ຓ ᩍ㸸㉥℩ၿኴ㑻
Ꮫ㝔⏕㸸ᇛᏹኴ⏣ᩔኵబ⸨㑥➉㔝㞝ክ
ᮧᬛ㕥ᮌᾈ㰻⸨ᬛᗈᮌୗ୍
ᮏ◊✲ศ㔝䛷䛿䠈㟁Ꮚ⥺䝩䝻䜾䝷䝣䜱䞊䛸䝻䞊䝺䞁䝒㢧ᚤ㙾ἲ䛻䜘䜛ඛ➃ᮦᩱ䛾㟁Ẽⓗ䞉☢Ẽⓗᵓ㐀䛾ゎ ᯒ䜢ᐇ䛧䛶䛔䜛䠊䜎䛯䠈䝢䜶䝌㥑ື䠎᥈㔪䝩䝹䝎䜢⏝䛔䠈ᒁᡤ㡿ᇦ䛷䛾㟁ᅽ༳ຍ䜔ᑟ㟁ᛶ䛾ホ౯䜒⾜䛳䛶䛔 䜛䠊ᮏᖺᗘ䛾ලయⓗ䛺◊✲ᡂᯝ䛿௨ୗ䛾㏻䜚䛷䛒䜛䠊㻌
㻝䠊㻺㼐㻙㻲㼑㻙㻮↝⤖☢▼䛻䛚䛡䜛⢏⏺┦䛾☢᮰ᐦᗘ ᐃ
Nd-Fe-BỌஂ☢▼䛾◊✲䛻䜃䛝䛺㛵ᚰ䛜㞟䜎䛳䛶䛔䜛䠊≉䛻Dy➼䛾ᕼᑡඖ⣲䜢䜟䛪䠈↝⤖☢▼䛾ᚤ
⣽ᵓ㐀䛾᭱㐺䛻䜘䜚ಖ☢ຊ䜢㧗䜑䜛䛸䛔䛖ほⅬ䛛䜙䠈┦䠄
Nd2Fe14B┦䠅䛾⤖ᬗ⢏䜢ศ᩿䛩䜛䛂⢏⏺┦䛃䛾☢
ᛶ䜢᫂䜙䛛䛻䛩䜛䛣䛸䛜㔜せど䛥䜜䛶䛔䜛䠊䛧䛛䛧ᖜ䛜3nm⛬ᗘ䛾ⷧ䛔⢏⏺┦䛛䜙☢Ẽ䝅䜾䝘䝹䜢ᚓ䜛䛣䛸䛿 㞴䛧䛟䠈ヲ⣽䛺◊✲䛿㜼䜎䜜䛶䛔䛯䠊ᮏ◊✲䛷䛿㟁Ꮚ⥺䝩䝻䜾䝷䝣䜱䞊䛻䜘䜛┦䛾ゎᯒ⢭ᗘ䜢
0.08rad䛻䜎䛷 㧗䜑䛶䠈3nmᖜ䛾⢏⏺┦䛾☢᮰ᐦᗘ䜢ホ౯䛷䛝䜛ᐇ㦂ᇶ
┙䜢ᩚ䛘䛯䠊ᅗ
1(a)䛾㯤⥺䛻♧䛩㏻䜚䠈┦
A, B䜢㝸䛶 䜛⢏⏺┦䠄㯤⥺䠅䛻ὀ┠䛧䛯䠄⤖ᬗ⢏F䛿㠀☢ᛶ䛾Nd㓟
≀䠅䠊ᅗ
1(b)䛿╔☢䛧䛯ヨᩱ䛷ほᐹ䛧䛯☢᮰⥺䛾ศᕸ䜢
♧䛩䠊⢏⏺┦䜢䜎䛯䛠X-Y⥺䛻ἢ䛳䛶┦ኚ䜢 ᐃ䞉 ゎᯒ䛧䛯䛸䛣䜝䠈⢏⏺┦䛾Ꮡᅾ䛻క䛖┦ኚ䜢
0.34rad䛸 Ỵᐃ䛧䛯䠊TEM䛻䜘䜚ヨᩱ䛾ᙧ≧䠈⭷ཌ䠈⤖ᬗ⢏䛾᪉䠈
⢏⏺┦䛾ഴ䛝ලྜ➼䛾⤖ᬗᏛ䝟䝷䝯䞊䝍䜢Ỵᐃ䛧䠈ᙜヱ ヨᩱ䛻ᑐ䛩䜛☢ሙศᕸ䛸㟁Ꮚ⥺䝩䝻䜾䝷䝣䜱䞊䛷᳨ฟ䛷 䛝䜛┦ኚ䜢䝅䝭䝳䝺䞊䝖䛧䛯䠊ᐇ㦂䝕䞊䝍䛸ẚ㍑᳨ウ䛧 䛯⤖ᯝ䠈⢏⏺┦䛾☢᮰ᐦᗘ䜢1.0T(㼼0.1T)䛸Ỵᐃ䛧䛯䠊ᮏ
◊✲䛿⌮◊䛸≀ᮦᶵᵓ䛸䛾ඹྠ◊✲䛸䛧䛶⾜䜟䜜䛯䠊
㻞䠊⏕యᵓᡂせ⣲䛾㟁Ꮚ⥺䝩䝻䜾䝷䝣䜱䞊ゎᯒ㻌 㻌
⏕యヨᩱ࡞ࡢ㠀ᑟ㟁ᛶ≀㉁ࢆ㏱㐣㟁Ꮚ㢧ᚤ㙾࡛ほᐹࡍࡿ㝿㸪㟁Ꮚ⥺↷ᑕక࠺ḟ㟁Ꮚࡢᨺฟࡼ
ࡗ࡚ヨᩱࡢᖏ㟁ࡀ⏕ࡌࡿ㸬ᮏ◊✲࡛ࡣ㸪ヨᩱᑟ㟁ᛶࡢࣉ࣮ࣟࣈࢆ᥋ゐࡉࡏࡿ᪉ἲࢆヨࡳ㸪ࣉ࣮ࣟࣈ
᥋ゐ๓ᚋࡢヨᩱ࿘㎶ࡢ㟁ሙゎᯒࢆ⾜ࡗࡓ㸬ᅇࡣࢿࢬ࣑ࡢ࢟ࣞࢫ⭝ࡢࢥ࣮ࣛࢤࣥ⥺⥔ࢆほᐹ⏝ヨᩱ
ࡋ࡚⏝࠸ࡓ㸬㟁Ꮚ㢧ᚤ㙾ほᐹ୰ヨᩱᑟ㟁ᛶࣉ࣮ࣟࣈࢆ㏆࡙ࡅࡿࡓࡵ㸪᥈㔪ࣆ࢚ࢰ㥑ື࣍ࣝ
ࢲࢆ⏝࠸ࡓ㸬ᑟ㟁ᛶࣉ࣮ࣟࣈࡣ㸪Pt-Ir㔪ࡢඛ
➃ࢆ㞟᮰࢜ࣥࣅ࣮࣒ࢆ⏝࠸࡚⣽ࡃຍᕤࡋࡓࡶ
ࡢࢆ⏝࠸ࡓ㸬ᅗ2ᐇ㦂⤖ᯝࢆ♧ࡍ㸬ࣉ࣮ࣟࣈࡀ
㏆࡙ࡃࡘࢀ࡚㸪㟁ศᕸࡶኚࡋ࡚࠸ࡿࡀ㸪 ᚲࡎࡋࡶヨᩱࣉ࣮ࣟࣈ㛫ࡢ㊥㞳ẚࡋࡓ༢⣧
࡞ኚ࡛ࡣ࡞࠸ࡇࡽ㸪ヨᩱࣉ࣮ࣟࣈࡢ㛫
࡛ḟ㟁Ꮚࡢᨺฟ྾ࡢ」㞧࡞⌧㇟ࡀ㉳ࡇࡗ
࡚࠸ࡿࡇࡀീ࡛ࡁࡿ㸬ࡲࡓ㸪ࣉ࣮ࣟࣈࡢ᥋ ゐࡼࡿᖏ㟁ࡢᢚไຠᯝࡶ᳨ド࡛ࡁࡓ㸬ᖏ㟁ࡋ ࡓࢥ࣮ࣛࢤࣥ⥺⥔࿘㎶ࡢ㟁ሙศᕸࢆ࢚ࣝࣇ♫〇 ࡢ㟁☢ሙゎᯒࢯࣇࢺࢆ⏝࠸࡚ࢩ࣑࣮ࣗࣞࢺࡋ㸪 ほᐹ⤖ᯝẚ㍑ࡋࡓࡇࢁ㸪ほᐹど㔝ෆࡢᖏ㟁 㔞ࢆ0.84 fC ぢ✚ࡶࡿࡇࡀ࡛ࡁࡓ㸬
ᅗ1㻌 㻌 ⷧ∦䛧䛯Nd-Fe-B☢▼䛾(a)TEMീ䛸(b)┦
⏕┦ീ䠊㉥▮༳䛿⤖ᬗ⢏㻭㻘㻮䛾☢᪉ྥ䜢⾲䛩䠊㻌
ᅗ2㻌(a) 䝛䝈䝭䛾䜰䜻䝺䝇⭝䛾䝁䝷䞊䝀䞁⥺⥔࿘㎶䛾㟁Ꮚ⥺䝩䝻 䜾䝷䝮䠊(b) (a)䛛䜙ᚓ䜙䜜䛯┦⏕ീ䠊(c)-(f) 䝁䝷䞊䝀䞁⥺⥔䛻 ᑟ㟁ᛶ䝥䝻䞊䝤䜢㏆䛵䛡䛶䛔䛳䛯㝿䛾┦⏕ീ䛾ኚ䠊(g) 䝥 䝻䞊䝤䛜⥺⥔䛻᥋ゐ䛧䛯䛾┦⏕ീ䠊(h) 䝥䝻䞊䝤䜢⥺⥔䛛 䜙䜃㞳䛧䛯䛸䛝䛾┦⏕ീ䠊
99 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌
䠏䠊㧗㕲⃰ᗘ䝘䝜⤖ᬗ㌾☢ᛶయ㻲㼑㻤㻡㻿㼕㻞㻮㻤㻼㻠㻯㼡㻝䛾ືⓗ䝻䞊䝺䞁䝒㢧ᚤ㙾ほᐹ
㏆ᖺぢฟ䛥䜜䛯䠈Feᇶ䜰䝰䝹䝣䜯䝇୰䛻䝷䞁䝎䝮᪉䛾Į㕲䝘䝜⤖ᬗ⢏䛜ศᩓ䛧䛯⤌⧊䜢᭷䛩䜛㧗㕲⃰ᗘ䝘䝜
⤖ᬗ㌾☢ᛶయ䛿䠈ᚑ᮶䛾㧗㏱☢⋡ᮦᩱ୪䜏䛾ప㕲ᦆ䜢ᣢ䛱䛺䛜䜙䠈䜿䜲⣲㗰୪䜏䛾㧗䛔Bs䜢ᣢ䛴ඃ䜜䛯≉
ᚩ䜢ᣢ䛳䛶䛔䜛䠊ᮏ◊✲䛷䛿䠈䝘䝜⤖ᬗ㌾☢ᛶయ䛾ẕᮦ䛸䛺䜛Fe85Si2B8P4Cu1䜰䝰䝹䝣䜯䝇䝸䝪䞁䛻ᵝ䚻䛺 ᗘ 䛷⇕ฎ⌮䛧䛶☢Ẽ≉ᛶ䜢ኚ䛘䛯ヨᩱ䛛䜙TEMほᐹ⏝ヨ
ᩱ䜢స〇䛧䠈TEMෆ䛷ືⓗ☢ሙ䠄±~1.6 kA/m, 0.5 ~ 1 Hz䠅䜢ヨᩱ䛻༳ຍ䛧䛶䠈☢ቨ䛜⛣ື䛩䜛ᵝᏊ䜢ほᐹ䛧䛯䠊
᭱㐺䛺⇕ฎ⌮ ᗘ䛷䛒䜛430䉝䛷⇕ฎ⌮䛥䜜䛯ヨᩱ䛿䝘 䝜⤖ᬗ⤌⧊䜢᭷䛧䠈☢ቨ䛾ື䛝䛜䜙䛛䛷䛒䛳䛯䛾䛻ᑐ䛧䠈 470䉝⇕ฎ⌮ヨᩱ䛿䠈䝘䝜⤖ᬗ⤌⧊䜢᭷䛧䛶䛔䛯䜒䛾䛾䠈
☢ቨ䛾ື䛝䛿䜋䛛䛾ヨᩱ䛻ẚ䜉䛶䜙䛛䛷䛿䛺䛔ᵝᏊ䛜 ぢ䜙䜜䛯䠄ᅗ3䠅䠊ᅇᢡᅗᙧ䛛䜙䛿䛾ヨᩱ䛻䛿↓䛔ᅾ
≀䛾ᯒฟ䛜☜ㄆ䛥䜜䛯䛣䛸䛛䜙䠈ᅾ≀䛻䝢䞁Ṇ䜑䛥䜜䛶 䛔䜛䜒䛾䛸⌮ゎ䛥䜜䛯䠊ᮏ◊✲䛿䠈ᩥ㒊⛉Ꮫ┬䞉⯆ᗇ 䛂ᮾⓎ ⣲ᮦᢏ⾡ඛᑟ䝥䝻䝆䜵䜽䝖䛃䛻䛚䛔䛶ᐇ䛥䜜䛯 䜒䛾䛷䛒䜛䠊
䠐䠊㻌 㻹㼚㼂㻞㻻㻠䛻䛚䛡䜛⤖ᬗᏛⓗ䝗䝯䜲䞁䛸☢༊䛾ゎᯒ㻌
㢧ⴭ䛺☢ሙㄏ㉳ᙧ≧ኚ䜢♧䛩MnV2O4䛾⤖ᬗᏛⓗ䝗䝯䜲䞁ᵓ㐀䛸☢༊ᵓ㐀䜢䠈䝻䞊䝺䞁䝒㢧ᚤ㙾䜢⏝䛔䛶 ゎᯒ䛧䛯䠊ⷧ⭷䛧䛯MnV2O4䛷䛿䠈෭༷䛻䜘䛳䛶⏕䛨䛯ṇ᪉ᬗ┦䛜䠈䝥䝺䞊䝖ᖜ10nm䜸䞊䝎䞊䛾㠀ᖖ䛻⣽䛛 䛺ᬗ⤌⧊䜢♧䛩䛣䛸䛜䜟䛛䛳䛯䠊ṇ᪉ᬗ┦䛾☢༊ᵓ㐀䛿㢧ⴭ䛺 ᗘ౫Ꮡᛶ䜢♧䛧䛯䠊䛘䜀᱁Ꮚኚែ┤
ᚋ䛾40K䛻䛚䛔䛶䛿䠈ᅗ4(a)䛻♧䛩䜘䛖䛻」ᩘ䛾ᬗ䝥䝺䞊䝖䜢ྵ䜐䛝䛺㑏ὶ☢༊ᵓ㐀䛜ほᐹ䛥䜜䛯䠊䛣䜜 䛻ᑐ䛧䛶䠈ヨᩱ䜢6K䜎䛷෭༷䛩䜛䛸䠈ᅗ4(b)䛻♧䛩䜘䛖䛻㡿ᇦA䠈B䛷䛿ᬗ䝥䝺䞊䝖䛸୍ᑐ୍䛾ᑐᛂ㛵ಀ䜢ᣢ 䛴⣽䛛䛺☢༊䛜Ⓨ㐩䛧䛯䠊୍᪉䠈㡿ᇦC䛷䛿౫↛
䛝䛺☢༊ᵓ㐀䛜ṧᏑ䛧䛶䛔䛯䠊☢༊ᵓ㐀䛾 ᗘ౫Ꮡᛶ䛻䛿䠈෭༷䛻䜘䛳䛶ቑ䛧䛯⤖ᬗ☢Ẽ
␗᪉ᛶ䛜㛵䜟䛳䛶䛔䜛䛸⪃䛘䜙䜜䜛䠊䜎䛯䠈ᅗ1(b) 䛾㡿ᇦA䠈B䛷䛿ᬗ䝥䝺䞊䝖ᖜ䛜20~30nm䠈㡿 ᇦC䛷䛿ᬗ䝥䝺䞊䝖ᖜ䛜10~14nm䛷䛒䜚䠈ṇ᪉ ᬗ┦䛻䛚䛡䜛☢༊ᵓ㐀䛿ᬗ䝥䝺䞊䝖ᖜ䛻ᑐ䛧 䛶䜒౫Ꮡᛶ䜢♧䛩䠊䛣䛾⤖ᯝ䛿䠈ᬗ䝥䝺䞊䝖ᖜ 䛸☢Ẽ㛗䛾ᑠ㛵ಀ䛷ㄝ᫂䛥䜜䛯䠊ᮏ◊✲
䛿ᮾ䞉᭷㤿Ꮥᑦᩍᤵ䛾䜾䝹䞊䝥䛸䛾ඹྠ◊✲
䛸䛧䛶⾜䜟䜜䛯䠊
䠑䠊⮬ᕫ⤌⧊䛧䛯㻲㼑㻟㻻㻠䝘䝜⢏Ꮚ䛾☢᮰ศᕸ䛾ホ౯㻌
2ẁ䝞䜲䝥䝸䝈䝮ᆺ㟁Ꮚ⥺䝩䝻䜾䝷䝣䜱䞊䜢⏝䛔䛶䠈䝸䞁䜾≧䛻⮬ᕫ⤌⧊䛧䛯ᖹᆒ⢏ᚄ25nm䛾Fe3O4䝘䝜⢏Ꮚ 䛜ᣢ䛴ᚤᑠ䛺☢᮰䛾᳨ฟ䛻ᡂຌ䛧䛯䠊ᅗ6(a)(b)䛻䠈Fe3O4䝘䝜⢏Ꮚ䛾TEMീ䛸䠈100ಸ䛾┦ቑᖜฎ⌮䜢䛧 䛯┦⏕ീ䜢♧䛩䠊ᅗ5(b)୰䛾㟷▮༳䛿䠈㧗ศゎ⬟㟁Ꮚ㢧ᚤ㙾ἲ䛻䜘䜚Ỵᐃ䛧䛯䠈ྛ䝘䝜⢏Ꮚ䛾☢ᐜ᫆
㍈䛾㟁Ꮚ⥺ධᑕ᪉ྥ䜈䛾ᢞᙳᡂศ䜢⾲䛩䠊ゎᯒ䜢⾜䛳䛯 䝘䝜⢏Ꮚ䛿㉸ᖖ☢ᛶ䛾⮫⏺⢏ᚄ㏆ഐ䛾⢏ᚄ䜢ᣢ䛴䛜䠈☢
᮰ศᕸ䛸☢ᐜ᫆㍈䛸䛾㛫䛻䛿ᑐᛂ㛵ಀ䛜Ꮡᅾ䛧䠈⤖ᬗ
☢Ẽ␗᪉ᛶ䛜ಖᣢ䛥䜜䛶䛔䜛䛣䛸䛜᫂䜙䛛䛻䛺䛳䛯䠊䜎䛯䠈
┦⏕ീ䛾䝅䝭䝳䝺䞊䝅䝵䞁䛛䜙䠈䝘䝜⢏Ꮚ䛾☢᮰ᐦᗘ䛿 ᴫ䛽0.6T䛸ぢ✚䜒䜙䜜䠈ᮏ䝘䝜⢏Ꮚ䛜䝞䝹䜽ヨᩱ䛾㣬☢
䛸ྠ➼䛾☢䜢ᣢ䛴䛣䛸䛜♧䛥䜜䛯䠊ᑦ䠈ᮏ◊✲䛿䠈᪥❧
䝝䜲䝔䜽䝜䝻䝆䞊䝈䛾బ⸨ᓅᚿ༤ኈ䠈⌮Ꮫ◊✲ᡤ䛾㇂ᇉ ಇ᫂༤ኈ䠈H.S.Park༤ኈ䠈䝽䝅䞁䝖䞁Ꮫ䛾K.M.Krishnan ᩍᤵ䛸䛾ඹྠ◊✲䛸䛧䛶⾜䜟䜜䛯䠊
㻌
ᅗ5 Fe3O4ࢼࣀ⢏Ꮚࡢ(a)TEMീ(b)┦⏕ീ㸬
ᅗ3 Fe85S2B8P4Cu1ᛴ෭ࣔࣝࣇࢫ470䉝⇕ฎ⌮
ヨᩱࡢືⓗ☢ሙୗ࣮ࣟࣞࣥࢶ㢧ᚤ㙾ീࡢ࢟ࣕࣉࢳ
࣮ࣕ⏬ീ㸬
ᅗ4 MnV2O4䛾☢༊ᵓ㐀䜢⾲䛩䝻䞊䝺䞁㢧ᚤ㙾ീ䠊᫂⥺䞉ᬯ⥺䛿
☢ቨ䜢♧䛩䠊
研 究 活 動 報 告 100
◊ ✲ ά ື ሗ ࿌
࠙◊✲άືሗ࿌ࠚ ㉮ᰝࣉ࣮ࣟࣈィ ᢏ⾡◊✲ศ㔝
㸦2013.1㹼2013.12㸧ᩍ ᤵ㸸⡿⏣ᛅᘯ
ㅮ ᖌ㸸㧗ᒸẎ
ຓ ᡭ㸸㐨♽ᑿᜤஅ
◊ ✲ ᨭ ⪅㸸Syed Mohammad Fakruddin Shahed
Ꮫ 㝔 ⏕㸸㛗㇂ᕝᬛ㕥ᮌ㻌 ဴஓ㻘㻌 ี㻌 ᮽ㻘㻌 ▼ᕝ㻌 ⤮㻘㻌 ⵗⱑ㻌 ᆅ㻘㻌 ᑠᯘ㻌 ▱ᗈ㻘㻌 Ლཎ㻌 ⨾⌔㻘㻌 㔠Ꮚ㻌 ஓ㻌
◊✲ᡤ➼◊✲⏕㸸ᩧ ᚿᆞ㻌
ᮏ◊✲㒊㛛䛻䛚䛔䛶䛿⾲㠃䛾ཎᏊ䝺䝧䝹䛷䛾≀ᛶホ౯䛾䛯䜑䛾ඛ➃ⓗ䛺㉮ᰝ䝥䝻䞊䝤㢧ᚤ㙾㛤
Ⓨ䜢⾜䛳䛶䛔䜛䚹2013ᖺ䛾άື䜢⥲ᣓ䛩䜛䛸௨ୗ䛾㏻䜚䛷䛒䜛䚹
㻝㻚㻌䛆◊✲┠ⓗ䛇㻌
㏆ᖺ䝇䝢䞁䝖䝻䝙䜽䝇䜢ึ䜑䛸䛧䛶䚸䝇䝢䞁䛾⮬⏤ᗘ䜢⏕䛛䛧䛯㟁ὶไᚚ䛻㛵ᚰ䛜䜒䛯䜜䚸≉䛻䛭䛾ᮦ
ᩱ䛻ศᏊ䜢⏝䛔䛯ศᏊ䝇䝢䞁䝖䝻䝙䜽䝇䛻䛴䛔䛶ከ䛟䛾◊✲䛜䛺䛥䜜䛶䛔䜛䚹䜎䛯䛭䛾㟁ᴟ䛻䜒ᚤᑡ㔠 ᒓ㟁ᴟ䛰䛡䛷䛺䛟䚸ඃ䜜䛯㟁Ẽఏᑟ≉ᛶ䛸䚸ຍᕤ䜔ศᏊ䛸䛾ᩚྜᛶ䛾ᐜ᫆䛥䛛䜙䜾䝷䝣䜵䞁䛜ὀ┠䜢㞟 䜑䛶䛔䜛䚹䜾䝷䝣䜵䞁䛸⤌䜏ྜ䜟䛫䛯☢ᛶ㔠ᒓ䜢ෆໟ䛧䛯ศᏊ䜢ᮦᩱ䛸䛧䚸䛭䛾䝇䝢䞁䜢㟁ὶไᚚ䛻⏝
䛔䜘䛖䛸䛩䜛◊✲䛿≉䛻ὀ┠䜢㞟䜑䜛䚹ᮏ◊✲䜾䝹䞊䝥䛷䛿䚸㉮ᰝᆺ䝖䞁䝛䝹㢧ᚤ㙾䠄STM䠅䜢䛯䜛ィ ᡭἲ䛸䛧䛶䚸༢ศᏊ㔞Ꮚ☢▼䠄SMM䠅,SiC⾲㠃䛻ᡂ㛗䛥䛫䛯䜾䝷䝣䜵䞁⾲㠃䜢⏝䛔䚸䛥䜙䛻STMᡭἲ 䛾≉ᚩ䛷䛒䜛ཎᏊศゎ⬟䜢䜒䛳䛯䝇䝢䞁≧ែ䛾ㄞ䜏ྲྀ䜚䡡᭩䛝㎸䜏䛾ไᚚᢏ⾡䜢㧗ᗘ䛩䜛䚹ྠ䛻ཎ Ꮚ䞉ศᏊ᧯సᢏ⾡䜢ά⏝䛩䜛䛣䛸䛷䚸༢ศᏊ䝯䝰䝸䞊䞉ศᏊ䝇䝢䞁䝖䝻䝙䜽䝇ᐇ⌧䛾ᇶ┙ᢏ⾡䜢☜❧䛩 䜛䚹
㻌
㻞㻚㻌 㻿㻹㻹ศᏊ䛷䛒䜛㼀㼎㻼㼏㻞ศᏊ䜢⏝䛔䛯䝇䝢䞁䝞䝹䝤ຠᯝ㻌
TbPc2ศᏊ䛿㧗䛔䝤䝻䝑䜻䞁䜾 ᗘ䜢ᣢ䛴༢ศᏊ㔞Ꮚ☢▼䠄SMM䠅䛸䛧䛶ὀ┠䜢㞟䜑䛶䛔䜛䚹ᮏᖺ䛿䛣 䛾ศᏊ䜢䚸☢ᛶ᥈㔪䛸☢ᛶᇶᯈ䛾㛫䛾䝖䞁䝛䝹䜼䝱䝑䝥䛻ᤄධ䛧䚸䝖䞁䝛䝹㟁ὶ䛾☢ሙ౫Ꮡᛶ䚸䛩䛺䜟 䛱TMRẚ䜢ㄪ䜉䛯䚹ᐇ㦂䛻䛿䝦䝸䜴䝮 ᗘ䛷ືస䛩䜛㉮ᰝᆺ䝖䞁䝛䝹㢧ᚤ㙾䠄STM䠅䜢⏝䛔䚸dI/dV᭤
⥺䛾Co3d㌶㐨䛻⏤᮶䛩䜛䝢䞊䜽䛾ᙉᗘ䛛䜙TMRຠᯝ䜢ぢ✚䜒䛳䛯䚹䜎䛪Cr᥈㔪䛸䚸Co(111)ᇶᯈ䜢⏝
䛔䛯ᐇ㦂䛻䛚䛔䛶䛿䚸ᅗ䠍(a)䛻♧䛩☢ሙ䛸TMR⋡䛾䝥䝻䝑䝖䛛䜙䜟䛛䜛䜘䛖䛻䚸Coᇶᯈ䛾ṧ␃☢ሙศᴟ 䛻⏤᮶䛩䜛䝞䝍䝣䝷䜲ᙧ≧䛾TMRS䛾ᣲື䛜ぢ䜜䜛䚹䛣䛾䜼䝱䝑䝥䛻TbPc2䜢ᤄධ䛧䛯ሙྜ䚸ᅗ䠍(b)䛻♧
䛩」㞧䛺᭤⥺䛻ኚ䛧䛯䚹䛣䜜䛿ᙅ☢ሙ䛻䛚䛔䛶䚸TbPc2ศᏊ䛸Coᇶᯈ䛜antiferromagnetic䛻⤖ྜ䛩䜛 䛣䛸䛷ㄝ᫂䛩䜛䛣䛸䛜䛷䛝䛯䚹ศᏊ䜢⏝䛔䛯᪂䛧䛔䝇䝢䞁䝞䝹䝤ຠᯝ䛸⪃䛘䜙䜜䜛䚹
㻌
101 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌
㻌 㻌 㻌
㻟㻚䝣䜷䝜䞁 ᐃ䛻䜘䜛䜾䝷䝣䜵䞁䝞䝑䝣䜯ᒙ䛾ᐇ✵㛫 ᐃ㻌
䜾䝷䝣䜵䞁䛿ඃ䜜䛯㟁Ẽⓗ䛺≉ᛶ䛛䜙ὀ┠䜢㞟䜑䜛䛜䚸ᐇ㝿䛾䝕䝞䜲䝇ᛂ⏝䛻䛚䛔䛶䛿⤯⦕≀ୖ䛻 ᙧᡂ䛩䜛䛣䛸䛜ᮃ䜎䛧䛔䚹䛣䜜䛿䚸㔠ᒓୖ䛻ᡂ㛗䛥䛫䛯䜾䝷䝣䜵䞁䛻䛚䛔䛶䛿䛭䜜䜢⤯⦕య⾲㠃䛻㌿
䛩䜛ᚲせ䛜᭷䜛䛣䛸䜢♧၀䛧䛶䛚䜚ᕤ⛬䛾」㞧䛻䛴䛺䛜䜛䚹SiC⾲㠃䜢㧗 䛷㐣⇕䛩䜛䛣䛸䛷SiཎᏊ 䛜㑅ᢥⓗ䛻⬺㞳䛩䜛䛣䛸䜢⏝䛔䛯䜾䝷䝣䜵䞁ᙧᡂἲ䛿䚸SiC䛜䛝䛺䝞䞁䝗䜼䝱䝑䝥䜢ᣢ䛴༙ᑟయ䛷䛒䜛 䛣䛸䛛䜙䚸䛣䛾㌿䛾ᚲせᛶ䛜䛺䛟䚸䝕䝞䜲䝇ᛂ⏝䛻䜒ᩚྜᛶ䛜䜘䛟ὀ┠䛥䜜䜛䚹䛧䛛䛧䛺䛜䜙䚸ᐇ⏝ୖ᭷
⏝䛺Si㠃䛻ᙧᡂ䛥䜜䛯䜾䝷䝣䜵䞁䛻䛿䝞䝑䝣䜯ᒙ䛸䜀䜜䜛⏺㠃ᒙ䛜Ꮡᅾ䛧䚸䝕䝞䜲䝇≉ᛶ䛻ᙳ㡪䜢ཬ 䜌䛩䛣䛸䛜▱䜙䜜䛶䛚䜚䚸䛣䛾ᒙ䛾ไᚚ䛜ᚋ䛾ᛂ⏝䛷㘽䛸䛺䜛䛸⪃䛘䜙䜜䜛䚹䠄ᅗ2(a),(b)䠅
ᮏ◊✲䛷䛿䚸䝦䝸䜴䝮 ᗘ䛷䛾STM ᐃ䛷䚸䝣䜵䝹䝭‽㏆䛾㧗ศゎ⬟dI/dV䝇䝨䜽䝖䝹䜢 ᐃ䛧䚸 䛭䛾䝇䝨䜽䝖䝹䛻ྵ䜎䜜䜛䝣䜷䝜䞁䛾ᡂศ䛻ὀ┠䛧䛯 ᐃ䜢⾜䛳䛯䚹ᅗ䠎(c)䛷ぢ䜙䜜䜛䝣䜵䝹䝭‽㏆
䛾㗦䛔䝕䜱䝑䝥䜢ᣢ䛱䚸䛣䜜䛿䜾䝷䝣䜵䞁䛾䝣䜷䝜䞁⏤᮶䛾䜒䛾䛸⪃䛘䜙䜜䜛䚹䝣䜷䝜䞁䛾ᣲື䛿䝞䝑䝣䜯 ᒙ䛾ᙳ㡪䜢䛝䛟ཷ䛡䜛䚹䛭䛾䛣䛸䜢ᛂ⏝䛧䝬䝑䝢䞁䜾䜢 ᐃ䛧䛯䜒䛾䛜ᅗ2(d)䛷䛒䜚䚸STMീほᐹ䛰䛡 䛷䛿ᚓ䜙䜜䛺䛔䚸䝞䝑䝣䜯ᒙ䛾䝗䝯䜲䞁ቃ⏺䜢ྍど䛩䜛䛣䛸䛻ᡂຌ䛧䛯䚹䛣䛾ᡭἲ䛿䚸䜾䝷䝣䜵䞁䛾≉ᛶ 䜢Ỵᐃ䛩䜛䚸䝞䝑䝣䜯ᒙ䛾≀ᛶ᥈⣴䛻≉䛻᭷ຠ䛸⪃䛘䜙䜜䜛䚹
ᅗ㻝㻌(a)㻌Cr᥈㔪/Coᇶᯈ䛷ほᐹ䛥䜜䜛☢ሙ-TMRẚ䛾䝥䝻䝑䝖䚹䝞䝍䝣䝷䜲ᙧ≧䛾䝠䝇䝔䝸䝅
䝇䛜ほᐹ䛥䜜䜛䚹(b) Cr᥈㔪/TbPc2/Coᇶᯈ䛷ほᐹ䛥䜜䜛☢ሙ-TMRẚ䝥䝻䝑䝖䚹B=0௨๓ 䛷ῶᑡ䛜⏕䛨䜛」㞧䛺ᵓ㐀䜢ᣢ䛴䚹㻌
ᅗ䠎㻌(a) SiC⾲㠃䛻ᡂ㛗䛥䛫䛯䜾䝷䝣䜵䞁⾲㠃䛷ほᐹ䛥䜜䜛ཎᏊീ䛚䜘䜃㉸࿘ᮇᵓ㐀䚹(b)SiC-Si
㠃䛻ᡂ㛗䛧䛯䜾䝷䝣䜵䞁ୗᒙ䛻Ꮡᅾ䛩䜛䝞䝑䝣䜯ᒙ䚹 (c)䜾䝷䝣䜵䞁ୖ䛷䛾dI/dV䝇䝨䜽䝖䝹䚹 (d)
研 究 活 動 報 告 102
◊ ✲ ά ື ሗ ࿌
࠙◊✲άືሗ࿌ࠚ 㧗ศᏊࣁࣈࣜࢵࢻࢼࣀᮦᩱ◊✲ศ㔝 㸦2013.1㹼2012.12㸧 㻌 㻌
ᩍ ᤵ㸸ᐑୗᚨࠥ2013.3)㸪୕ࢶ▼᪉ஓ2013.4ࠥ)
ᩍ ᤵ㸸୕ࢶ▼᪉ஓࠥ2013.3)㸪Ώ㎶᫂ࠥ2013.3)
ຓ ᩍ㸸ᯇ῟ࠥ2013.3)㸪ᒣᮏ ಇ(2013.4ࠥ)
◊ ✲ ဨ㸸Ali Demirci
Ꮫ㝔⏕㸸Huie ZhuYu Gao
㛛ᩥ㤶⳥ᆅ㔛ᯞᅬ㒊㍤᪩ᆏ⿱ኴ ෆᒣ㥴༳⸨ஓ
Ꮫ㒊Ꮫ⏕㸸㭯㇂⪽⣖Ọ⃝㸪ோ⛉㔜
㻌
ᮏ◊✲ศ㔝䛷䛿䚸㧗ศᏊ䞉⏕యศᏊ䞉䝘䝜⢏Ꮚ䞉䝘䝜⤖ᬗ䛺䛹䛾ከᵝ䛺䝘䝜≀㉁䜢ᶵ⬟ศᢸ䛻ᚑ䛔⮬ᅾ㞟
✚䞉⤌⧊䠄䜰䝉䞁䝤䝹ᆺ䜎䛯䛿䝪䝖䝮䜰䝑䝥ᆺ䠅䛧䚸䝝䜲䝤䝸䝑䝗⼥ྜ䛧䛯᪂つ䛺㧗ศᏊ䝝䜲䝤䝸䝑䝗䝘䝜ᮦᩱ䛾 㛤Ⓨ䜢┠ᣦ䛧䛶䛔䜛䚹䛚䜒䛻䝷䞁䜾䝭䝳䜰䞊䝤䝻䝆䜵䝑䝖
(LB)ἲ䛻䜘䜚స〇䛥䜜䜛㧗ศᏊ䝘䝜䝅䞊䝖䜢ᇶ┙≀㉁䛸 䛧䛶⏝䛔䚸✀䚻䛾䝘䝜≀㉁䜢㝵ᒙⓗ䛻⤌⧊䛧䛶䝕䝞䜲䝇䛩䜛䝘䝜㡿ᇦ䛻䛚䛡䜛ᇶ┙ᢏ⾡䚸䛚䜘䜃䛂䝪䝖䝮䜰 䝑䝥ᆺ䝘䝜䝔䜽䝜䝻䝆䞊䛃䛾Ⓨᒎ䜢┠ᣦ䛧䛯᪂⣲ᮦ䛾◊✲㛤Ⓨ䜢⾜䛳䛶䛔䜛䚹
2013ᖺ䛾◊✲άື䛸䛧䛶䛿䚸௨ୗ
䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䚹
㻝㻚㻌 䝪䝖䝮䜰䝑䝥ⓗ㞟✚䛻䜘䜛᭷ᶵ䠉↓ᶵ䝝䜲䝤䝸䝑䝗ᆺගᶵ⬟ᛶ䝘䝜䝕䝞䜲䝇䛾㛤Ⓨ㻌
㏆ᖺග䛾ఏไᚚᢏ⾡䛾ྥୖ䛻䜘䜚䚸ගグ㘓፹య䜔ග㏻ಙ䛾ሗศ㔝䛻䛚䛔䛶䚸ሗ䛾ᐜ㔞䜔㧗㏿
䛜ᐇ⌧䛥䜜䛯䚹䛧䛛䛧䚸᪥䛾ሗ♫䛻䜘䜛㏻ಙ㔞ቑ䛻క䛔䚸䛥䜙䛺䜛ሗ䛾㧗ᐦᗘ䛜ồ䜑䜙䜜䜛䚹
⌧ᅾග䛾ሗ䛿ᙉᗘ䛸Ἴ㛗䜢⏝䛧䛶䛔䜛䛜䚸䛣䜜䜙䛻ຍ䛘䛶೫ග᪉ྥ䜢ሗ䛸䛧䛶⏝䛩䜛䛣䛸䛷䚸ሗ䛾 㧗ᐦᗘ䛜ྍ⬟䛸䛺䜛䚹䛭䛣䛷䚸୍ḟඖ㖟ᅇᢡ᱁Ꮚୖ䛷Ⓨ⏕䛩䜛೫ග䛻౫Ꮡ䛧䛯␗䛺䜛䠎䛴䛾⌧㇟䠄⾲㠃䝥䝷 䝈䝰䞁ඹ㬆䚸ᑟἼ䝰䞊䝗䠅䛾ඹᏑ䛻╔┠䛧䚸೫ග᳨ฟ䝕䝞䜲䝇䜈䛾ᛂ⏝䜢ヨ䜏䛯䚹䛣䜜䜙䛾⌧㇟䛿䚸ᚑ᮶༢⊂
䛷⏝䛥䜜䛶䛔䛯䛜䚸ᡃ䚻䛿
1䡚
2 nm䛷⭷ཌไᚚྍ⬟䛺㧗ศᏊ䝘䝜䝅䞊䝖䜢⏝䛔䛶ᅇᢡ᱁Ꮚୖ䛾⭷ཌ䜢⢭ᐦ 䛻ไᚚ䛩䜛䛣䛸䛷䚸
2䛴䛾⌧㇟䜢ྠ୍⣔ෆ䛷Ⓨ⏕ྍ⬟䛺ྠ୍ບ㉳᮲௳䛜Ꮡᅾ䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹䜎䛯Ⓨ
ගయ䛸䛧䛶䚸
2✀㢮䛾
CdSe䝘䝜⢏Ꮚ䜢㧗ศᏊ䝘䝜䝅䞊䝖୰䛻⨨㑅ᢥⓗ䛻ᑟධ䛧䚸ྠ୍ບ㉳᮲௳䛷ගᶵ⬟ᛶ 䝘䝜䝕䝞䜲䝇䜢స〇䛩䜛䛣䛸䛷䚸ධᑕග䛾೫ග᪉ྥ㆑ูྍ⬟䛺䝕䝞䜲䝇䜈䛾ᛂ⏝䛻ᡂຌ䛧䛯䚹
㻞㻚 Preparation of Hybrid Network Polymers Using Double-Decker Silsesquioxane Monomers
New approaches on polymerization suggest the construction of nano hybrid materials based on polyhedal oligomeric silsesquioxanes (POSS), which possess a rigid and cubic-octomeric core structure with attached organic moieties (R) at each of the eight vertices. The incorporation of POSS into organic polymers has been extensively investigated to afford organic-inorganic hybrids because of expected unique and improved physical properties such as thermal and mechanical stability, solubility, flammability, oxidative resistance, and low dielectric constant. In this study, silsesquioxane/siloxane based hybrid polymers were synthesized using one-pot hydrosilylation reaction of multifunctional 1,3,5,7-tetramethylcyclotetrasiloxane (TMCS) monomer with divinyl-terminated double-decker silsesquioxane (DDSQ). Controlling conditions of hydrosilylation reaction was studied at the changing total monomer concentration and stoichiometric monomer ratio to obtain soluble and processable polymers without gelation. The average molecular weights, polydispersity, and remaining functional groups of hybrid polymer were examined using the GPC, FT
㸫
IR, 1H and 29Si NMR. Utilizing the crosslinking of hybrid polymers through self-crosslinking (hydrolysis/condensation), transparent freestanding and spin-coated hybrid polymer film were fabricated. Thermal stability, optical transparency, and mechanical properties of films were investigated. Three-component hybrid network polymer films consisting of TMCS, DDSQ and hydride-terminated polydimethylsiloxane (DMHS) monomers were also investigated.103 ◊ ✲ ά ື ሗ ࿌研 究 活 動 報 告
㻟㻚
Solvent-Dependent Properties of Poly(vinylidene fluoride) Monolayers at the Air-Water Interface For building two-dimensional Langmuir-Blodgett (LB) films with high density and dominant ferroelectric phase, poly(vinylidene fluoride) (PVDF), a semicrystalline polymer, was demonstrated in our previous work. The present work addresses the solvent-dependent properties of mixed Langmuir films of PVDF and amphiphilicpoly(N-dodecylacrylamide) (pDDA) at different mixing ratios. The pDDA Langmuirfilm has the highest compressibility modulus up to 172.6 mN/m reported for a polymer to date, which represents very good film formation ability. After introducing pDDA nanosheets, PVDF Langmuir films obtain a tremendously enhanced modulus as well as high transfer ratios using the vertical dipping method caused by the support of the pDDA two-dimensional hydrogen bonding network. Brewster angle microscopy (BAM) was used to investigate PVDF monolayers at the air--water interface in-situ. Spreading from different solvents, the PVDF molecules take completely different aggregation states at the air-water interface. The PVDF molecules aggregate to become large domains when spread from N-methyl-2-pyrrolidone (NMP). However, the volatile and low-polarity methylethyl ketone (MEK) made the PVDF molecules more dispersive on the water surface according to the limiting surface area of VDF repeating units from surface pressure ( ) - area (A) isotherms. Phase separation can be observed only in the PVDF(MEK) mixed Langmuir films using -A isotherms as well as BAM images.Crystalline structures in the obtained PVDF mixed LB films using different solvents were tuned from
!-dominant for NMP to "-dominant for MEK. Therefore, we can easily modulate film properties at the air--water interface by changing spreading solvents. Effective transferring was also achieved for different PVDF monolayers from the air-water interface onto substrates through the introduction of the pDDA two-dimensional hydrogen bonding network. This study provides valuable information related to the morphological evolution of semicrystalline PVDF confined in a pDDA two-dimensional geometry at the air--water interface and gives fundamental insight into the influence of solvents on the Langmuir film properties. This study also presents very interesting and controllable crystal structures in mixtures of nonamphiphilic PVDF and amphiphilic pDDA at the air--water interface, which are expected to afford much useful information for additional interface manipulation of PVDF crystals.
㻠㻚㻌 䝣䝑⣲୧ぶ፹ᛶ㧗ศᏊ䛻䜘䜛ከᏍᛶⷧ⭷䛾స〇䛚䜘䜃㧗ឤᗘⓎගᆺ㓟⣲䝉䞁䝃䞊䜈䛾ᛂ⏝㻌
㻌 䝣䝑⣲⣔୧ぶ፹ᛶ㧗ศᏊ䜢⏝䛔䛶⡆༢䛺ᡭἲ䛷ᚤ⣽ᵓ㐀䜢స〇䛧䛯䚹ᚤ⣽ᵓ㐀䛾ᵓ⠏䛻䛴䛔䛶䛿䚸㈋⁐፹ 䛸Ⰻ⁐፹䜢⏝䛧䛶䝣䝑⣲⣔୧ぶ፹ᛶ㧗ศᏊΰྜ⁐ᾮ䜢స〇䛧䛯䚹ᇶᯈୖ䛻⁐ᾮ䜢ୗᚋ䚸⁐፹䛾⮬↛
⇱䛻䜘䜚䝣䝑⣲⣔୧ぶ፹ᛶ㧗ศᏊ䛾ᚤ⣽ᵓ㐀䜢స〇䛧䛯䚹䛭䛾⤖ᯝ䚸ᚤ⣽ᵓ㐀䛜ᙧᡂ䛥䜜䚸䛺䛚䛛䛴䝣䝑⣲
⣔ᮦᩱ䛾⾲㠃䜶䝛䝹䜼䞊䛜ᑠ䛥䛔䛯䜑䚸స〇䛧䛯ᚤ⣽⢏Ꮚ䛛䜙䛺䜛ⷧ⭷䛜㉸Ỉᛶ䜢♧䛧䛯䚹䜎䛯䚸స〇䛧䛯 ヨᩱ䛿ከᏍᛶ䜒ᣢ䛳䛶䛔䛯䚹䛭䛣䛷䝣䝑⣲⣔ᮦᩱ䛜䜺䝇㏱㐣ᛶ䚸⾲㠃䜜ᛶ䛚䜘䜃ከᏍᛶ䜢⏝䛧䛶⁐Ꮡ㓟
⣲䝉䞁䝃䞊䜈䛾ᛂ⏝䜢᳨ウ䛧䛯䚹㓟⣲ᛂ⟅ᛶ䛾Ⰽ⣲䜢㉸Ỉᛶ䜢䜒䛴ⷧ⭷୰䛻ᑟධ䛩䜛䛣䛸䛷䚸⁐Ꮡ㓟⣲䝉 䞁䝃䞊䜢స〇䛧䛯䚹䛣䛾⁐Ꮡ㓟⣲䝉䞁䝃䞊䛾ឤᗘ䜢 ᐃ䛧䛯䛸䛣䜝㧗ឤᗘ䛾⁐Ꮡ㓟⣲䝉䞁䝃䞊䛷䛒䜛䛣䛸䛜ศ 䛛䛳䛯䚹㻌
㻌
㻡㻚㻌 䝗䞊䝟䝭䞁䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛻䜘䜛྾╔䞉᥋╔≉ᛶ㻌
䝮䝷䝃䜻䜲䜺䜲䛾᥋╔䝍䞁䝟䜽㉁୰䛻ྵ䜎䜜䜛䝗䞊䝟䝭䞁䛜Ỉ⣔䛻䛚䛔䛶ᙉ䛔᥋╔ຊ䜢♧䛩Ⅼ䛻╔┠䛧䛯䚹䝗 䞊䝟䝭䞁䜢ྵ䜐㧗ศᏊ䝘䝜䝅䞊䝖䜢స〇䛧䚸䛭䛾᥋╔䞉྾╔≉ᛶ䜢᳨ウ䛧䛯䚹䝗䞊䝟䝭䞁ྵ᭷䝘䝜䝅䞊䝖䜢
2ᒙ⣼
✚䛧䛯ᇶᯈ䛻䝅䝸䜹䝘䝜⢏Ꮚ䛾྾╔䜢⾜䛳䛯䛸䛣䜝䚸
pH6.5䜘䜚㧗
pH䛷䛿⢏Ꮚ䛾྾╔䛜㉳䛝䛺䛛䛳䛯䛾䛻ᑐ䛧䚸
pH6.5