⿵ బ ဨ㸸᭶㤋⩏㝯ᬗᏊ⳥ᆅⱥ㔛(~2015.9) ᘅⰪ⨾బಖ(~2015.3)ၿ✚ెᏊ
Ꮫ 㝔 ⏕㸸ఀᮾ㥴ஓୖཎ༟ஓ⿇ᮧᕦ⏣㎶᫂
␁ᰗᚿᕹబ⸨ៅᘺ㛵ᩯ⳥ᆅⱥ㔛
▮㔝⳯
Ꮫ 㒊 Ꮫ ⏕㸸㔠ཎᚭᑦ⇃㇂┿Ⳁ
ᮏ◊✲ศ㔝䛷䛿䠈ᮦᩱᏛ䛾どⅬ䛛䜙䠈ศᏊ䝺䝧䝹䛷⢭ᐦ䛻᭷ᶵ㧗ศᏊ䛸㔠ᒓ䞉↓ᶵ≀㉁䛾⏺㠃䜢タィ 䛧䛶⏺㠃ᶵ⬟䜢ไᚚ䛩䜛⏺㠃ᶵ⬟ศᏊไᚚᕤᏛ䛾ᡂ䜢┠ᣦ䛧䛶䛔䜛䠊᪂䛯䛺ගᶵ⬟ᮦᩱ䛾ฟ䜔ග䛻䜘 䜛ᚤ⣽ຍᕤἲ䜔᳨ᰝἲ䛾◊✲䜢⾜䛔䠈䝅䞁䜾䝹䝘䝜䛛䜙䝬䜲䜽䝻㡿ᇦ䛾㟁Ꮚ䞉ග䝕䝞䜲䝇䛾〇䜢◊✲䛧䛶䛔 䜛䠊≉䛻䠈ᚤ⣽ຍᕤἲ䛸䛧䛶䛿䠈䝟䝍䞊䞁䝃䜲䝈䛸䝟䝍䞊䝙䞁䜾㠃✚䜢ᗈ⠊ᅖ䛷୧❧䛷䛝䠈ḟୡ௦䛾㔞⏘ᇶ┙
ᢏ⾡䛸䛧䛶ὀ┠䛧䛶䛔䜛䠈䝘䝜䜲䞁䝥䝸䞁䝖ᢏ⾡䜢㍈䛻◊✲䜢ᒎ㛤䛧䠈ඛ㐍䝘䝜䜲䞁䝥䝸䞁䝖䝸䝋䜾䝷䝣䜱(NIL)䛻
㈨䛩䜛᪂つ䛺ᮦᩱ䛸䝥䝻䝉䝇䛾㛤Ⓨ䜔䠈NIL䝕䝞䜲䝇䛾ᛂ⏝◊✲䜢㐍䜑䛶䛔䜛䠊2015ᖺ䛾◊✲άື䛸䛧䛶䛿䠈 ௨ୗ䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䠊
㻝㻚㻌ග䝘䝜䜲䞁䝥䝸䞁䝖䝸䝋䜾䝷䝣䜱䜢┠ᣦ䛧䛯Ꮝ∧༳ๅ䛻䜘䜛ග◳ᛶᾮయ䛾⨨㑅ᢥⓗᾮ㓄⨨
᫆ᨃ⦰ᛶ䜺䝇䜢⏝䛔䛯䝞䝤䝹Ḟ㝗䝣䝸䞊ග䝘䝜䜲䞁䝥䝸䞁䝖䝸䝋䜾䝷䝣䜱䛷䛿䠈ᙜ◊✲䜾䝹䞊䝥䛜⊂⮬䛻㛤Ⓨ
䛧䛯ග◳ᛶᾮయNL-SK1䛜⏝䛩䜛䜺䝇䛻ᑐ䛩䜛྾㔞䛜ᑡ䛺䛟䠈⢭ᐦ䛺◳ᶞ⬡䝟䝍䞊䞁㌿䛻᭷ຠ䛷 䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛶䛝䛯䠊䝰䞊䝹䝗㠃ෆ䛾䝟䝍䞊䞁ᐦᗘ䛾⢒ᐦ䛻ᛂ䛨䛶䠈⨨㑅ᢥⓗ䛻ග◳ᛶᾮయ䛾ᾮ
䜢㓄⨨䛩䜛䛣䛸䛷䠈ග䝘䝜䜲䞁䝥䝸䞁䝖ᡂᙧ䛻䛚䛡䜛ṧ⭷ཌ䛾ᆒ୍䛜ྍ⬟䛸䛺䜛䛣䛸䛜▱䜙䜜䛶䛔䜛䛜䠈௦
⾲ⓗ䛺ᾮ㓄⨨ᢏ⾡䛷䛒䜛ᚑ᮶䛾䜲䞁䜽䝆䜵䝑䝖ἲ䛷䛿䠈
⏝ྍ⬟䛺ᾮయ䛜⢓ᗘ10 mPa s⛬ᗘ䛾ప⢓ᛶᾮయ䛻ไ㝈䛥 䜜䜛䛯䜑䠈NL-SK1䠄⢓ᗘ12,800 mPa s䠅䜢䛿䛨䜑䛸䛧䛯㧗⢓
ᗘ䛾ග◳ᛶᾮయ䜢⏝䛔䜛ሙྜ䛻䛿᪂䛯䛺ᾮ㓄⨨᪉ἲ 䛜ᚲせ䛸䛺䛳䛯䠊ᙜ◊✲䜾䝹䞊䝥䛷䛿䠈Ꮝ∧༳ๅ䜢⏝䛔䛯 ග◳ᛶᾮయ䛾⨨㑅ᢥⓗྤฟ䛻㛵䛩䜛◊✲䛻ྲྀ䜚⤌䜏䠈 Ꮝ∧༳ๅ䛷ග䝘䝜䜲䞁䝥䝸䞁䝖䛾㝿䛾ṧ⭷ཌᆒ୍䛻ຠᯝ 䛜䛒䜛䛣䛸䜢ぢฟ䛧䛯䠊䝢䝁⛊䝺䞊䝄䞊✰䛒䛡ຍᕤ䝅䝇䝔䝮䜢 ᪂䛯䛻ᵓ⠏䛧䠈䝫䝸䜲䝭䝗䛺䛹䛾Ꮫⓗ䞉ᶵᲔⓗ⪏ᛶ䛻ඃ䜜 䛯ྛ✀䛾䜶䞁䝆䝙䜰䝸䞁䜾䝥䝷䝇䝏䝑䜽䛾⭷䛻௵ព䛾䝟䝍䞊 䞁ຍᕤ䜢ྍ⬟䛻䛧䠈䝇䝔䞁䝺䝇䝯䝑䝅䝳䛸ឤගᛶங⭷䛾䝺䝆 䝇䝖䝟䝍䞊䞁䛛䜙䛺䜛ỗ⏝༳ๅ䝬䝇䜽䛸ẚ䜉䠈䝺䞊䝄䞊ຍᕤ Ꮝ∧䛷䛿ྤฟḞ㝗䜢㜵䛞䠈ග◳ᛶᾮయ䛾⢭ᐦ㓄⨨䛸ᾮ 㔞䛾⢭ᐦタィ䛻ᙺ❧䛴䛣䛸䜢♧䛧䛯䠊
䝫䝸䜲䝭䝗Ꮝ∧䜢⏝䛔䛯䝇䜽䝸䞊䞁༳ๅἲ䛻䜘䜚ሬᕸ䛧䛯 ග◳ᛶ⤌ᡂ≀䛾⺯ග㢧ᚤ㙾
㻞䠊䝘䝜䝟䝍䞊䞁䜺䜲䝗䛷䛾ㄏᑟ⮬ᕫ⤌⧊䜢┠ᣦ䛧䛯ගᶵ⬟㧗ศᏊᮦᩱ䛾㛤Ⓨ
༙ᑟయ䜢䛿䛨䜑䛸䛩䜛ඛ➃ᚤ⣽䝘䝜ຍᕤᢏ⾡䛷䛿䠈䝕䝞䜲䝇䝁䝇䝖䛻ぢྜ䛳䛯䝃䝤20nm䝃䜲䝈䛾㔞⏘ຍᕤ ἲ䛜ồ䜑䜙䜜䛶䛔䜛䠊䛭䛾ೃ⿵䛾୍䛴䛻ḟୡ௦䝸䝋䜾䝷䝣䜱ἲ䛻㧗ศᏊ䛾ㄏᑟ⮬ᕫ⤌⧊䜢⤌ྜ䛫䜛᪉ἲ䛜 䛒䜛䠊ᮏ◊✲䛷䛿䠈ᾮᬗᛶ㧗ศᏊᮦᩱ䛾㐍ᒎ䜢㐍䜑䛶䛔䜛䠊䜻䝷䝹䝛䝬䝏䝑䜽┦䜢♧䛩ᾮᬗ㧗ศᏊ䛿䠈ᾮᬗ䝯 䝋䝀䞁䛜୍᪉ྥ䛻㓄ྥ䛧䛯ᒙ䛜䜙䛫䜣≧䛻㔜䛺䛳䛯ḟᵓ㐀䜢ᙧᡂ䛧䠈䜙䛫䜣ᵓ㐀䜢䜺䝷䝇≧ែ䛷ᅛᐃ䛷 䛝䜛䛣䛸䛜▱䜙䜜䛶䛔䜛䠊ᮏᖺᗘ䛾◊✲䛷䛿䠈⢭ᐦ㔜ྜ䛷ྜᡂ䛩䜛༢ᓠᛶ䝛䝬䝏䝑䜽ᾮᬗ㧗ศᏊ䛾ᾮᬗᛶഃ
㙐䛾పᐦᗘ䛻䜘䜛䜻䝷䝹ศᏊ䛸䛾┦⁐ᛶ䛾ྥୖ䜢┠ⓗ䛸䛧䠈㠀ᾮᬗᛶ㒊䜢ᑟධ䛧䛯䝷䞁䝎䝮ඹ㔜ྜయ䜢
ྜᡂ䛧䛯䠊䛣䛾䝷䞁䝎䝮ඹ㔜ྜయ䛻䜻䝷䝹ศᏊ䜢ῧຍ䛧䛯䛸䛣䜝୧⪅䛾┦ศ㞳䛜ᢚไ䛥䜜䠈䜻䝷䝹䝛䝬䝏䝑䜽┦
䜢Ⓨ⌧䛩䜛䛣䛸䛜䜟䛛䛳䛯䠊䜎䛯䠈㠀ᾮᬗᛶ㒊䛾Ꮫᵓ㐀䜢ኚ䛥䛫䜛䛣䛸䛷䠈䜻䝷䝹ศᏊ䛸䛾┦⁐ᛶ䛜ኚ
䛩䜛䛣䛸䛜䜟䛛䛳䛯䠊䛥䜙䛻䠈䝛䝬䝏䝑䜽ᾮᬗ㧗 ศᏊ䛻ᑐ䛧㧗䛔┦⁐ᛶ䛸㧗䛔䜙䛫䜣ㄏ㉳ຊ䜢♧
䛩䛸⪃䛘䜙䜜䜛䜻䝷䝹ศᏊ䜢᪂つ䛻ྜᡂ䛧䛯䠊ᚓ 䜙䜜䛯䜻䝷䝹ศᏊ䜢䝛䝬䝏䝑䜽ᾮᬗศᏊ䛻ῧຍ䛧 䛯䛸䛣䜝䠈ᖜᗈ䛔ῧຍ㔞䛻䛚䛔䛶䜻䝷䝹䝛䝬䝏䝑 䜽┦䜢Ⓨ⌧䛧䛯䠊ᚋ䛿ᙜ◊✲ᐊ䛷㛤Ⓨ䛧䛯୧ ぶ፹ᛶ䝤䝻䝑䜽ඹ㔜ྜయ䛻䜻䝷䝹ศᏊ䜢ῧຍ䛧䛯
ᮦᩱ⣔䛷◊✲䜢㐍䜑䜛䠊
㻟䠊ཎᏊᒙሁ✚ἲ䜢⏝䛧䛯ᴟ㝈䝘䝜ᵓ㐀䛾స〇ᢏ⾡䛾㛤Ⓨ㻌
ཎᏊᒙሁ✚(ALD; atomic layer deposition)ἲ䛿䠈ศᏊ䛾⾲㠃྾╔䛸Ꮫᛂ䜢⧞㏉䛧䛩䛣䛸䛷䠈✀䚻䛾
ᮦᩱ⾲㠃䛻ཎᏊ䝺䝧䝹䛷ᖹ䛷䠈3ḟඖⓗ䛺ᙧ≧㏣ᚑᛶ䛻ඃ䜜䛯↓ᶵⷧ⭷䜢ᡂ⭷䛩䜛ᡭἲ䛷䛒䜛䠊ALD䛸ᚤ
⣽ຍᕤ䛾୧᪉ἲ䜢⤌ྜ䛫䜛䛣䛸䛷䠈3ḟඖ↓ᶵ䝘䝜ᵓ㐀䛾స〇䛻ྲྀ䜚⤌䜣䛷䛔䜛䠊ᮏᖺᗘ䛿䠈Ꮫ⤌ᡂ䛾␗䛺 䜛ග◳ᶞ⬡䛾⾲㠃䛷䛾Al2O3䛾ᡂ㛗䜢᳨ウ䛧䛯䠊Sub-50nm䝃䜲䝈䛷ᡂᙧ䛧䛯◳ᶞ⬡䛾䝷䜲䞁䝟䝍䞊䞁䜢
⏝䛔䛶䠈sub-20nm䛾ゎീᗘ䜢䜒䛴䝘䝜ᵓ㐀䛾స〇䛻ᡂຌ䛧䛯䠊䜎䛯䠈Ꮫ⤌ᡂ䛾␗䛺䜛◳ᶞ⬡䛾⾲㠃䛛䜙 ᶞ⬡ෆ㒊䜈䛾ᾐ㏱䛜␗䛺䜚䠈ෆ㒊䛻ᙧᡂ䛥䜜䜛Al2O3䛾㡿ᇦ䛜␗䛺䜛䛣䛸䛜䜟䛛䛳䛯䠊≉䛻䠈Al2O3䛾ᙧᡂ䛿Ỉ 㓟ᇶ䛰䛡䛷䛺䛟䠈䜹䝹䝪䝙䝹ᇶ䛸䜒ᛂ䛩䜛䛣䛸䛜᥎ 䛥䜜䛯䠊ᶞ⬡䛾Ꮫ⤌ᡂ䛻Ỉ㓟ᇶ䜢ྵ䜐䠄䝯䝍䠅䜰䜽䝸䝺 䞊䝖ᶞ⬡䜢ᇶᮦ䛸䛧䛶⏝䛔䜛䛣䛸䛷䠈ᶞ⬡ෆ㒊䛾䜰䝹䝭䝘๓㥑య䛾ᾐ㏱⌧㇟䜢ᢚไ䛩䜛䛣䛸䛜ྍ⬟䛷䛒䜛䛣䛸䜢 ぢฟ䛧䛯䠊
ᮏ◊✲䛷⏝䛔䛯Ꮫ⤌ᡂ䛾␗䛺䜛ᶞ⬡䛾䝧䞊䝇 䝰䝜䝬䞊(a) BPAGDM, (b) BPAPDA,
䠄c䠅AC-10䛾Ꮫᵓ㐀ᘧ
Al2O3䜢ሁ✚ࡉࡏࡓ␗࡞ࡿᏛ⤌ᡂࡢ᩿㠃SEMീ㸬
⏝࠸ࡓ࣮࣋ࢫࣔࣀ࣐࣮ࡣ(a) BPAGDM, (b) BPAPDA
(a) ࣛࣥࢲ࣒ඹ㔜ྜయ, (b) ࣛࣥࢲ࣒ඹ㔜ྜయ࢟ࣛࣝศᏊࢆῧ ຍࡋࡓヨᩱࡢ೫ග㢧ᚤ㙾ീ
࠙◊✲άືሗ࿌ࠚ ⮬ᕫ⤌⧊㧗ศᏊᮦᩱ◊✲ศ㔝
䠄2015䠊1䡚2015䠊12䠅㻌ᩍ ᤵ㝕ෆᾈྖ
ᩍ ᤵ⸭ ᾈ
ຓ ᩍᵽཱྀ๛ᚿ
Ꮫ 㝔 ⏕㰺⸨♸ኴட ₶బ⸨ᾈ႐ᔱᐶஅ ᖹ⿱ኴ㑻
Ꮫ 㒊 Ꮫ ⏕ᑠụ ㄹᖹ㔝ගྖ
㻌
ᮏ◊✲ศ㔝䛷䛿䚸⮬ᕫ⤌⧊䝋䝣䝖䝬䝔䝸䜰䝹䛾స〇䛸ᶵ⬟䚸䛭䛾ᛂ⏝䛻䛴䛔䛶◊✲άື䜢⾜䛳䛶䛔䜛䚹 2015ᖺ䛾◊✲άື䛸䛧䛶䛿䚸௨ୗ䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䚹
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1. 䝖䝸䝤䝻䝑䜽ඹ㔜ྜయ䛜ᙧᡂ䛩䜛2㔜䜙䛫䜣ᵓ㐀䜈䛾㔠䝘䝜⢏Ꮚ䛾㑅ᢥᑟධ
䝤䝻䝑䜽ඹ㔜ྜయ䛿␗䛺䜛䝫䝸䝬䞊㙐䛜ඹ᭷⤖ྜ䛷⧅䛜䛳䛯䝫䝸䝬䞊䛷䛒䜚䚸䛭䛾䝤䝻䝑䜽ẚ⋡䜔ศᏊ㔞䛻ᚑ 䛳 䛶 䚸 ᵝ 䚻 䛺 䝭 䜽 䝻 ┦ ศ 㞳 ᵓ 㐀 䜢 ᙧ ᡂ 䛩 䜛 䚹 ᡃ 䚻 䛿 䛣 䜜 䜎 䛷 䛻 䚸3 ᡂ ศ ┤ 㙐 ≧ 䝖 䝸 䝤 䝻 䝑 䜽 ඹ 㔜 ྜ య Poly(styrene-b-isoprene-b-methyl methacrylate)(PS-b-PI-b-PMMA)䛜PMMA 䝬䝖䝸䝑䜽䝇┦୰䛻භ᪉≧䛻䝟䝑 䜻䞁䜾䛧䛯PS䝅䝸䞁䝎䞊䛜ᙧᡂ䛧䚸䛣䛾PS䝅䝸䞁䝎䞊䛾
࿘䜚䛻PI ┦䛜 2 㔜䜙䛫䜣ᵓ㐀䜢ᙧᡂ䛩䜛䛣䛸䜢ሗ࿌䛧 䛶䛔䜛䚹䛣䛾䝖䝸䝤䝻䝑䜽ඹ㔜ྜయ䛜ᙧᡂ䛩䜛䝭䜽䝻┦ศ 㞳ᵓ㐀䜢䝔䞁䝥䝺䞊䝖䛻䛧䛶㔠ᒓ䝘䝜⢏Ꮚ䜢㑅ᢥⓗ䛻 ᑟධ䛩䜛䛣䛸䛜䛷䛝䜜䜀䚸㔠ᒓ䛾㟁Ẽⓗᛶ㉁䜔☢Ẽⓗ
ᛶ㉁䜢㧗ศᏊᮦᩱ䛻ຍ䛩䜛䛣䛸䛜䛷䛝䚸᪂つ䝘䝜ᮦ
ᩱ䛾ᡂ䛻⧅䛜䜛䛿䛪䛷䛒䜛䚹ᅇ䚸ᡃ䚻䛿ศᏊ㔞䛾
␗䛺䜛PS㙐䜢䜾䝷䝣䝖䛧䛯㔠⢏Ꮚ䜢ྜᡂ䛧䚸2㔜䜙䛫䜣 ᵓ㐀䜈䛾㑅ᢥⓗᑟධ䜢ヨ䜏䛯䚹䝖䝸䝤䝻䝑䜽ඹ㔜ྜయ୰
䛾PS䝤䝻䝑䜽㙐䛾ศᏊ㔞䜘䜚䜒ศᑠ䛥䛺ศᏊ㔞䛾PS 㙐䜢䜾䝷䝣䝖䛧䛯㔠⢏Ꮚ䛿䚸PI ┦䛻ᑟධ䛥䜜䜛䛣䛸䜢ぢ ฟ䛧䛯䠄ᅗ1䠅䚹
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2. Ẽᅽ㉮ᰝ㟁Ꮚ㢧ᚤ㙾䠄ASEM䠅䜢⏝䛔䛯ඹᙺ㧗ศᏊ䛾┤᥋䝘䝜䝟䝍䞊䝙䞁䜾
㻌ᚑ᮶䛾㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾䠄SEM䠅 䛷䛿䚸㟁Ꮚ⥺䛾ῶ⾶䜢㜵䛠ᚲせ䛛䜙䚸ほᐹヨᩱ䜢┿✵୰䛻⨨䛟ᚲせ䛜䛒 䜚䚸䛭䛾䛯䜑ᾮయୗ䜔Ẽᅽ୰䛷㉳䛣䜛ከ䛟䛾≀⌮䞉Ꮫ⌧㇟䜢ほᐹ䛩䜛䛣䛸䛿㠀ᖖ䛻ᅔ㞴䛷䛒䛳䛯䚹㏆ᖺ䚸 SEM 䛾ヨᩱᐊ䜢ᨵ Ⰻ䛧 䚸 ヨᩱ䜢Ẽ ᅽୗ䛾 䜎䜎 ほ ᐹྍ⬟䛺 Ẽᅽ㉮ᰝ ᆺ㟁 Ꮚ㢧ᚤ㙾䠄Atmospheric Scanning Electron Microscope䠖ASEM䠅䛜㛤Ⓨ䛥䜜䚸ᾮయ୰䛻䛚䛡䜛⣽⬊䛾ほᐹ䜔⤖ᬗᡂ㛗㐣⛬䛾┤᥋ほᐹ
䛾ሗ࿌䛜䛺䛥䜜䛶䛔䜛䚹ᡃ䚻䛿䚸ᾮయ䛻㟁Ꮚ⥺䜢↷ᑕ䛩䜛䛣䛸䛜ྍ⬟䛸䛔䛖ASEM䛾Ⅼ䛻╔┠䛧䚸ほᐹ䛾 䛯䜑䛷䛿䛺䛟㟁Ꮚ⥺䜢Ꮫᛂ䛻⏝䛔䜛䛣䛸䜢⪃䛘䛯䚹ᅇ䚸䛔䛟䛴䛛䛾ඹᙺ㧗ศᏊ䛾ᾮయ䝰䝜䝬䞊䛻㟁Ꮚ⥺
↷ᑕ䜢⾜䛳䛯䛸䛣䜝䚸㟁Ꮚ⥺↷ᑕ㡿ᇦ䛻ᵓ㐀య䛜ᙧᡂ䛩䜛䛣䛸䜢Ⓨぢ䛧䛯䚹ᅗ2(b)䛻3-hexylthiophene䛻㟁Ꮚ
⥺䜢 1 Ⅼ↷ᑕ䛧䚸↷ᑕ⨨䜢ኚ䛘䛶⧞䜚㏉䛧㟁Ꮚ⥺↷ᑕ䜢⾜䛔ᙧᡂ䛧䛯ᵓ㐀య䛾 SEM ീ䜢♧䛩䚹┤ᚄ 130
nm䚸㧗䛥270 nm䛾䝢䝷䞊ᵓ㐀య䛜ᙧᡂ䛧䛶䛔䜛䛣䛸䛜㟁Ꮚ⥺↷ᑕ⨨䛻ᙧᡂ䛧䛶䛔䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䚹
ᅗ䠍䠊PS-b-PI-b-PMMA䛜ᙧᡂ䛩䜛2㔜䜙䛫䜣ᵓ㐀䠄PI┦䠅 䛻 PS 㙐䜢䜾䝷䝣䝖䛧䛯㔠⢏Ꮚ䜢ᑟධ䛩䜛䛣䛸䛻ᡂຌ䛧䛯䚹㔠
⢏Ꮚ䛾⾲㠃䛻䜾䝷䝣䝖䛩䜛 PS 㙐䛾ศᏊ㔞䜢ኚ䛥䛫䜛䛣䛸 䛷䚸PS┦䚸PI┦䛾䛹䛱䜙䛾┦䛻㑅ᢥⓗ䛻ᑟධ䛥䜜䜛䛛䜢᫂䜙 䛛䛻䛧䛯䚹ྑᅗ䠖㟁Ꮚ⥺䝖䝰䜾䝷䝣䜱䞊ほᐹ䛻䜘䛳䛶ᚓ䜙䜜䛯 2㔜䜙䛫䜣ᵓ㐀䠄PI┦䠅䛸㔠䝘䝜⢏Ꮚ⢏Ꮚ䛾3ḟඖ
㢧ᚤFT-IR ᐃ䜘䜚䚸㟁Ꮚ⥺↷ᑕ䛻䜘䜚ᙧᡂ䛧䛯ᵓ㐀≀䛿Poly(3-hexylthiophene)䛷䛒䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䛣 䛸䛛䜙䚸ᮏᡭἲ䛿䛟᪂䛧䛔ඹᙺ㧗ศᏊ䛾┤᥋䝘䝜䝟䝍䞊䝙䞁䜾䛸䛧䛶᭷⏝䛷䛒䜛䛸⪃䛘䜙䜜䜛䚹
㻌
3. 㔠ᒓ䝣䝍䝻䝅䜰䝙䞁䝘䝜⤖ᬗ䛾One-potྜᡂ
㻌㔠ᒓ䝣䝍䝻䝅䜰䝙䞁䠄PC䚸 ᅗ 3(a)䠅䛿Ꮫⓗ䞉⇕ⓗᏳᐃᛶ䛾㧗䛔㢦ᩱ䛸䛧䛶ྂ䛟䛛䜙⏝䛔䜙䜜䛶䛝䛯䚹㏆ᖺ䛿䚸 Ⰽ⣲ቑឤᆺኴ㝧㟁ụ䜔㠀⥺ᙧගᏛᮦᩱ➼䛾ᶵ⬟ᛶᮦᩱ䛻䜒⏝䛔䜙䜜䛶䛔䜛䛜䚸㔠ᒓPC䜢䝘䝜䝃䜲䝈䛾⤖ᬗ 䛻䛩䜛䛣䛸䛻䜘䛳䛶䚸䛭䛾ගᏛ䞉㟁Ẽⓗ≉ᛶ䛜㠀ᖖ䛻ྥୖ
䛩䜛䛣䛸䛛䜙ὀ┠䛥䜜䛶䛔䜛䚹ᚑ᮶䚸㔠ᒓPC䛿Wylerἲ䜔 䝣䝍䝻䝙䝖䝸䝹ἲ䜢⏝䛔䛶స〇䛥䜜䛶䛔䜛䛜䚸䛣䜜䜎䛷䛻㔠 ᒓ PC 䝘䝜⤖ᬗ䜢๓㥑య⁐ᾮ䛛䜙┤᥋ྜᡂ䛩䜛ᡭἲ䛿ሗ
࿌䛥䜜䛶䛔䛺䛔䚹ᡃ䚻䛿䚸䝘䝜䝭䝉䝹୰䛷㔠ᒓ PC 䛾ྜᡂ
ᛂ䜢⾜䛖䛣䛸䛻䜘䛳䛶䚸㔠ᒓ PC 䝘䝜⤖ᬗ䜢๓㥑య䛛䜙┤
᥋స〇䛩䜛䛣䛸䛻ᡂຌ䛧䛯䚹స〇䛧䛯㖡 PC 䛾㏱㐣ᆺ㟁Ꮚ 㢧ᚤ㙾䠄TEM䠅ീ䜘䜚┤ᚄ100 nm⛬ᗘ䛾⌫≧⢏Ꮚ䛜ከᩘ
ほᐹ䛥䜜䛯䚹ᅗ 3(c)♧ࡍࡼ࠺ࠊ㖡PC ศᩓᾮࡣ㏱᫂
࡞㟷Ⰽࢆ࿊ࡋ࡚࠾ࡾࠊ㖡PCศᩓᾮࡢ⣸እྍど྾ࢫ࣌
ࢡࢺࣝ࠾ࡼࡧ㏱㐣ࢫ࣌ࢡࢺࣝ㸦ᅗ 3(d)㸧ࡽࠊ㏱㐣⋡
ࡢ᭱ᑠ್ࡣ3.17% (607 nm)ࠊ್᭱ࡣ80.2% (490 nm)
࡛࠶ࡾࠊࡑࡢᕪࡣ77%࡛࠶ࡗࡓࠋࡇࢀࡼࡾࠊCuPCࢆࢼ
ࣀ⢏Ꮚࡍࡿࡇ࡛ᩓගࢆᢚไ࡛ࡁ࡚࠸ࡿࡇࡀ♧
ࡉࢀࡓࠋ
ᅗ2䠊(a) Ẽᅽ㉮ᰝ㟁Ꮚ㢧ᚤ㙾䜢⏝䛔䛯ඹᙺ㧗ศᏊ䛾┤᥋䝘䝜䝟䝍䞊䝙䞁䜾䛾ᶍᘧᅗ䚹(b) ᐊ 䚸Ẽᅽୗ䛷3-hexylthiophene
䛻㟁Ꮚ⥺↷ᑕ䛩䜛䛣䛸䛻䜘䛳䛶ᙧᡂ䛥䜜䛯䝢䝷䞊ᵓ㐀య䛾SEMീ䠄Top view & Side view䠅䚹
ᅗ3䠊(a) 㔠ᒓPC䛾Ꮫᵓ㐀ᘧ䚹(b) 㖡PC䛾TEM
ീ䚹㖡 PC ศᩓᾮ䛾(c)┿䛚䜘䜃(d)྾䞉㏱㐣⋡䝇 䝨䜽䝖䝹䚹
࠙◊✲άືሗ࿌ࠚ ↓ᶵᅛయᮦᩱྜᡂ◊✲ศ㔝
䠄2015䠊1䡚2015䠊12䠅㻌 㻌ᩍ ᤵ ᒣ᰿ ஂ
ᩍ ᤵ ᒣ⏣ 㧗ᗈ
ຓ ᩍ ᳃ᡞ ᙪ Ẹ㛫➼ඹྠ◊✲ဨ ྜྷᮧ ᩥᏕ
Ꮫ 㝔 ⏕ ኳ㔝 సⳢ㔝 㞞༤ୗ⏣ ᑗྖ
┦ሙ㧗ᖹⰪ㔝ᑗኴΏ㑓ᆂ
ᮏ◊✲ศ㔝䛷䛿䠈㔠ᒓ⼥ᾮᛂሙ䜢⏝䛧䛯㠀㓟≀⣔䝉䝷䝭䝑䜽䝇䜔㔠ᒓ㛫ྜ≀䛾ྜᡂ䛚䜘䜃ᅛ┦
ᛂἲ䛻䜘䜛᪂つከඖ⣔↓ᶵྜ≀䛾᥈⣴䛸䠈䛭䜜䜙䛾ᵓ㐀ゎᯒ䜔≉ᛶホ౯䛻䛴䛔䛶◊✲άື䜢⾜䛳䛶䛔 䜛䠊2015ᖺ䛾◊✲άື䛸䛧䛶䛿௨ୗ䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䠊
1.㻌䝖䞁䝛䝹ᵓ㐀䜢᭷䛩䜛Na2+xGa2+xSní[䛾⤖ᬗᵓ㐀䛸⇕㟁≉ᛶ
⇕㟁ኚᮦᩱ䛾ೃ⿵≀㉁⩌䛸䛧䛶䠈䛛䛤≧䛾㦵᱁ᵓ㐀䜢ᣢ䛱䠈䛭䛾✵㝽ෆ䛻㦵᱁ᵓᡂཎᏊ䛸ᙅ䛟⤖ྜ䛧䛯 ཎᏊ䜢ྵ᭷䛩䜛䜽䝷䝇䝺䞊䝖ྜ≀䛜┒䜣䛻◊✲䛥䜜䛶䛔䜛䠊㦵᱁ᵓ㐀䛾✵㝽䛻⨨䛩䜛ཎᏊ䛾␗ᖖ䛻䛝 䛺⇕ື䠄䝷䝑䝖䝸䞁䜾䠅䛻䜘䜛䝣䜷䝜䞁ᩓ䛷䜺䝷䝇䛸ྠ⛬ᗘ䛾ప⇕ఏᑟ⋡䛜䜒䛯䜙䛥䜜䜛୍᪉䠈㟁Ꮚ䛾⛣ືᗘ 䛿䛣䜜䛻䜘䜚䛝䛺ᙳ㡪䜢ཷ䛡䛺䛔䛯䜑䠈㧗䛔⇕㟁≉ᛶ䛜Ⓨ⌧䛩䜛䛸⪃䛘䜙䜜䛶䛔䜛 1) 䠊ᮏ◊✲䛷䛿䠈ᵓ㐀ෆ 䛻䝖䞁䝛䝹≧䛾✵㝽䜢᭷䛧䛯䝆䞁䝖䝹ྜ≀ NaGaSn2䛻╔┠䛧 2)䠈䛭䛾ྜᡂ䛸⇕㟁≉ᛶ䛾ホ౯䜢⾜䛳䛯䠊䛣䛾
ྜ≀䛿䠈㦵᱁ᵓ㐀ෆ䛾䝖䞁䝛䝹✵㛫䛻 Na ཎᏊ䛜䛝䛺䝕䜱䝇䜸䞊䝎䞊䜢క䛳䛶㓄⨨䛧䛶䛚䜚䠈䜽䝷䝇䝺䞊䝖
ྜ≀䛸ྠᵝ䛻ప䛔⇕ఏᑟ⋡䜢᭷䛩䜛䛣䛸䛜ᮇᚅ䛥䜜䛯䠊䛣䛾ྜ≀䛾ከ⤖ᬗ↝⤖య䛚䜘䜃༢⤖ᬗヨᩱ䛾 స〇䜢ヨ䜏䛯䛸䛣䜝䠈ᚓ䜙䜜䛯ヨᩱ䛿භ᪉ᬗ⣔㻌(✵㛫⩌ P6122, a = 6.3471–6.3150 Å, c = 6.1341–6.1718 Å) 䛾Na2+xGa2+xSní[,í0.04 < x < 0.30 䛸⾲䛥䜜䜛ྜ≀䛷䛒䜛䛣䛸䛜X⥺ᅇᢡ䜘䜚᫂䜙䛛䛻䛺䛳䛯䠊䛣䜜䜙䛾⤖ᯝ 䛿䠈䛣䜜䜎䛷䛾ሗ࿌(NaGaSn2, ᩳ᪉ᬗ⣔, ✵㛫⩌C2221, a = 6.309(3) Å, b = 10.986(4) Å, c = 6.162(2) Å)2)䛸 䛿␗䛺䛳䛶䛔䛯䠊Na2+xGa2+xSní[䛾⤖ᬗᵓ㐀䛻䛿䠈Ga䛸Sn䛾ΰྜ䝃䜲䝖䛷ᵓᡂ䛥䜜䜛୕ḟඖⓗ䛺⼺᪕㦵᱁ᵓ 㐀䛾୰䛻c㍈᪉ྥ䛻ఙ䜃䜛䝖䞁䝛䝹✵㛫䛜Ꮡᅾ䛧䠈䛭䛾୰䛻༨᭷⋡䛜⣙1/3䛾Na䝃䜲䝖䛜⼺᪕≧䛻㓄⨨䛧䛶 䛔䜛(ᅗ1)䠊
Na2+xGa2+xSní[(x = 0.0, 0.19)䛾↝⤖యヨᩱ䜢䛭䜜䛮䜜6ಶస〇䛧䠈䛭䜜䜙䛾295 K䛻䛚䛡䜛⇕ఏᑟ⋡䜢 䝩䝑䝖䝕䜱䝇䜽ἲ䛻䛶 ᐃ䛧䛯䛸䛣䜝䠈x = 0.19 䛾䛒䜛ヨᩱ䠄↝⤖ᐦᗘ
73 %䠅䛾⇕ఏᑟ⋡䛿0.56 Wmí1Kí1䛸䜺䝷䝇୪䛾ప䛔್䜢♧䛧䛯䠊䛣䛾 ヨᩱ䛾䝊䞊䝧䝑䜽ಀᩘ䛚䜘䜃㟁Ẽఏᑟ⋡䛿䠈䛭䜜䛮䜜í209 µVKí1䛚 䜘䜃4.3×104Smí1䛷䛒䜚䠈䛣䜜䜙䛾 ᐃ್䜘䜚ồ䜑䜙䜜䜛ZT䛾್䛿0.98 䛷䛒䛳䛯䠊䛣䛾್䛿䠈ᐇ⏝䛥䜜䛶䛔䜛 Bi2Te3 ⣔⇕㟁ኚᮦᩱ䛾 ZT 䛾್䛻༉ᩛ䛩䜛䠊Na2+xGa2+xSní[䛸ྠᵝ䛺䝖䞁䝛䝹ᵓ㐀䜢᭷䛩䜛ྠᆺ䞉
ྠ㢮ᵓ㐀䛾ྜ≀䜒䠈㧗䛔⇕㟁≉ᛶ䜢♧䛩ྍ⬟ᛶ䛜䛒䜚䠈ᚋ䠈⇕㟁
ኚᮦᩱ䛾᪂䛧䛔ೃ⿵≀㉁⩌䛸䛧䛶䛾◊✲䛾ᒎ㛤䛜ᮇᚅ䛥䜜䜛䠊 ᅗ1. 䝖䞁䝛䝹ᵓ㐀䜢᭷䛩䜛 Na2+xGa2+xSn4íx(x= 0.24)䛾⤖ᬗᵓ㐀.
ཧ⪃ᩥ⊩㸸1) G. A. Slack, in CRC Handbook of Thermoelectrics, CRC, Boca Raton, FL, (1995), 40. 2) J. T. Vaughey and J.
D. Corbett, Am. Chem. Soc. 118(1996) 12098.
2.㻌Na-Sn䝣䝷䝑䜽䝇䜢⏝䛔䛯Na-Si䜽䝷䝇䝺䞊䝖༢⤖ᬗ䛾స〇㻌
SiཎᏊ䛜䜹䝂≧䛻⤖ྜ䛧䠈䛭䛾䜹䝂䛾୰䛻Na䜢ෆໟ䛧䛯ྜ≀䛿䠈䛂Na-Si䜽䝷䝇䝺䞊䝖䛃䛸䜀䜜䠈䛣䜜䜎䛷 䛻Na8Si46䠄Iᆺ䠅䛸NaxSi136䠄[䠈IIᆺ䠅䛜ሗ࿌䛥䜜䛶䛔䜛1, 2)䠊䛣䜜䜙䛾ྜ≀䛿䠈䝣䝷䞊䝺䞁䛸㢮ఝ䛾✵
㛫ᵓ㐀䜢᭷䛩䜛䛣䛸䛛䜙䠈ኴ㝧㟁ụ䜔⇕㟁ኚᮦᩱ䠈≀㉁㈓ⶶ䛺䛹ᵝ䚻䛺ศ㔝䛷䛾ᛂ⏝䛜ᮇᚅ䛥䜜䛶䛔䜛䠊 ᚑ᮶䠈Na-Si䜽䝷䝇䝺䞊䝖䛿Na4Si4ྜ≀䛾⇕ศゎ䛻䜘䛳䛶స〇䛥䜜䜛䛯䜑䠈⤖ᬗᡂ㛗䛜㞴䛧䛟䠈⢊ᮎ≧ヨᩱ䛷 䛾䜏ᚓ䜙䜜䛶䛔䜛䠊ᮏ◊✲䛷䛿䠊Na-Sn⼥ᾮ䜢䝣䝷䝑䜽䝇䛸䛧䛶⏝䛔䜛䛣䛸䛻䜘䜚䠈Na-Si 䜽䝷䝇䝺䞊䝖䛾༢⤖ᬗ⫱
ᡂ䜢ヨ䜏䛯䠊
Na䠖Si䠖Sn = 10䠖2䠖1䛾ฟⓎཎᩱ䜢⣙104 Pa䛾ῶᅽୗ䠈723 K 䛷ຍ⇕䛧䠈Na䜢Ⓨ䛥䛫䛯䛸䛣䜝䠈ᅗ2䛻♧䛩䜘䛖䛺ᩘⓒPm ~ 1.5 mm䛾⢏≧༢⤖ᬗ䛜ᚓ䜙䜜䛯䠊༢⤖ᬗX⥺ᵓ㐀ゎᯒ䛾⤖ᯝ䠄R್ 1.6%䠅䠈ᚓ䜙䜜䛯༢⤖ᬗ䛿❧᪉ᬗ⣔䠈✵㛫⩌Pm3തm䠄No. 233䠅䠈᱁ Ꮚᐃᩘa = 1.02023䠄3䠅nm䛾Na8Si46䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䠊ᚓ䜙䜜 䛯ヨᩱ୰䛻䛿䠄110䠅㠃䛜Ⓨ㐩䛧䛯༢⤖ᬗ䛜ከ䛟ほᐹ䛥䜜䛯䠊䛥䜙 䛻䠈ᚓ䜙䜜䛯༢⤖ᬗヨᩱ䜢⢊○䛧䠈⢊ᮎX⥺ᅇᢡ䝟䝍䞊䞁䜢 ᐃ 䛧䛯䛸䛣䜝䠈༢⤖ᬗ䛿䛩䜉䛶Na8Si46䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䠊ྠᵝ䛾 ฟⓎཎᩱ䜢773 K䛷ຍ⇕䛧䛯䛸䛣䜝䠈䛝䛥ᩘ༑Pm ~ 500 Pm⛬ ᗘ䛾Na8Si46䜔Na24Si136䛚䜘䜃Si⤖ᬗ䛾จ㞟య䛜⏕ᡂ䛧䛯䠊823
K䛾ຍ⇕䛷䛿䠈䛝䛥ᩘ༑Pm ~ 300 Pm⛬ᗘ䛾Si⤖ᬗ䛾จ㞟య䛜ᚓ䜙䜜䛯䠊ᮏ䝥䝻䝉䝇䛷䛿Na-Sn⼥ᾮ䛻 Na4Si4䛜⁐ゎ䛧䛶Na-Si-Sn⼥ᾮ䛸䛺䜚䠈䛣䛾⼥ᾮ䛛䜙Na䛜Ⓨ䛩䜛䛣䛸䛷Na8Si46䜽䝷䝇䝺䞊䝖䛜⤖ᬗᡂ㛗䛧䛯 䛸⪃䛘䜙䜜䜛䠊ฟⓎཎᩱ䛾⤌ᡂẚ䜔ཎᩱ䛾ᢞධ㔞䠈ຍ⇕㛫䜢ไᚚ䛩䜛䛣䛸䛷䠈䛥䜙䛻䛝䛺༢⤖ᬗ䛜ᚓ䜙䜜 䜛䛣䛸䛜ᮇᚅ䛥䜜䜛䠊
ཧ⪃ᩥ⊩䠖1) C. Cros, M. Pouchard, P. Hagenmuller,Compt. Rend. 260(1965) 4764. 2) J. S. Kasper, P. Hagenmuller, M.
Pouchard, C. Cros,Science 150(1965) 1723.
3. Ba-La-Si⣔䛚䜘䜃Ba-B-Si-N⣔᪂つྜ≀䛾ྜᡂ䛸⤖ᬗᵓ㐀
Ba䇵Si⣔䛷䛿ᖖᅽ┦䛾BaSi䜔BaSi2䜢䛿䛨䜑㧗ᅽ┦䜢ྵ䜐✀䚻䛾⤌ᡂ䛾ྜ≀䛜▱䜙䜜䛶䛚䜚䠈BaSi2䛿 ኴ㝧㟁ụᮦᩱ䜔㉸㟁ᑟᮦᩱ䛸䛧䛶◊✲䛜⾜䜟䜜䛶䛔䜛䠊䜎䛯䠈La䇵Si⣔䛷䛿LaSi䜔LaSi2䛺䛹䛾ྜ≀䛜ሗ
࿌䛥䜜䛶䛔䜛䠊ᮏ◊✲䛷䛿䠈BN 䝹䝒䝪䜢⏝䛔䛶 Ba䇵La䇵Si ⣔䛻䛚䛡䜛᪂つྜ≀䛾᥈⣴䜢⾜䛳䛯䛸䛣䜝䠈 BaLaSi2䛸Ba5LaSi6䛻ຍ䛘䠈Ba䇵B䇵Si䇵N⣔䛷Ba26B12Si5N27䛜᪂䛯䛻ぢ䛔䛰䛥䜜䛯䠊Ar㞺ᅖẼୗ䛷 Ba䠈La䠈 Si䠈Na䜢ᡤᐃ䛾ྜ䛷BN䝹䝒䝪䛻ධ䜜䠈䝇䝔䞁䝺䝇㗰〇(SUS)⟶୰䛻ᑒධᚋ䠈1173 K䛷ຍ⇕䛧䛯䛸䛣䜝䠈ヨ
ᩱ୰䛻㯮Ⰽ䛷ගἑ䜢᭷䛩䜛BaLaSi2䛾㯮Ⰽᰕ≧༢⤖ᬗ䜔Ba5LaSi6䛾㖟Ⰽᰕ≧༢⤖ᬗ䛜䠈䜎䛯BN䝹䝒䝪ቨ
ୖ䛻Ba26B12Si5N27㯮Ⰽᯈ≧༢⤖ᬗ䛜⏕ᡂ䛧䛯䠊
⤖ᬗᵓ㐀ゎᯒ䛾⤖ᯝ䠈BaLaSi2䛿ᩳ᪉ᬗ⣔䠄a = 4.6414(2) Å䠈b = 14.8851(7) Å䠈c = 6.7519(5) Å䠈✵㛫⩌
Cmcm)䛷䠈⤖ᬗෆ䛻䛿SiཎᏊ䛾䝖䝷䞁䝇䞉䝅䝇1ḟඖ㙐䛜ᙧᡂ䛥䜜䛶䛔䜛䛣䛸䛜♧䛥䜜䛯(ᅗ3ᕥ)䠊Ba5LaSi6䛿
ᅗ2. Na-Sn䝣䝷䝑䜽䝇䜢⏝䛔䛶స〇䛥䜜䛯
Na8Si46ࢡࣛࢫ࣮ࣞࢺ༢⤖ᬗࡢ┿㸬 1 mm