࠙◊✲άືሗ࿌ࠚ ᭷ᶵࣁࣈࣜࢵࢻࢼࣀ⤖ᬗᮦᩱ◊✲ศ㔝
㸦2019.1㹼2019.12㸧ᩍ ᤵ㻌 㻦㻌 ཬᕝⱥಇ㻌
ຓ ᩍ 㻦 ᑠ㔝ᑎ ᜏಙ
䝙䜰䛾ගᦆኻ㜈್䛿100 GW cm-2䛸㧗䛟䚸䛭䛾ගᏛⓗရ㉁䛿ᴟ䜑䛶㧗䛔䚹䝋䞊䝥䝣䝸䞊ங㔜ྜ䛷ྜᡂ䛧䛯䝃 䜲䝈ไᚚ䛥䜜䛯䝫䝸䝇䝏䝺䞁NPs䠄PS NPs䠅䜢㗪ᆺ䛸䛧䛶⏝䛔䚸䝆䝹䝁䝙䜰๓㥑య䠄ZrOCl28H2O䛾EtOH⁐ᾮ䠅䛸 ΰྜ䛧䛶↝⤖䠄350qC for 4 hrs, 3 K min-1䛷᪼ , 580qC for 6 hrs䠅䛥䛫䚸䝆䝹䝁䝙䜰䛾䝌䝹䠉䝀䝹⏕ᡂ䛸䛸䜒䛻䚸
⇕ศゎ䛻䜘䜛PS NPs䛾㝖ཤ䜢⾜䛳䛯䚹ᅗ.3䛿㗪ᆺ䛸䛧䛶⏝䛔䛯PS NPs䛸ᑐᛂ䛩䜛ከᏍ㉁䝆䝹䝁䝙䜰䛾SEMീ
䛷䛒䜛䚹⺯ගⰍ⣲䠄RhB䠅䛾EG⁐ᾮ䜢ሸ䛧䚸䛭䛾ᨺฟග䝇䝨䜽䝖䝹䠄ᅗ.4䠅䜢 ᐃ䛧䛯䠄Nd: YAG laser (O= 532 nm (SH), 䝟䝹䝇ᖜ䠖6 nm, ⧞䜚㏉䛧ᩘ䠖10 Hz), ศගჾ䠖Ocean Photonics, USB2000䠅䚹ບ㉳ගᙉᗘ䛾ቑຍ䠄2 MW cm-2ࠥ 26 MW cm-2䠅䛸䛸䜒䛻䚸ᨺ
ฟග䝇䝨䜽䝖䝹䛾್༙ᖜ䛿140 meV䛛䜙 40 meV䜈ᛴῶ䛧䛯䚹䛥䜙䛻䚸䝇䝨䜽䝖䝹 ᙉᗘ䛸ບ㉳ගᙉᗘ䛾┦㛵䛛䜙Ⓨ㜈್
䜢 ồ 䜑 䛯 ⤖ ᯝ 䚸4.0 MW cm-2 ࠥ 5.6 MW cm-2䛸䛺䜚䚸䝆䝹䝁䝙䜰ᚤ⢏Ꮚ⣔䝷 䞁 䝎 䝮 ፹㉁䝺䞊䝄䞊䛾Ⓨ 㜈್䠄6.8 MW cm-2: J. Opt. Am. B, 31, 2363 (2014)䠅 䜘䜚᫂䜙䛛䛺పῶ䛻ᡂຌ䛧䛯䚹 䜎䛯䚸Ⓨ㜈್䛿ከᏍ㉁䝆䝹䝁䝙䜰䛾
⣽Ꮝᚄ䛚䜘䜃ሸ㔞䛻౫Ꮡ䛩䜛䛣䛸䛜
᫂䜙䛛䛸䛺䛳䛯䚹
㟁Ⲵ⛣ື㘒యࢼࣀ⤖ᬗࡢ㟁Ꮚ≀ᛶ࠾ࡅࡿࢻ࣮ࣆࣥࢢຠᯝ
㟁Ꮚ౪య䛸㟁Ꮚཷᐜయ㛫䛾㟁Ⲵ⛣ື䜢క䛖㘒య䚸䛩䛺䜟䛱㟁Ⲵ⛣ື㘒య䛿䛭䛾⤌ᡂ✀䛾✀㢮䛸⤌ᡂẚ䚸 㟁Ⲵ⛣ື㔞䠄J䠅䛻ᙉ䛟౫Ꮡ䛧䛯⯆῝䛔ග䞉㟁Ꮚ≀ᛶ䜢♧䛩䚹㏻ᖖ䛾䝞䝹䜽⤖ᬗ≧ែ䛷䛿䚸㟁Ⲵศ㞳≧
ែ䠄J= 1䠅䛾ᑟయ䠄Mott⤯⦕య䠅䛷䛒䜛䚹
䛣䛣䛷䛿䚸㑏ඖඹỿἲ䜢☜❧䛧䚸䝃䜲䝈䛚䜘䜃⤌ᡂẚ䛜ไᚚ䛥䜜䛯Cu-TCNQ䝘䝜⤖ᬗ䠄NCs䠅䛻ὀ┠䛧䚸᪂ つ䛺≀ᛶⓎ⌧䛸ᵓ㐀┦㛵䛾ゎ᫂䜢┠ᣦ䛧䛯䚹ᨩᢾ䛧䛶䛔䜛TCNQ䛾MeOH⁐ᾮ䛻㑏ඖ䠄NaBH4䠅䜢ຍ䛘䚸 䛥䜙䛻◲㓟㖡䠄CuSO45H2O䠅䛾MeOH⁐ᾮ䜢ୗ䛧䛯䚹Cu2+䛿Cu+䛻䚸TCNQ䛿䝷䝆䜹䝹䜰䝙䜸䞁䠄TCNQ䞉-䠅 䛻㑏ඖ䛥䜜䚸㘒యᙧᡂ䛸䛸䜒䛻⁐䚸䝘䝜⤖ᬗ䛜㐍⾜䛩䜛䚹䛣䛣䛷䚸䝘䝜⤖ᬗ㐣⛬䛻䛚䛡䜛㏿ᗘㄽⓗ䛺ຠ
ᯝ䛻䜘䜚䚸㐣䛾Cu+䛜ྲྀ䜚㎸䜎䜜䜛䠄Doped Cu-TCNQ NCs䠅䚹Cu+䛾㐣㔞䛿ඖ⣲ศᯒ䛻䜘䜚ホ౯䛥䜜䛯䚹 Doped Cu-TCNQ NCs䛾SEMീ䜢ᅗ.5䛻♧䛩䚹ᛂ ᗘ䛾ୖ᪼䛸䛸䜒䛻䚸ᙧ≧䛿▴ᙧ≧䛛䜙䝻䝑䝗≧䛻ኚ䛧䚸 㛗㍈᪉ྥ䛾䝃䜲䝈䜒ቑຍ䛧䛯䚹䛥䜙䛻䚸⤌ᡂẚ䜒1.4䜎䛷ୖ᪼䛧䛯䚹ᛂ ᗘ䛾௦䜟䜚䛻䚸◲㓟㖡䛾⃰ᗘ䜢㧗䜑䜛 䛸⤌ᡂẚ䛿1.7 ࠥ 1.9⛬ᗘ䜎䛷ኚ䛩䜛䛣䛸䜒☜ㄆ䛥䜜䛯䚹䛧䛛䛧䛺䛜䜙䚸⤖ᬗ᱁Ꮚᵓ㐀䛿䛔䛪䜜䛾⤌ᡂẚ䛷䛒 䛳䛶䜒ᑟ㟁┦䛷䛒䜛Phase I䛻ಖᣢ䛥䜜䛶䛔䜛䛣䛸䛜⢊ᮎἲXRD ᐃ䛛䜙☜ㄆ䛥䜜䛯䚹䜎䛯䚸Doped Cu-TCNQ NCs䛾䝷䝬䞁䝇䝨䜽䝖䝹䛛䜙䚸TCNQ䝷䝆䜹䝹䜰䝙䜸䞁䛸䛸䜒䛻䝗䞊䝥䛥䜜䛯㐣䛾Cu+䛸䛾㟁Ⲵᖹ⾮䜢ྲྀ䜛䛯䜑䛻䚸 TCNQ䝆䜰䝙䜸䞁䛜ᑟ㟁䝟䝇䛷
䛒䜛TCNQ✚ᒙ䜹䝷䝮ෆ䛻ඹᏑ 䛧䛶䛔䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䚹 䛥䜙䛻䚸ගᾘኻ䝇䝨䜽䝖䝹䛻䛿 TCNQ䝷䝆䜹䝹䜰䝙䜸䞁䛻ᖐᒓ 䛥䜜䜛྾䝢䞊䜽䠄O = 381 nm 䛚䜘䜃700 nm䠅䛸㏆㉥እᇦ䛻 TCNQ䝆䜰䝙䜸䞁䛸TCNQ䝷䝆 䜹䝹䜰䝙䜸䞁㛫䛾䝞䞁䝗ෆ㑄⛣
ᅗ.3 PS NPs䛸ከᏍ㉁䝆䝹 䝁䝙䜰䛾SEMീ
ᅗ.4 ᨺฟග䝇䝨䜽䝖䝹䛾ບ㉳ගᙉᗘ ౫Ꮡᛶ
ᅗ.5 㑏ඖඹỿἲ䛷స〇䛥䜜䛯Doped Cu-TCNQ NCs䛾SEMീ䠖ᛂ ᗘ䚸㛗㍈᪉
ྥ䝃䜲䝈䚸⤌ᡂẚ䠄Cu䠖TCNQ䛾ẚ䠅䛾౫Ꮡᛶ
䛻┦ᙜ䛩䜛ᖜᗈ䛔྾䝢䞊䜽䠄O= 1700 nm ࠥ 2500 nm䠅䛜ฟ⌧䛧 䛯䚹䛣䛾㏆㉥እᇦ䛾྾䝢䞊䜽䛿㛗㍈᪉ྥ䝃䜲䝈䛾ቑຍ䛸䛸䜒䛻㛗 Ἴ㛗䝅䝣䝖䛧䛯䚹୍᪉䚸Cu-TCNQ䝞䝹䜽⤖ᬗ䛸ẚ㍑䛧䛶䚸Doped Cu-TCNQ NCs䛾I-V≉ᛶ䠄ᤲᘬ㏿ᗘ䠖1.2 V s-1䠅䛻ከẁ㝵䛾䝇䜲䝑䝏 䞁䜾ᣲື䠄పᢠ≧ែ LRS I 䠙䠚 㧗ᢠ≧ែ HRS 䠙䠚 ప
ᢠ≧ែ LRS II䠅䛜ほ 䛥䜜䛯䠄ᅗ.6䠅䚹䛩䛺䜟䛱䚸㟁ሙ༳ຍ䛻䜘䜛
ᢠྍኚᆺ䝇䜲䝑䝏䞁䜾⣲Ꮚ䛸䛧䛶ᶵ⬟䛩䜛䛣䛸䛜♧䛥䜜䛯䚹ᐇ㝿䛾
Ⓨ⌧ᶵᵓ䛸䛧䛶䚸LRS I䛷䛿TCNQ䝆䜰䝙䜸䞁䛾୍㟁Ꮚ䛜䜻䝱䝸䜰䛸 䛧䛶䜛⯙䛖䚹㟁ሙᤲᘬ䛻క䛔㏫㟁Ꮚ⛣ື䛜⏕䛨䛶䚸TCNQ✚ᒙ䜹 䝷䝮䛜TCNQ䝷䝆䜹䝹䜰䝙䜸䞁䛷‶䛥䜜䛯≧ែ䛜HRS䛻┦ᙜ䛩䜛䚹 䛥䜙䛻䚸㟁ሙᤲᘬ䛷Cu+䛾㑏ඖ䛜㐍⾜䛩䜛䛸ྠ䛻୰ᛶ䛾TCNQ0 䛜୍㒊⏕䛨䛶䚸TCNQ䝷䝆䜹䝹䜰䝙䜸䞁䛾୍㟁Ꮚ䛜䜻䝱䝸䜰䛸䛧䛶
䜛⯙䛖䚹䛣䜜䛜LRS II䛷䛒䜛䛸ゎ㔘䛥䜜䛯䚹
ࢳࢱࢽѸ ᭷ᶵⰍ⣲ࣁࣈࣜࢵࢻࢼࣀᵓ㐀య࠾ࡅࡿⓎගቑᙉ
㔠ᒓNPs䛾LSPR䛻䜘䜛ቑᙉຠᯝ䛸䛧䛶䚸“Excitation Enhancement”䛸”Emission Enhancement”䛜ᥦၐ䛥䜜䛶 䛚䜚䚸㔠ᒓNPs䛸⺯ගⰍ⣲䛸䛾䝝䜲䝤䝸䝑䝗䝘䝜ᵓ㐀య䛷䛿ᚋ⪅䛾ᶵᵓ䛻ᇶ䛵䛟⺯ගቑᙉ䜔㏫䛾ᾘගᶵᵓ䛾䝘 䝜ᵓ㐀┦㛵䛜ᖜᗈ䛟᳨ド䛥䜜䛶䛔䜛䚹䛧䛛䛧䛺䛜䜙䚸㔠ᒓNPs䛷䛿䛭䛾䝗䝹䞊䝕྾䛻䜘䜛ධᑕග䜶䝛䝹䜼䞊 䛾྾ᦆኻ䜢ᮏ㉁ⓗ䛻ᅇ㑊䛩䜛䛣䛸䛿ྍ⬟䛷䛒䜛䚹
䛣䛣䛷䛿䚸྾ᦆኻ䛾↓䛔㧗ᒅᢡ⋡㓟≀NPs䛾㏆᥋ሙ䛻ὀ┠䛧䛯䚹䛥䜙䛻䚸䝇䝖䞊䜽䝇䝅䝣䝖䛜㠀ᖖ䛻ᑠ䛥䛔 J-ྜయⰍ⣲䜢⏝䛔䜜䜀䚸䛭䛾྾䛚䜘䜃Ⓨග䝇䝨䜽䝖䝹䛾Ἴ㛗⨨䜢㧗ᒅᢡ⋡㓟≀NPs䛾ᩓ䝇䝨䜽䝖䝹 䛸䝏䝳䞊䝙䞁䜾䛥䛫䜛䛣䛸䛻䜘䛳䛶䠄ᅗ.7䠅䚸ບ㉳㐣⛬䛸Ⓨග㐣⛬䛾᪉䛷䛾ቑᙉຠᯝ䛜ᮇᚅ䛷䛝䜛䚹䜺䝷䝇ᇶᯈ
ୖ䛻䝏䝍䝙䜰NPs䠄nD=2.7 at 530 nm, d=250nm, ሸ㔞䠖0mgࠥ1.0mg䠅Ỉศᩓᾮ䜢䜻䝱䝇䝖䞉⇱䛥䛫䛯ᚋ䚸 TDBCⰍ⣲䛾J-ྜయỈศᩓᾮ䠄0.1 mM, 200 PL䠅䜢ᒎ㛤䞉⇱䛧䛶䚸䝝䜲䝤䝸䝑䝗䝘䝜ᵓ㐀య䠄ᅛయⷧ⭷⣔䠅䜢ᵓ
⠏䛧䛯䚹䛭䛾⤖ᯝ䚸᫂䜙䛛䛺Ⓨගቑᙉᣲື䛜☜ㄆ䛥䜜䛯䠄ᅗ.8䠅䚹TDBCⰍ⣲䛾J-ྜయ༢య䛸ẚ㍑䛧䛶䚸䝏䝍䝙 䜰NPs䛾ሸ㔞䛜0.5 mg䛾䛸䛝䚸Ⓨගᙉᗘ䛿⣙10ಸ䛾ᴟ್䜢䛘䛯䚹୍᪉䚸䝌䝹䌦䝀䝹ἲ䛷స〇䛧䛯Silica
coated 䝏䝍䝙䜰NPs䛛䜙ᵓᡂ䛥䜜䜛䝝䜲䝤䝸䝑䝗䝘䝜ᵓ㐀య䛾Ⓨගᙉᗘ䛿㏫䛻J-ྜయ༢య䛾༙ศ௨ୗ䛻పୗ
䛧䛯䚹䛣䛾䜘䛖䛺Ⓨගᙉᗘ䛾ቑᙉ䛿䚸䝏䝍䝙䜰NPs࿘ᅖ䛻ᙧᡂ䛥䜜䜛㏆᥋ሙ䛻䜘䜛ບ㉳☜⋡䛾ྥୖ䛸䚸J-ྜయ Ⰽ⣲䛾ບ㉳䜶䝛䝹䜼䞊䛜
䝏䝍䝙䜰NPs䛻⛣ື䛧䛶䚸 䛭䛾ෆ㒊䛻ືศᴟ䛜⏕
䛨䚸ᩓග䛸䛧䛶ᨺฟ䛥䜜 䜛䛯䜑䛸⪃䛘䜙䜜䜛䚹㐺ᗘ 䛺ሸ㔞䛾䛿䚸㞄᥋䛩䜛 䝏䝍䝙䜰NPs㛫䛾㏆᥋ሙ䛻 䝩䝑䝖䝇䝫䝑䝖䛜ᙧᡂ䛥䜜䛶䚸 䜘䜚ቑᙉ䛥䜜䜛䚹୍᪉䚸㐣
䛺ሸ㔞䛾ሙྜ䛿Ⓨග䛾 㛢䛨㎸䜑ຠᯝ䜔⮬ᕫ྾
䛜ᙳ㡪䛩䜛䛸ᛮ䜟䜜䜛䚹
ᅗ.6 Doped Cu-TCNQ NCs䛸Cu-TCNQ䝞 䝹䜽⤖ᬗ䛻䛚䛡䜛I-V≉ᛶ
ᅗ.8 J-ྜయTDBCⰍ⣲䛸䝏䝍䝙䜰NPs䛸 䛾䝝䜲䝤䝸䝑䝗䝘䝜ᵓ㐀య䠄ᅛయⷧ⭷⣔䠅䛻 䛚䛡䜛Ⓨගቑᙉᣲື
ᅗ.7 Mie⌮ㄽ䝅䝭䝳䝺䞊䝅䝵䞁䛻䜘䜛䝏䝍䝙 䜰NPs䛾ᩓ䝇䝨䜽䝖䝹䛸J-ྜయⰍ⣲䛛 䜙䛾྾䞉Ⓨග䝢䞊䜽䛾⨨㛵ಀ