ຓ ᩍ㸸ᒣᮏ ಇ, Huie Zhu ༤ኈ◊✲ဨ 㸸Ali Demirci
Ꮫ 㝔 ⏕㸸Yu Gao Yida Liu Md. Mahbubul Bashar
༳⸨ஓ୰ᏕᑦỌ⃝ோ⛉㔜 ᑠ㔝ளἋ⨾㔝༤㈗ཎᏹ᫂YongJoon Im, Ꮫ 㒊 Ꮫ ⏕㸸␊㯞⏤ᯇ⌮ᜨ
◊ ✲ ⏕㸸Buket Akkus
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2015ᖺ䛾◊✲άື䛸䛧䛶䛿䚸௨ୗ
䛾䜘䛖䛻ᴫᣓ䛥䜜䜛䚹
㻝㻚 Non-Volatile Memories Fabricated with Organic Hybrid Nanofilms
Polymer ferroelectrics, especially poly(vinylidene fluoride) (PVDF), because of its outstanding ferroelectricity, easy processing, low cost and good flexibility have gained much interest for nonvolatile memories. To realize non-destructive read-out and low-energy writing in ferroelectric devices, a novel design philosophy was proposed which utilizes built-in electrostatic potential originating from ferroelectric polarization states to modulate the charge transfer and accumulation in semiconductors, thereby leading to resistance switching at on-(polarization up) and off-state on-(polarization down) of the devices. Ferroelectric PVDF and semiconductive conjugated polymers (CPs) phase-separated blends were studied a few times based on phase-separation blend nanofilms. However, the domain size of CPs smaller than a few tens of nanometers (e. g. 50 nm) is extremely challenging so far for higher information storage density. From another aspect, to decrease the writing and read-out voltages, ultrathin films (thinner than 100 nm) with high-content ferroelectric crystals are also necessary.
In this study, I fabricated ultrathin hybrid films of poly(vinylidene fluoride) (PVDF) nanofilms and conjugated polymers (CPs) (e.g. poly[3-(5-carboxypentyl) thiophene-2,5-diyl] (P3CPenT)) using Langmuir-Blodgett (LB) technique. The film morphologies were investigated by atomic force microscopy (AFM). The PVDF-P3CPenT blend nanofilms were confirmed with molecular-level dispersion. In the PVDF-P3CPenT LB hybrid nanofilm at 23 wt% content of P3CPenT, regular nanofibers were formed and oriented in one direction. From current (I)-voltage (V) characteristics, resistance switching was successfully detected in the PVDF-P3CPenT LB blend nanofilms at different polarization states. These properties make the hybrid ultrathin films very promising for non-volatile memories.
㻞㻚㻌Preparation of Amphiphilic Fluorinated Polymer Nanoparticles in Immiscible Solvents
Preparation and application of amphiphilic fluorinated polymer (pC7F15MAA) nanoparticles were studied through self-assembly at an immiscible solvent’s interface. The nanoparticles with less than 50 nm diameter can disperse into water solution with oil-soluble dyes (PtOEP), which were encapsulated into pC7F15MAA. The embedded PtOEP nanoparticle has Soret and Q bands at 380 nm and 540 nm, respectively. The nanosensor exhibited a strong luminescence at 645 nm. The luminescence intensity decreased greatly as the dissolved oxygen concentration was increased. The distilled water of different dissolved oxygen concentrations was obtained by gas bubbling for at least 10 min at room temperature. A linear relationship was obtained between the luminescence intensity and dissolved oxygen concentration, which was fitted with the Stern-Volmer equation.
The optical dissolved nanosensor showed a sensitivity of 42 (I0/I40in the range of 0~ 40 mg/L). The optical dissolved oxygen nanosensor has a response time of 10~15 s when switching from deoxygenated condition to oxygenated condition, and 250~300 s when switching from oxygenated condition to deoxygenated condition.
That is a fast response time, compared with that of other nanoparticle systems.
3. Synthesis of Catechol Functionalized Polysiloxane
Silicones, as a general class of materials, are ubiquitous in technology, with applications ranging widely from electrical materials to biomaterials as a result of their unique properties, such as low glass transition temperature, a flexible backbone, good thermal and oxidative stability, excellent dielectric properties, water repellency, physiological inertness and biocompatibility. Although it is possible using such multifunctional degree siloxane monomers to prepare three dimensional cross-linking polymers, antiadhesive properties as well as difficulty of controlling the cross-linking degree during thermal curing restrain its application as wet adhesive materials.
Herein, we design a facile synthetic strategy to introduced catechol group into silicone backbone based on a readily available precursor (eugenol) and efficient chemistries [tris(pentafluorophenyl)borane-catalyzed silation and hydrosilylation] using a post functionalization method. Catechol functional silicone can serve as a versatile adhesive layer to bind various inorganic materials such as nanocarbons, metal oxide nanomaterials. This biomimic polymer with high content of catechol functional groups are anticipated as a polymer mediator to prepare adhesive nanocomposites film.
4. Assembly of Cellulose Nanofiber Nanosheets by Langmuir-Blodgett Technique
Today the people are searching for green, sustainable and bio-based materials for next generation products and processes. Cellulose is one of the most ubiquitous, abundant and renewable biopolymer on earth from various sources. Its repeating unit is composed of two anhydroglucose rings which are connected with covalent bond called glycosidic linkage. In the plant cell wall, cellulose nanofibers (CNFs) are the main component of multiple cellulose chain. They have 3-4 nm thickness and length in several microns. Recently, CNFs have drawn the attraction to be applied as supporting materials for various applications such as novel functional composites and electronics devices due to its non-toxicity, biodegradability, high transparency, flexibility, and desired electrical properties. Thereby we successfully fabricated cellulose nanofiber (CNF) monolayers at the air-water interface assisted by an amphiphilic polymer poly(N-dodecylacrylamide) (pDDA). The collapse surface pressure shows steady increase up to 50 mN/m which is higher than the pure pDDA. This suggests that the CNF fiber remains in the pDDA polymer network. Therefore, the film was deposited uniformly both on hydrophobic and hydrophilic substrates. The presence of CNF was also confirmed by the FT-IR study. Moreover, the film shows high optical transparency in the visible light wavelength region.
㻌
5. 䝗䞊䝟䝭䞁䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛻䜘䜛྾╔䞉᥋╔≉ᛶ
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䜢䝘䝜䝯䞊䝖 䝹䝇䜿䞊䝹䛷⢭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྾╔ᐇ㦂䛻䛿SiO2, Al2O3, WO3䛾
ྛ✀䝘䝜⢏Ꮚ(NPs)Ỉศᩓᾮ䜢䚸Ỉ㓟䝘䝖䝸䜴䝮䚸ሷ㓟䜒䛧䛟䛿䜽䜶䞁㓟䜢⏝䛔䛶pHㄪᩚ䜢⾜䛳䛶䛛䜙⏝䛧 䛯䚹⣼✚ᚋ䛾ᅛయᇶᯈ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pH6௨ୖ䛷䛿⭷୰䛾䜹䝔䝁䞊䝹ᇶ䛜Ỉ⣲⤖ྜᛶ䜢᭷䛧䛺䛔䜻䝜䞁య䜈䛸ኚ
䛩䜛䛣䛸䛜⾲㠃㟁 ᐃ䜘䜚☜ㄆ䛥䜜䛯䛣䛸䛛䜙䚸⭷୰䛻Ꮡᅾ䛩䜛䜹䝔䝁䞊䝹ᇶ䛻䜘䛳䛶SiO2 NPs䛿Ỉ⣲⤖
ྜ䛻䜘䛳䛶྾╔䛷䛝䜛䛣䛸䛜ศ䛛䛳䛯䚹୍᪉䚸Al2O3 NPs䛷䛿䚸⢏Ꮚ䛾⾲㠃㟁䛜ṇ䛸䛺䜛pH10௨ୗ䛷྾╔䛜 ぢ䜙䜜䚸㟼㟁┦స⏝䛻䜘䜛྾╔䛷䛒䜛䛣䛸䛜ศ䛛䛳䛯䚹䛥䜙䛻WO3 NPs䛿䜽䜶䞁㓟䜢pHㄪᩚ䛸䛧䛶⏝䛔䛯
ሙྜ䛾䜏྾╔䛜ぢ䜙䜜䚸⢏Ꮚ⾲㠃䛻྾╔䛧䛯䜽䜶䞁㓟䛸⭷୰䛾䜹䝔䝁䞊䝹ᇶ䛸䛾Ỉ⣲⤖ྜ䛻䜘䜛྾╔䛷䛒䜛䛣 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⌧ᅾᬑཬ䛧䛶䛔䜛䝯䝰䝸䛿䛻䝅䝸䝁䞁༙ᑟయᢏ⾡䜢⏝䛧䛶䛔䜛䚹䝥䝻䝉䝇䛾ᚤ⣽䛻䜘䜛ᚑ᮶䝯䝰䝸䛾㝈
⏺䚸ሗᶵჾ䛾ᬑཬ䛻క䛔䚸᪂䛯䛺䝯䜹䝙䝈䝮䛻䜘䜛Ⓨᛶ䝯䝰䝸䛾㛤Ⓨ䛜㐍䜑䜙䜜䛶䛔䜛䚹୰䛷䜒䚸ὀ┠䛥 䜜䛶䛔䜛䛾䛜ᢠኚ䝯䝰䝸(resistance random access memory: ReRAM)䛷䛒䜛䚹ReRAM䛿⤯⦕ᒙ䜢㟁ᴟ 䛷ᣳ䜣䛰ᵓ㐀䜢䛧䛶䛚䜚䚸㟁ᅽ༳ຍ䛻䜘䜛⤯⦕ᒙ䛾ᢠኚ䜢⏝䛧䛯Ⓨᛶ䝯䝰䝸䛷䛒䜛䚹ReRAM䛿༢
⣧䛺ᵓ㐀䛻䜘䜚㧗㞟✚䛜ᐜ᫆䛷䛒䜛䛸䛔䛖Ⅼ䜢᭷䛧䛶䛚䜚䚸 䜘䜚⡆౽䛺ᡭἲ䛻䜘䜛⤯⦕ᒙ䛾స〇䛜ồ䜑䜙䜜 䜛䚹䛣䜜䜎䛷䛻䛛䛤ᆺ䝅䝹䝉䝇䜻䜸䜻䝃䞁䛸N-䝗䝕䝅䝹䜰䜽䝸䝹䜰䝭䝗䛸䛾ඹ㔜ྜయ䛾Langmuir-Blodgett⭷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
⣲ᏊAg/SiO2/PEDOT:PSS䜢స〇䛧䚸㟁Ẽ≉ᛶ䜢ホ౯䛧䛯䚹⤖ᯝ䚸ᐊ Ẽୗ䛻䛚䛔䛶㼼1V௨ୗ䛻䛚䛔䛶
ᢠኚືస䜢ᐇ⌧䛧䛯䚹ḟ䛻ᢠኚ䛾ཎ⌮ゎ᫂䜢ヨ䜏䛯䛸䛣䜝䚸ᢠኚືస䛻⣲Ꮚෆ䛾Ỉศ䚸PEDOT:
PSS䛜㔜せ䛺ᙺ䜢ᢸ䛖䛣䛸䛜ศ䛛䛳䛯䚹
㻣㻚㻌 䃟ඹᙺ䝴䝙䝑䝖䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛾ྜᡂ䛸䛭䛾༢ศᏊ⭷ᣲື㻌
ʌඹᙺ⣔ᶵ⬟ᅋ䜢㧗㓄ྥ䞉㧗ᐦᗘ䛻ྵ䜐ḟඖ⣔ᮦᩱ䛾స〇䜢┠ⓗ䛸䛧䚸Langmuir-Blodgett(LB)ἲ䜢⏝䛔 䛶䜹䝹䝞䝌䞊䝹ᇶ䜢ഃ㙐䛻᭷䛩䜛୧ぶ፹ᛶ㧗ศᏊ(pCzAA)䜢ྵ䜐㉸ⷧ⭷䜢స〇䛧䛯䚹pCzAA䜢✀䚻䛾ྜ
䛷ྵ䜐LB⭷䜢㞟✚䛧䚸X⥺ᑕ⋡ἲ䜢⏝䛔䛶ⷧ⭷䛾ᵓ㐀䜢ㄪᰝ䛧䛯⤖ᯝ䚸pCzAA䛾ྜ䛜35~90 %䛾ⷧ⭷
䛻䛚䛔䛶᫂░䛺Bragg䝢䞊䜽䛸Kiessig䝣䝸䞁䝆䛜ぢ䜙䜜䛯䚹䛣䜜䜘䜚䚸LB⭷䛿ᆒ୍䛺ᒙ≧ᵓ㐀䜢᭷䛧䛶䛔䜛䛣䛸 䛜᫂䜙䛛䛸䛺䜚䚸pCzAA䜢᭱90 %ྵ䜐㧗⛛ᗎⷧ⭷䛾స〇䛻ᡂຌ䛧䛯䛣䛸䛜☜ㄆ䛥䜜䛯䚹䜎䛯䚸pCzAA䜢ྵ䜐 LB⭷䛾ග㟁Ꮚ㔞 ᐃ䜢⾜䛳䛯⤖ᯝ䚸ⷧ⭷䛾䜲䜸䞁䝫䝔䞁䝅䝱䝹䛿5.33 eV䛸ồ䜑䜙䜜䚸ඃ䜜䛯䝩䞊䝹㍺
㏦ᛶᮦᩱ䛷䛒䜛poly(N-vinylcarbazole)(PVK䚸䜲䜸䞁䝫䝔䞁䝅䝱䝹 5.77 eV)ྠᵝ䚸䝩䞊䝹㍺㏦ᛶ䜢ᣢ䛴䛣䛸 䛜♧䛥䜜䛯䚹᭦䛻䚸pCzAA䛾䜻䝱䝇䝖⭷䜢⏝䛔䛶Time of Flightἲ䛻䜘䛳䛶䝩䞊䝹⛣ືᗘ䜢 ᐃ䛧䛯⤖ᯝ䚸༳ຍ 㟁ᅽ50 V䛾ሙྜ䝩䞊䝹⛣ືᗘ䛿2.2㽢10-5 cm2/Vs䛸ồ䜑䜙䜜䚸ྠ᮲௳䛷 ᐃ䛧䛯PVK䛾䝩䞊䝹⛣ືᗘ6.9㽢 10-6cm2/Vs䜢ୖᅇ䜛⤖ᯝ䛜ᚓ䜙䜜䛯䚹
㻤㻚㻌 䝏䜸䞊䝹䜢㓄Ꮚ䛸䛧䛯㔠䝘䝜䜽䝷䝇䝍䞊䛾స〇䛸Ⓨග≉ᛶホ౯㻌
䃐-䝸䝫㓟䜢㓄Ꮚ䛸䛧䛯㔠䝘䝜䜽䝷䝇䝍䞊(AuNC)䜢స〇䛧䚸䛭䛾ホ౯䜢⾜䛳䛯䚹ሷ㔠㓟Ỉ⁐ᾮ䛸䃐-䝸䝫㓟 Ỉ⁐ᾮ䜢ΰྜ䛧䚸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
⢏Ꮚ䛾ᖹᆒ⢏ᚄ䜢ồ䜑䜛䛸┤ᚄ1.4 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ศ ᯒ䛾⤖ᯝ䜘䜚䚸AuNC䛾ศᏊ㔞䛿䛚䜘䛭3000䡚7000⛬ᗘ䛷䛒䜛䛣䛸䛜ศ䛛䛳䛯䚹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ཎᏊ22ಶ䛸 䃐-䝸䝫㓟16ಶ䛷ᵓᡂ䛥䜜䜛AuNC䜢
୰ᚰ䛸䛧䛶⢏Ꮚ䛜ศᕸ䛧䛶䛔䜛䛣䛸䛜ศ䛛䛳䛯䚹⺯ග䝇䝨䜽䝖䝹 ᐃ䜘䜚䚸స〇䛧䛯AuNC䛿Ἴ㛗720 nm䜢䝢䞊 䜽䛸䛧䛶㉥䡚㏆㉥እ㡿ᇦ䛷䝤䝻䞊䝗䛺Ⓨග䜢♧䛩䛣䛸䛜᫂䜙䛛䛻䛺䛳䛯䚹Ⓨගᑑ ᐃ䜘䜚䚸AuNC䛾ᖹᆒⓎග ᑑ䛿1.1 ȝV⛬ᗘ䛷䛒䜛䛣䛸䛜ศ䛛䛳䛯䚹ᚓ䜙䜜䛯AuNC䛿ᩘ䞄᭶㛫จ㞟䛩䜛䛣䛸䛺䛟Ⓨග䜢♧䛧䚸䃐䇲䝸䝫㓟䛻 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➨4᪘ඖ⣲(Ti, Zr, Hf)ࡢ㓟≀ⷧ⭷ࡣࠊ㧗ᒅᢡ⋡࣭㧗ㄏ㟁⋡ࢆᣢࡘhigh-țᮦᩱࡋ࡚㟁Ꮚࢹࣂࢫ➼
ࡢᛂ⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋᵝࠎ࠶ࡿ㔠ᒓ㓟≀ⷧ⭷ࡢస〇ἲࡢ୰࡛ࡶࠊ᭷ᶵ-↓ᶵࣁࣈࣜࢵࢻⷧ⭷ࢆ
๓㥑యࡍࡿ᪉ἲࡣࠊࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮ࣝࡢᚤ⣽ᵓ㐀ࢆẼᅽ࣭ᐊ ࡛ᙧᡂ࡛ࡁࡿࡓࡵὀ┠ࡉࢀ࡚
࠸ࡿࠋࡑࡇ࡛ࠊ᭷ᶵ-↓ᶵࣁࣈࣜࢵࢻᮦᩱࡢ〇⭷ἲࡋ࡚ࠊ୧ぶ፹ᛶ㧗ศᏊࢆᇶᯈୖ༢ศᏊࣞ࣋ࣝ
࡛㞟✚࡛ࡁࡿLangmuir-Blodgett(LB)ἲὀ┠ࡋࠊ㧗ศᏊࢳࢱࣥ㘒యࢆLBἲࡼࡾ㞟✚ࡍࡿࡇࢆヨࡳ
ࡓࠋྜᡂࡋࡓ㧗ศᏊࢳࢱࣥ㘒యࡣࠊSEC ᐃ࠾࠸࡚Ti(acac)๓㥑యࡢLMCT㑄⛣⏤᮶ࡍࡿ330 nmࡢ
྾ࢆᣢࡘ㧗ศᏊ㔞ᡂศࡀ☜ㄆ࡛ࡁࠊ㧗ศᏊࡢTi(acac)๓㥑యᑟධࡀ♧ࡉࢀࡓࠋḟࠊ㧗ศᏊࢳࢱࣥ
㘒యࢆLBἲࡼࡾỈฎ⌮ࡋࡓ▼ⱥᇶᯈୖ⣼✚ࡋࠊྛᒙᩘࡢ྾ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋࡑࡢ⤖ᯝࠊ
330 nm㏆ࡲ࡛ࣈ࣮ࣟࢻ࡞྾ᖏࡀほᐹࡉࢀࠊỈ㠃ୖ࡛ࢳࢱࣥ㘒యࡀእࢀࡿࡇ࡞ࡃ✚ᒙࡉࢀ࡚࠸ࡿ
ࡇࡀࢃࡗࡓࠋࡉࡽἼ㛗320 nm࠾࠸࡚྾ගᗘᒙᩘࡢ㛵ಀࡣ⥺ᙧⓗ࡛࠶ࡗࡓࡓࡵࠊྜᡂࡋࡓ㧗 ศᏊࢳࢱࣥ㘒యࡣLBἲࡼࡾᆒ୍࡞ከᒙ㞟✚ࡀྍ⬟࡛࠶ࡿࢃࡗࡓࠋ௨ୖࡼࡾࠊࢳࢱࣥࢆྵࡴ㧗ศ Ꮚ㉸ⷧ⭷ࡢస〇ᡂຌࡋࡓࡇࡀ♧ࡉࢀࡓࠋ
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䛧䛯䝫䝸䝬䞊䛾GPC ᐃ䛻䜘䜚䚸Mn=2.6×104䛾 p(DDA/PCBEA/NAS)䜢ᚓ䛯䚹䜎䛯䚸1H-NMR䛾 ᐃ⤖ᯝ䜘䜚䚸p(DDA/PCBEA/NAS)䜈䛾䝣䝷䞊䝺䞁䛾ᑟධ⋡
䜢1.4%䛸ぢ✚䜒䛳䛯䚹ḟ䛻䚸Ỉฎ⌮䜢⾜䛳䛯▼ⱥᇶᯈୖ䛻p(DDA/PCBEA/NAS)䜢10ᒙ⣼✚䛧䚸䛭䛾䛾⣼
✚ẚ䜢ㄪ䜉䛯䚹⣼✚䛿䚸p(DDA/PCBEA/NAS)䜢Ỉ㠃ୖ䛻ᒎ㛤ᚋ䚸⣼✚ᅽ䜢30 mN m-1䛻タᐃ䛧䚸▼ⱥᇶᯈ䜢 ᾐₕ䛩䜛䛣䛸䛷⾜䛳䛯䚹䛭䛾⤖ᯝ䚸⣼✚䛻క䛖⾲㠃✚䛾ῶᑡ್䛿䚸ྛ⣼✚䛷䜋䜌➼䛧䛟䚸⣼✚ẚ䜢ィ⟬䛩䜛䛸䚸 䛭䛾್䛿⣙1.0䛸䛺䛳䛯䚹䛣䛾⤖ᯝ䜘䜚䚸p(DDA/PCBEA/NAS)䛿䚸LBἲ䛻䜘䜚ᇶᯈୖ䛻Ᏻᐃ䛧䛶⣼✚ྍ⬟䛷䛒 䜛 䛣 䛸 䛜 ☜ 䛛 䜑 䜙 䜜 䛯 䚹 ⥆ 䛔 䛶 䚸 స 〇 䛧 䛯LB⭷ ෆ 䛻 䝣 䝷 䞊 䝺 䞁 䛜 ྵ 䜎 䜜 䛶 䛔 䜛 䛣 䛸 䜢 ☜ ㄆ 䛩 䜛 䛯 䜑 䚸 p(DDA/PCBEA/NAS)ཬ 䜃p(DDA/NAS)LB⭷ 䛾 ⣸ እ ྍ ど ྾ ᐃ 䜢 ⾜ 䛳 䛯 䚹 䝣 䝷 䞊 䝺 䞁 䜢 ྵ 䜎 䛺 䛔 p(DDA/NAS)LB⭷䛷䛿䚸250 nm䜘䜚㛗Ἴ㛗ഃ䛻྾㡿ᇦ䜢ᣢ䛯䛺䛔䛜䚸p(DDA/PCBEA/NAS)LB⭷䛿䚸䛭䛾 㡿ᇦ䛻྾䛜ぢ䜙䜜䛯䚹䛣䛾྾䛿䚸䝣䝷䞊䝺䞁ⷧ⭷䛾྾䝢䞊䜽䛻ᖐᒓ䛷䛝䜛䛣䛸䛛䜙䚸స〇䛧䛯LB⭷୰䛻 䝣䝷䞊䝺䞁䛜ྵ䜎䜜䛶䛔䜛䛣䛸䛜᫂䜙䛛䛻䛺䛳䛯䚹䜎䛯䚸྾ගಀᩘ䜘䜚ⷧ⭷୰䛾䝣䝷䞊䝺䞁ᐦᗘ䜢ィ⟬䛩䜛䛸䚸 0.12 ಶ nm-2䛸䛺䛳䛯䚹䛣䜜䜘䜚䚸ᆒ୍ศᩓ䜢௬ᐃ䛩䜛䛸䚸༢ศᏊ⭷୰䛾䝣䝷䞊䝺䞁䛿ḟඖᖹ㠃䛷Ꮩ❧䛧䛶䛔 䜛䛸⪃䛘䜙䜜䜛䚹䜎䛯䚸LB⭷䛾ᵓ㐀䜢ㄪᰝ䛩䜛䛯䜑䚸p(DDA/PCBEA/NAS)ཬ䜃pDDA䛾LB⭷䛾XRD ᐃ䜢⾜
䛳䛯䚹p(DDA/PCBEA/NAS)LB⭷䛷䛿䚸2.8°㏆䛻pDDA䛻ᖐᒓ䛥䜜䜛㗦䛔䝢䞊䜽䛜ぢ䜙䜜䛯䚹䛣䛾䛣䛸䛿䚸 p(DDA/PCBEA/NAS)䜢ᇶᯈୖ䛻⣼✚䛧䛶䜒䚸࿘ᮇⓗ䛺ᒙᵓ㐀䛜ಖᣢ䛥䜜䛶䛔䜛䛣䛸䜢♧䛧䛶䛔䜛䚹Bragg䛾ᘧ 䜢⏝䛔䛶䚸p(DDA/PCBEA/NAS)LB⭷䛾୍ᒙ䛒䛯䜚䛾⭷ཌ䜢ィ⟬䛩䜛䛸䚸䛭䛾್䛿⣙1.60 nm䛸䛺䛳䛯䚹௨ୖ䜘 䜚䚸䝣䝷䞊䝺䞁䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䜢ྜᡂ䛧䚸䛥䜙䛻䚸LBἲ䛻䜘䜚䝣䝷䞊䝺䞁䜢⢭ᐦ㞟✚ྍ⬟䛺༢ศᏊ⭷䛜 ᚓ䜙䜜䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹
㻝㻝㻚㻌㧗ศᏊ䝘䝜䝅䞊䝖䜢䝔䞁䝥䝺䞊䝖䛸䛧䛯㔠ᒓ᭷ᶵᵓ㐀య䛾䝝䜲䝤䝸䝑䝗䝘䝜✚ᒙ㻌
㔠ᒓ᭷ᶵᵓ㐀య(MOF)䛿ㄪᩚྍ⬟䛺⣽Ꮝᵓ㐀䛸Ꮫⓗᶵ⬟ᛶ䛛䜙䜺䝇㈓ⶶ䚸ゐ፹䚸䝉䞁䝅䞁䜾䛺䛹䛾ᛂ⏝
䛜ྍ⬟䛷䛒䜛䚹㏆ᖺ䚸ᅛయᇶᯈୖ䜈䛾MOFⷧ⭷䛾✚ᒙ䛜ከ䛟ሗ࿌䛥䜜䛶䛔䜛䚹䛧䛛䛧䛺䛜䜙䚸㧗ศᏊᮦᩱୖ
䜈MOF䜢 ✚ ᒙ 䛧 䛯 ሗ ࿌ 䛿 ᑡ 䛺 䛔 䚹 䛧 䛯 䛜 䛳 䛶 䚸Langmuir-Blodgett(LB)ἲ 䛻 䛶 స 〇 䛧 䛯 poly(N-dodecylacrylamide)(pDDA)䝘䝜䝅䞊䝖䜢䝔䞁䝥䝺䞊䝖䛸䛧䛶䚸䛭䛾ୖ䛻Cu䛾MOF(HKUST-1)䛾✚ᒙ䜢ヨ 䜏䚸䛭䛾✚ᒙ≉ᛶ䜢ㄪᰝ䛧䛯䚹pDDA䛿䚸LBἲ䜢⏝䛔䛶⾲㠃䛻ぶỈᇶ䛜ฟ䜛䜘䛖䛻9ᒙ✚ᒙ䛧䛯䚹HKUST-1䛻 䛿䚸Cu(OAc)2䛸1,3,5-benzenetricarboxylate(btc)䜶䝍䝜䞊䝹⁐ᾮ䜢⏝䛔䛯䚹྾╔⨨䜢⏝䛧䚸Cu(OAc)2
⁐ᾮ䚸䜶䝍䝜䞊䝹䚸btc⁐ᾮ䚸䜶䝍䝜䞊䝹䛾㡰䛻ᇶᯈ䜢ᾐₕ䛩䜛䛣䛸䛷1䝃䜲䜽䝹䛸䛧䛯䚹FT-IR䝇䝨䜽䝖䝹䛾⤖ᯝ 䛛䜙䚸pDDAୖ䛻HKUST-1䜢✚ᒙ䛧䛯䝃䞁䝥䝹䛻䛚䛔䛶1374 cm-1䛻HKUST-1䛷ほ 䛥䜜䜛㗦䛔䝢䞊䜽䛜ほᐹ 䛷䛝䚸HKUST-1䛾✚ᒙ䛜☜ㄆ䛷䛝䛯䚹ཎᏊ㛫ຊ㢧ᚤ㙾(AFM)ീ䛛䜙䚸⮬ᖹᆒ⢒䛥(RMS)䛿 1 nm⛬ᗘ䛷䛒 䜚䚸㠀ᖖ䛻ᖹ䛺⾲㠃䛷䛒䜛䛣䛸䛜䜟䛛䛳䛯䚹᭱ᚋ䛻䚸pDDA䝘䝜䝅䞊䝖ୖ䛻40䝃䜲䜽䝹✚ᒙ䛧䛯HKUST-1䛾 XRD䝟䝍䞊䞁䜘䜚䚸11.7°䛻HKUST-1䛾(111)㠃䛻ᖐᒓ䛥䜜䜛䝢䞊䜽䛜ほ 䛷䛝䚸pDDA䝘䝜䝅䞊䝖ୖ䜈⤖ᬗ㠃䜢
䛭䜝䛘HKUST-1䛾⤖ᬗⷧ⭷䛜ᡂ㛗䛩䜛䛣䛸䛜☜ㄆ䛷䛝䛯䚹௨ୖ䛛䜙䚸㧗⛛ᗎ䛻✚ᒙ䛧䛯㧗ศᏊ䝘䝜䝅䞊䝖ୖ
䛻MOF䜢✚ᒙ䛷䛝䜛䛣䛸䛜䜟䛛䛳䛯䚹
12. Superhydrophobic nanoparticles film preparation of pyrene containg amphiphilic fluorinated copolymer
Amphiphilic fluorinated polymer p(C7F15MAA) (poly(1H,1H-perfluorooctyl methacrylamide)) is well known for providing a superhydrophobic surface, good gas permeability and amphiphilic characteristics. Pyrene is known for taking an excimer formation and being sensitive to solvent polarity. First, two comonomers C7F15MMA and PyMMA (pyrene methyl methacrylate) were synthesized and their structures were confirmed by
1H-NMR measurement. Pyrene-containing fluorinated copolymers were synthesized by free radical copolymerization initiated by AIBN. The PyMMA content of the copolymer was confirmed by elemental analysis, UV-vis spectroscopy. After dissolving the polymer in a mixture of AK225 and acetic acid, the solution was drop-casted on a substrate. Nanoparticles assemblies formation of the copolymer was confirmed using SEM.
The surface showed a superhydrophobic nature with a water contact angle of more than 160㽅.
13. 䝏䜸䝣䜵䞁䜢ྵ䜐୧ぶ፹ᛶ㧗ศᏊ䛾ྜᡂ䛸༢ศᏊ⭷㞟✚
3-Aminophenylboronic Acid Pinacol Ester䛸5-Bromo-5䇻-hexyl-2,2䇻-bithiophene䜢⏝䛔䛶㕥ᮌ䞉ᐑᾆ䜹䝑䝥䝸 䞁䜾䜢⾜䛔䚸䜰䝭䝜ᇶ䜢䜒䛴䝏䜸䝣䜵䞁ㄏᑟయ䜢ྜᡂ䛧䛯䚹䛣䛾䝏䜸䝣䜵䞁ㄏᑟయ䛸acryloyl chloride䛸䛾ồ᰾⨨
ᛂ 䛻 䜘 䜚 䚸 䝰 䝜 䝬 䞊 䜢 ྜ ᡂ 䛧 䛯 䚹 䛣 䛾 䝰 䝜 䝬 䞊 䜢 ⏝ 䛔 䛶 䝣 䝸 䞊 䝷 䝆 䜹 䝹 㔜 ྜ 䜢 ⾜ 䛔 䚸 䝫 䝸 䝬 䞊
p(PhAA-m-HBT)䛾ྜᡂ䛻ᡂຌ䛧䛯䚹p(PhAA-mHBT)䜢⏝䛔䛶䛾⾲㠃ᅽ(䃟)- 㠃✚(A)➼ ⥺䛾 ᐃཬ䜃䚸
LB⭷㞟✚䜢⾜䛔䚸AFM ᐃ䛻䜘䜚LB⭷䜢ホ౯䛧䛯䚹䃟-A ᐃ⤖ᯝ䛛䜙䝰䝜䝬䞊䝴䝙䝑䝖䛒䛯䜚䛾ᴟ㝈༨᭷㠃
✚䛿0.285 nm2䛸䛺䜚䚸ⰾ㤶⎔䛜Ỉ㠃䛻ᑐ䛧䛶䜋䜌ᆶ┤䛻㓄ྥ䛧䚸༢ศᏊ⭷䜢ᙧᡂ䛧䛶䛔䜛䛣䛸䛜䜟䛛䛳䛯䚹䜎 䛯䚸p(PhAA-m-HBT)༢య䛷䛿ᇶᯈ䛻⣼✚ฟ᮶䛺䛛䛳䛯䛜䚸p(PhAA-m-HBT):pDDA=4:1䜢Ỉ㠃䛻ඹᒎ㛤䛩䜛 䛣䛸䛷ᇶᯈୖ䛻Ᏻᐃ䛧䛶⣼✚䛧䚸ୟ䛴ᖹ䛺༢ศᏊ⭷䛾ᙧᡂ䜢☜ㄆ䛧䛯䚹
14. άᛶ䜶䝇䝔䝹ᇶ䜢᭷䛩䜛䝫䝸䝬䞊䛾ྜᡂ䛸ᶵ⬟
ཎᏊ⛣ື䝷䝆䜹䝹㔜ྜ(ATRP)䜢⏝䛔䛶䚸ศᏊ㔞䜢⢭ᐦ䛻ไᚚ䛧䚸 (N-methacryloxy sccinimide䠄N-ms䠅䛾 άᛶ䜶䝇䝔䝹ᇶ䜢᭷䛩䜛䝫䝸䝬䞊ྜᡂ䛩䜛䛣䛸䜢┠ⓗ䛸䛧䛯䚹䛣䛾ศᏊ䛿䚸άᛶ䜶䝇䝔䝹ᇶ䛾㒊ศ䛜䜰䝭䞁䛸ᐜ
᫆䛻⨨ᛂ䜢㉳䛣䛩䛯䜑䚸䜰䝭䝜ᇶᮎ➃䛾ᵝ䚻䛺ᶵ⬟ᅋ䛾ᑟධ䛜ྍ⬟䛸䛺䜛䛣䛸䛜ᮇᚅฟ᮶䜛䚹ᑟධ䛩䜛䝰 䝕䝹ศᏊ䛸䛧䛶䛿 N-dodecylacrylamide䠄DDA䠅䛸䛾㧗ศᏊᛂ䛻䛴䛔䛶᳨ウ䛧䛯䚹䜎䛪䚸p(N-ms)䛾㔜ྜ㐣⛬
䛷䛿䚸䝰䝜䝬䞊⃰ᗘ䜢㧗䛟䛩䜛䛸䚸㧗䛔㌿⋡䛜ᚓ䜙䜜䜛䛣䛸䛜ศ䛛䛳䛯䚹 䜎䛯䚸䝰䝕䝹ศᏊ䛾ᑟධ䛻㛵䛧䛶 䛿䚸䝇䜽䝅䞁䜲䝭䝗ᇶ⏤᮶䛾䝢䞊䜽䛾ῶᑡ䜘䜚䚸⣙9 䜋䛹⨨ᛂ䛜㉳䛣䛳䛶䛔䜛䛣䛸䛜䜟䛛䛳䛯䚹స〇䛧䛯䝫 䝸䝬䞊䛿䚸SEC䛻䜘䜛ศᏊ㔞䛾 ᐃ⤖ᯝ䛛䜙䚸10000௨ୖ䛾ศᏊ㔞䜢ᣢ䛱䚸ศᏊ㔞ศᕸ䛜1.5⛬ᗘ䛾ẚ㍑ⓗศ Ꮚ㔞䛾ᥞ䛳䛯㧗ศᏊ䝫䝸䝬䞊䛷䛒䜛䛣䛸䛜䜟䛛䛳䛯䚹