䜢≉ᚩ௜䛡䜛䝞䝸䜸䞁㠀ᑐ⛠䠄䝞䝸䜸䞁ᩘᐦᗘ䠋䝣䜷䝖䞁ᩘᐦᗘ䠅䛾ほ ್ 㽢 䜢ㄝ᫂䛷䛝䛺䛔䚹᫬㛫཯㌿ኚ᥮䛷䚸୰ᛶᏊ䛾☢Ẽ䝰䞊䝯䞁䝖䛿཯㌿䛩䜛䛾䛻ᑐ䛧䛶୰ᛶᏊ㟁Ẽ཮ᴟᏊ⬟⋡䠄Q('0䠅䛿཯㌿䛫䛪䚸᭷㝈䛾 Q('0 䛿᫬㛫཯㌿ᑐ⛠ᛶ䜢◚䜛䚹᫬㛫཯㌿ᑐ⛠ᛶ䜢◚䜛 Q('0 䛿䚸60 䜢㉸䛘䜛᪂≀⌮䛾᳨ド䛻᭷⏝䛷䛒䜚䚸≀㉁䛾๰ᡂ䛾ㅦ䜢ゎ䛟㘽䜢ᥱ䛳䛶䛔䜛䛸⪃䛘䜙䜜䛶䛔䜛䚹Q('0 䛻䛴䛔䛶䚸䛣䜜䜎䛷ୡ⏺᭱㧗⢭ᗘ䛾ᐇ㦂䛿 ,// 䛷㉸෭୰ᛶᏊ䠄8&1䠅䜢⏝䛔䛯䜒䛾䛷䚸 㽢 HFP 䛾ୖ㝈್䜢୚䛘䛶䛔䜛>@䚹60 䜢㉸䛘䜛᪂≀⌮䛾ከ䛟䛿 HFP ⛬ᗘ䛾 Q('0 䜢ணゝ䛩䜛䛯䜑䚸 ᐃ⢭ᗘ䛾䠍䠌ಸ䛾ྥୖ䛷᭷㝈್䛜ほ 䛥䜜䜛ྍ⬟ᛶ䛜䛒䜛䚹Q('0 䛾 ᐃ䛷䛿䚸8&1 䜢ᐜჾ䛻㛢䛨㎸䜑䚸⢭ᐦ䛺㟁☢ሙ୰䛷୰ᛶᏊ䝇䝢䞁䛾ṓᕪ㐠ື䜢⢭ᐦほ䛩䜛䚹䛧䛯䛜䛳䛶䚸Q('0 䛾⢭ᐦ ᐃ䛻䛿䚸8&1 䛾኱㔞⏕ᡂ䛸䚸⢭ᐦ୍ᵝ☢ሙ䛜㔜せ䛻䛺䜛䚹ᡃ䚻䛿䚸㉸ὶື䝦䝸䜴䝮୰䛷䛾䝣䜷䝜䞁⾪✺䜢⏝䛔䛯䝇䞊䝟䞊䝃䞊䝬䝹ἲ䜢䚸䝇䝟䝺䞊䝅䝵䞁୰ᛶᏊ※䛸䝁䞁䝟䜽䝖䛻⤌䜏ྜ䜟䛫䚸8&1 䜢 FP 䛾㧗ᐦᗘ䛷኱㔞⏕ᡂ䛩䜛䛣䛸䛻ᡂຌ䛧䛯>@䚹䛭䛧䛶䚸8&1 䝇䝢䞁䛾ṓᕪ㐠ື䜢䝷䝮䝊䞊ඹ㬆ἲ䛷ほ 䛧䛯>@䚹䛥䜙䛻㧗ᐦᗘ䜢㐩ᡂ䛩䜛᪂ᆺ䛾 8&1 ※䜢㛤Ⓨ୰䛷䛒䜛䚹୍ᵝᛶ䛜᏶඲䛷䛺䛔☢ሙ୰䛷䝇䝢䞁೫ᴟ䛧䛯 8&1 䛜㐠ື䛩䜛䛸䚸ṓᕪ㐠ື䛾఩┦䛜ᣑ䛜䛳䛶䝇䝢䞁䛾ᶓ⦆࿴䛷೫ᴟᗘ䛜ୗ䛜䜚䚸⤫ィ⢭ᗘ䜢ᝏ໬䛥䛫䜛䚹䜎䛯䚸㏿ᗘ v 䛷䛾㐠ື䛻䜘䜚䚸㟁ሙ E 䛛䜙 v㽢E 䛾ᶓ☢
ሙ䛜Ⓨ⏕䛧䛶䚸㠀୍ᵝ☢ሙ䛛䜙䛟䜛ᶓᡂศ䛸┦䜎䛳䛶ṓᕪ䛾఩┦䛻䠎ḟ䛾ຠᯝ䜢ཬ䜌䛩䚹䛣䜜䜙䠎䛴䛾ᶓ☢
ሙ䛾஺ᕪ㡯䛛䜙䚸㟁ሙ䛾䠍ḟ䛻౫Ꮡ䛩䜛ᗄఱᏛⓗ఩┦ຠᯝ䠄*3(䠅䛸࿧䜀䜜䜛䝙䝉䛾 ('0 ຠᯝ䛜Ⓨ⏕䛧䚸⣔⤫ㄗᕪ䜢⏕䛨䛥䛫䜛>@䚹䛣䛾䛯䜑䚸⌧ᅾ䛾 Q('0 䛾⢭ᗘ䜢㉸䛘䜛  HFP 䛾 ('0 ᐃ䛻䛿䚸䠍䃛7䚸໙㓄  Q7P ௨ୗ䛾⢭ᐦ୍ᵝ☢ሙ䛜ᚲせ䛻䛺䜛䚹௒ᅇ䚸⢭ᐦ☢ሙ㛤Ⓨ䛾䛯䜑䚸≉䛻 䃛7 䛻ୖ䜛ᆅ☢Ẽ䜢䛿䛨䜑䛸䛩䜛⎔ቃ☢ሙ䛸☢ሙ໙㓄䜢⮬ືⓗ䛻⿵ൾ䛩䜛⮬ື⿵ൾ䝅䝇䝔䝮䠄䜰䜽䝔䜱䝤☢Ẽ䝅䞊䝹䝗䠅
䜢㛤Ⓨ䛧䛯䚹 ᐇ㦂୍ᵝ☢ሙ䛾⏕ᡂ
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㻌 )LJ䛿䠍ḟඖ䠄x ㍈᪉ྥ䠅䛻㓄⨨䛧䛯⮬ື⎔ቃ☢ሙ⿵ൾ䝅䝇䝔䝮䛾ᴫ␎ᅗ䛷䛒䜛䚹㽢㽢 P 䛾኱䛝䛥䜢ணᐃ䛩䜛ᮏ␒䛾䝅䝇䝔䝮䛾  䝇䜿䞊䝹䛾ヨస䝅䝇䝔䝮䛷䚸㽢㽢 P 䛾኱䛝䛥䜢ᣢ䛴䚹ᐇ㝿䛻䛿䚸y ᪉ྥ䛸 z ᪉ྥ䛻䜒ྠᵝ䛾䜒䛾䛜ධ䜜Ꮚ䛻䛺䛳䛯䠏ḟඖ䝅䝇䝔䝮䜢ᵓᡂ䛩䜛䚹䠍ḟඖ䝅䝇䝔䝮䛿䚸 ᅇᕳ䛝䛾ṇ᪉ᙧ䝁䜲䝹䠐ᮏ䛛䜙䛺䜚䚸ᅗ䛾⅊Ⰽ䛷♧䛩䜘䛖䛻䚸 P 㛫㝸䛷タ⨨䠄䝦䝹䝮䝩䝹䝒㓄⨨䠅䛥䜜䛯䝦䝹䝮䝩䝹䝒䝁䜲䝹䠍ᑐ䛸䚸䛭䜜䜘䜚ᗈ䛔 P 㛫㝸䛷タ⨨䛥䜜䛯䚸ⓑⰍ䛷♧䛩໙㓄䝁䜲䝹䠍ᑐ䛸䛻༊ู䛧䛶౑⏝䛩䜛䚹䝦䝹䝮䝩䝹䝒䝁䜲䝹䛿䚸ྠ᪉ྥ䛻ὶ䛧䛯㟁ὶ䛻䜘䜚୍ᵝ☢ሙ䜢⏕ᡂ䛧䚸໙㓄䝁䜲䝹䛿஫䛔䛻㏫᪉ྥ䛻ὶ䛧䛯㟁ὶ䛻䜘䜚䚸☢ሙ໙㓄䛾䜏䜢⏕ᡂ䛩䜛䚹㻌 㻌 㽢㽢 P 䛾⠊ᅖ䛻⨨䛛䜜䛯ᐇ㦂⿦⨨䠄ᅗ䛻Ⅼ⥺䛷♧䛥䜜䛯෇⟄ᙧ䛾㡿ᇦ䠅䜢᝿ᐃ䛧䚸[ ㍈᪉ྥ䛻ྥ䛡䛯䠎ྎ䛾☢Ẽ䝉䞁䝃䞊䜢 [ ㍈᪉ྥ䛻  P 㞳䛧䛶㓄⨨䛩䜛䚹䛣䛾☢Ẽ䝉䞁䝃䞊䛿䚸ᕧ኱☢Ẽ᢬ᢠ
䠄*05䠅䜢฼⏝䛧䛯䝉䞁䝃䞊䛷䚸⣙ 䃛7 䛾ឤᗘ䛸ศゎ⬟䜢ᣢ䛴䚹ᡭື䛾☢ሙ⿵ൾ䜢⾜䛖䛸䛝䛿䚸䝦䝹䝮䝩䝹䝒䝁䜲䝹䛷㏫᪉ྥ䛾☢ሙ䜢Ⓨ⏕䛧䚸䠎ྎ䛾䝉䞁䝃䞊䛾ᖹᆒ್䛜  䃛7 䛸䛺䜛䜘䛖⿵ൾ䛩䜛䚹䜎䛯䚸䛣䜜䜙䝉䞁䝃䞊䛾ᕪ䛜  䃛7 䛸䛺䜛䜘䛖䛻໙㓄䝁䜲䝹䛻㟁ὶ䜢ὶ䛩䚹⮬ື⿵ൾ䜢⾜䛖䛸䛝䛿䚸)LJ 䛻♧䛩䜘䛖䛻䚸䠎ྎ䛾䝉䞁䝃䞊䛛䜙䛾ಙྕ䛾࿴䛸ᕪ䜢䚸'& 䜰䞁䝥䜢㏻䛧䛶䚸䝦䝹䝮䝩䝹䝒䝁䜲䝹䛸䚸໙㓄䝁䜲䝹䛻౪⤥䛧䚸㈇ᖐ㑏䛾㟁ὶ䜢ὶ䛩䚹௒ᅇ䛾ᐇ㦂䛷䛿䚸࿴䛾ಙྕ䛾㈇ᖐ㑏䛾䝀䜲䞁䛿 䚸ᕪ䛾ಙྕ䛾䝀䜲䞁䛿  䛷䛒䛳䛯䚹䝀䜲䞁䛾್䛿䚸䝉䞁䝃䞊䛛䜙䛾☢ሙ䛾ಙྕ䛸㈇ᖐ )LJ$XWRPDWLFFRPSHQVDWLRQV\VWHPIRU
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ሙ໙㓄䛿䚸䃛7P 䜎䛷ᢚ䛘䜙䜜䛯䚹୰ᚰ☢ሙཬ䜃☢ሙ໙㓄䛻ᑐ䛩䜛ᢚไ⋡䛿䚸䛭䜜䛮䜜䛾㈇ᖐ㑏⋡䛾㏫ᩘ 䚸ཬ䜃䚸 䛸䜋䜌୍⮴䛧䛶䛔䜛䚹㻌 ḟ䛻䚸x ㍈᪉ྥ䛾➃䚸[ P䛻䚸䜒䛖  ᮏ䛾⿵ຓ䝁䜲䝹䜢タ⨨䛧䚸ேⅭⓗ䛻 x ㍈᪉ྥ䛻☢ሙ໙㓄䜢
Ⓨ⏕䛥䛫䛯䚹䛭䛾⤖ᯝ䚸☢ሙศᕸ䛿䚸ᅗ䛾኱䛝䛺㯮୸䛾䜘䛖䛻䛺䜚䚸☢ሙ໙㓄䛜䃛7P 䛸䠎ಸ㏆䛟䜎䛷ቑຍ䛧䛯䚹䛣䜜䛻ᑐ䛧䛶⮬ື⿵ൾ䜢ാ䛛䛫䜛䛸䚸ᑠ䛥䛺㯮୸䛾䜘䛖䛻䃛7P 䜎䛷⿵ൾ䛥䜜䛯䚹䛣䛣䛷䜒ᢚไ⋡䛿㈇ᖐ㑏⋡䛾㏫ᩘ䛻୍⮴䛧䛶䛔䜛䚹䜘䜚ᙉ䛔㈇ᖐ㑏䜢䛛䛡䜜䜀䚸⿵ൾᛶ⬟䜒ྥୖ䛩䜛䛿䛪䛷䛒䜛䛜䚸⌧᫬Ⅼ䛷䛿䚸㈇ᖐ㑏䛾䝀䜲䞁䜢ୖ䛢䜛
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Fig. 1 (left) Zero-field spin relaxation spectra observed at 200 K and 280 K for base Al (black
marks) and hydrogen plasma charged Al (blue marks).
Fig. 2 (right) Temperature dependences of dipole widths for base Al, plasma charged Al and sparkcharged Al.
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ཎᏊ  ಶ䛻ᑐ䛧⣙  ಶ䜒䛾Ỉ⣲ཎᏊ + 䜢྾ⶶ䛩䜛ඃ䜜䛯Ỉ⣲྾ⶶ≀㉁䛷䛒䜚䚸䜎䛯㧗䛔⣧໬⬟ຊ䜢䜒䛴䛣䛸䛛䜙Ỉ⣲⢭〇䛻䜒฼⏝䛥䜜䛶䛔䜛 >@䚹6KLUDL 䜙䛿䚸/D1L ⣔䜔 $J3G ⣔Ỉ⣲྾ⶶྜ㔠୰䛾㝧㟁Ꮚᑑ࿨ ᐃ䛻䜘䜛◊✲䜢㏻䛧䛶䚸Ỉ⣲྾ⶶ䞉ᨺฟ䝃䜲䜽䝹䛻䛚䛔䛶ཎᏊ✵Ꮝ䛜ከᩘᙧᡂ䛥䜜 >@䚸/D1L
䛻䛚䛔䛶䛿ྍ㏫ⓗ䛻ไᚚ䛷䛝䜛Ỉ⣲䛾㔞䛜పୗ䛩䜛䛣䛸䜢♧䛧 >@䚸⇕ᖹ⾮≧ែ䛻䛚䛔䛶䜒ᨺฟ䛥䜜䛺䛔ṧ␃Ỉ⣲䛜✵Ꮝ䛻䝖䝷䝑䝥䛥䜜䛶䛔䜛ྍ⬟ᛶ䜢ᣦ᦬䛧䛯䚹䜎䛯 )XNDL 䜙䛿 3G 䜔 1L 䛻䛚䛔䛶㧗 䞉㧗Ỉ⣲ᅽຊ䛺䛹ᴟ➃䛺⎔ቃୗ䛷✵Ꮝ䌦Ỉ⣲」ྜయ䛜Ᏻᐃ䛺⛛ᗎ┦䛜ᙧᡂ䛥䜜䜛ྍ⬟ᛶ䜢♧䛧䛯 >@䚹䛧䛛䛧䛺䛜䜙䚸✵Ꮝ䌦Ỉ⣲䜽䝷䝇䝍䞊䛾䜘䛖䛺ᒁᡤ≧ែᙧᡂ䛾┤᥋ⓗドᣐ䛿䜎䛰ᚓ䜙䜜䛶䛔䛺䛔䚹䝥䝻䝖䞁䛸㟁Ⲵ䛜➼䛧䛔ṇ䝭䝳䜸䞁䛿䚸≀㉁ෆ㒊䛷Ỉ⣲䛾㍍䛔ྠ఩య䛸䛧䛶᣺䜛⯙䛖䚹䛛䛴䝭䝳䜸䞁䛿㧗ឤᗘ䛺☢Ẽ䝥䝻䞊䝤䛸䛧䛶ാ䛝䚸ȝ65 ἲ䛻䜘䜚Ỉ⣲఩⨨䛻䛚䛡䜛ᒁᡤ☢ሙ䜢┤᥋ほ 䛩䜛䛣䛸䛷䚸3G ୰Ỉ⣲䛾ᒁᡤᵓ㐀䜢᥈⣴䛩䜛䛣䛸䛜ྍ⬟䛸䛺䜛䚹䝊䝻䜎䛯䛿ప☢ሙୗ䛻䛚䛔䛶䛿䚸Ỉ⣲᰾ + 䛩䛺䜟䛱䝥䝻䝖䞁䛸䛾཮ᴟᏊ䌦཮ᴟᏊ┦஫స⏝䛜ᒁᡤ☢ሙ䛾୺せ䛺㉳※䛸䛺䜚䝭䝳䜸䞁䝇䝢䞁⦆࿴䜢ᘬ䛝㉳䛣䛩䚹⦆࿴䝇䝨䜽䝖䝹䛛䜙䝭䝳䜸䞁㏆ഐ䛾Ỉ⣲䛾ᗄఱᏛⓗ㓄⨨䚸䛩䜟䛺䛱 3G ୰Ỉ⣲䛾ᒁᡤᵓ㐀䛻㛵䛩䜛᝟ሗ䛜ᚓ䜙䜜䜛䚹㧗☢ሙୗ䛷䛿ఏᑟ㟁Ꮚ䛾䝇䝢䞁೫ᴟ䛻㉳ᅉ䛩䜛☢ሙ䛾䝅䝣䝖䛜⏕䛨䚸䝭䝳䜸䞁఩⨨䛻䛚䛡䜛䝅䝣䝖䠄䝘䜲䝖䝅䝣䝖䠅䛿 3G ୰Ỉ⣲䛾ᒁᡤ㟁Ꮚ≧ែ䜢཯ᫎ䛧䛯㔞䛸䛺䜛䚹௨๓䛾ሗ࿌䛷䚸Ỉ⣲྾ⶶᚋ䚸Ꮩ❧䝭䝳䜸䞁䛸䛿␗䛺䜛䝘䜲䝖䝅䝣䝖䜢ᣢ䛴ᡂศ䛜᪂䛯䛻ฟ⌧䛩䜛䛣䛸䜢♧䛧䛯 >@䚹ᡃ䚻䛿䚸3G 䛻䛚䛡䜛Ỉ⣲྾ⶶ䞉ᨺฟ㐣⛬䛻䛚䛔䛶⏕䛨䜛ṧ␃Ỉ⣲䛾᥈⣴䛸䚸䛭䛾ᒁᡤᵓ㐀䜢᫂䜙䛛䛻䛩䜛䛣䛸䜢┠ᣦ䛧䚸Ỉ⣲྾ⶶ䛒䜛䛔䛿ᨺฟ㐣⛬䛻䛚䛡䜛 3G 䛾 䝭䝳䜸䞁䝇䝢䞁⦆࿴ ᐃ䛸䝘䜲䝖䝅䝣䝖䛾 ᐃ䜢 -3$5&䚸⌮◊5$/ 䛚䜘䜃 75,80) 䛷⾜䛳䛯䚹43 ([SHULPHQW DQGUHVXOWV ȝ65 VSHFWUD GXULQJ K\GURJHQDEVRUSWLRQSURFHVV
㻌 3G 䜈䛾Ỉ⣲྾ⶶ䛿䚸㟁ゎ䝏䝱䞊䝆䠄(&䠅䛻䜘䜛᪉ἲ䜢䛸䛳䛯䚹)LJ 䛻♧䛩䜘䛖䛻㟁ゎᾮ୰䛻ᯈ≧䛾 3W 䜢ṇᴟ䚸3G 䜢㈇ᴟ䛻䛧䛶ᾐ䛧䚸3G ⾲㠃䛻䛚䛡䜛㟁ὶᐦᗘ⣙  $FP 䛷㟁ὶ䜢ὶ䛧䛯䚹
)LJ  䛻 (& ฎ⌮䛻䜘䜛 3G ୰ ȝ65 䝇䝨䜽䝖䝹䛾ኚ໬䛾ᵝᏊ䜢♧䛩䚹 ᐃ䛿 75,80) 䛷⾜䛳䛯䚹䝊䝻☢ሙ =)ȝ65 ⏝䛾 /$03) )LJ  6FKHPDWLF YLHZ RI WKH䛸㧗ᶓ☢ሙ +7)ȝ65 ⏝䛾 1X7LPH 䛾䠎䛴䝇䝨䜽䝖䝻䝯䞊䝍䜢ྠ᫬ HOHFWURO\WLF FKDUJLQJ SURFHVV LQWR 3G
䛻㉮䜙䛫䜛䛣䛸䛻䜘䜚䚸ྠ୍䛾ヨᩱ䛻䛴䛔䛶䜋䜌ྠ᫬䛻 =)ȝ65 䛸+7)ȝ65 䛾 ᐃ䜢⾜䛳䛯䚹྾ⶶ๓䛾⣧ 3G 䛻䛚䛔䛶䛿䚸䝩䝇䝖䛾 3G ᰾䛛䜙䛾཮ᴟᏊ☢ሙ䛜ᑠ䛥䛔䛯䜑=)ȝ65 䝇䝨䜽䝖䝹䛿䜋䛸䜣䛹⦆࿴䜢♧䛧䛶䛔䛺䛔䚹䛣䜜䛻ᑐ䛧䚸(& 䛻䜘䜚⦆࿴䛜⏕䛨䚸ᅇᩘ䜢㔜䛽䜛䛻䛴䜜䛶⦆࿴ᡂศ䛾 IUDFWLRQ 䛜኱䛝䛟䛺䛳䛶䛔䜛䚹7䛻䛚䛡䜛䝭䝳䜸䞁䝇䝢䞁ᅇ㌿ +7)ȝ65 䛾 ))7 䝇䝨䜽䝖
䝹䛿䚸(& 䛻䜘䜚㧗࿘Ἴᩘഃ䛻᪂䛯䛺䝢䞊䜽䛜⌧䜜䚸྾ⶶ๓䛻ぢ䛘䛶䛔䛯ప࿘Ἴᩘഃ䛾䝢䞊䜽䛜ᚎ䚻䛻ᾘኻ䛧䛶䛔䛟ᵝᏊ䛜ほ 䛥䜜䛯䚹㻌 ௨ୖ䛾䛣䛸䛛䜙䚸3G 䜈䛾Ỉ⣲྾ⶶ㐣⛬䛷䛾Ỉ⣲䛻䛴䛔䛶䚸Ꮩ❧≧ែ䛻䛒䜛 Į ┦䛛䜙྾ⶶ䛜㐍䜐䛻㐃䜜䛶 ȕ ┦䛜ᙧᡂ䛥䜜䚸Ỉ⣲㛫䛾㊥㞳䛜⦰䜎䜛䛣䛸䛻䜘䜚䝭䝳䜸䞁䝇䝢䞁⦆࿴䛜⏕䛨䚸䛛䛴ᒁᡤᵓ㐀䛾ኚ໬䛜㟁Ꮚ≧ែ䛻䜒ᙳ㡪䜢ཬ䜌䛧䝘䜲䝖䝅䝣䝖䛜䝆䝱䞁䝥䛧䛯䛸ゎ㔘䛷䛝䜛䚹䛩䛺䜟䛱䚸ȝ65 䛜 3G ୰䛾Ỉ⣲䛾ᒁᡤ≧ែ䛾ኚ໬䜢᫂☜䛻ᤕ䜙䛘䛶䛚
䜚䚸(& ฎ⌮䜢」ᩘᅇ⾜䛖䛣䛸䛻䜘䜚༑ศ䛻Ỉ⣲䛜྾ⶶ䛥䜜䜛䛣䛸䛜♧䛥䜜䛯䛸ゝ䛘䜛䚹྾ⶶ๓䛾䝘䜲䝖䝅䝣䝖
䛿㈇䛾್䜢♧䛧䚸 ᗘ౫Ꮡᛶ䜢䜒
䛴 >@䚹㐣ཤ䛾⣧ 3G 䛾⤖ᯝ䛸䜒Ⰻ䛟୍⮴䛧䛶䛚䜚 >@䚸䝅䝣䝖䛾ཎᅉ䛿 3G 䛾 G 㟁Ꮚ䛸Ꮩ❧Ỉ⣲䛻䜘䜛 V 㟁Ꮚ䛸䛾 VG ΰᡂ䛻䜘䜛䜒䛾䛸⪃䛘䜙䜜䜛 >@䚹Ỉ⣲྾ⶶ (&䛻䜘䜚䝘䜲䝖䝅䝣䝖䛿ṇ䛻㌿䛨䚸 ᗘ䛻䜘䜙䛪䜋䜌୍ᐃ್䜢䛸䜛䚹䝘䜲䝖䝅䝣䝖䛿㐣ཤ䛾 ȕ3G+x x  䇵  䛾⤖ᯝ >@ 䛻㏆䛔್䜢♧䛧 )LJ  =)ȝ65 DQG ))7 RI +7)ȝ65 VSHFWUD LQ 3G GXULQJ WKH K\GURJHQ
DEVRUSWLRQ SURFHVV E\ PHDQV RI WKH HOHFWURO\WLF FKDUJLQJ䛶䛚䜚䚸ᮏ◊✲䛻䛚䛔䛶䜒 (& 䛻䜘䜚 ȕ ┦䛾ᙧᡂ䛜☜ㄆ䛷䛝䛯䛸ゝ䛘䜛䚹 /RFDO VWUXFWXUH GXULQJK\GURJHQGHVRUSWLRQ SURFHVV㻌 䝭䝳䜸䞁䝘䜲䝖䝅䝣䝖䛻䛴䛔䛶䛿ᐊ 䛷䛾 ᐃ䛻䛚䛔䛶䜒 3G ୰䛾Ỉ⣲䛜Ꮩ❧≧ែ Į ┦ 䛛䚸ᐦ䛺≧ែ ȕ┦  䛻䛒䜛䛛䛜ุᐃ䛷䛝䛭䛖䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䚹䛣䜜䜢ᣦᶆ䛸䛧䛶Ỉ⣲྾ⶶᚋ䛾 3G ヨᩱ䛻䛴䛔䛶ㄪ䜉䛯䛸䛣䜝䚸)LJ 䛻♧䛩䜘䛖䛻 (& ฎ⌮ᚋ኱Ẽ୰䛷⣙  䞄᭶ᨺ⨨䛧䛯ᚋ䛷䜒 ))7 䝇䝨䜽䝖䝹䛿䜋䛸䜣䛹ኚ໬䛧䛶䛔䛺䛔䚹䛣䜜䜘䜚䚸(& 䛻䜘䜚྾ⶶ䛧䛯Ỉ⣲䛿䜋䛸䜣䛹 3G ୰䛻␃䜎䜚 ȕ ┦䜢ಖ䛳䛶䛔䜛䛣䛸䛜♧၀䛥䜜䜛䚹୍᪉䚸Ỉ⣲䜺䝇䛛䜙྾ⶶ䛧䛯ሙྜ䛿ᩘ᪥⛬ᗘ䛷ᢤ䛡䛶䛧䜎䛖䚹(& ヨᩱ䜢  & 䛷↝㕌䛧䛯ሙྜ䚸Ỉ⣲䛿䜋䜌ᨺฟ䛥䜜 ))7 䝇䝨䜽䝖䝹䛿⣧ 3G 䛸ྠᵝ䛻䛺䛳䛯䚹㻌 ௨ୖ䜘䜚 (& ヨᩱ୰䛻䛿ᐊ 䛷䛿ᨺฟ䛥䜜䛺䛔ṧ␃Ỉ⣲䛜Ꮡᅾ䛩䜛䛣䛸䛜♧၀䛥䜜䜛䚹ṧ␃Ỉ⣲䛾Ᏻᐃᛶ䜔ᒁᡤᵓ㐀䛻䛴䛔䛶ㄪ䜉䜛䛯䜑䛻䚸(& ฎ⌮ᚋ䛾ヨᩱ䛻䛴䛔䛶䚸↝㕌 ᗘ䛸ᨺฟỈ⣲㔞䛾㛵ಀ䚸䛚䜘44)LJ  7\SLFDO =)ȝ65 VSHFWUD LQ SRVWDQQHDOHG 3G+x 䜃ྛ↝㕌 ᗘ䛷䛾 =)ȝ65 䝇䝨䜽䝖䝹 ᐃ䜢 -3$5& 䛚䜘䜃⌮◊5$/ 䛷⾜䛳䛯䚹㟁Ẽ⅔䜢 ȝ65 ᐃ⌧ሙ䛻タ⨨䛧䚸┿✵୰䛷  ᫬㛫↝㕌ᚋ䚸㔜㔞䛾ኚ໬䛛䜙ᨺฟỈ⣲㔞䜢ồ䜑䚸䛯䛰䛱䛻ヨᩱ䜢䜽䝷䜲䜸䝇䝍䝑䝖䛻ྲྀ䜚௜䛡䛶 . 䛻෭༷䛧䚸=)ȝ65 䝇䝨䜽䝖䝹 ᐃ䜢⾜䛳䛯䚹୍㒊䛾ヨᩱ䛻䛴䛔䛶䛿䝇䝨䜽䝖䝹䛾 ᗘ౫Ꮡᛶ䜒 ᐃ䛧䛯䚹)LJ 䛻♧䛩䜘䛖䛻䚸↝㕌䛻䜘䜚⦆࿴䝇䝨䜽䝖䝹䛜ᣢ䛱ୖ䛜䜚䚸
)LJ  &KDQJH LQ WKH ))7 VSHFWUD LQ 3G DW .
 & 䛷䛿 3G ᰾䛻䜘䜛䛸ᛮ䜟䜜䜛䜖䛳䛟䜚䛸⦆࿴䛩䜛ᡂ
DIWHU K\GURJHQ DEVRUSWLRQศ䛧䛛ぢ䛘䛺䛟䛺䜛䚹䝇䝨䜽䝖䝹䛿ୗグ䛻♧䛩  ᡂศ䛾䜺䜴䝅䜰䞁ஂಖ䌦㫽㇂㒊㛵ᩘG t  r G.7' ¨+ Ȟ t  ±r G.7 ¨3G t ࡟ࡼࡾ෌⌧ࡋࡓࠋ➨  㡯ࡣ࣑ࣗ࢜ࣥ㏆ഐ࡟Ỉ⣲ࡀᏑᅾࡍࡿᡂศࡍ࡞ࢃࡕỈ⣲໬≀࠶ࡿ࠸ࡣỈ⣲ࢡࣛ ࢫࢱ࣮࡜ ⪃࠼ࡽ ࢀࡿ┦ ࠿ࡽࡢᐤ ୚࡛ࠊ Ỉ⣲᰾ + ࡟ ࡼࡿ ෆ㒊☢ሙศ ᕸᖜ ¨+ ࡜ ࡑ ࡢᦂ ື
㸦IOXFWXDWLRQ UDWH Ȟ㸧ࢆྲྀࡾධࢀࡓືⓗஂಖѸ㫽㇂㒊㛵ᩘ࡛࠶ࡿࠋr ࡣࡑࡢ IUDFWLRQ ࡛࠶ࡿࠋ➨  㡯ࡣᏙ❧࣑ࣗ࢜ࣥࡍ࡞ࢃࡕỈ⣲ࡀᢤࡅࡓ⎔ቃ࠿ࡽࡢᐤ୚࡛࠶ࡾࠊ3G ᰾࡟ࡼࡿ㐜࠸⦆࿴ࢆ♧ࡍࠋ⣧ 3G
ࡢࢫ࣌ࢡࢺࣝ࠿ࡽ ¨3G V± ࡜ࡋࡓࠋ)LJ ࡟ᨺฟỈ⣲㔞 įx ࡜ ILWWLQJ ࡟ࡼࡾồࡵࡓ r ࡟ࡘ࠸࡚ࠊ↝㕌 ᗘࡢ㛵ᩘ࡛ࣉࣟࢵࢺࡋࡓ⤖ᯝࢆ♧ࡍࠋ(& ฎ⌮᪉ἲࡢ␗࡞ࡿヨᩱ࡟ࡘ࠸࡚࠸ࡃࡘ࠿ ᐃࡋࡓ୰࡛௦⾲ⓗ࡞ࡶࡢ࡟ࡘ࠸࡚♧ࡋ࡚࠸ࡿࠋ࠸ࡎࢀࡢヨᩱࡶ↝㕌 ᗘ  & ࢆ㉺࠼ࡓ㎶ࡾ࠿ࡽỈ⣲ࡀᨺฟࡉࢀࠊ⣙&࡛኱㒊ศࡢỈ⣲ࡀᨺฟࡉࢀࡿࠋr ࡣ įx ࡜࡯ࡰྠࡌ౫Ꮡᛶ
ࢆ♧ࡋ࡚࠸ࡿࠋᅗ㸵࡟ ¨+ ࡜ Ȟ ࡢ⤖ᯝ࡟ࡘ࠸࡚♧ࡍࠋ¨+ ࡢ್ࡣ↝㕌 ᗘ࡟ࡼࡽࡎ࡯
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Ƃ±ħÂ 1Ƃď±Ɖőĝ 2dƈƓ½ 3q±śĶ 4
xŗ ĕ 1,2ÀûīĎl 2,3ŗďğ 2łjŏč 2ø÷r 2±k}¡Ɠ 4

W. Sato1,3, S. Komatsuda2, T. Fujisawa3, S. Takanaka3, T. Sugimoto3, and Y. Ohkubo4
1

Institute of Science and Engineering, Kanazawa Univ.

2

Graduate School of Natural Science and Technology, Kanazawa Univ.

3

National Institute of Technology, Ichinoseki College

4

Institute for Integrated Radiation and Nuclear Science, Kyoto Univ.


1. %-# £ŽeƃƔFe3O4ƕ%²ĝ#%V@NF9K ĩ43ƅġ6ăÚ3Žƃ$dľ3$Ƌċu¿×/ĸ×"!$ġħįb¶įĢ× 1EQaK`M?E/L\H@J]
O]cCEIW¶Öţ³MRI $ŵÌ"!Ą"Īų6.sÎ1#°Á#53
ƀ$ÖĪ õÍ43ġŪ3ŉó%ŲEQN^©ăŵ6.Žņ$ƎÕŁîÿ´6
ƒÿ 3Ɨ$ÿ´ƔFe3+6,£ƎyB9KƔA B9Kƕ 0& Fe3+ Fe2+6Ɩ»Ɩ,ƎyB9KƔB B9Kƕƕ pŹ#ż3ăŵ6ô3Fe3O4 6íąŐ×ùë
źĪ3-#%ĢÔį"ġ×$ĮĦ $Ò ſŜ "3÷ĶĿ%Fe3O4 #hŅġ6¿3 #0íąŐ6ĮĦ3 6İÞ34*$ĶĿ# Fe3O4 j#ç¾×$ 111mCd(111Cd) 111In(111Cd)6ĂÓƁ$hŅġ ¿416T`c
S 3æšĲƈƔPACƕĐ#044$hŅġ$ôB9K µ¨ģÙ$·6ť+
[1]¹ė%iT`cS . A B9K6ô3 6Ĺŉý Ñ14 
111
In(111Cd)%>[]cėÇƔTC = 858 Kƕtf$Ę·#  B B9K#µ¨3ķĥ ĨėÇ #$ķĥ fï3Ħũ ŠĘ44%hŅġ9<a$B9Kļ ĸċŮ
ļ#vŨū4Ħũ .ō 143-9<au¿ ĸċŮļ $Ĳƈ6Ĺ 3ƍÅ#œĒŉý3 fŤ$ĶĿÛĐ%şþ $ 111In B9Kļ6ū$ŉý6ç¾­®ĨÚ 111Cd ŠĘ3-¸Ɗ$hŅġ In $ŷ×#$Ƈã
į"Ø«6Ñ#Ÿ"Ð÷ĶĿ%Fe3O4 #n-ƍç¾× In 6LcTťë#
111m
Cd(111Cd)T`cS6ĔA B9Kƌć3 111Cd T`cS ŠĘŎ "2$
¦6 In ´ ŷ3Ħũ6ıãį#Šº3 6İį ¸Ƒ6Ř
2. ¸Ƒ
 Fe #» In $´éĊ 0.5% "30 #ńö$Ž9aD:WƔIn2O3ƕ6ĺƁFe3O4
ńö #-$ mƄjēēťë6ƆÚ©ĵŕŃ#ĳŀ¼ 1073 K  3
òƇĞÚ6ŘĞÚÎńö X Ŋ¤ÜĘ·#0oĆĲ$ôĜ6ķŧİį 3ťëƔ0.5
at.% In-doped Fe3O4ƔtgIFOƕƕ Ú43 6ķŧ111mCd(111Cd)T`cS%
q±śĶ$ĶĿĪ´Ě#  110Cd ęŌ CdO #j×´6ğ¾3 #0ĨÚ$ç¾×$ńö Cd(111mCd)O 6 IFO ēńö$**ĵŕŃ#ĳŀ¼1173 K $Ġ ħ#0ťëj#T`cS6ÝèIn $įß$ėÇ{µ×6ŠĘ3-¹ė800 K900 K  PAC Ę·6Ř111mCd(111Cd)T`cS$­®§6 Fig. 1 #ĹPAC Ę

47

·#% BaF2 CaG_cF#03Ðú$ 4 ā¢Đ6âĪ÷ĶĿ%=EAcL  Ŋ$šÇ
 0& 1 – 2 $çòƇÃ t # 3ŶÈò|é~ N(, t)6Ć$(1)É ħ3 #0 Ŋ$çî$ĭî×$òƇ® A22G22(t)6Ñ                 A22G22 (t) =2[N( , t)  N( / 2, t)].   (1)N( , t) + 2N( / 2, t) 
 
 A22 %šĲƈ|é=EAcL  Ŋ$ĭî
×$±6řG22(t)%òƇÓæ|éT`cSþ þ¯¬ $ĲpzĪ#0Ĩ3æ$Ø«6,P\XcF3

!   







Fig. 1. Simplified decay scheme of 111Cd














A22G22(t)3. ŉý ōº
 Fig. 2 # IFO j#¿4 111mCd(111Cd)T`cS$ PAC EU?K^6Ĺ¹ė%R;]ĸ×#03Żĸ¬ T`cSþ $ĲpzĪ6ñõįPFca6Ĺ3àÆòƇ$ňŸ.#Ï#ĖŚ3$%hŅġ ¿4 In3+9<a T`cSþ
ů#hŞ#µ¨3 #ū¥ŬÓŇ¬#Ä Ĩ3- ō 143TC 0
2.5 #wė3 800 K %Ë" 1Żĸ¬$ÌƏ ĉ3-À"đé
6vàPFca ŠĘ441$ TC
tg$EU?K^$Ţü%Ć$(2)É#ĹòƇÓæ|é G22(t)6ĪŘ






G22 (t) = 1

1
1+ 2 exp    2 L2 t 2  cos( L t)
 2
5



4


 1 2 2 2 
    + 2 exp    L t  cos(2 L t)  (2)
 2




 L %\cY8đé%\cY8đé$Ä3¹ė$EU?K^$Ţü$ŉý\cY8đé%L = 171.9(5) Mrad/sÄ% =3.6(4)%\cY8đé%ŘĶĿ# Fe3O4 j$ 111mCd(111Cd)T`cSÑ1
4~L = 171.5(2) Mrad s-1 ŔdŒ6Ĺ
2IFO # .T`cS ¹ė#  A

48

 




















t (ns)
111m
Fig. 2. PAC spectra of 111
Cd(111Cd) in
0.5 at.% In-doped Fe3O4 measured attemperatures indicated.

B9K6ô3 6Ĺ3[1]Ą#ŘĶĿ$ŉý 1800 K # . Cd
% A B9K6ô3
ä·43 TCƔ= 858 Kƕtf$ 900 K Ñ14 PAC EU?K^%1 – 2 $ĭî× Þéƈéį#ĖŚ3 ŠĘ44%þEQa$ŋĦũ6ñEU?K^3 ìĆ$(3)ÉŢü6Ř (3)
G22 (t) = exp( t)
In 6Ĕ" Fe3O4 %ĽÇ$ėÇƐªƔ= 873 KƘTCƕ#  300 ns $ŠĘòƇj#ĭî×%) 7!®"[1]$ %111mCd(111Cd)T`cSþ Ɠė# .»Ļ×$Ŕ A B9K#Ĭ* 2ĜæģÙ6}3 6Ĺ 3Ð÷ĶĿ 900 K
ŠĘ4Þéƈéį"ŋ%In $Ĕ#03.$3
ð1 2In $į"ß#0 111Cd T`cSþ ŋ3Ħũ6á ŉý3 Ţž3hŅġ In 9<a%őŭ$ƋŖÄ#03T`cSþ$ĈÃŷ$õ#Ċ( "2ŴòƇEAc^ŷ3 6Ĺ 3.$3fŰ$
2$ėÇƐª# 111mCd(111Cd)T`
cS% A B9K#µ¨3- A B9K$ŀÿ´ě6ŷ3 In T`cS$þEQaŋ6Êū3 ō 143
4. *  ŘĶĿ% In 9<a$ A B9K 1 B B9K'$B9Kļ6åĀ ÷ĶĿ% Fe3O4$ A B9K# 3 In 9<a$ŷģÙ602ıãį#Ĺ #ÚsÎ% B B9K#
3hŅġ In $ŷ×#.02ŦŇ"Ĵŝ6ÑEQN^ġ# 3hŅġ9<au¿$Ő×6űČ3n·3
ōêĤ
[1] W. Sato, T. Ida, S. Komatsuda, T. Fujisawa, S. Takenaka, and Y. Ohkubo, J. Appl. Phys. 129, 145104(2016).

49

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ࢱ࡟ࡼࡿప࢚ࢿࣝࢠ࣮E⥺᳨ฟჾ࡜ '666' ࢆ⤌ࡳྜࢃࡏࡓ᰾ศ⿣㞀ቨ ᐃჾࡢ㛤Ⓨࢆጞࡵࡓࠋ

0572)06 ࡢ⌧≧ 0752)06 ࡣ  ௨ୖࡢ

Fig. 2. Predicted fission barrier height5) and KISS researchregion covered by dashed black line, where MNT reactions
with uranium beam could reach to.

㉁㔞ศゎ⬟ࢆ᭷ࡋࠊPV ௨ෆࡢ ᐃ᫬㛫࡛  ಶ⛬ᗘࡢ࢖᳨࢜ࣥฟ࡟ࡼࡾ NH9 ௨ୗ࡛㔜࠸㉁㔞ᩘ㡿ᇦࡢཎᏊ᰾㉁㔞ࢆỴᐃ࡛ࡁࡿࠋࡇࢀࡲ࡛࡟⾜ࢃࢀࡓ㸲ࡘࡢ㉸㔜᰾㡿ᇦྠ఩యࢆྵࡴ㸶㸮௨ୖ
ࡢཎᏊ᰾㉁㔞ࡢ┤᥋ ᐃࡢ⤖ᯝࡣ࡯ࡰ඲࡚බ㛤ࡉࢀࡓ㸦)LJ㸧 ࠋ

Fig. 3 Mass measured
region (indicated by
red circle ) with the
MRTOF during 
experiments from2016 to 2017 at the
GARIS II focal plane.
Masses of over 80
isotopes were directly
determind.

51

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Fig. 4 D-TOF detector
set downstream the
MRTOF. (a) Setup for
performance test. (b)Measured ToF - Energy
correlation ofDparticles emitted from
244Cm, 237Np, 241Am

sources. (c) Photo.
Observed timeresolution is enoughshort as 251(7) ps forfurther massmeasurements.

Fig. 5. KISS-MRTOF system. (a) KISS beam switcher for the mass/decay
measurements. (b) Photo of the system.

52

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1 䝡䞊䝮䛿ヨᩱ䛾⣙  FP ୖὶഃ䛻タ⨨䛧䛯  PP 㽢PP 䛾䝁䝸䝯䞊䝍䜢㏻㐣ᚋ䚸ᐜჾ䛾ቨ䜢✺䛝ᢤ䛡䛶ヨᩱෆ㒊䛻☜ᐇ䛻೵Ṇ䛩䜛䚹೫ᴟಖᣢ䛚䜘䜃 ȕ105 ᐃ䛾䛯䜑䛻䚸ヨᩱ఩⨨䛻䛿㖄┤ୖྥ䛝䛻㟼☢ሙ B   7 䛜༳ຍ䛥䜜䛶䛔䜛䚹䝥䝷䝇䝏䝑䜽䝅䞁䝏䝺䞊䝍䛛䜙䛺䜛䜹䜴䞁䝍䞊䝔䝺䝇䝁䞊䝥䜢ヨᩱ䛾ୖୗ䛻タ⨨䛧䚸ヨᩱ୰䛻೵Ṇ䛧䛯 1䛛䜙ᨺฟ䛥䜜䜛 ȕ ⥺䛾᳨ฟ䛻⏝䛔䛯䚹䝇䝢䞁೫ᴟ䛧䛯᰾䛛䜙ᨺฟ䛥䜜䜛 ȕ⥺䛿㠀ᑐ⛠䛺ゅᗘศᕸ䜢♧䛧䚸P 䛾᪉ྥ䛻ᑐ䛩䜛 ȕ ⥺䛾ᨺฟゅᗘ䜢 Į 䛸䛩䜛䛸䚸 W Į  APFRVĮ 䛸⾲䛥䜜䜛䚹ᚑ䛳䛶䚸ୖୗ༶䛱 Į 䛚䜘䜃 ʌ ᪉ྥ䛻⨨䛛䜜䛯᳨ฟჾ䛾 ȕ ⥺ィᩘẚ䛿䚸AP ‫ࡢا‬ሙྜ r P  
N P N ʌP Ҹ G AP ࡜⾲ࡉࢀ P ࡟ẚ౛ࡍࡿ㔞࡛࠶ࡿ ȕ ⥺㠀ᑐ⛠ᗘ AP ࢆ཯ᫎࡍࡿࠋࡇࡇ࡛
G ࡣ᳨ฟჾࡢᗄఱᏛⓗ㠀ᑐ⛠ᗘࢆ⾲ࡍࠋʌ 䝟䝹䝇࡟ࡼࡾ೫ᴟࢆ཯㌿ࡉࡏࡓ࡜ࡁࡢィᩘẚ r ±P  ࡜ࡢẚࢆ࡜ࡿࡇ࡜࡟ࡼࡾ G ࡀᡴࡕᾘࡉࢀࠊr P r ±P  ± Ҹ AP ࡟ࡼࡾ AP ࡀᚓࡽࢀࡿࠋ௒ᅇ౑⏝䛧䛯
2䝡䞊䝮䛿᫬㛫ᖜ⣙PV ࡢࣃࣝࢫࣅ࣮࣒࡛ࠊ࿘ᮇࡣ 1䛾༙ῶᮇ䜢⪃៖䛧䛶V䛸䛧䛶䝡䞊䝮↷ᑕ䇶ȕ ⥺ィᩘ䛾䝃䜲䜽䝹䜢⧞ࡾ㏉ࡋࡓࠋࢧ࢖ࢡࣝࡢ㸰ᅇࡢ࠺ࡕ㸯ᅇࡣࠊࣅ࣮࣒↷ᑕ┤ᚋ࡜ ȕ ⥺ィᩘᚋ䛻 ʌ 䝟䝹䝇ࢆ༳ຍࡋࡓࠋヨᩱ఩⨨䛾㟼☢ሙ䜢ᖖ᫬䝰䝙䝍䞊䛩䜛䛯䜑䛻ヨᩱ䛛䜙⣙  FP 㞳䜜䛯఩⨨䛻䝥
䝻䝖䞁 105 䝥䝻䞊䝤䜢タ⨨䛧䚸☢ሙ䛾್䛿 ± ௨ୗ䛾⠊ᅖෆ䛷ᖖ䛻୍ᐃ䛻䛺䜛䜘䛖ㄪᩚ䛧䛯䚹 5HVXOWV DQG GLVFXVVLRQ $GMXVWPHQW RIDʌ SXOVH ZLGWK㻌 ʌ 䝟䝹䝇䛾᮲௳䜢Ỵᐃ䛩䜛䛯䜑䛻䚸୰ᚰ࿘Ἴᩘ䛜䜘䜚⢭ᗘ䜘䛟ศ䛛䛳䛶䛔䜛䝙䝖䝻䝯䝍䞁୰䛻 1 䜢ᡴ䛱㎸䜏䚸5) 䝟䝹䝇ᖜ䜢ኚ䛘䛺䛜䜙 ȕ ⥺㠀ᑐ⛠ᗘ AP 䛾ኚ໬䜢ᐃ䛧䛯䚹)LJ䛻♧䛩䜘䛖䛻䚸䝟䝹䝇ᖜ䛸ඹ䛻᣺ື䛧䛶䛔䜛ᵝᏊ䛜ほ 䛥䜜䛯䚹ῶ⾶䜢⪃៖䛧䛯㛵ᩘᙧ AP^ ±
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  * 䛜ᚓ䜙䜜䛯䚹䛣䛾⤖ᯝ䜢䜒䛸䛻䚸+2 ୰ 1 䛾
105 ᐃ䛷䛿䚸⥺ᖜ䜢⊃䜑䜛䛯䜑䛻 B 䜢༙ศ䛻ୗ䛢䚸ʌ 䝟䝹䝇䛾᫬㛫ᖜ䜢  ȝV 䛻タᐃ䛧䛯䚹)LJ  ȕUD\ DV\PPHWU\ FKDQJH YV 5) SXOVH ZLGWK IRU
 ȕ105 VSHFWUXP RI 1LQ+2

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P65 ࡛ ࡣ ࢫ ࣆ ࣥ ೫ ᴟ ࡋ ࡚ ⏕ ᡂ ࡋ ࡓ ࣑ ࣗ ࢜ ࣥ ࢆ ヨ ᩱ ࡟ ᡴ ࡕ ㎸ ࡴ ࠋ ࣑ ࣗ ࢜ ࣥ ࡀ ቯ ኚ ࡋ࡚ ᨺ ฟ ࡉ ࢀ ࡿ 㟁 Ꮚ ࡢ 㐠 ື ᪉ ྥ ࡣ ࠊᙅ ࠸ ┦ ஫ స ⏝ ࡟ ࡼ ࡿ ࡓ ࡵ ࡟ ࣑ ࣗ ࢜ ࣥ ࡢ ࢫ ࣆ ࣥ ᪉ ྥ࡟೫ࡿࠋヨᩱ࠿ࡽᨺฟࡉࢀࡿ㟁Ꮚࡢ㐠ື᪉ྥࡢࠊᡴࡕ㎸ࡳ᫬࠿ࡽࡢ᫬㛫౫Ꮡᛶࢆࠊ
࣑ࣗ࢜ࣥࢆከᩘᅇᡴࡕ㎸ࢇ࡛ఱᗘࡶᐃ ࡍ ࡿ ࠋ㟁 Ꮚ ࡢᐃ࡟ࡼࡗ࡚≀㉁ෆ࡛࣑ࣗ࢜ࣥ ࢫ ࣆ ࣥ ᪉ ྥ ࡢ ᫬ 㛫 ኚ ໬ ࡢ ᝟ ሗ ࠿ ࡽ ࠊ≀ ㉁ ෆ 㒊 ࡢ ☢ ᛶ ࡟ ࡘ ࠸ ࡚ ࡢ ᝟ ሗ ࢆ ᚓ ࡿ ࡇ ࡜ ࡀ࡛ࡁ ࡿ ࠋ࣑ࣗ ࢜ ࣥ఩ ⨨࡛ ࡢ ☢ሙ ࡀ ᆒ୍ ࡛ ᫬㛫 ኚ ໬ࡀ ࡞ ࡅࢀ ࡤ ࠊ࣑ࣗ ࢜ ࣥࢫ ࣆ ࣥࡣ ୍
ᐃゅ㏿ᗘࡢṓᕪ㐠ືࢆࡍࡿ㸦ࢫࣆࣥᅇ㌿㸧ࠋ☢ሙࡀ୙ᆒ୍࡛࠶ࡗࡓࡾࠊ᫬㛫ኚ໬ࡍࡿሙ ྜ ࡟ࡣ ࠊ࣑ ࣗ࢜ ࣥࢫ ࣆ ࣥࡢ ṓ ᕪ㐠 ື ࡀ୍ ᵝ ࡛ࡣ ࡞ ࡃ࡞ ࡿ ࡢ࡛ ࠊ࣑ ࣗ࢜ ࣥ ࢫࣆ ࣥࡢ೫ᴟᗘࡀ᫬㛫࡜࡜ࡶ࡟ῶᑡ࠸ࡃᵝ ࢫࣆࣥ⦆࿴ ࡀほࡉ ࢀ ࡿ >@ࠋṇ ࣑ ࣗ ࢜ ࣥ ࢆ ౑ ࠺ P65 ࡛ ࡣ ࠊṇ ࣑ ࣗ ࢜ ࣥ ࡀ ᱁ Ꮚ 㛫 ఩ ⨨㸦 ཎ Ꮚ 㛫 ఩ ⨨ 㸧࡟ ࠸ ࡿ ࡢ ࡛ ࠊཎ Ꮚ ᰾ ࢆ ࣉ ࣟ ࣮ ࣈ ࡜ ࡍ ࡿ 105 ࡸ 3$& ࡜ ࡣ ᝟ ሗ ࢆ ᚓ ࡿ ࡇ ࡜ ࡀ ࡛ ࡁ ࡿ ࠋࡲ ࡓ ṇ ࣑ ࣗ ࢜ࣥ ࡣ 㝧 Ꮚ ࡢ  ࡢ ㉁ 㔞 ࡛  ࡢ 㟁 Ⲵ ࢆ ᣢ ࡘ ࡢ ࡛ ࠊ⮬ ㌟ ࡀ ≀ ㉁ ୰ ࢆ ⛣ ື KRSSL QJ ࡍ ࡿ ࡇ࡜ ࡶ ࠶ ࡾ ࠊࢫ ࣆ ࣥ ⦆ ࿴ ࡀ ㉳ ࡇ ࡿ ࠋ≀ ㉁ ୰ ࡛ ṇ ࣑ ࣗ ࢜ ࣥ ࡜ 㟁 Ꮚ ࡢ ᮰ ⦡ ≧ ែ ࡛ ࠶ ࡿ ࣑ ࣗ࢜ ࢽ ࢘ ࣒ ࡀ ⏕ ᡂ ࡍ ࡿ ࡜ ࠊ Ỉ ⣲ ࡢ ㍍ ࠸ ྠ ఩ య ࡜ ࡋ ࡚ ᣺ ࡿ ⯙ ࠸ ࠊ P65 ࡛ ࡑ ࡢ ᣲ ື ࢆ ㄪ ࡭ࡿࡇ࡜ࡀ࡛ࡁࡿࠋ୍ ᪉ ㈇ ࣑ ࣗ ࢜ ࣥ ࡣ ࠊ 㟁 Ꮚ ࡼ ࡾ  ಸ 㔜 ࠸  ࡢ 㟁 Ⲵ ࢆ ᣢ ࡘ ⢏ Ꮚ ࡜ ࡋ ࡚ ≀ ㉁ ୰ ࡛ ᣺ ࡿ⯙࠺ ࡜ ⪃࠼ ࡿ ࡇ࡜ ࡀ ࡛ࡁ ࡿ ࠋ㟁Ꮚ ࡼ ࡾ㔜 ࠸ࡢ ࡛ ࠊ≀㉁ ୰ ࡟ධ ᑕࡋ ࡚ ೵Ṇ ࡋ ࡓ㈇ ࣑ ࣗ࢜ࣥ ࡣ ࠊཎᏊ ᰾ ࡟ᤕ ࡽࢃ ࢀ ࡚࣑ ࣗ ࢜ࣥ ཎ Ꮚࢆ ᙧ ᡂࡍ ࡿ ࠋ▷᫬ 㛫ࡢ ࠺ ࡕ࡟ ㈇ ࣑ࣗ ࢜ ࣥࡣ ࠊ࣑ ࣗ ࢜ ࣥ V ㌶ 㐨 ࡲ ࡛ 㑄 ⛣ ࡋ ࡚ ཎ Ꮚ ᰾ ㏆ ഐ ࢆ 㐠 ື ࡋ ࠊࡑ ࡇ ࡛ ቯ ኚ ࡋ ࡚ 㟁 Ꮚ ࡜ ࡞ ࡿ࠿ ࠊཎ Ꮚ ᰾ ࡟ ྾ ཰ ࡉ ࢀ ࡿ ࠋ࣑ ࣗ ࢜ ࣥ V ㌶ 㐨 ࡣ 㟁 Ꮚ ࡢ V ㌶ 㐨 ࡟ ẚ ࡭ ࡚ ኱ ࡁ ࡉ ࡀ  ࡛࠶ ࡾ ࠊ㈇࣑ ࣗ ࢜ࣥ ࡣཎ Ꮚ ᰾࡟ 㠀 ᖖ࡟ ㏆ ࠸ሙ ᡤ ࡛ࡢ ☢ ሙࣉ ࣟ ࣮ࣈ ࡜ ࡞ࡿ ࠋཎ Ꮚ᰾ ࡀ☢ Ẽ ࣔ ࣮ ࣓ ࣥ ࢺ ࢆ ᣢ ࡘ ሙ ྜ ࡟ ࡣ ࠊ㈇ ࣑ ࣗ ࢜ ࣥ ࢫ ࣆ ࣥ ࡣ ᰾ ☢ Ẽ ࣔ ࣮ ࣓ ࣥ ࢺ ࡜ ┦ ஫ స ⏝ࡍࡿ ࠋཎ Ꮚ᰾ ࡢ ࢫࣆ ࣥ ࡀ  ௨ୖ ࡢ ࡜ࡁ ࠊ㈇࣑ ࣗ ࢜ࣥ ࢫ ࣆࣥ ࡣ ㏿ࡸ ࠿ ࡟⦆ ࿴ ࡍࡿ ࡜ ࡳ57࡚ Ⰻ ࠸ ࠋཎ Ꮚ ᰾ ࡢ ࢫ ࣆ ࣥ ࡀ ࢮ ࣟ ࡛ ࠶ ࡿ ࡼ ࠺ ࡞ ཎ Ꮚ ᰾ ࡜ ㈇ ࣑ ࣗ ࢜ ࣥ ࡢ ⤌ ྜ ࡏ ࡣ ࠊࢫ ࣆࣥ ࢮ ࣟ ࡢ ཎ Ꮚ ᰾ ࡀ ㈇ ࣑ ࣗ ࢜ ࣥ ࡟ ࡼ ࡗ ࡚ ࢫ ࣆ ࣥ  ࡛ ࣛ ࣋ ࣝ ࡉ ࢀ ࠊ ᪂ ࡓ ࡞ ࢫ ࣆ ࣥ ࣉ ࣮ࣟࣈ࡜ࡋ࡚ᣲືࡍࡿ࡜⪃࠼࡚ࡼ࠸ࠋ
 ㈇ ࣑ ࣗ ࢜ ࣥ ࡢ P65

ᐃ ࡢ ᅔ 㞴 ࡉ ࡜ -3$5&086(㈇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡢ ◊ ✲ ౛ >@ ࡀ ࡇ ࢀ ࡲ ࡛ 㠀 ᖖ ࡟ 㝈 ࡽ ࢀ ࡚ ࠸ ࡓ ኱ ࡁ ࡞ ཎ ᅉ ࡣ ୺ ࡟ 㸰ࡘ࠶ࡿࠋ㸯ࡘࡣࠊ࣑ࣗ࢜ࣥཎᏊࡀ⏕ᡂࡋࠊ㈇࣑ࣗ࢜ࣥࡀཎᏊ᰾࠿ࡽ㐲࠸㌶㐨࠿ࡽ࣑ࣗ ࢜ ࣥ V ㌶ 㐨 ࡟ 㑄 ⛣ ࡍ ࡿ 㛫 ࡟ ࠊ ㌶ 㐨 㟁 Ꮚ ࡜ ࡢ ┦ ஫ స ⏝ ࡟ ࡼ ࡗ ࡚ ࢫ ࣆ ࣥ ೫ ᴟ ࡢ ኱ 㒊ศ ࡀ ኻ ࢃ ࢀ ࠊ  ⛬ ᗘ ࡟ ῶ ᑡ ࡋ ࡚ ࡋ ࡲ ࠺ ࡇ ࡜ ࡀ ᣲ ࡆ ࡽ ࢀ ࡿ ࠋ ࢫ ࣆ ࣥ ࣉ ࣟ ࣮ ࣈ ࢆ ౑ ࠺ᐃ ࡢ 6 1 ࡣ ೫ ᴟ ᗘ ࡢ 㸰 ஌ ࡛ ຠ ࡃ ࡢ ࡛ ࠊ ྠ ࡌ ㉁ ࡢ ࢫ ࣌ ࢡ ࢺ ࣝ ࢆ ᚓ ࡿ ࡓ ࡵ ࡟ ࠊ ㈇ ࣑ ࣗ࢜ ࣥ ࡢ P65 ࡛ ࡣ ṇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡢ  ಸ ࡢࣗ࢜ࣥᐇ㦂᪋タ࡛ࡣ᪥ᖖⓗ࡟ᐃ᫬㛫ࡀᚲせ࡜࡞ࡾࠊࡇࢀࡲ࡛ࡢ࣑ᐃ ࡛ࡁ ࡿ ࡶࡢ ࡛ ࡣ࡞ ࠿ ࡗࡓ ࠋࡶ࠺ 㸯 ࡘࡢ ⌮ ⏤ࡣ ࠊ༑ศ ࡞ ᙉ ᗘ ࡢ ㈇ ࣑ ࣗ ࢜ ࣥ ࣅ ࣮ ࣒ ࡀ ฼ ⏝ ࡛ ࡁ ࡿ ᪋ タ ࡀ ࡞ ࠿ ࡗ ࡓ ࡇ ࡜ ࡛ ࡿ ࠋ࣑ ࣗ ࢜ ࣥ ࣅ ࣮࣒ ฼ ⏝ ᪋ タ ࡛ ࡣ ࠊ㝧 Ꮚ ࣅ ࣮ ࣒ ࢆ ࣃ ࢖ ࢜ ࣥ ⏕ ᡂ ᶆ ⓗ ࡟ ↷ ᑕ ࡋ ࡚ ṇ ㈇ ࡢ ࣃ ࢖ ࢜ ࣥ ࢆ ⏕ ᡂࡋ ࠊࣃ ࢖ ࢜ ࣥ ࠿ ࡽ ᑑ ࿨ QV ࡛ ⏕ ᡂ ࡍ ࡿ ṇ ㈇ ࡢ ࣑ ࣗ ࢜ ࣥ ࢆ ౑ ࠺ ࠋ36,ࠊ,6,6ࠊ7 5,8 0)ࡢ ࡼ ࠺ ࡞ ࣑ ࣗ ࢜ ࣥ ᪋ タ ࡛ ࡣ ࠊ㝧 Ꮚ ࢚ ࢿ ࣝ ࢠ ࣮ ࡀ a 0H9 ࡛ ࠶ ࡾ ࠊ㈇ ࣃ ࢖ ࢜ ࣥ ࡢ⏕ ᡂ ᩿ 㠃 ✚ ࡀ ṇ ࣃ ࢖ ࢜ ࣥ ࡢ ⏕ ᡂ ᩿ 㠃 ✚ ࡼ ࡾ ࠿ ࡞ ࡾ ᑠ ࡉ ࠸ ࠋ㝧 Ꮚ ࢚ ࢿ ࣝ ࢠ ࣮ ࡀ 㧗 ࠸ ࡯࡝ ṇ ㈇ ࡢ ⏕ ᡂ ᩿ 㠃 ✚ ࡢ ᕪ ࡣ ᑠ ࡉ ࡃ ࡞ ࡿ ࠋࡇ ࢀ ࡟ ᑐ ࡋ ࡚ ࠊ- 3$5& ࣑ ࣗ ࢜ ࣥ ᪋ タ 086(
ࡢ 㝧 Ꮚ ࢚ ࢿ ࣝ ࢠ ࣮ ࡣ *H9 ࡛ ࠶ ࡾ ࠊ㈇ ࣑ ࣗ ࢜ ࣥ ࡀ ㇏ ᐩ ࡟ ⏕ ᡂ ࡍ ࡿ ࠋ- 3$5&086( ࡢึ ࣅ ࣮ ࣒ ࡣ  ᖺ  ᭶ ࡔ ࡗ ࡓ ࡀ ࠊ P65 ᐇ 㦂 タ ഛ ࡢ ᩚ ഛ ࡜ ࠊ ⭾ ኱ ࡞ ປ ຊ ࡜ ᫬ 㛫 ࡀ ㈝ࡸ ࡉ ࢀ ࡓ ࣅ ࣮ ࣒ ㄪ ᩚ ࡟ ࡼ ࡿ ㈇ ࣑ ࣗ ࢜ ࣥ ࣅ ࣮ ࣒ ࡢ ᙉ ᗘ ࡜ ㉁ ࡢ ྥ ୖ ࡟ ࡼ ࡾ ࠊࡸ ࡗ ࡜ ㈇ ࣑ࣗ ࢜ ࣥ ࡢ P65 ࡀ ⌧ ᐇ ⓗ ࡞ ᫬ 㛫 ෆ ࡟ᐃ࡛ࡁࡿ᪋タࡀㄌ⏕ࡋࡓࠋ ㈇ ࣑ ࣗ ࢜ ࣥ ࢆ ౑ ࡗ ࡚ ≀ ㉁ ୰ ࡟ Ỉ ⣲ ࡀ ࡘ ࡃ ࡿ ☢ ሙ ࢆ ど ࡿᮡ ᒣ ⣧ 㸦 ㇏ ⏣ ୰ ኸ ◊ ✲ ᡤ 㸧 ࡽ ࡣ ࠊ - 3$5&
086( ࡢ ㈇ ࣑ ࣗ ࢜ ࣥ ࣅ ࣮ ࣒ ࢆ ౑ ࡗ ࡚ ࠊ0J+ ୰ ࡟ ㈇ ࣑ ࣗ ࢜ ࣥ ࢆ ᡴ ࡕ ㎸ ࡳ ࠊ࣐ ࢢ ࢿ ࢩ ࢘ ࣒ཎ Ꮚ ᰾   0Jࠊ   0J ࢆ ㈇ ࣑ ࣗ ࢜ ࣥ ࡛ ࢫ ࣆ ࣥ ࡟ ࣛ ࣋ ࣝ ࡋ ࡓ >@ ࠋ ࡇ ࡢ ≀ ㉁ ࡢ ሙ ྜ ࠊ ㈇࣑ࣗ࢜ࣥࡣ࣐ࢢࢿࢩ࣒࢘࡟ᤕ⋓ࡉࢀࡿ࡜ࡳ ࡞ ࡋ ࡚ ࡼ ࠸ ࠋྠ ఩ య Ꮡ ᅾ ᗘ ࡛ ࢫ ࣆ ࣥ
 ࡢ



0J ࡟ ᤕ ⋓ ࡉ ࢀ ࡓ ㈇ ࣑ ࣗ ࢜ ࣥ ࡣ ㏿ࡸ ࠿ ࡟ ࢫ ࣆ ࣥ ⦆ ࿴ ࡋ ࡚ P65 ಙ ྕ ࡟ ࡣ ᐤ ୚ࡋ ࡞ ࠸ ࠋ )L JXUH  ࡟ P65 ࢫ ࣌ ࢡ ࢺ ࣝ ࢆ ♧ ࡍ>@ࠋ㈇ ࣑ ࣗ ࢜ ࣥ ࡣ ⏕ ᡂ ᫬ ࠿ ࡽ ࢫ ࣆ ࣥ ೫ ᴟ ࡋ ࡚ ࠸ ࡿ ࡢ ࡛ ࠊࢮ ࣟ ☢ ሙ ୗ ࡛ ࢫ ࣆ ࣥ ⦆ ࿴ ࢆほࡍ ࡿ ࡇ ࡜ ࡀ ࡛ ࡁ ࡿ ࠋࡇ ࡇ ࡛ ࡳ ࡽ ࢀ ࡿ ࢮ ࣟ ☢ ሙ ࢫ ࣆ ࣥ ⦆ ࿴ ࡢ ≉ ᚩ ࡣ ࠊ࢞ ࢘ ࢫ 㛵 ᩘᆺ࡛⦆࿴ࡋ࡚࠸ࡁࠊᴟᑠࡢ࠶࡜ᑡࡋᅇ᚟ࡋ ࡚ ࠸ ࡿ ࡇ ࡜ ࡛ ࠶ ࡿ ࠋࡲ ࡓ ⦪ ☢ ሙ ࢫ ࣆ ࣥࢆಖᣢࡍࡿ᪉ྥ ࢆ༳ຍࡍࡿ࡜⦆࿴ࡀ㐜) L J     1 H J D W L Y H  PX R Q  V S L Q  U H O D [D WL R Q V S H FWU D 
L Q 0 J +  ࡃ ࡞ ࡗ ࡚ ࠸ ࡿ ࠋࡇ ࢀ ࡽ ࡢ ᣲ ື ࡣ ࠊṇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡛ ࡼ ࡃ ▱ ࡽ ࢀ ࡚ ࠸ ࡿ ஂ ಖ 㫽 ㇂ 㒊ᆺ ࢫ ࣆ ࣥ ⦆ ࿴ ࡛ ࠶ ࡿ ࠋ࣐ ࢢ ࢿ ࢩ ࢘ ࣒ ఩ ⨨ ࡟ Ỉ ⣲ 㝧 Ꮚ ࡢ ᰾ ☢ Ẽ ࣔ ࣮ ࣓ ࣥ ࢺ ࡀ ࡘ ࡃ ࡿ ࠊ    7 ⛬ ᗘ ࡢ ኱ ࡁ ࡉ ࡛ ࠊ ሙ ᡤ ࡟ ࡼ ࡗ ࡚ ᪉ ྥ ࡀ ࣛ ࣥ ࢲ ࣒ ࡞ ☢ ሙ ࡟ ࡼ ࡗ ࡚ ㈇ ࣑ ࣗ ࢜ ࣥ ࢫ58ࣆ ࣥ ࡀ ⦆ ࿴ ࡋ ࡚ ࠸ ࡿ ࡇ ࡜ ࡀ ࢃ ࠿ ࡿ ࠋィ ⟬ ࡟ ࡼ ࡿ ࣐ ࢢ ࢿ ࢩ ࢘ ࣒ ఩ ⨨ ࡢ ☢ ሙ ࡢ ኱ ࡁ ࡉ ࡜ࡶ⤖ᯝࡀࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ
 ㈇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡢ ࠶ ࡅ ࡰ ࡢṇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡛ ࡣ ࠊᖖ ࡟ ṇ ࣑ ࣗ ࢜ ࣥ ࡢ ≀ ㉁ ୰ ࡛ ࡢ ೵ Ṇ㸦 Ꮡ ᅾ 㸧ሙ ᡤ ࡀ ㆟ ㄽ ࡢ ⓗ࡟࡞ࡗ࡚ࡁࡓࡀࠊ㈇࣑ࣗ࢜ࣥࡣཎᏊ᰾఩⨨㸦ṇ☜࡟ࡣࡈࡃ㏆ഐࢆ㐠ືࡋ࡚࠸ࡿ㸧࡜⪃ ࠼ ࡚ ࡼ ࠸ ࡓ ࡵ ࠊ఩ ⨨ ࡢ ୙ ☜ ࠿ ࡉ ࡣ ࡞ ࠸ ࡓ ࡵ ࠊゎ 㔘 ࡀ ⡆ ༢ ࡟ ࡞ ࡿ ࡜ ࠸ ࠺ ᭷ ฼ ࡞ Ⅼ ࡀ࠶ ࡿ ࠋࡲ ࡓ ࡇ ࢀ ࡲ ࡛ ዲ 㒔 ྜ ࡞ ཎ Ꮚ ᰾ ࣉ ࣟ ࣮ ࣈ ࡀ Ꮡ ᅾ ࡋ ࡞ ࠿ ࡗ ࡓ ᰾ ࡟ ᑐ ࡋ ࡚ ࢫ ࣆ ࣥ ࣛ࣋ ࣝ ࡛ ࡁ ࡿ ࡜ ࠸ ࠺ ࡢ ࡣ ኱ ࡁ ࡞ ඃ ఩ Ⅼ ࡛ ࠶ ࡿ ࠋࡓ ࡔ ࡋ ࠊ㈇ ࣑ ࣗ ࢜ ࣥ ࡜ ࢝ ࢵ ࣉ ࣝ ࡋ ࡚ ࠸ࡿ ࡓ ࡵ ࡟ ࠊࡑ ࡢ ཎ Ꮚ ࡢ 㟁 Ꮚ ⣔ ࠿ ࡽ ࡣ ࠊཎ Ꮚ ᰾ 㟁 Ⲵ ࡀ 㸯 ࡔ ࡅ ᑠ ࡉ ࡃ ࡞ ࡗ ࡓ ࡼ ࠺ ࡟ ぢ ࠼ࡿ ࠋ ㏫ ࡟ ✚ ᴟ ⓗ ࡟ ࡣ z ୙ ⣧ ≀ ࡜ ࡜ ࡽ ࠼ ࡿ ࡇ ࡜ ࡶ ࡛ ࡁ ࡿ ࡋ ࠊ ໬ Ꮫ ⪅ ࡢ ど Ⅼ ࠿ ࡽ ࡣ ࠊཎ Ꮚ ␒ ྕ ࢆ  ࡔ ࡅ ᑠ ࡉ ࡃ ࡍ ࡿ ཎ Ꮚ ኚ ᥮ ࡀ ࡛ ࡁ ࡿ ࡇ ࡜ ࢆ ព ࿡ ࡋ ࠊࡇ ࢀ ࡲ ࡛ ࡟ ࡞ ࠸ ᪂ ࡋ࠸໬ྜ≀ࡢྜᡂἲࡢ㛤Ⓨ࡜ࡶゝ࠼ࡿࠋṇ ࣑ ࣗ ࢜ ࣥ ࡢ P65 ࡟ ẚ ࡭ ࡚ ኱ ᖜ ࡟ 㛗 ࠸ᐃ᫬㛫ࡀᚲせ࡛ࡣ࠶ࡿࡀࠊࡲࡗࡓࡃ᪂ࡋ࠸ ࢫ ࣆ ࣥ ࣉ ࣟ ࣮ ࣈ ࡀ ฼ ⏝ ྍ ⬟ ࡟ ࡞ ࡗ ࡓ ࠋ᪂ つ ࡞ ࢔ ࢖ ࢹ ࢕ ࢔ ࡛ ኱ ࠸ ࡟ ฼ ⏝ ࡉ ࢀ ࡿ ࡇ ࡜ࢆᮇᚅࡍࡿࠋཧ⪃ᩥ⊩>@-6XJL \DPDHWDO3K\V5HY/HWW     
>@ 㛛 㔝 Ⰻ ඾ ࠕ ࣑ ࣗ ࢜ ࣥ ࢫ ࣆ ࣥ ᅇ ㌿ ἲ ࠖ ඹ ❧ ฟ ∧ >@ 6 1DJDPL \D HW  DO  3K\V 5HY /HWW     . 1DJDPLQH HW  DO +\SHUIL QH
,QW HUDFW  11LVKL GD+\SHUIL QH,QWHUDFW   -%UHZHUHWDO
3K\V5HY&   ࡞ ࡝>@.(. ࣉ ࣞ ࢫ ࣜ ࣜ ࣮ ࢫ KWWSV ZZZNHNM SM DQHZVURRPDWWL FSUHVVSGI ࠿ ࡽ59࣓ࢱࣥ㞺ᅖẼୗࡢ㕲࣮ࣞࢨ࣮⵨╔࡟ࡼࡾ⏕ᡂࡋࡓ‽Ᏻᐃ┦ࡢⅣ໬㕲ⷧ⭷
0HWDVWDEOHLURQFDUELGHWKLQILOPVSURGXFHGE\
SXOVHGODVHUGHSRVLWLRQ RILURQ LQ WKH PHWKDQHDWPRVSKHUHᮾ ⌮ ኱ ࠊ 㟁 ㏻ ኱ ࠊ ⌮ ◊ ⯚ ᶫ ᣅ ᕫ ࠊ す ⏣ ┤ ᶞ ࠊ ᑠ ᯘ ⩏ ⏨ ࠊ ᒣ ⏣ ᗣ ὒ 7 )XQDEDVKL  11LVKLGD  <.RED\DVKL     DQG<<DPDGD 
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7KH8QLYHUVLW\RI(OHFWUR&RPPXQLFDWLRQV5,.(1㸬 ࡣ ࡌ ࡵ ࡟Ⅳ໬㕲ࡣඃࢀࡓ☢Ẽ≉ᛶࡸゐ፹άᛶࢆᣢࡘࡇ࡜࠿ࡽᐇ⏝ⓗ࡞⏘ᴗศ㔝ࡸᇶ♏ⓗ࡞ᮦᩱ ศ 㔝 ࡛ ◊ ✲ ࡀ ┒ ࢇ ࡟ ⾜ ࢃ ࢀ ࡚ ࡁ ࡓ >@ࠋ Ⅳ ໬ 㕲 ࢆ ᵓ ᡂ ࡍ ࡿ 㕲 ࡣ  ౯ ࡛ ࠶ ࡾ ࠊ Į)H ࡟Ⅳ ⣲ ࡀ ౵ ධ ࡋ ࡓ ࣇ ࢙ ࣛ ࢖ ࢺ ࡸ Ȗ)H ࡟ Ⅳ ⣲ ࡀ ౵ ධ ࡋ ࡓ ࢜ ࣮ ࢫ ࢸ ࢼ ࢖ ࢺ ࡣ ࠊ ࡑ ࢀ ࡒ ࢀ Ⅳ ⣲ࢆ ࠊ 㸣 ⛬ ᗘ ྵ ࡴ ࡇ ࡜ ࡀ ࡛ ࡁ ࡿ ࠋ ࡉ ࡽ ࡟ Ⅳ ⣲ ࡢ 㔞 ࡀ ቑ ࠼ ࡿ ࡜ 㕲 ࡜ Ⅳ ⣲ ࡢ ⤖ ྜ ࡟ ࡼࡗ ࡚ ⤖ ᬗ ᵓ 㐀 ࡀ ⏕ ࡌ ࠊ Ᏻ ᐃ ࡞ Ⅳ ໬ 㕲 ࡛ ࠶ ࡿ ࢭ ࣓ ࣥ ࢱ ࢖ ࢺ ș)H  & ࡀ ⏕ ᡂ ࡍ ࡿ ࠋ ࡑ ࡢ ࡯ ࠿࡟ ࡶ ‽ Ᏻ ᐃ ࡞ Ⅳ ໬ 㕲 ࡜ ࡋ ࡚ Ȗ )H&ࠊȘ)H  &ࠊȗ)H  &ࠊȤ)H  &  ࠊK)H  &  ࠊR)H  &  ࠊȖ )H  &ࠊȖ )H  &ࠊĮ )H   &  ࡀ Ꮡ ᅾ ࡍ ࡿ ࡀ ࠊᖖ ᅽ ୗ ࡢ )H& ⣔ ≧ ែ ᅗ ࡟ ࡣ ࡇ ࢀ ࡽ ࡢ Ⅳ ໬ 㕲 ࡣ ࡳ ࡽࢀ ࡞ ࠸ >@ ࠋ ᚤ ⢏ Ꮚ ࡸ ⷧ ⭷ ࡟ ࡍ ࡿ ࡇ ࡜ ࡛ ࡇ ࢀ ࡽ ࡢ ‽ Ᏻ ᐃ ࡞ Ⅳ ໬ 㕲 ࡀ ⌧ ࢀ ࡿ ࡇ ࡜ ࡀ ࠶ࡿ ࡀ ࠊ 㓟 ໬ 㕲 ࡞ ࡝ ࡀ ΰ ᅾ ࡋ ࡚ ࡋ ࡲ ࠺ ࡓ ࡵ ⣧ ⢋ ࡞ ࡶ ࡢ ࢆ ྜ ᡂ ࡍ ࡿ ࡢ ࡣ 㞴 ࡋ ࠸ >@ࠋ ᮏ◊ ✲ ࡛ ࡣ ࣃ ࣝ ࢫ ࣞ ࣮ ࢨ ࣮ ⵨ ╔ ἲ 3/' ࢆ ⏝ ࠸ ࡚ Ⅳ ໬ 㕲 ⷧ ⭷ ࢆ ྜ ᡂ ࡋ ࡓ ࠋ3/' ࡣ ┿ ✵ ୰ ࡛⵨Ẽᅽࡢప࠸ヨᩱࢆẼ໬࣭⵨╔ࡋ࡚ⷧ⭷ࢆస〇ࡍࡿ⡆౽࡞᪉ἲ࡛࠶ࡿࡀࠊ཯ᛂ࢞ࢫ㞺ᅖ Ẽ ୗ ࡛ 㕲 ࡢ 3/' ࢆ ⾜ ࠺ ࡜ 㧗 ࢚ ࢿ ࣝ ࢠ ࣮ ࡢ 㕲 ཎ Ꮚ ࡜ ࢞ ࢫ ࡀ ཯ ᛂ ࡋ ࡚ 㕲 ໬ ྜ ≀ ⷧ ⭷ ࡀᚓ ࡽ ࢀ ࡿ ࠋᡃ ࠎ ࡣ ࡇ ࢀ ࡲ ࡛ ࡟ ࢔ ࢭ ࢳ ࣞ ࣥ 㞺 ᅖ Ẽ ୗ ࡛ ࡢ 㕲 3/' ࡟ ࡼ ࡾ )H  &ࠊ)H  &  ࠊᖖ ☢
ᛶ ࡢ ࢔ ࣔ ࣝ ࣇ ࢓ ࢫ )H& ࡀ ⏕ ᡂ ࡍ ࡿ ࡇ ࡜ ࢆ ᫂ ࡽ ࠿ ࡟ ࡋ ࡓ ࠋࡋ ࠿ ࡋ ࠊ࢔ ࢭ ࢳ ࣞ ࣥ ࡣ ศ ゎ ࡟ࡼࡗ࡚࢔ࣔࣝࣇ࢓ࢫⅣ⣲ࢆ⏕ࡌࡸࡍ࠸ᛶ㉁ࡀ࠶ࡿࡓࡵⅣ⣲ࡀ㐣๫࡟࡞ࡿഴྥࡀぢࡽࢀࡿ >@ࠋᮏ ◊ ✲ ࡛ ࡣ ࠊࡇ ࡢ ࢔ ࣔ ࣝ ࣇ ࢓ ࢫ Ⅳ ⣲ ࡢ ⏕ ᡂ ࢆ ᢚ ไ ࡍ ࡿ ࡓ ࡵ ࡟ Ⅳ ⣲ ࡢ ౪ ⤥ 㔞 ࢆ ῶࡽ ࡋ ࣓ ࢱ ࣥ ࢆ ⏝ ࠸ ࡚ 㕲 3/' ࢆ ⾜ ࠸ Ⅳ ໬ 㕲 ⷧ ⭷ ࢆ స 〇 ࡋ ࡓ ࠋ㸬 ᐇ 㦂⵨ ╔ ⿦ ⨨ ෆ ࡟ ࣓ ࢱ ࣥ ࢞ ࢫ ࢆ ὶ 㔞 ㄪ ᩚ ࡋ ࡞ ࡀ ࡽ ᑟ ධ ࡋ ࠊ᤼ Ẽ ㏿ ᗘ ࢆ ไ ᚚ ࡍ ࡿ ࡇ ࡜ ࡟ ࡼ ࡗ࡚ ࣓ ࢱ ࣥ ᅽ ຊ ࢆ ୍ ᐃ ࡟ ࡋ ࡓ ࠋ 1G<$* ࣞ ࣮ ࢨ ࣮ 1HZ:DYH 7(13(67ࠊ QPࠊ P-SXOVHࠊ+] ࢆ ⏝ ࠸ ࡚ 㔠 ᒓ   )H ヨ ᩱ ࡟ SXOVH ↷ ᑕ ࡋ ࠊ$O ᇶ ᯈ PPîPPୖ ࡟ ⵨ ╔ ࡉ ࡏ ࡓ ࠋ$O ᇶ ᯈ ࡣ ࢭ ࣛ ࣑ ࢵ ࢡ ࣄ ࣮ ࢱ ࣮ ࡟ ࡼ ࡗ ࡚ ຍ ⇕ ࡋ ࠊタ ᐃ ᗘ ࠥ .
࡛ ୍ ᐃ ࡜ ࡞ ࡿ ࡼ ࠺ ࡟ ไ ᚚ ࡋ ࡓ ࠋᚓ ࡽ ࢀ ࡓ Ⅳ ໬ 㕲 ⷧ ⭷ ࡣ   &R5K ⥺ ※ ࢆ ⏝ ࠸ ࡓ ㏱ 㐣 ᆺ ࣓ ࢫࣂ ࢘ ࢔ ࣮ ศ ග ἲ ࡜ ⢊ ᮎ ; ⥺ ᅇ ᢡ ἲ ;5' 5,*$.85,17ࠊ&X.Į ⥺ ࡟ ࡼ ࡾ ᐃ ࡋ ࡓ ࠋࡲ ࡓ ࠊ ⷧ ⭷ ࡢ ⾲ 㠃 ᙧ ≧ ࢆ ㉮ ᰝ ᆺ 㟁 Ꮚ 㢧 ᚤ 㙾 6(0 -(2/-60) ࡟ ࡼ ࡗ ࡚ ほ ᐹ ࡋ ࡓ ࠋ60㸬 ⤖ ᯝ ࡜ ⪃ ᐹ)LJ ࡟ ࣓ ࢱ ࣥ ᅽ ຊ ࢆ 3D ࡛ ୍ ᐃ ࡟ ࡋ ࠊ ⏕ ᡂ᫬ ࡢ ᇶ ᯈ ᗘ ࢆ ኚ ໬ ࡉ ࡏ ࡓ ࡜ ࡁ ࡢ ;5' ࣃ ࢱ ࣮ࣥ ࢆ ♧ ࡍ ࠋ ᇶ ᯈ ᗘ . )LJD ࡛ ⏕ ᡂ ࡋ ࡓ࡜ࡁ࡟ࡣࠊᇶᯈ࡟⏝࠸ࡓ࢔࣑ࣝࢽ࣒࢘
3')  ࡟ ࡼ ࡿ ᅇ ᢡ ࡢ ௚ ࡟ ࡣ ࣈ ࣟ ࣮ ࢻ ࡞ᅇᢡࡢࡳࡀࡳࡽࢀࠊ࢔ࣔࣝࣇ࢓ࢫࡀ⏕ᡂࡋࡓ࡜⪃࠼ࡽࢀࡿࠋᇶᯈ ᗘࢆୖ᪼ࡉࡏ࡚ⷧ⭷ࢆ⏕ᡂࡍࡿ࡜ࠊ⤖ᬗᡂ㛗࡟ࡼࡾᅇᢡࣃࢱ࣮ࣥࡣࢩ࣮ࣕࣉ ࡟ ࡞ ࡾ ࠊ. )LJF ࠾ ࡼ ࡧ . )LJG࡛ ࡣ Ȥ)H  &  3')  ࡟ ࡼ ࡿ ᅇ ᢡ ࡀࡳ ࡽ ࢀ ࡓ ࠋ ࡋ ࠿ ࡋ ș)H  & 3')  ࡶ ㏆
࠸ゅᗘ࡟ᅇᢡࡀࡳࡽࢀࡿࡓࡵࠊࡇࢀࡢᏑᅾࢆྰ
ᐃ࡛ࡁ࡞࠸ࠋࡇࢀࡽࢆヲ⣽࡟ศᯒࡍࡿࡓࡵ࡟࣓
ࢫࣂ࢘࢔࣮ศග ᐃࢆ⾜ࡗࡓࠋ)LJ ࡟ ࣓ ࢫ ࣂ ࢘ ࢔ ࣮ ࢫ ࣌ ࢡ ࢺ ࣝ ᐊࢆ♧ࡍࠋྠ୍ࡢᡂศ࡛」ᩘࡢࢧ࢖ࢺࢆᣢࡘሙྜࠊྛࢧ࢖
ࢺࡢ⥺ᖜࡣྠࡌ࡛࠶ࡿ࡜௬ᐃࡋ࡚ࣇ࢕ࢵࢸ࢕ࣥࢢ ࢆ ⾜ ࡗ ࡓ ࠋᇶ ᯈ ᗘ . ࡛ ⏕ ᡂ ࡋ ࡓ ⷧ ⭷ ヨᩱ )LJD ࡛ ࡣ ᖜ ࡢ ᗈ ࠸ ࢫ ࣌ ࢡ ࢺ ࣝ ࡀ ᚓ ࡽ ࢀ ࠊ㕲 ࡢ ⎔ ቃ ࡟ ศ ᕸ ࡀ ࠶ ࡾ ࠾ ࡼ ࡑ N2H ࡛ ᴟ ኱ ࡜࡞ࡿෆ㒊☢ሙศᕸࡀࡳࡽࢀࡓࠋᇶᯈࡢ ᗘࡀప࠸ሙྜ࡟ࡣ༑ศ࡟⤖ᬗᡂ㛗ࡀ㉳ࡁ࡞࠸࡜⪃࠼ࡽࢀ ࡿ ࠋ . )LJE  ࠾ ࡼ ࡧ . )LJF ࡛⏕ ᡂ ࡍ ࡿ ࡜ Ȥ)H  &  ࡟ ࡼ ࡿ  ⤌ ࡢ ࢭ ࢡ ࢫ ࢸ ࢵ ࢺ ࡢᡂ ศ >@ࡀ ࡳ ࡽ ࢀ ࡓ ࠋ ࡇ ࢀ ࡽ  ࡘ ࡢ ࢫ ࣌ ࢡ ࢺࣝࡢᙧ≧ࡣ୍ぢ␗࡞ࡿࡼ࠺࡟ࡳ࠼ࡿࡀࠊྛࢧ࢖
ࢺࡢࣃ࣓࣮ࣛࢱࡣ➼ࡋࡃࠊ⥺ᖜࡢ㐪࠸ࡢࡳࡀ␗
࡞ࡗ࡚࠸ࡿࠋ ᗘୖ᪼࡟క࠸⤖ᬗᡂ㛗ࡀಁ㐍ࡉࢀࡓࡓࡵ࡟ࠊ☢ሙࡢศᕸࡀῶᑡࡋ࡚⥺ᖜࡀ⊃ࡃ࡞ ࡗ ࡓ ࡜ ⪃ ࠼ ࡽ ࢀ ࠊࡇ ࢀ ࡣ ;5' ࡢ ⤖ ᯝ ࡜ ࡶ ୍ ⮴ࡋ ࡚ ࠸ ࡿ ࠋȤ)H  &  ࡢ ᏶ ඲ ࡞ ⤖ ᬗ ࡛ ࡣ  ⤌ ࡢ ࢭ ࢡࢫࢸࢵࢺࡢඹྠࡣෆ㒊☢ሙࡢ኱ࡁ࠸ࢧ࢖ࢺ࠿ࡽ㡰 ࡟ 㸸 㸸  ࡢ ẚ ࡜ ࡞ ࡿ >@ࠋ ᮏ ◊ ✲ ࡛ ᚓ ࡽ ࢀࡓ ࢫ ࣌ ࢡ ࢺ ࣝ ࡢ ྛ ࢧ ࢖ ࢺ ࡢ ẚ ࡣ 㸸 㸸  ࡟ ㏆ ࠸್ࢆᣢࡘࡓࡵࠊⰋዲ࡞⤖ᬗࡀᚓࡽࢀࡓ࡜⪃࠼ࡽࢀ ࡿ ࠋࡲ ࡓ ࠊᴟ ᚤ 㔞 ࡢ Į)H ࡢ ᡂ ศ ࡀ ࡳ ࡽ ࢀ ࡿ ࡀ ࠊࡇࢀࡣ⤖ᬗᡂ㛗᫬ࡢ୙ᆒ໬཯ᛂ࡟ࡼࡗ࡚⏕ࡌࡓࡶࡢ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ⭷ཌࡣ⵨╔㔞ࢆȤ)H  &  ࡟ ᥮ ⟬ ࡋ ࡚ ィ ⟬ ࡍ ࡿ ࡜ QP ࡛ ࠶ ࡗ ࡓ ࠋ

61)LJ;5'SDWWHUQ VR IWKHILOPVS URGXFHGE\
WKH3 /' R I)H RQWR$OVXE VWUDWHVDW D 
. E . F .DQ G G . LQ WKHPHWK DQH DWPRVSKHUH R I3D

)LJ5RRPWHPSHUDWX UH0|VVE DX HUVSHFWUDRIWKHILOPVSURGXFHGE\ WKH 3/' RI)H RQWR$OVXEVWUDWHVDW D  . E . F 
.DQG G . LQ WK H PHWKDQH DWPR VSKHUH
RI3D

7DEOH0|VVEDXHU SDUDPHWHUVRIWKHVS HFWUDVKR ZQLQ)LJ)LJ6(0LPDJHV R IWKHILOPVS URGXFHGE \ WKH
3/' RI)H RQWR$OVXEVWUDWHVDW D .DQG 
E . LQ WKH PHWKDQH DWPRVSKHUH RI3Dᇶ ᯈ ᗘ . ࡛ ⏕ ࡌ ࡓ ⷧ ⭷ ヨ ᩱ )LJG  ࡣ Ȥ)H  &  ࡢ ࡳ ࡛ ࡣ ࣇ ࢕ ࢵ ࢸ ࢕ ࣥ ࢢ ࡛ ࡁ ࡎ ࠊș)H  & ࢆ ຍ ࠼ ࡚ ࣇ ࢕ ࢵ ࢸ ࢕ ࣥ ࢢ ࢆ ⾜ ࡗ ࡓ ࠋᮏ ᮶ ș)H  & ࡣ  ⤌ ࡢ ࢭ ࢡ ࢫ ࢸ ࢵ ࢺ ࢆ ࡶ ࡘ >@ࡀ ࠊࡑ ࢀ ࡒ ࢀ ࡢ ࣃ ࣛ ࣓ ࣮ ࢱ ࣮ ࡀ 㠀 ᖖ ࡟ ㏆ ࠸ ࡓ ࡵ ࠊ್༙ᖜࡢᗈ࠸  ⤌ࡢࢭࢡࢫࢸࢵࢺ࡜ࡋ࡚ࣇ࢕ࢵࢸ ࢕ ࣥ ࢢ ࡋ ࡓ ࠋȤ)H  &  ࡢ ྛ ࢧ ࢖ ࢺ ࡢ ẚ ࡣ 㸸㸸 ࡟ ㏆ ࠸ ᙉ ᗘ ࢆ ࡜ ࡗ ࡚ ࠾ ࡾ ࠊ . ࡛ ࡣ Ȥ)H  & ࡜ ș)H  & ࡀ ΰ ᅾ ࡍ ࡿ ⭷ ࡀ ⏕ ᡂ ࡋ ࡓ ࠋ)LJ ࡟ ᇶ ᯈ ᗘ . ࠾ ࡼ ࡧ . ࡜ ࡋ ࡚ ⏕ᡂ ࡋ ࡓ ⷧ ⭷ ࡢ 6(0 ീ ࢆ ♧ ࡍ ࠋ࡝ ࡕ ࡽ ࡶ ⁥ ࡽ ࠿ ࡞⭷ ࡀ ⏕ ᡂ ࡋ ࡚ ࠸ ࡿ ࡀ ࠊ . ࡛ ⏕ ᡂ ࡋ ࡓ ⭷)LJE ࡢ ᪉ ࡀ ẚ ㍑ ⓗ ๭ ࢀ ┠ ࡀ ᑡ ࡞ ࡃ ࠊ⥡ 㯇 ࡞ ⭷ࡀ⏕ᡂࡋࡓࠋḟ ࡟ ࠊⷧ ⭷ ⏕ ᡂ ཯ ᛂ ᫬ ࡢ Ⅳ ⣲ ౪ ⤥ 㔞 ࢆ ቑ ࡸ ࡍ ࡓࡵ ࡟ ࠊ ࣓ ࢱ ࣥ ᅽ ຊ ࢆ 3D ࡜ ࡋ ࡚ ྠ ᵝ ࡟ ᐇ 㦂 ࢆ
⾜ ࡗ ࡓ ࠋ ᚓ ࡽ ࢀ ࡓ ⷧ ⭷ ࡢ ;5' ࣃ ࢱ ࣮ ࣥ ࢆ )LJ࡟ ♧ ࡍ ࠋ ⏕ ᡂ ᫬ ࡢ ᇶ ᯈ ᗘ . )LJD  ࠾ ࡼࡧ . )LJE ࡛ ࡣ ࠊ ᇶ ᯈ ࡢ ࢔ ࣝ ࣑ ࢽ ࢘ ࣒ ࡟)LJ;5'SDWWHUQ VR IWKHILOPVS URGXFHGE \ࡼࡿᅇᢡ࡜ࣈ࣮ࣟࢻ࡞ᅇᢡࡢࡳࡀࡳࡽࢀࡓࡀࠊ
WKH3 /' R I)H RQWR$OVXEVWUDWHVDW D 
. )LJF  ࠾ ࡼ ࡧ . )LJG  ࡛ ࡣ )H  & . E . F .DQ G G . LQ WKHࡢ ᅇ ᢡ ࣃ ࢱ ࣮ ࣥ ࡜ ୍ ⮴ ࡋ ࡓ ࠋ)H  &  ࡟ ࡣ ࠊR)H  & 
PHWK DQH DWPRVSKHUH R I 3D3') ࡜ K)H  & 3') ࡢ  ✀ 㢮 ࡀ Ꮡ ᅾ ࡍ ࡿ ࡀ ࠊ ᅇᢡ ࣃ ࢱ ࣮ ࣥ ࡀ ఝ ࡚ ࠸ ࡿ ࡓ ࡵ ;5' ࠿ ࡽ ࡇ ࢀ ࡽ ࢆ ༊ ู ࡍ ࡿ ࡇ ࡜ ࡣ 㞴 ࡋ ࠸ ࠋࡑ ࡇ ࡛ ࡇ ࢀ ࡽ ࢆヲ⣽࡟ศᯒࡍࡿࡓࡵ࡟࣓ࢫࣂ࢘࢔࣮ศග ᐃࢆ⾜ࡗࡓࠋ)LJ ࡟ ࣓ ࢫ ࣂ ࢘ ࢔ ࣮ ࢫ ࣌ ࢡ ࢺ ࣝ ᐊࢆ ♧ ࡍ ࠋ ᇶ ᯈ ᗘ . )LJD  ࡛ ࡣ ࣓ ࢱ ࣥ ᅽຊ 3D ࡛ ⏕ ᡂ ࡋ ࡓ ヨ ᩱ ࡜ ྠ ᵝ ࡟ ෆ 㒊 ☢ ሙ ศ ᕸ ᡂ ศ ࡀ ࡳ ࡽ ࢀ ࠊ . )LJE  ࡛ ࡣȤ)H  &  ࡢ  ⤌ ࡢ ࢭ ࢡ ࢫ ࢸ ࢵ ࢺ ࡀ ࡳ ࡽ ࢀ ࡓ ࠋ ࡉ ࡽ ࡟ ᇶ ᯈ ᗘ ࢆ ୖ ࡆ ࡓ . )LJF  ࠾

62

D  3D

E 3D

F 3D

G 3D)LJ5RRPWHPSHUDWXUH0|VVEDXHUVSHFWUD)LJ5RRPWHPSHUDWX UH0|VVE DX HUVSHFWUDR I

RIWKHILOPVSURGXFHGE\ WKH3/' RI)H RQWR

WKHILOPVSURGXFHGE\ WKH3/' RI)H RQWR$O

$OVXEVWUDWHVDW D . E . F VXEVWUDWHVDW.LQWKH PHWKDQH DWPRVSKHUH.DQG G . LQ WKH PHWKDQH DWPRVSKHUH

RI D 3D E 3D F 3DDQG G 

RI3D

3D

7DEOH 0|VVEDXHU SDUDPHWHUVRIWKHVS HFWUD

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࠸್ࢆᣢࡘࡓࡵࠊⰋዲ࡞⤖ᬗࡀᚓࡽࢀࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ୙ᆒ໬཯ᛂ࡟ࡼࡿᴟᚤ㔞 ࡢ Į)H ࡢ ᡂ ศ ࡶ ࡳ ࡽ ࢀ ࡓ ࠋࡉ ࡽ ࡟ ࠊ࣓ ࢱ ࣥ ᅽ ຊ ࢆ 3D ࡜ 3D ௨ እ ࡟ ࡋ ࡓ ᮲ ௳ ୗ ࡛ ࡶ ྠ ᵝ ࡢ ᐇ 㦂 ࢆ ⾜ ࡗ ࡓ ࠋ)LJ࡟ ᇶ ᯈ ᗘ ࢆ . ࡛ ୍ ᐃ ࡟ ࡋ ࠊ ࣓ ࢱ ࣥ ࡢ ᅽ ຊ ࢆ ኚ ໬ ࡉ ࡏ ࡓ ࡜ ࡁ ࡢ ࣓ ࢫ ࣂ ࢘ ࢔ ࣮ ࢫ ࣌ࢡ ࢺ ࣝ ࢆ ♧ ࡍ ࠋ ࣓ ࢱ ࣥ ࡢ ᅽ ຊ ࡀ 3D )LJDF  ࡢ ࡜ ࡁ ࡟ ࡣ ࠊ 3D ࡢ ࡜ ࡁ ࡜ ྠ ᵝ࡟ Ȥ)H  &  ࡢ  ⤌ ࡢ ࢭ ࢡ ࢫ ࢸ ࢵ ࢺ ࡀ ࡳ ࡽ ࢀ ࡓ ࡀ ࠊ ᅽ ຊ ࡀ ప ࠸ ࡯ ࡝ Į)H ࡢ ᡂ ศ ࡀ ቑ ຍ ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡇࢀࡣᮍ཯ᛂࡢ㕲࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ࣮ࣞࢨ࣮ࡢࣉ࣮࣒ࣝ୰ࡢ 㕲 ࡢ ཎ Ꮚ ᩘ ࡜ ࣓ ࢱ ࣥ ࡢ ศ Ꮚ ᩘ ࢆ ᴫ ⟬ ࡍ ࡿ ࡜ ࠊ ࣓ ࢱ ࣥ ࡀ 3D ⛬ ᗘ ࡢ ࡜ ࡁ )H㸸 & 㸸 ࡜ ࡞ ࡾ ࠊⅣ ໬ 㕲 ࡜ ࡋ ࡚ Ȥ)H  &  ࡢ ࡳ ࡀ ⏕ ᡂ ࡍ ࡿ ࡜ ௬ ᐃ ࡋ ࡓ ࡜ ࡁ 3D ௨ ୗ ࡛ ࡣ 㕲 ࡀ 㐣 ๫ ࠊ3D ௨ ୖ ࡛ ࡣ Ⅳ ⣲ ࡀ 㐣 ๫ ࡜ ࡞ ࡿ ࠋࡑ ࡢ ࡓ ࡵ ࠊᅽ ຊ ࡀ ప ࠸ ࡜ ࡁ ࡟ ࡣ ཯ ᛂ ࡟ ༑ ศ ࡞ Ⅳ ⣲ ࡀ౪ ⤥ ࡉ ࢀ ࡎ ᮍ ཯ ᛂ ࡢ 㕲 ࡀ ṧ ࡗ ࡓ ࡜ ⪃ ࠼ ࡽ ࢀ ࡿ ࠋ㏫ ࡟ ࣓ ࢱ ࣥ ᅽ ຊ ࢆ ୖ ࡆ ࡚ 3D )LJG ࡜ ࡋ ࡓ ࡜ ࡁ ࡟ ࡣ ࠊ 3D ࡢ ࡜ ࡁ ࡟ ࡳ ࡽ ࢀ ࡓ R)H  &  ࡀ ⏕ ᡂ ࡋ ࠊ ࡑ ࢀ ࡟ ຍ ࠼ ࡚ ᖜ ࡢ ᗈ ࠸ ࢲࣈࣞࢵࢺᡂศࡀࡳࡽࢀࡓࠋࡇࢀࡣඛ⾜◊✲࡟࠾ࡅࡿ࢔ࣔࣝࣇ࢓ࢫⅣ⣲୰ࡢ㕲ࡢࣃ࣓࣮ࣛ ࢱ >@࡜ ୍ ⮴ ࡋ ࡚ ࠾ ࡾ ࠊⅣ ⣲ ࡀ ኱ 㐣 ๫ ࡜ ࡞ ࡗ ࡚ ࢔ ࣔ ࣝ ࣇ ࢓ ࢫ Ⅳ ⣲ ࡀ ⏕ ᡂ ࡋ ࡓ ࡜ ⪃ ࠼ ࡽࢀࡿࠋ㸬 ⤖ ㄽ࣓ ࢱ ࣥ 㞺 ᅖ Ẽ ୗ ࡢ 㕲 ࣞ ࣮ ࢨ ࣮ ⵨ ╔ ࡟ ࡼ ࡾ Ⅳ ໬ 㕲 ⷧ ⭷ ࢆ ྜ ᡂ ࡋ ࡓ ࠋ;5' ࡜ ࣓ ࢫ ࣂ ࢘ ࢔ ࣮ࢫ ࣌ ࢡ ࢺ ࣝ ࠿ ࡽ ࠊ ࣓ ࢱ ࣥ ᅽ ຊ ࡀ 3D ࡢ ࡜ ࡁ ࡟ ࡣ ᇶ ᯈ ᗘ . ࠾ ࡼ ࡧ . ࡟ ࠾ ࠸࡚ Ȥ)H  &  ࡀ ⏕ ᡂ ࡋ ࠊ . ࡟ ࠾ ࠸ ࡚ Ȥ)H  &  ࠾ ࡼ ࡧ ș)H  & ࡀ ⏕ ᡂ ࡋ ࡓ ࠋ ࣓ ࢱ ࣥ ᅽ ຊ ࡀ3D ࡢ ࡜ ࡁ ࡟ ࡣ . ࡛ ࡣ Ȥ)H  &  ࡀ ⏕ ᡂ ࡋ ࡓ ࡀ ࠊ. ࠾ ࡼ ࡧ . ࡛ ࡣ R)H  &  ࡀ⏕ᡂࡋࡓࠋࡲࡓࠊ࣓ࢱࣥᅽຊࡀప࠸࡜ࡁ࡟ࡣ㕲ࡀ㐣๫࡜࡞ࡾᮍ཯ᛂࡢ㕲ࡀࠊ࣓ࢱࣥᅽ
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ᗘ(297 K䠉573 K)䛻ಖᣢ䛧䛯䚹ᚓ䜙䜜䛯ⷧ⭷ヨᩱ䛿

57Co/Rh ⥺※䜢⏝䛔䛯㏱㐣ᆺ䝯䝇䝞䜴䜰䞊ศගἲ䛸⢊ᮎ X ⥺ᅇᢡ(XRD)䛻䛶ศᯒ䜢⾜䛳䛯䚹

3㸬⤖ᯝ࡜⪃ᐹ66ⷧ⭷⏕ᡂ᫬ࡢ Al ᇶᯈ ᗘࢆ 293 K ࡟ಖᣢࡋࠊ❅⣲࢞ࢫࡢὶ㔞(10 – 30 sccm)ࢆኚ໬ࡉࡏ࡚⏕ᡂࡋࡓⷧ⭷ヨᩱࡢ XRD ࣃࢱ࣮ࣥࢆ Fig. 1 ࡟♧ࡍࠋ❅⣲ὶ㔞ࡀ 10
sccm ࡛⏕ᡂࡋࡓヨᩱ࡛ࡣࠊᇶᯈࡢ Al ࡜ ǂ-Fe ࡢᅇᢡࣃࢱ࣮ࣥࡢࡳࡀࡳࡽࢀࡓࠋAl ࡜ ǂ-Fe ࡢࣆ࣮ࢡ఩⨨ࡣ࡯ࡰྠࡌ࡛࠶ࡿࡓࡵࠊࡇࢀࡽࢆ᫂☜࡟༊ูࡍࡿࡇ࡜ࡣ
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sccm ࡜ࡍࡿ࡜ࠊపゅഃ࡟ᖜࡢᗈ࠸ᅇᢡࣆ࣮ࢡࡀࡳࡽ
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ࡎࠊ୺ᡂศࡣ ǂ-Fe ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟❅⣲࢞ࢫࡢὶ㔞ࢆ 20 sccm ࡜ࡋࡓ࡜ࡁࠊ᪂ࡓ࡞ᅇᢡࣆ࣮ࢡࡀࡳࡽ

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Fe2N(PDF#00-050-0958)ࡢᩥ⊩್࡟㏆࠸ࣃࢱ࣮࡛ࣥ

1LWURJHQIORZUDWHZHUH D  VFFP E VFFP F ࠶ࡗࡓࠋ❅⣲ὶ㔞 30 sccm ࡟࠾࠸࡚ࡶ㢮ఝࡢ XRD ࣃVFFP G VFFPࢱ࣮ࣥࡀぢࡽࢀࡓࡀࠊࣆ࣮ࢡ఩⨨ࡀపゅഃ࡬ࢩࣇࢺࡋ࡚࠸ࡓࠋࡇࢀࡣࠊ❅⣲౪⤥㔞ࡀከ࠸ሙྜ࡟ࡣ
౵ධࡍࡿ N ཎᏊᩘࡀከࡃࠊ❅໬㕲ࡢ᱁Ꮚᐃᩘࡀ኱ࡁࡃ࡞ࡗࡓࡓࡵ[7]࡛࠶ࡿ࡜⪃࠼ࡽࢀ

)LJ 0|VVEDXHU VSHFWUD PHDVXUHG DW  . RI WKH ILOPVSURGXFHGE\DUFGHSRVLWLRQ RI)HRQWRDQ$OVXEVWUDWH DW
. 1LWURJHQIORZUDWHZHUH D VFFP E VFFP
7KH GLVWULEXWLRQV RI K\SHUILQH PDJQHWLF ILHOGV DUH

)LJ 5RRPWHPSHUDWXUH 0|VVEDXHU VSHFWUD RI ILOPVLQGLFDWHGRQWKHULJKWVLGH

SURGXFHGE\DUFGHSRVLWLRQ RI)HRQWRDQ$OVXEVWUDWHDW.1LWURJHQIORZUDWHZHUH D VFFP E VFFP
F   VFFP G   VFFP 7KH GLVWULEXWLRQV RI K\SHUILQH
PDJQHWLFILHOGVDUHLQGLFDWHGRQWKHULJKWVLGH

67ࡿࠋXRD ࣃࢱ࣮࡛ࣥࡣȜ-࡜ȝ- Fe2N ࡢุูࡀ㞴ࡋ࠸ࡇ࡜࠿ࡽࠊ࣓ࢫࣂ࢘࢔࣮ศගἲ࡛ヨᩱࡢศᯒࢆ⾜ࡗࡓࠋᐊ ࡛ᐃࡋࡓ࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝࢆ Fig.2 ࡟♧ࡍࠋ❅⣲ὶ㔞 10 sccm ࡜ 15 sccm

ࡢヨᩱࡣ᱁ᏊḞ㝗ࢆከࡃྵࢇࡔ ǂ-Fe ࡛࠶ࡾࠊෆ㒊☢ሙศᕸࢆࡶࡗࡓᡂศࡀぢࡽࢀࡓࠋ❅⣲ὶ㔞 20
sccm ࡛⏕ᡂࡋࡓヨᩱ࡟ࡣ ǂ-Fe ࡟ࡼࡿࢭࢡࢫࢸࢵࢺࡢ௚࡟ࠊᑠࡉ࠸ෆ㒊☢ሙ࡟ᴟ኱ࢆᣢࡘෆ㒊☢ሙศᕸᡂศࡀࡳࡽࢀࡓࠋෆ㒊☢ሙࡢ኱ࡁࡉ[8]࠿ࡽࠊࡇࡢヨᩱࡣ ǆ-Fe2.3N ࡜⪃࠼ࡽࢀࡿࠋ❅⣲ὶ㔞 30
sccm ࡛⏕ᡂࡋࡓヨᩱࡢ୺ᡂศࡣᖖ☢ᛶࢲࣈࣞࢵࢺ࡛࠶ࡗࡓࠋǆ-Fe3-2N ࡣ㢮ఝࡢᵓ㐀ࢆᣢࡗࡓᵝࠎ࡞❅⣲⤌ᡂࡢࡶࡢࡀᏑᅾࡋࠊ࠶ࡿ⤌ᡂࢆቃ࡟ᐊ ࡛ᖖ☢ᛶࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ[9]ࠋᮏ◊✲࡛ᚓࡽࢀࡓࡇࡢⷧ⭷ヨᩱࡣᐊ࡟ᐊ࡛ᖖ☢ᛶࢆ♧ࡍࡇ࡜࠿ࡽ ǆ-Fe2.2-2N ࡜⪃࠼ࡽࢀࡿࡀࠊǇ-Fe2N ࡶྠᵝ࡛ᖖ☢ᛶࢆ♧ࡋࠊ࣓ࢫࣂ࢘࢔࣮ࣃ࣓࣮ࣛࢱࡶ㏆࠸್[9,10]ࢆࡶࡘࡓࡵ༊ูࡍࡿࡇ࡜ࡣ࡛ࡁ࡞

࠸ࠋࡶ࠺ᙉᗘࡢᑠࡉ࠸ࢲࣈࣞࢵࢺᡂศ㸦X㸧ࢆᖐᒓࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ
❅⣲ὶ㔞 20 sccm ࡜ 30 sccm ࡢヨᩱ࡟ࡘ࠸࡚ 3 K ࡛࣓ࢫࣂ࢘࢔࣮ࢫ࣌ࢡࢺࣝ

ᐃࢆ⾜ࡗࡓ㸦Fig.3㸧ࠋ❅⣲ὶ㔞 20 sccm ࡢヨᩱࡣࠊǂ-Fe ࡟ࡼࡿࢭࢡࢫࢸࢵࢺ࡜ෆ㒊☢ሙศᕸࢆࡶࡗࡓ ǆ-Fe2.3N ࡜ᖐᒓࡉࢀࡓࠋȝ-Fe2N ࡣ 4.2 K ࡜ప࡛ࡶᖖ☢ᛶࢲࣈࣞࢵࢺࢆಖࡘࡇ࡜[10]ࡀ▱ࡽࢀ࡚࠸ࡿࡓࡵࠊ☢Ẽศ⿣ࢆ♧ࡋࡓࡇࡢヨᩱࡣȜ-Fe2.3N ࡜⪃࠼ࡽࢀࡿࠋ❅⣲ὶ㔞 30 sccm ࡢヨᩱࡣࠊ3 K ࡛ᖖ☢ᛶᡂศࢲࣈࣞࢵࢺࡣᾘኻࡋࡓࠋ஧⤌ࡢࢭࢡࢫࢸࢵࢺD-Fe ࡜ᮍᖐᒓᡂศ X ࡛࠶ࡿࠋ୺ᡂศࡣෆ㒊☢ሙศᕸࢆᣢࡘࡀࠊ࣓ࢫࣂ࢘࢔࣮ࣃ࣓࣮ࣛࢱࡣ ǆ-Fe2.2N ࡢᩥ⊩್[9]࡜Ⰻ࠸୍⮴ࢆ♧ࡋࡓࠋᮍᖐᒓᡂศ X ࡣᐊ࡛ᖖ☢ᛶࢲࣈࣞࢵࢺ࡛࠶ࡾࠊ3K ࡛☢Ẽศ⿣ࢆ♧ࡋࡓࡀࠊ᪤▱ࡢ❅໬㕲ࡢᩥ⊩್ࡢ୰୍࡛⮴ࡍࡿࡶࡢࢆぢฟࡍࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ

7DEOH 0|VVEDXHUSDUDPHWHUVRIWKHVSHFWUDVKRZQLQ)LJ

ᇶᯈ

7DEOH 0|VVEDXHUSDUDPHWHUVRIWKHVSHFWUDVKRZQLQ)LJᗘ 293K ࡛⏕ᡂࡋࡓⷧ⭷ヨᩱࡣࠊ᱁ᏊḞ㝗ࢆྵࢇ࡛࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ䛭䛣䛷 Al ᇶᯈ䜢䝉䝷䝭䝑䜽䝠䞊䝍䞊䛻䜘䛳䛶 573 K 䛻ຍ⇕䛧䛺䛜䜙ྠᵝ䛻❅⣲㞺ᅖẼୗ䛷㕲䜰䞊䜽⵨╔䜢⾜䛖䛣䛸䛷䚸⤖ᬗᛶ䛾ⷧ⭷ヨᩱ䜢⏕ᡂ䛧䛯䚹ᚓ䜙䜜䛯ヨᩱ䛾 XRD 䝟䝍䞊䞁䜢 Fig.4 䛻♧䛩䚹❅⣲ὶ㔞 15䡚30 sccm 䛷⏕68ᡂ䛧䛯඲䛶䛾ヨᩱ䛷 ǆ-Fe2N(PDF#04-007-1467)䛸 Ǉ-Fe2N(PDF#00-050-0958)䛻㏆䛔ᅇᢡ䝟䝍䞊䞁䛜䜏䜙䜜䛯䚹ᐊ 䛷 ᐃ䛧䛯䝯䝇䝞䜴䜰䞊䝇䝨䜽䝖䝹䜢 Fig.5 䛻♧䛩䚹䛩䜉䛶䛾䝇䝨䜽䝖䝹䛷䝎䝤䝺䝑䝖䜢♧䛧䚸ⷧ⭷ヨᩱ䛿ᐊ 䛷ᖖ☢ᛶ䜢♧䛩䛣䛸䛜䜟䛛䛳䛯䚹ᐊ 䛾 ᐃ䛷䛿 ǆ-䛸 Ǉ-Fe2N 䜢༊ู䛩䜛䛣䛸䛜䛷䛝䛺䛔䛯䜑䚸ప䛷䝯䝇䝞䜴䜰䞊

ᐃ䜢⾜䛳䛯䠄Fig.6䠅䚹䛣䜜䜙䛾䝇䝨䜽䝖䝹䛿❅⣲ὶ㔞䛻䜘䛳䛶ኚ໬䛧䚸15 sccm

䛷⏕ᡂ䛧䛯ヨᩱ䛿䠏⤌䛾䝉䜽䝇䝔䝑䝖䛸䝎䝤䝺䝑䝖䛸䛧䛶䝣䜱䝑䝖䛩䜛䛣䛸䛜䛷䛝䛯䚹䛭䜜䛮䜜䛾䝯䝇䝞䜴䜰䞊䝟䝷䝯䞊䝍[8,10]䛛䜙䚸ᚤ㔞䛾D-Fe 䛾௚䚸ǆ-Fe2.5N䠄䠎⤌䛾䝉䜽䝇䝔䝑䝖䠅䚸Ǉ-Fe2N䠄䝎䝤䝺䝑䝖䠅䛸⪃䛘䜙䜜䜛䚹ǇFe2N 䛾ᅄᴟᏊศ⿣䛿ᩥ⊩್[10]䜘䜚䜒኱䛝䛔್䜢♧䛧䛯䛜䚸Ḟ㝗䜢ྵ䜣䛷䛔䜛䛯䜑䛷䛒䜛䛸⪃䛘䜙䜜䜛䚹❅⣲ὶ㔞 20 sccm 䛸 30 sccm 䛷⏕ᡂ䛧䛯ヨᩱ䛻䛿䚸ᚤ㔞䛾D-Fe 䛾௚䛻䛿䚸3K 䛻䛚䛔䛶䜒ᖖ☢ᛶ䝎䝤䝺䝑䝖䜢ಖ䛳䛶䛔䜛୺ᡂศ䛜ぢ䜙䜜䚸䛭䛾䝯䝇䝞䜴䜰䞊䝟䝷䝯䞊䝍[10]䛛䜙 Ǉ-Fe2N 䛸ᖐᒓ䛥䜜䜛䚹䛣䛾⤖ᯝ䛛䜙䚸ᇶᯈ ᗘ䜢 573 K 䛻ୖ䛢䜛䛣䛸䛷䚸୺ᡂศ䛸䛧䛶 Ǉ-Fe2N 䛜ᚓ䜙䜜䜛䛣䛸䛜䜟䛛䛳䛯䚹)LJ 5RRPWHPSHUDWXUH0|VVEDXHUVSHFWUDRIILOPV)LJ 0|VVEDXHU VSHFWUD PHDVXUHG DW  . RI WKHSURGXFHGE\DUFGHSRVLWLRQRI)HRQWRDQ$OVXEVWUDWHILOPVSURGXFHGE\DUFGHSRVLWLRQ RI)HRQWRDQ$O

DW.1LWURJHQIORZUDWHZHUH D VFFP E VXEVWUDWH DW.1LWURJHQIORZUDWHZHUH D VFFP F   VFFP 7KH GLVWULEXWLRQV RI K\SHUILQH

VFFP E VFFP F VFFP7KHGLVWULEXWLRQVRI

PDJQHWLFILHOGVDUHLQGLFDWHGRQWKHULJKWVLGHK\SHUILQHPDJQHWLFILHOGVDUHLQGLFDWHGRQWKHULJKW

7DEOH 0|VVEDXHUSDUDPHWHUVRIWKHVSHFWUDVKRZQLQ)LJ

7DEOH 0|VVEDXHUSDUDPHWHUVRIWKHVSHFWUDVKRZQLQ)LJ

69

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࢔࣮ࢡࣉࣛࢬ࣐࢞ࣥࢆ⏝࠸࡚❅⣲㞺ᅖẼୗ࡛㔠ᒓ㕲ࡢ࢔࣮ࢡᨺ㟁ࢆ⾜࠸ࠊ㕲ࣉࣛࢬ࣐ࡢ⏕ᡂ࡜ྠ᫬࡟❅⣲ศᏊࡢศゎࢆ⾜࠺ࡇ࡜࡟ࡼࡗ࡚ࠊAl ᇶᯈୖ࡟❅໬㕲ⷧ⭷ࢆ⏕ᡂࡋࡓࠋⷧ⭷⏕ᡂ᫬ࡢ Al ᇶᯈࡢᗘࢆ 298K ࡜ࡋࡓሙྜࠊ❅⣲ὶ㔞 20-30 sccm ࡛❅໬㕲ࡢ⏕ᡂࡀ☜ㄆࡉࢀࠊ୺࡟ ǆ-Fe3-2N ࡀᚓࡽࢀࡓࠋࡋ࠿ࡋࠊࡍ࡭࡚ࡢヨᩱ࡛᱁ᏊḞ㝗ࢆྵࢇ࡛࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࡇ࡛ᇶᯈ

ᗘࢆ 573K

࡟ຍ⇕ࡋ࡞ࡀࡽ⏕ᡂࡍࡿ࡜ࠊ❅⣲ὶ㔞 15-30 sccm ࡛⤖ᬗᛶࡢ㧗࠸ Ǉ-Fe2N ࡢⷧ⭷ࡀᚓࡽࢀࡓࠋཧ⪃ᩥ⊩>@ .+-DFNProc. Roy. Soc. A   
>@ 6 %KDWWDFKDU\\DJ. Phys. Chem. C   >@ 513DQGD16*DMEKL\HJ. Appl. Phys   
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䛿䛨䜑䛻 䡚㻌 㻌 㻌㸦ᗙ㛗 ໭⃝Ꮥྐ㸧䡚 ͤ ி኱」ྜ◊䛻䛚䛡䜛䝯䝇䝞䜴䜰䞊ศග䛾⌧≧ⰾ㤶⎔䜢᭷䛩䜛䝡䝇䠄䝢䝸䝆䝹䠅ᆺᯫᶫ㓄఩Ꮚ䛜୚䛘䜛㕲஧౯㞟✚ᆺ㘒య䛾䝇䝢䞁䜽䝻䝇䜸䞊䝞䞊⌧㇟䜈䛾ᙳ㡪㞟✚ᆺ㔠ᒓ㘒య䛻䛚䛡䜛ືⓗ䝇䝢䞁ᖹ⾮䛸㐃㙐䛩䜛☢Ẽ≉ᛶ

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㸦ᗙ㛗 ୕ཎᇶႹ㸧䡚 ͤ ᅄ㓟໬୕㕲୰䛻ᑟධ䛥䜜䛯୙⣧≀䜲䞁䝆䜴䝮䛾ཎᏊ䝆䝱䞁䝥
.,660572) 䛾⌧≧᫨㣗 䡚
㸦ᗙ㛗 㓇஭㝧୍㸧䡚

S䝟䝹䝇䛻䜘䜛 +2 ୰ 1 䛾⢭ᐦ 105 䝇䝨䜽䝖䝹㈇䝭䝳䜸䞁䛾 ȝSRᐃఇ᠁ 䡚
㸦ᗙ㛗 ஂಖㅬဢ㸧䡚
䝯䝍䞁㞺ᅖẼୗ䛾㕲䝺䞊䝄䞊⵨╔䛻䜘䛳䛶⏕ᡂ䛧䛯‽Ᏻᐃ┦䛾Ⅳ໬㕲ⷧ⭷❅⣲㞺ᅖẼୗ䛾㕲䜰䞊䜽⵨╔䛻䜘䛳䛶⏕ᡂ䛧䛯❅໬㕲ⷧ⭷71

ᖹᡂ  ᖺᗘᑓ㛛◊✲఍ࠕ▷ᑑ࿨ 5, ࢆ⏝࠸ࡓ᰾ศග࡜᰾≀ᛶ◊✲Ϭࠖฟ ᖍ ⪅ ྡ ⡙㸦㡰୙ྠ࣭ᩗ⛠␎㸧
Ặྡ

ᡤᒓ

Ặྡ

ᡤᒓ

ᚋ⸨῟

᪂₲኱Ꮫ

㧗஭ⱱ⮧

ி኱

すᮧඞᙪ

ᐩᒣ኱Ꮫ

୰▼㞙ே

ி኱

ᑠᓥ᠇㐨

㇏⏣⌮໬Ꮫ◊

໭⃝Ꮥྐ

ᮾ㑥኱

໭Ύ⯟㍜

ᮾ㑥኱

ᯇከ೺⟇

㜰኱

୕ཎᇶႹ

㜰኱

㓇஭㝧୍

኱ྠ኱

(ᡤෆ)

୰ᓥぬ

ᗈ኱

኱ஂಖ჆㧗

ᒾ஭ဏᶞ

ᗈ኱

໭ᑿ┿ྖ

ᐑṊᏱஓ

KEK, WISC

ᑠ⏣㐩㑻

బ⸨΅

㔠ἑ኱

❑⏣༟ぢ

ᒣ⏣ᗣὒ

ᮾ⌮኱

㇂ᇉᐇ

す⏣┤ᶞ

ᮾ⌮኱

ᑠᯘᗣᾈ

℈ᓮ୍㈗

ᮾ⌮኱

ቑ⏣ு

⯚ᶫᣅᕫ

ᮾ⌮኱

኱ᵳ໅

ஂಖㅬဢ

ᅜ㝿ᇶ╩ᩍ኱

⸈ෆᩔ

ᑠᯘ⩏⏨

㟁㏻኱

㇂ཱྀ⛅ὒ

㸦௨ୖ  ྡ㸧

72

KUR16 REPORT OF
INSTITUTE FOR INTEGRATEDRADIATION AND NUCLEAR SCIENCE,
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