◊ ✲ ⏕㸸Md. Mahbubul Bashar, YongJoon Im
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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2014ᖺ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
ග䛿䚸↷᫂䚸་⒪䚸㏻ಙ䚸䝕䜱䝇䝥䝺䜲䛸䛔䛳䛯ᵝ䚻䛺⏘ᴗศ㔝䛷ᛂ⏝䛥䜜䛶䛔䜛䚹䛣䜜䜙䛾ᛂ⏝䛻䛿ග䛾ఏ ᦙไᚚ䛜ྍḞ䛷䛒䜛䚹ග䛾ఏᦙไᚚ䛻䛿䚸ග䛸≀㉁䛾┦స⏝䛾⌮ゎ䛜㔜せ䛸䛺䜛䚹ᒅᢡ⋡䛾␗䛺䜛⏺㠃 䜔䝃䝤Ἴ㛗䝃䜲䝈䜢ᣢ䛴䝘䝜ᵓ㐀య୰䛻䛚䛔䛶䚸ᑕ䜔ᒅᢡ䛺䛹䛻ᇶ䛵䛟≉␗ⓗ䛺ఏᦙ⌧㇟䜢♧䛩䛣䛸䛜▱
䜙䜜䛶䛔䜛䚹䝘䝜䝺䝧䝹䛷ᵓ㐀䜢ไᚚ䛧ග䛾ఏᦙ⌧㇟䜢⌮ゎ䛩䜛䛣䛸䛷ග䛾ఏᦙไᚚ䛜ྍ⬟䛸䛺䜛䚹ᮏ◊✲䛷 䛿䚸䝃䝤Ἴ㛗㡿ᇦ䛾࿘ᮇᵓ㐀䜢ᣢ䛴୍ḟඖ㔠ᒓᅇᢡ᱁Ꮚᇶᯈୖ䜢⏝䛧䛶䚸㔠ᒓ⾲㠃䛻Ꮡᅾ䛩䜛⮬⏤㟁Ꮚ 䛾㞟ᅋື䛷䛒䜛⾲㠃䝥䝷䝈䝰䞁 (SP)䛸ㄏ㟁యⷧ⭷୰䛻ග䛜㛢䛨㎸䜑䜙䜜⭷୰䜢ᑟἼ䛩䜛ᑟἼ䝰䞊䝗 (WGM)䛾2䛴䛾≉␗ⓗ䛺ග䛾ఏᦙ⌧㇟䛻╔┠䛧䛯䚹Langmuir-Blodgett (LB)ἲ䛻䜘䜚స〇䛥䜜䛯㧗ศᏊ㉸ⷧ
⭷ (㧗ศᏊ䝘䝜䝅䞊䝖) 䜢ᇶ┙ᮦᩱ䛸䛧䛶䚸 㔠ᒓᅇᢡ᱁Ꮚᇶᯈୖ䛻䝪䝖䝮䜰䝑䝥ⓗ䛻䝘䝜ᵓ㐀䜢స〇䛩䜛䛣䛸
䛷䚸SP䛸WGM䛜ඹᏑ䛩䜛᮲௳ (ඹᏑ᮲௳)䜢Ⓨぢ䛧䛯䚹䛣䛾ඹᏑ᮲௳䜢⏝䛩䜛䛣䛸䛷Ⓨගయ䛾≉␗ⓗ䛺Ⓨ
ගᣲື䛾Ⓨ⌧䛻ᡂຌ䛧䛯䚹
㻞㻚㻌Hybrid Network Polymers Based on Multifunctional Siloxane Monomers
Hybrid inorganic-organic materials have attracted much interest in recent years because they offer considerable opportunities of developing new functional and performance materials through the combination of inorganic and organic components. Among the bottom-up approach on the development of new polymer hybrid materials, the polymerization of multi-functional organic and inorganic monomers can be performed as a way to developing hybrid organic-inorganic polymers. In this study, the synthesis of hybrid network polymers based on multifunctional siloxane monomers is described. The controlled hydrosilylation reaction of four-functional cyclosiloxane monomers with di-functional monomers provides chemically soluble and processable hybrid polymers with residual functionalities. This straightforward method also enables multifunctional hybrid polymers to crosslink taking the advantages of residual functional groups under the ambient conditions.
Crosslinking of hybrid polymers in films makes cyclosiloxane-based hybrid polymers freestanding, highly optically transparent, thermally stable, as well as mechanically robust. Hybrid network polymer films via thermal self-condensation and/or chemical crosslinking offer tremendous routes to develop hybrid materials with enhanced physical/chemical performance and multiple functionalities.
㻟㻚Crystal Structuring of Poly(vinylidene fluoride) at the Air-Water Interface
The present work addresses the solvent-dependent properties of Langmuir films of PVDF and amphiphilic
97 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌
poly(N-dodecylacrylamide) (pDDA) at different mixing ratios. 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. Spreading from different solvents with different polarity, such as N-methyl-2-pyrrolidone (NMP) and methylethyl ketone (MEK), the PVDF molecules take completely different aggregation states at the air–water interface by Brewster angle microscopy (BAM). Effective transferring was achieved for different PVDF monolayers from the air-water interface onto substrates through the introduction of the pDDA two-dimensional hydrogen bonding network, which is usually difficult in the reported horizontal deposition of pure PVDF Langmuir films. This study also discovers a versatile crystallization control of PVDF homopolymer from complete ȕphase to completeĮphase at the air-water interface using different solvents, thereby eliciting useful information for further manipulation of film morphologies and film applications.
㻠㻚㻌Highly sensitive dissolved oxygen sensor based on the superhydrophobic surface
As we know, the liquid water was repelled on the surperhydrophobic surface. An air-liquid-solid interface could be formed when the solid material has porosity in itself. Here, the functional interface was demonstrated to apply to a luminescent dissolved oxygen sensor system. For obtaining the superhydrophobic surface, an amphiphilic fluorinated polymer (pC7F15MAA) was synthesized using the free radical reaction method. It was dissolved in mixed solvent (acetic-acid and AK-225). To fabricate the porous and surperhydrophobic film, the solution was dropped on the solid substrate, and the solvent evaporated in atmospheric environment. The surface wettability of films was characterized using the sessile drop method. The water contact angle was higher than 150°, the roll-off angle < 2°. The other amphiphilic oxygen sensitive copolymer was embedded into the porous film by mixing the polymer with the solution. A highly sensitive dissolved oxygen sensor was obtained and the sensitivity (I0/I40) reached approximately 126, which is the highest value reported so far.
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㻡㻚㻌䝗䞊䝟䝭䞁䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛻䜘䜛྾╔䞉᥋╔≉ᛶ㻌
䜹䝔䝁䞊䝹ᇶ䛿pH䛻ᛂ䛨䛶䜹䝔䝁䞊䝹య䠄పpH䠅䛸䜻䝜䞁య䠄㧗pH䠅䛾㛫䛷Ꮫኚ䜢㉳䛣䛧䚸䛺䛚䛛䛴䜹䝔 䝁䞊䝹య䛿Ỉ୰䛷䜒ᵝ䚻䛺⾲㠃䛻ྍ㏫ⓗ䛺྾╔䞉᥋╔ᛶ⬟䜢♧䛩䛣䛸䛛䜙䜹䝔䝁䞊䝹ᇶ䜢ྵ᭷䛩䜛ᶵ⬟ᛶᮦ
ᩱ䛜ὀ┠䛥䜜䛶䛔䜛䚹䛧䛛䛧䛺䛜䜙㐣ཤ䛾◊✲䛷䛿䝞䝹䜽ᮦᩱ䜢⏝䛔䛯᳨ウ䛜ከ䛟䚸䜹䝔䝁䞊䝹ᇶ䜢䝘䝜䝇䜿 䞊䝹䛷⢭ᐦ㞟✚䛧䛯⣔䛷྾╔≉ᛶ䜢᳨ウ䛧䛯䛿ᑡ䛺䛔䚹䛭䛣䛷ᮏ◊✲䛷䛿䚸䜹䝔䝁䞊䝹ᇶ䜢ྵ䜐㧗ศᏊ䝘 䝜䝅䞊䝖䜢స〇䛧䚸䛭䛾䝘䝜ᮦᩱ䛻ᑐ䛩䜛྾╔≉ᛶ䛻䛴䛔䛶᳨ウ䜢⾜䛳䛯䚹dopamine methacrylamide (DMA) 䛸N-dodecyl acrylamide(DDA)䜢⏝䛔䛶䝣䝸䞊䝷䝆䜹䝹㔜ྜ䛻䜘䜚ඹ㔜ྜయp(DDA/DMA)䜢ྜᡂ䛧䚸䛥䜙䛻 Langmuir-Blodgett(LB)ἲ䛻䜘䜚p(DDA/DMA)䜢ᅛయᇶᯈୖ䛻⣼✚䛧䛯䚹྾╔䛻⏝䛔䛯䝅䝸䜹䝘䝜⢏Ꮚ(SiO2 NPs)Ỉศᩓᾮ䛿䚸⢏ᚄ50 nm䛾ᕷ㈍䛾Ỉศᩓᾮ䜢ᕼ㔘䛧ሷ㓟䛷pH䜢ㄪ〇䛧䛯䜒䛾䜢⏝䛔䛯䚹⣼✚ᚋ䛾ᅛయ ᇶᯈ䛻䛴䛔䛶Ỉ᥋ゐゅ ᐃ䛚䜘䜃ỈᬗືᏊ䝬䜲䜽䝻䝞䝷䞁䝇(QCM)ἲ䛻䜘䜚྾╔㔞䜢ホ౯䛧䛯䚹䛭䛾⤖ᯝ䚸 㔜ྜ䛻䜘䛳䛶䝁䝫䝸䝬䞊୰䛾DMA䛾ᑟධ⋡x= 9, 19, 32䛚䜘䜃50 %䛾✀䚻䛾p(DDA/DMAx)䜢ᚓ䛯䚹Ỉฎ
⌮䜢䛧䛯Siᇶᯈୖ䛻p(DDA/DMA9)䜢2ᒙ⣼✚䛧䛯ᚋ䚸✀䚻䛾pH䜢᭷䛩䜛SiO2 NPsỈ⁐ᾮ(5 wt%)䛻1ศ㛫 ᾐₕ䛧䛶྾╔䜢⾜䛳䛯䛒䛸䛾⾲㠃䛾᥋ゐゅ䛾ኚ䜢㏣㊧䛧䛯䚹䛭䛾⤖ᯝ䚸SiO2 NPs䜢ྵ䜎䛺䛔␃Ỉ䛻ᾐₕ 䛧䛯ሙྜ䚸pH䜢ኚ䛥䛫䛶䜒䝘䝜䝅䞊䝖⾲㠃䛾᥋ゐゅ䛻ኚ䛿ぢ䜙䜜䛺䛛䛳䛯䚹୍᪉䚸SiO2 NPs䜢ྵ䜐Ỉ⁐
ᾮ䛻ᾐₕ䛧䛯ሙྜ䚸pH6௨ୗ䛷䛿᥋ゐゅ䛜ᑠ䛥䛟䛺䛳䛯䚹SiO2 NPs䛿ぶỈᛶ䛷䛒䜚䚸䛺䛚䛛䛴SEMほᐹ䛻䜘䛳 䛶⢏Ꮚ䛾྾╔䛜☜ㄆ䛷䛝䛯䛣䛸䛛䜙pH6௨ୗ䛷䝘䝜䝅䞊䝖⾲㠃䛻SiO2 NPs䛜྾╔䛥䜜䛯䛣䛸䛜ศ䛛䛳䛯䚹䜎䛯䚸 ỈᬗືᏊୖ䛻p(DDA/DMAx)䜢⣼✚䛧䚸SiO2NPs䛾྾╔㔞䜢ホ౯䛧䛯䛸䛣䜝DMAᑟධ⋡䛾ቑຍ䛻క䛳䛶྾
╔㔞䛜ቑຍ䛧䛯䚹௨ୖ䛾䛣䛸䛛䜙䚸pH䛚䜘䜃䝘䝜䝅䞊䝖୰䛻Ꮡᅾ䛩䜛䜹䝔䝁䞊䝹ᇶ䛻䜘䛳䛶SiO2 NPs䛾྾╔≉
ᛶ䜢⮬ᅾ䛻ไᚚ䛷䛝䜛䛣䛸䛜ศ䛛䛳䛯䚹
㻢㻚㻌 䝅䝹䝉䝇䜻䜸䜻䝃䞁ྵ᭷䝁䝫䝸䝬䞊䜢⏝䛔䛯㓟䜿䜲⣲㉸ⷧ⭷䛾స〇䛸ᢠኚ䝯䝰䝸䜈䛾ᛂ⏝㻌 㻌㏆ᖺ䚸⤯⦕య䜢⏝䛧䛯᪂䛯䛺䝯䜹䝙䝈䝮䛻䜘䜛Ⓨᛶ䝯䝰䝸䛸䛧䛶ᢠኚ䝯䝰䝸䛜ὀ┠䛥䜜䛶䛔䜛䚹䛣䜜 䜎䛷䛻䚸䛛䛤ᆺ䝅䝹䝉䝇䜻䜸䜻䝃䞁䠄SQ䠅䛸N-䝗䝕䝅䝹䜰䜽䝸䝹䜰䝭䝗䠄DDA䠅䛸䛾ඹ㔜ྜయ䛾Langmuir-Blodgett
研 究 活 動 報 告 98
◊ ✲ ά ື ሗ ࿌
⭷䛻䚸ᐊ Ẽୗ䛻䛶⣸እග䜢↷ᑕ䛩䜛䛣䛸䛻䜘䜚䚸SiO2㉸ⷧ⭷䛾స〇䛻ᡂຌ䛧䛶䛔䜛䚹䛭䛣䛷ᮏ◊✲䛷䛿䚸 㧗ศᏊ䝘䝜䝅䞊䝖䛛䜙ᚓ䛯ග㓟SiO2㉸ⷧ⭷䛾㟁Ẽ≉ᛶ䜢ホ౯䛧䚸ᢠኚ䝯䝰䝸䛾⤯⦕ᒙ䜈䛾ᛂ⏝ᛶ䜢᳨
ウ䛧䛯䚹ୗ㒊㟁ᴟ䛸䛧䛶Ag䠄50 nm䠅䜢╔䛧䛯䜺䝷䝇ᇶᯈୖ䛻䚸p(DDA/SQ)䜢LBἲ䛻䜘䛳䛶16ᒙ䠄37 nm䠅⣼
✚䛧䛯䚹ᚓ䜙䜜䛯p(DDA/SQ)䝘䝜䝅䞊䝖䛻ᐊ Ẽୗ䛻䛶⣸እග䠄300 mWcm-2, 2 h䠅䜢↷ᑕ䛧䚸SiO2㉸ⷧ⭷
䠄6.4 nm䠅䜢స〇䛧䛯䚹䛥䜙䛻ୖ㒊㟁ᴟ䛸䛧䛶poly(3,4- ethylenedioxythiophene):polystyrene sulfonate䠄PEDOT:
PSS䠅䠄150 nm䠅䜢䝇䝢䞁䝁䞊䝖䛧䚸1ᬌ┿✵⇱䛧䛯䚹స〇䛧䛯⣲Ꮚ䛾㟁Ẽ ᐃ䛿䚸ᐊ Ẽୗ䛷Ag㟁ᴟ䜢䜾
䝷䜴䞁䝗䛸䛧䛶⾜䛳䛯䚹㟁ᅽ䛾༳ຍ䛿4䛴䛾STEP䠄STEP1 0䡚-2 V, STEP2 -2䡚0 V, STEP3 0䡚2 V, STEP 4 2䡚0 V䠅䛷⾜䛳䛯䚹 STEP1 䛾-0.6 V㏆䛻䛚䛔䛶㧗ᢠ≧ែ䛛䜙పᢠ≧ែ䜈䛾ᢠኚ䛜ほᐹ䛥䜜
䛯䚹⥆䛟STEP2䛷䛿పᢠ≧ែ䜢⥔ᣢ䛧䛯䚹STEP3, 4䛷䛿䛔䛪䜜䜒㧗ᢠ≧ែ䜢⥔ᣢ䛧䛶䛔䛯䚹-0.4 V䛻䛚
䛡䜛పᢠ≧ែ䛸㧗ᢠ≧ែ䛾㟁ὶᐦᗘ䛾ẚ䛿103䡚104䛷䛒䛳䛯䚹䜎䛯 STEP1䡚4䜢」ᩘᅇ⧞䜚㏉䛧䛯䛸䛣 䜝䚸ྠᵝ䛾J-V≉ᛶ䜢♧䛧䛯䚹୍᪉䚸┿✵䚸N2䚸O2㞺ᅖẼୗ䛷䛾 ᐃ䛷䛿䚸ᢠኚືస䛿☜ㄆ䛷䛝䛺䛛䛳䛯 䛣䛸䛛䜙䚸PEDOT:PSSෆ䛾Ỉศ䛜ᢠኚືస䛻ᙳ㡪䛧䛶䛔䜛䛸⪃䛘䜙䜜䜛䚹௨ୖ䚸ᐊ Ẽୗ䛻䛚䛔䛶䚸⣲
Ꮚ䠄Ag|SiO2|PEDOT:PSS䠅䛾㟁Ẽ≉ᛶ䜢ホ౯䛧䚸±1 V௨ୗ䛷䛾ᢠኚືస䜢ᐇ⌧䛧䛯䚹 㻌
㻣㻚㻌 䃟ඹᙺ䝴䝙䝑䝖䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛾ྜᡂ䛸䛭䛾༢ศᏊ⭷ᣲື㻌
䃟ඹᙺ⣔ᶵ⬟ᅋ䜢㧗㓄ྥ䞉㧗ᐦᗘ䛻㞟✚䛩䜛䛣䛸䜢┠ⓗ䛸䛧䚸Langmuir-Blodgett(LB)ἲ䜢⏝䛔䛶䜹䝹䝞䝌 䞊䝹ᇶ䜢ഃ㙐䛻ᣢ䛴୧ぶ፹ᛶ㧗ศᏊ(pCzAA)䜢ྵ䜐㉸ⷧ⭷䜢స〇䛧䛯䚹pCzAA䛾⾲㠃ᅽ(䃟)-㠃✚(A)᭤⥺
䛾 ᐃ䜢⾜䛔䚸ᚓ䜙䜜䛯᭤⥺䛛䜙䝰䝜䝬䞊䝴䝙䝑䝖䛒䛯䜚䛾༨᭷㠃✚䜢ồ䜑䛯⤖ᯝ䚸0.33 nm2䛸䛺䛳䛯䚹䛣䜜䛿 䜶䝏䝹䜹䝹䝞䝌䞊䝹䛾ⰾ㤶⎔䛾㠃እ᪉ྥ䚸䛚䜘䜃㛗㍈᪉ྥ䛻ᖹ⾜䛺ྥ䛝䛛䜙䛾ᢞᙳ㠃✚䛻୍⮴䛧䛶䛚䜚䚸䛣 䛾䛣䛸䛛䜙pCzAA䛿Ỉ㠃ୖ䛷䜹䝹䝞䝌䞊䝹ᇶ䛾ⰾ㤶⎔䛜Ỉ㠃䛻ᑐ䛧䛶ᆶ┤䛻㓄ྥ䛧䛯༢ศᏊ⭷䜢ᙧᡂ䛧䛶 䛔䜛䛸⪃䛘䜙䜜䜛䚹䛣䜜䛿pCzAA䛻ྵ䜎䜜䜛䜰䝭䝗ᇶ䛜䝫䝸䝬䞊㙐㛫䛻Ỉ⣲⤖ྜ䜢ᙧᡂ䛧ᵓ㐀䜢Ᏻᐃ䛧䛶䛔䜛 䛯䜑䛰䛸⪃䛘䜙䜜䜛䚹䜎䛯䚸pCzAA༢య䛷䛿〇⭷ᛶ䛜ప䛟LB⭷䜢స〇䛩䜛䛣䛸䛜ᅔ㞴䛷䛒䛳䛯䛜䚸ᑡ㔞䛾 pDDA䛸ඹᒎ㛤䛩䜛䛣䛸䛻䜘䜚〇⭷ᛶ䛜ⴭ䛧䛟ྥୖ䛩䜛䛣䛸䛜᫂䜙䛛䛸䛺䛳䛯䚹䛣䛾⤖ᯝ䛛䜙䚸pCzAA:pDDA=4:1 䛾ྜ䛷ඹᒎ㛤䛧LB⭷䛾⣼✚䜢ヨ䜏䛯䚹⣼✚ᒙᩘ䛻ᑐ䛩䜛䜹䝹䝞䝌䞊䝹䛾྾ගᗘ䛜⥺ᙧⓗ䛺ቑຍ䜢♧䛧䚸 䜎䛯⣼✚᭤⥺䛛䜙ィ⟬䛧䛯⣼✚ẚ䛜ྛẁ䛻䛚䛔䛶0.9๓ᚋ䛸䛺䛳䛯䛣䛸䛛䜙䚸pCzAA䜢80%ྵ䜐LB⭷䛾⣼✚䛻 ᡂຌ䛧䛯䛣䛸䛜䜟䛛䛳䛯䚹
㻤㻚㻌 㧗ศᏊಟ㣭ᆺ㔠䝘䝜䜽䝷䝇䝍䞊䛾స〇㻌
㏆㉥እ㡿ᇦ䛷Ⓨග䜢♧䛩㔠䝘䝜䜽䝷䝇䝍䞊(AuNC)䜢స〇䛧䚸䛭䛾ホ౯䜢⾜䛳䛯䚹ሷ㔠㓟䛸䝏䜸䞊䝹ᮎ➃ ᇶ䜢᭷䛩䜛䝫䝸䜶䝏䝺䞁䜾䝸䝁䞊䝹䛾ΰྜ⁐ᾮ䛻ᙉຊ䛺㑏ඖ䛷䛒䜛NaBH4䜢ຍ䛘䛶⃭䛧䛟ᨩᢾ䛧䛯䚹ᚓ䜙䜜 䛯⁐ᾮ䛿㐲ᚰ㝈እ䜝㐣䜢⧞䜚㏉䛧⾜䛖䛣䛸䛷⢭〇䛧䚸TEM䚸㉁㔞ศᯒ䚸⺯ග䝇䝨䜽䝖䝹䛻䜘䜚స〇䛧䛯ヨᩱ䛾ホ ౯䜢⾜䛳䛯䚹ヨᩱ䛾TEMീ䜘䜚ᚤ⢏Ꮚ䛜ほᐹ䛥䜜䚸䛣䜜䜙䛾⢏Ꮚ䛾ᖹᆒ⢏ᚄ䜢ồ䜑䜛䛸┤ᚄ1.5 nm䛷䛒䛳䛯䛣 䛸䛛䜙䚸AuNC䛜ᚓ䜙䜜䛯䛣䛸䜢☜ㄆ䛧䛯䚹䛣䛾ヨᩱ䛾㉁㔞ศᯒ䛾⤖ᯝ䜘䜚䚸⏕ᡂ䛧䛯AuNC䛾ศᏊ㔞䛿䛚䜘䛭
8000䡚12000⛬ᗘ䛷䛒䜛䛣䛸䛜ศ䛛䛳䛯䚹䜎䛯㉁㔞䝇䝨䜽䝖䝹䛻䛿䝢䞊䜽䛸䝢䞊䜽䛜ぢ䜙䜜䚸䝢䞊䜽䛾㛫
㝸䛿㔠䚸䝢䞊䜽䛾㛫㝸䛿◲㯤䛾ཎᏊ㔞䛻ᑐᛂ䛧䛶䛔䜛䛣䛸䛛䜙䚸䛚䜘䛭㔠ཎᏊ50ಶ䛸PEG-SH 11ಶ䛷ᵓᡂ䛥 䜜䜛AuNC䛾⏕ᡂ䜢☜ㄆ䛧䛯䚹䛥䜙䛻AuNCỈ⁐ᾮ䛾Ⓨග䝇䝨䜽䝖䝹䛾 ᐃ⤖ᯝ䛛䜙䚸స〇䛧䛯AuNC䛿Ἴ㛗
800 nm䜢䝢䞊䜽䛸䛧䛶㏆㉥እ㡿ᇦ䛷䝤䝻䞊䝗䛺Ⓨග䜢♧䛩䛣䛸䛜ศ䛛䛳䛯䚹ᮏᡭἲ䛷ᚓ䜙䜜䛯AuNC䛿ᩘ䞄᭶
㛫จ㞟䛩䜛䛣䛸䛺䛟Ⓨග䜢♧䛧䚸PEG-SH䛻䜘䜛AuNCs䛾⾲㠃ಟ㣭䛜䝘䝜䜽䝷䝇䝍䞊䛾Ᏻᐃ䛻ຠᯝⓗ䛷䛒䜛䛣 䛸䜢ព䛩䜛䚹
㻥㻚㻌 㔠ᒓඖ⣲ྵ᭷㧗ศᏊ䝝䜲䝤䝸䝑䝗䝘䝜䝅䞊䝖䛾స〇㻌
㻌ࢳࢱࣥ(Ti)ࠊࢪࣝࢥࢽ࣒࢘(Zr)ࠊࣁࣇࢽ࣒࢘(Hf)ࡢ㓟≀ࡣ㧗ㄏ㟁⋡ࡢᮦᩱࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ
ᅇࡣTi㛵ࡋ࡚ࠊEࢪࢣࢺࣥ㒊ࢆᣢࡘࣔࣀ࣐࣮୧ぶ፹ᛶࢆ᭷ࡍࡿࣔࣀ࣐࣮ࡢඹ㔜ྜయTi๓㥑య
ࢆᛂࡋࡓᚋࠊLangmuir-Blodgett(LB)ἲࡼࡿ⢭ᐦ㞟✚ࢆ᳨ウࡋࡓࠋࡲࡎࠊTi(OiPr)4ࢭࢳࣝࢭ
ࢺࣥ(acac)ࡼࡾࢯࣉࣟࣃࣀ࣮ࣝ(IPA)୰࡛Ti๓㥑యࢆྜᡂࡋࡓࠋࡇࡢ᧯సࡣࠊඹ㔜ྜయᛂࡍࡿ㝿
99 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌
ඹ㔜ྜయࡢᯫᶫࢆ㜵ࡄ┠ⓗ࡛⾜ࡗࡓࠋ1H-NMRࢫ࣌ࢡࢺࣝࡼࡾࠊacacࢆ㐣㔞ධࢀࡓሙྜ࡛ࡶTi
2.5ಶࡢacacࡀ㓄ࡍࡿࡇࡀศࡗࡓࠋࡲࡓࠊ྾ࢫ࣌ࢡࢺࣝࡣᮦᩱࡣぢࡽࢀ࡞ࡗࡓ330 nmࡢ
྾ᖏࡀほᐹࡉࢀࡓࠋୖグࡢࡼ࠺ྜᡂࡋࡓ๓㥑యࢆࠊࢡ࣒ࣟࣟ࣍ࣝ୰⁐ࡋࡓඹ㔜ྜయΰྜࡍ
ࡿࡇ࡛㧗ศᏊᛂࢆヨࡳࡓࠋ྾ࢫ࣌ࢡࢺ࡛ࣝࡣ᪂ࡓ࡞ࣆ࣮ࢡࡣぢࡽࢀ࡞ࡗࡓࠋᅛయࡋ࡚ᚓࡓ
࣏࣐࣮ࣜࡢ1H-NMRࢫ࣌ࢡࢺࣝࡼࡾࠊࡇࡢᛂࡼࡗ࡚࣏࣐࣮ࣜࡢᵓ㐀ࡀ◚ቯࡉࢀࡿࡇ࡞ࡃᏳᐃ
Ꮡᅾࡍࡿࡇࡀ♧ࡉࢀࡓࠋࡲࡓࠊSEC ᐃࡽࠊ࣏࣐࣮ࣜTi๓㥑యࡀ㓄ࡋ࡚࠸ࡿࡇࡀศࡗࡓࠋ
⥆࠸࡚ࠊ㧗ศᏊᛂᚋࡢࢡ࣒ࣟࣟ࣍ࣝ⁐ᾮࢆ1 mMࡲ࡛ᕼ㔘ࡋࠊLBἲࡼࡾ㧗ศᏊ㔠ᒓ㘒యⷧ⭷ࢆỈ ࢩࣜࢥࣥࡲࡓࡣỈ▼ⱥᇶᯈୖ⣼✚ࡋࡓࠋᇶᯈୖࡢ⣼✚ẚࡽࠊ20ᒙࡲ࡛㧗ศᏊ㔠ᒓ㘒యࢆ⣼✚
ྍ⬟࡛࠶ࡿࡇࡀ♧ࡉࢀࡓࠋࡲࡓࠊ⣸እ⥺ฎ⌮ࡼࡿ㔠ᒓ㓟≀ⷧ⭷ࡢస〇ࢆ⾜ࡗࡓࠋXPS ᐃࡼࡾࠊ
⣸እ⥺ฎ⌮ࡼࡾTiO2ࡀస〇࡛ࡁࡓࡇࡀࢃࡗࡓࠋ
㻝㻜㻚㻌䝣䝷䞊䝺䞁ྵ᭷㧗ศᏊ䝝䜲䝤䝸䝑䝗䝘䝜䝅䞊䝖䛾స〇㻌
ග㟁Ꮚᶵ⬟ᛶ≀㉁䛷䛒䜛䝣䝷䞊䝺䞁䛿䚸㟁Ꮚཷᐜᛶ䛾㧗䛥䛛䜙ኴ㝧㟁ụ䛺䛹䛻⏝䛥䜜䛶䛔䜛䚹䛭䛾䝣䝷䞊 䝺䞁䜢ഃ㙐䛻ᣢ䛴୧ぶ፹ᛶ㧗ศᏊ䛾ྜᡂ䛸⢭ᐦ㞟✚䜢⾜䛳䛯䚹[6,6]-Phenyl-C61-Butyric Acid Methyl Ester(PCBM)䜢ฟⓎ≀㉁䛸䛧䚸ഃ㙐䛻䜰䝭䝜ᇶ䜢ྵ䜐䝣䝷䞊䝺䞁ㄏᑟయ䜢ྜᡂ䛧䛯䚹NMR ᐃ䛻䜘䜚䚸┠ⓗ≀䛾
ྜᡂ䜢☜ㄆ䛧䛯䚹䛭䛾ᚋ䚸άᛶ䜶䝇䝔䝹䛷䛒䜛N-䜰䜽䝸䝻䜻䝅䝇䜽䝅䞁䜲䝭䝗(NAS)䜢᭷䛩䜛㧗ศᏊ䛻䚸๓㏙䛾䜰 䝭䝜ᇶ䜢ྵ䜐䝣䝷䞊䝺䞁䜢ᛂ䛥䛫䛶䝁䝫䝸䝬䞊䜢ྜᡂ䛧䛯䚹ྜᡂ䛧䛯䝫䝸䝬䞊䛿NMR䚸GPC ᐃ䛻䜘䜚䚸⤌ᡂ ẚ䛸ศᏊ㔞䜢Ỵᐃ䛧䛯䚹䜎䛯䚸GPC ᐃ䛾⤖ᯝ䚸㧗ศᏊഃ䛷RI䛸UV䛾䝢䞊䜽䛾୍⮴䛜ぢ䜙䜜䛯䛣䛸䛛䜙䚸ഃ㙐 䛻䝣䝷䞊䝺䞁䜢ྵ䜐䝁䝫䝸䝬䞊䛾ྜᡂ䜢☜ㄆ䛧䛯䚹䛣䛾䝁䝫䝸䝬䞊䜢Langmuir-Blodgettἲ䛻䜘䜚䚸Ỉฎ⌮䜢⾜
䛳䛯▼ⱥᇶᯈୖ䛻⢭ᐦ㞟✚䛧䛯䚹䛣䛾⭷䛻䛴䛔䛶⣸እྍど྾ ᐃ䜢⾜䛳䛯䚹䝣䝷䞊䝺䞁䛾UV྾䝢䞊䜽䛷 䛒䜛250 nm㏆䛻䝢䞊䜽䛜ぢ䜙䜜䛯䛣䛸䛛䜙䚸༢ศᏊ⭷䝺䝧䝹䛷䝣䝷䞊䝺䞁䛜⢭ᐦ㞟✚䛥䜜䛯䛣䛸䛜☜䛛䜑䜙 䜜䛯䚹
研 究 活 動 報 告 100
◊ ✲ ά ື ሗ ࿌
ᅗ.2 䝝䜲䝤䝸䝑䝗䝘䝜ᵓ㐀య
䠷PDA䝘䝜⤖ᬗ䝣䜯䜲䝞䞊䝁䜰/䝅䝸䜹ᒙ/㔠䝅䜵䝹䠹䛾SEMീ
䠄ෆᤄᅗ䠖TEMീ䛸ඖ⣲䝬䝑䝢䞁䜾ീ䠅䛸ගᾘኻ䝇䝨䜽䝖䝹
ᅗ.1㻌PDA䝘䝜⤖ᬗ䛚䜘䜃䝘䝜⤖ᬗ䝣䜯䜲䝞䞊䛾
ᅛ┦㔜ྜ䝎䜲䝘䝭䜽䝇
࠙◊✲άືሗ࿌ࠚ ᭷ᶵࣁࣈࣜࢵࢻࢼࣀ⤖ᬗᮦᩱ◊✲ศ㔝
㸦2014.1㹼2014.12㸧