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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48519完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 童世煌(Shih-Huang Tung) | |
| dc.contributor.author | Xin-Guan Lin | en |
| dc.contributor.author | 林心冠 | zh_TW |
| dc.date.accessioned | 2021-06-15T07:00:15Z | - |
| dc.date.available | 2016-08-22 | |
| dc.date.copyright | 2011-08-22 | |
| dc.date.issued | 2011 | |
| dc.date.submitted | 2011-08-19 | |
| dc.identifier.citation | 1. Carothers WH, Dorough GL: Studies on polymerization and ring formation. IV. Ethylene succinates. Journal of the American Chemical Society 1930, 52:711-721.
2. Carothers WH, Van Natta FJ: Studies on polymerization and ring formation. III. Glycol esters of carbonic acid. Journal of the American Chemical Society 1930, 52:314-326. 3. Meier DJ: Theory of Block Copolymers .I. Domain Formation in a-B Block Copolymers. J Polym Sci Pol Sym 1969(26PC):81-&. 4. Helfand E: Block Copolymer Theory .3. Statistical-Mechanics of Microdomain Structure. Macromolecules 1975, 8(4):552-556. 5. Leibler L: Theory of Microphase Separation in Block Copolymers Macromolecules 1980, 13:1602-1617. 6. Vavasour JD, Whitmore MD: Self-Consistent Mean Field-Theory of the Microphases of Diblock Copolymers. Macromolecules 1992, 25(20):5477-5486. 7. Matsen MW, Bates FS: Unifying weak- and strong-segregation block copolymer theories. Macromolecules 1996, 29(4):1091-1098. 8. Khandpur AK, Forster S, Bates FS, Hamley IW, Ryan AJ, Bras W, Almdal K, Mortensen K: Polyisoprene-polystyrene diblock copolymer phase diagram near the order-disorder transition. Macromolecules 1995, 28(26):8796-8806. 9. Forster S, Khandpur AK, Zhao J, Bates FS, Hamley IW, Ryan AJ, Bras W: Complex Phase-Behavior of Polyisoprene-Polystyrene Diblock Copolymers near the Order-Disorder Transition. Macromolecules 1994, 27(23):6922-6935. 10. Hajduk DA, Takenouchi H, Hillmyer MA, Bates FS, Vigild ME, Almdal K: Stability of the perforated layer (PL) phase in diblock copolymer melts. Macromolecules 1997, 30(13):3788-3795. 11. Hajduk DA, Harper PE, Gruner SM, Honeker CC, Kim G, Thomas EL, Fetters LJ: The Gyroid - a New Equilibrium Morphology in Weakly Segregated Diblock Copolymers. Macromolecules 1994, 27(15):4063-4075. 12. Alward DB, Kinning DJ, Thomas EL, Fetters LJ: Effect of Arm Number and Arm Molecular-Weight on the Solid-State Morphology of Poly(Styrene-Isoprene) Star Block Copolymers. Macromolecules 1986, 19(1):215-224. 13. Thomas EL, Alward DB, Kinning DJ, Martin DC, Handlin DL, Fetters LJ: Ordered Bicontinuous Double-Diamond Structure of Star Block Copolymers - a New Equilibrium Microdomain Morphology. Macromolecules 1986, 19(8):2197-2202. 14. Bates FS, Fredrickson GH: Block copolymers - Designer soft materials. Phys Today 1999, 52(2):32-38. 15. Bucknall DG, Anderson HL: Polymers get organized. Science 2003, 302(5652):1904-1905. 16. Kim G, Libera M: Morphological development in solvent-cast polystyrene-polybutadiene-polystyrene (SBS) triblock copolymer thin films. Macromolecules 1998, 31(8):2569-2577. 17. Albalak RJ, Capel MS, Thomas EL: Solvent swelling of roll-cast triblock copolymer films. Polymer 1998, 39(8-9):1647-1656. 18. Fukunaga K, Hashimoto T, Elbs H, Krausch G: Self-assembly of a lamellar ABC triblock copolymer thin film. Macromolecules 2002, 35(11):4406-4413. 19. Knoll A, Horvat A, Lyakhova KS, Krausch G, Sevink GJA, Zvelindovsky AV, Magerle R: Phase behavior in thin films of cylinder-forming block copolymers. Phys Rev Lett 2002, 89(3):-. 20. Limary R, Green PF, Shull KR: Influence of surface ordering on the wetting of structured liquids. Eur Phys J E 2002, 8(2):103-110. 21. Limary R, Green PF: Dewetting instabilities in thin block copolymer films: Nucleation and growth. Langmuir 1999, 15(17):5617-5622. 22. Ruokolainen J, Saariaho M, Ikkala O, ten Brinke G, Thomas EL, Torkkeli M, Serimaa R: Supramolecular routes to hierarchical structures: Comb-coil diblock copolymers organized with two length scales. Macromolecules 1999, 32(4):1152-1158. 23. Ruokolainen J, Makinen R, Torkkeli M, Makela T, Serimaa R, ten Brinke G, Ikkala O: Switching supramolecular polymeric materials with multiple length scales. Science 1998, 280(5363):557-560. 24. Ruokolainen J, ten Brinke G, Ikkala O: Supramolecular polymeric materials with hierarchical structure-within-structure morphologies. Advanced Materials 1999, 11(9):777-780. 25. Ikkala O, Valkama S, Ruotsalainen T, Nykanen A, Laiho A, Kosonen H, ten Brinke G, Ruokolainen J: Self-assembled structures in diblock copolymers with hydrogen-bonded amphiphilic plasticizing compounds. Macromolecules 2006, 39(26):9327-9336. 26. Ruokolainen J, Ruotsalainen T, Turku J, Hiekkataipale P, Vainio U, Serimaa R, ten Brinke G, Harlin A, Ikkala O: Tailoring of the hierarchical structure within electrospun fibers due to supramolecular comb-coil block copolymers: polystyrene-block-poly(4-vinyl pyridine) plasticized by hydrogen bonded pentadecylphenol. Soft Matter 2007, 3(8):978-985. 27. Ikkala O, van Zoelen W, van Ekenstein GA, ten Brinke G: Incorporation of PPE in lamellar self-assembled PS-b-P4VP(PDP) supramolecules and PS-b-P4VP diblock copolymers. Macromolecules 2006, 39(19):6574-6579. 28. ten Brinke G, van Zoelen W, Asumaa T, Ruokolainen J, Ikkala O: Phase behavior of solvent vapor annealed thin films of PS-b-P4VP(PDP) supramolecules. Macromolecules 2008, 41(9):3199-3208. 29. Luyten MC, van Ekenstein GORA, ten Brinke G, Ruokolainen J, Ikkala O, Torkkeli M, Serimaa R: Crystallization and cocrystallization in supramolecular comb copolymer-like systems: Blends of poly(4-vinylpyridine) and pentadecylphenol. Macromolecules 1999, 32(13):4404-4410. 30. Ikkala O, ten Brinke G: Functional materials based on self-assembly of polymeric supramolecules. Science 2002, 295(5564):2407-2409. 31. Xu T, Tung SH: Templated Assembly of Block Copolymer toward Nonequilibrium Nanostructures in Thin Films. Macromolecules 2009, 42(15):5761-5765. 32. Kosonen H, Valkama S, Ruokolainen J, Torkkeli M, Serimaa R, ten Brinke G, Ikkala O: One-dimensional optical reflectors based on self-organization of polymeric comb-shaped supramolecules. Eur Phys J E 2003, 10(1):69-75. 33. Valkama S, Lehtonen O, Lappalainen K, Kosonen H, Castro P, Repo T, Torkkeli M, Serimaa R, ten Brinke G, Leskela M et al: Multicomb polymeric supramolecules and their self-organization: Combination of coordination and ionic interactions. Macromol Rapid Comm 2003, 24(9):556-560. 34. Ikkala O, ten Brinke G: Hierarchical self-assembly in polymeric complexes: Towards functional materials. Chem Commun 2004(19):2131-2137. 35. Ziegler K, Holzkamp E, Breil H, Martin H: The Mulheim Normal Pressure Polyethylene Process. Angew Chem Int Edit 1955, 67(19-2):541-547. 36. Natta G, Allegra G, Bassi IW, Carlini C, Chiellin.E, Montagno.G: Isomorphism Phenomena in Isotactic Poly(4-Methyl-Substituted Alpha-Olefins) and in Isotactic Poly(Alkyl Vinyl Ethers). Macromolecules 1969, 2(4):311-&. 37. McGehee MD, Heeger AJ: Semiconducting (conjugated) polymers as materials for solid-state lasers. Advanced Materials 2000, 12(22):1655-1668. 38. M.Gomberg: AN INSTANCE OF TRIVALENT CARBON. Journal of the American Chemical Society 1901, 22:757. 39. M.Gomberg: ON TRIVALENT CARBON. Journal of the American Chemical Society 1901, 25:320. 40. Szwarc M: Living Polymers. Nature 1956, 178(4543):1168-1169. 41. Darling TR, Davis TP, Fryd M, Gridnev AA, Haddleton DM, Ittel SD, Matheson RR, Moad G, Rizzardo E: Living polymerization: Rationale for uniform terminology. J Polym Sci Pol Chem 2000, 38(10):1706-1708. 42. Georges MK, Veregin RPN, Kazmaier PM, Hamer GK: Narrow Molecular-Weight Resins by a Free-Radical Polymerization Process. Macromolecules 1993, 26(11):2987-2988. 43. Hawker CJ: Molecular-Weight Control by a Living Free-Radical Polymerization Process. Journal of the American Chemical Society 1994, 116(24):11185-11186. 44. MacLeod PJ, Veregin RPN, Odell PG, Georges MK: Stable free radical polymerization of styrene: Controlling the process with low levels of nitroxide. Macromolecules 1997, 30(7):2207-2208. 45. Moad G, Solomon DH, Johns SR, Willing RI: Structure of Benzoyl Peroxide Initiated Polystyrene - Determination of the Initiator-Derived Functionality by C-13 Nmr. Macromolecules 1982, 15(4):1188-1191. 46. Bohrisch J, Wendler U, Jaeger W: Controlled radical polymerization of 4-vinylpyridine. Macromol Rapid Comm 1997, 18(11):975-982. 47. Wan XH, Tu HL, Tu YF, Zhang D, Sun L, Zhou QF, Dong YP, Tang M: Nitroxide-mediated free radical synthesis of mesogen-jacketed liquid crystal polymers. Chinese J Polym Sci 1999, 17(2):189-192. 48. Kazmaier PM, Daimon K, Georges MK, Hamer GK, Veregin RPN: Nitroxide-mediated 'living' free radical polymerization: A rapid polymerization of (chloromethyl)styrene for the preparation of random, block, and segmental arborescent polymers. Macromolecules 1997, 30(8):2228-2231. 49. Baethge H, Butz S, SchmidtNaake G: 'Living' free radical copolymerization of styrene and N-vinylcarbazole. Macromol Rapid Comm 1997, 18(10):911-916. 50. Fukuda T, Terauchi T, Goto A, Tsujii Y, Miyamoto T: Well-defined block copolymers comprising styrene acrylonitrile random copolymer sequences synthesized by 'living' radical polymerization. Macromolecules 1996, 29(8):3050-3052. 51. Listigovers NA, Georges MK, Odell PG, Keoshkerian B: Narrow-polydispersity diblock and triblock copolymers of alkyl acrylates by a 'living' stable free radical polymerization. Macromolecules 1996, 29(27):8992-8993. 52. Ananchenko GS, Souaille M, Fischer H, Le Mercier C, Tordo P: Decomposition of model alkoxyamines in simple and polymerizing systems. II. Diastereomeric N-(2-methylpropyl)-N-(1-diethyl-phosphono-2,2-dimethylpropyl)-aminoxyl-based compounds. J Polym Sci Pol Chem 2002, 40(19):3264-3283. 53. Georges MK, Lukkarila JL, Szkurhan AR: TEMPO-mediated n-butyl acrylate polymerizations. Macromolecules 2004, 37(4):1297-1303. 54. Zhang Y, Huan ACH, Tan KL, Kang ET: Surface modification of poly(tetrafluoroethylene) films by low energy Ar+ ion-beam activation and UV-induced graft copolymerization. Nucl Instrum Meth B 2000, 168(1):29-39. 55. Moon MW, Vaziri A: Surface modification of polymers using a multi-step plasma treatment. Scripta Mater 2009, 60(1):44-47. 56. Girardeaux C, Idrissi Y, Pireaux JJ, Caudano R: Etching and functionalization of a fluorocarbon polymer by UV laser treatment. Appl Surf Sci 1996, 96-8:586-590. 57. Mansky P: Controlling Polymer-Surface Interactions with Random Copolymer Brushes. Science 1997, 275(5305):1458-1460. 58. Ryu DY: A Generalized Approach to the Modification of Solid Surfaces. Science 2005, 308(5719):236-239. 59. In I, La YH, Park SM, Nealey PF, Gopalan P: Side-chain-grafted random copolymer brushes as neutral surfaces for controlling the orientation of block copolymer microdomains in thin films. Langmuir 2006, 22(18):7855-7860. 60. Han E, In I, Park SM, La YH, Wang Y, Nealey PF, Gopalan P: Photopatternable imaging layers for controlling block copolymer microdomain orientation. Advanced Materials 2007, 19(24):4448-+. 61. Han E, Gopalan P: Cross-Linked Random Copolymer Mats As Ultrathin Nonpreferential Layers for Block Copolymer Self-Assembly. Langmuir 2010, 26(2):1311-1315. 62. Han E, Stuen KO, Leolukman M, Liu C-C, Nealey PF, Gopalan P: Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions. Macromolecules 2009, 42(13):4896-4901. 63. Bang J, Bae J, Lowenhielm P, Spiessberger C, Given-Beck SA, Russell TP, Hawker CJ: Facile routes to patterned surface neutralization layers for block copolymer lithography. Advanced Materials 2007, 19(24):4552-+. 64. Ji S, Liu C-C, Son JG, Gotrik K, Craig GSW, Gopalan P, Himpsel FJ, Char K, Nealey PF: Generalization of the Use of Random Copolymers To Control the Wetting Behavior of Block Copolymer Films. Macromolecules 2008, 41(23):9098-9103. 65. http://highscope.ch.ntu.edu.tw. 66. J. R. Levine JBC, Y. W. Chung and P. Georgopoulos: Grazing-incidence small-angle X-ray scattering: new tool for studying thin film growth. Journal of Applied Crystallography 1989, 22:528-532 67. Flimetrics F20 User Manual, from Flimetrics, Inc. 68. Ahn B, Hirai T, Jin S, Rho Y, Kim KW, Kakimoto M, Gopalan P, Hayakawa T, Ree M: Hierarchical Structure in Nanoscale Thin Films of a Poly(styrene-b-methacrylate grafted with POSS) (PS214-b-PMAPOSS(27)). Macromolecules 2010, 43(24):10568-10581. 69. http://staff.chess.cornell.edu/~smilgies/gisaxs/GISAXS.php#levine. 70. Huang CF, Kuo SW, Chen JK, Chang FC: Synthesis and characterization of polystyrene-b-poly(4-vinyl pyridine) block copolymers by atom transfer radical polymerization. Journal of Polymer Research 2005, 12(6):449-456. 71. Cowie JMG, Henshall SAE: Influence of Chain-Length and Branching on Glass-Transition Temperature of Some Polyglucosans. European Polymer Journal 1976, 12(4):215-218. 72. Cowie JMG, Toporows.Pm: Dependence of Glass Temperature on Molecular Weight for Poly Alpha-Methyl Styrene. European Polymer Journal 1968, 4(5):621-&. 73. Tung SH, Lee CH: Microdomain control in block copolymer-based supramolecular thin films through varying the grafting density of additives. Soft Matter 2011, 7(12):5660-5668. 74. Maaloum M, Ausserre D, Chatenay D, Coulon G, Gallot Y: Edge Profile of Relief 2d Domains at the Free-Surface of Smectic Copolymer Thin-Films. Phys Rev Lett 1992, 68(10):1575-1578. 75. Nealey PF, Han E, Stuen KO, La YH, Gopalan P: Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains. Macromolecules 2008, 41(23):9090-9097. 76. van Ekenstein GORA, Meyboom R, ten Brinke G, Ikkala O: Determination of the Flory-Huggins interaction parameter of styrene and 4-vinylpyridine using copolymer blends of poly(styrene-co-4-vinylpyridine) and polystyrene. Macromolecules 2000, 33(10):3752-3756. 77. Russell TP, Hjelm RP, Seeger PA: Temperature-Dependence of the Interaction Parameter of Polystyrene and Poly(Methyl Methacrylate). Macromolecules 1990, 23(3):890-893. 78. Chin-Hung L: Grafting effects on the morphology of block copolymer-based supramolecular thin films. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48519 | - |
| dc.description.abstract | 本實驗研究以無規則共聚物表面改質後對於嵌段式共聚物PS-b-P4VP與超分子共聚物PS-b-P4VP(PDP)x薄膜微相分離之影響，以 BPO / TEMPO 所形成的氮氧自由基的方式合成無規則共聚物P(S-r-BCB-r-4VP)，將此無規則共聚物熱交聯在矽晶圓表面上形成一層網狀交聯的薄膜，探討嵌段式共聚物以及超分子共聚物薄膜在改質後的基板上之變化性。
在嵌段式共聚物系統下，我們使用層狀與柱狀兩種不同形態之嵌段式共聚物，以不同組成比例之無規則共聚物表面改質後，發現在未改質前 PS(20,000)-b-P4VP(17,000) 原本平躺於基板的層狀結構，在特定組成比例下可轉變成垂直於基板的層狀結構，且伴隨著島與洞的結構 (islands and holes)。在另一系統下，在未改質前PS(48,000)-b-P4VP(20,300) 原本平躺於基板的圓柱，在表面改質後可轉變為垂直於基板的圓柱。表面改質確是能夠改變嵌段式共聚物薄膜結構之方向性，因此，我們對於接枝上小分子之超分子共聚物薄膜在改質後的基板上之變化性也做更深入研究。 在超分子共聚物PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜系統下，將基板表面改質為一層P4VP網狀交聯的共聚物薄膜，可觀察到其大結構的轉變；在未改質前x = 0.5、1.0為平躺與垂直於基板的圓柱，在P4VP改質後其形態分別轉變為六角堆積之對穿層結構 (Hexagonally Perforated Layer，HPL) 以及平躺於基板的圓柱。另一方面，我們將表面以PS改質後，則觀察到在高接枝比例下 (x=0.8-1.5) ，小分子在薄膜底層排列的方向由垂直於基板方向轉變為平行於基板方向的層狀結構，然而大結構之形態與未改質前相似。 | zh_TW |
| dc.description.abstract | A series of benzocyclobutene-functionalized random copolymers of styrene and 4-vinylpyridine were synthesized by nitroxide-mediated controlled radical polymerization with BPO and TEMPO.Our research was to use these random copolymers [P(S-r-BCBr-4VP)] to control the orientation of microdomains in thin films of poly(styrene-b-4-vinylpyridine) block copolymer (PS-b-P4VP) and their supramolecules based on an ultrathin cross-linkable film.
We used PS(20,000)-b-P4VP(17,000) and PS(48,000)-b-P4VP(20,300) two kinds of block copolymers which possess lamella and cylinder in bulk morphology, respectively. In particular compositions of random copolymer,we found that the parallel orientation of lamella is switched to be perpendicular in PS(20,000)-b-P4VP(17,000) thin film with the formation of islands and holes.In another system,the parallel orientation of cylinders is switched to be perpendicular in PS(48,000)-b-P4VP(20,300) thin film.These results revealed that the modifid substrate can successfully control the orientation of microdomains in thin films.Therefore,we investigated the effects of modifid substrate on supramolecular thin films. On the P4VP-modified substrate, the surface morphology is dramatically changed.We found that the parallel and perpendicular orientation of cylinder is switched to be hexagonally perforated layer (HPL) and parallel orientation of cylinder,respectively.On the PS-modified substrate,we found that at the higher grafting density of PDP onto P4VP chains ,i.e x=0.8-1.5,the comb block lamellar orientation is switched to be perpendicular orientation of lamellae through the underlying thin film, nevertheless,the orientation of the large-scale cylinders were maintained. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T07:00:15Z (GMT). No. of bitstreams: 1 ntu-100-R98549020-1.pdf: 9786443 bytes, checksum: 6b3002b194c77460c6e648601baedbb6 (MD5) Previous issue date: 2011 | en |
| dc.description.tableofcontents | 目錄
口試委員會審定書 I 誌謝 II 摘要 III Abstract IV 目錄 V 圖目錄 VIII 表目錄 XIII 第一章 緒論 1 1-1 前言 1 1-2 研究動機 2 第二章 文獻回顧 3 2-1 嵌段式共聚物 3 2-2 嵌段式共聚物薄膜 8 2-3 超分子共聚物 12 2-4 高分子合成 18 2-4.1 自由基聚合 18 2-4.2 穩定自由基聚合 19 2-5 無規則共聚物表面改質對嵌段式共聚物微相分離之影響 24 第三章 實驗方法與儀器 32 3-1 實驗藥品 32 3-2 儀器原理 35 3-2.1 凝膠滲透層析儀 35 3-2.2 核磁共振儀 35 3-2.3 熱重分析儀 36 3-2.4 熱示差掃瞄卡量計 36 3-2.5 旋轉塗佈機 37 3-2.6 多波長折射率測量儀 37 3-2.7 表面輪廓計 38 3-2.8 原子力顯顯微鏡 38 3-2.9 掠角入射小角度X光散射儀 39 3-2.10 穿透式電子顯微鏡 39 3-2.11 接觸角測定儀 40 3-3 實驗步驟 43 3-3.1 單體純化 43 3-3.2 過氧化二苯甲醯再結晶 43 3-3.3 無規則共聚物P(S-r-BCB-r-4VP) 合成步驟 44 3-3.4 無規則共聚物 P(S-r-BCB) 合成步驟 44 3-3.5 無規則共聚物 P(4VP-r-BCB) 合成步驟 44 3-3.6 薄膜製備 45 3-3.7 退火裝置 46 第四章 結果與討論 50 4-1 無規則共聚物與單體結構鑑定 50 4-1.1 1H NMR光譜分析 50 4-1.2 無規則共聚物分子量及分子量分佈 59 4-2 無規則共聚物熱性質分析 61 4-2.1 熱示差掃瞄卡量計分析 61 4-2.2 熱重分析儀分析 61 4-3 無規則共聚物薄膜接觸角以及厚度量測 63 4-4 嵌段式共聚物PS-b-P4VP薄膜微相分離之形態 65 4-4.1 表面改質對PS(20,000)-b-P4VP(17,000)薄膜形態之影響 65 4-4.2 表面改質對PS(48,000)-b-P4VP(20,300)薄膜形態之影響 74 4-5 梳狀超分子共聚物PS(20,000)-b-P4VP(17,000)(PDP)x薄膜形態 78 4-5.1 超分子共聚物PS(20,000)-b-P4VP(17,000)(PDP)x薄膜形態 78 4-5.2 超分子共聚物薄膜在PB-4VP表面改質後之形態 85 4-5.3 超分子共聚物薄膜在PB-97表面改質後之形態 98 第五章 結論 107 第六章 文獻回顧 109 圖目錄 圖 2-1-1 各種嵌段式共聚物結構示意圖 5 圖 2-1-2 (1)交替式 (alternative) (2)無規則 (random)共聚物示意圖 5 圖 2-1-3 不同理論相圖之比較 6 圖 2-1-4 理論相圖與實驗相圖之比較 6 圖 2-1-5 雙嵌段式共聚物自組裝結構 7 圖 2-2-1 PS-P2VP-PtBMA以THF溶劑退火過程之側面TEM圖 10 圖 2-2-2 薄膜厚度影響薄膜之形態 10 圖 2-2-3 PS-b-PMMA薄膜厚度與自由能關係圖 11 圖 2-2-4 PS-b-PMMA薄膜隨著熱退火時間洞 (holes) 結構之演變 11 圖 2-3-1 PDP與PS-P4VP中P4VP鏈段形成氫鍵之示意圖 14 圖 2-3-2 PDP與PS-P4VP中P4VP鏈段形成離子鍵之示意圖 14 圖 2-3-3 配位錯化物形成自組裝結構 15 圖 2-3-4 PS-P4VP與過量之PDP鍵結之示意圖 15 圖 2-3-5 超分子共聚物自組裝後將雙親性小分子移除示意圖 16 圖 2-3-6 n-hexane將PDP移除後保留完整的六角堆積的結構 16 圖 2-3-7 P4VP(MSA)1.0(PDP)1.0 結構以及自組裝結構示意圖 17 圖 2-3-8 各類型超分子共聚物自組裝結構示意圖 17 圖 2-4-1 BPO/TEMPO控制自由基聚合反應之反應機構 23 圖 2-4-2 常見的氮氧化合物與其化學結構式 23 圖 2-5-1 官能基團位於高分子鏈上的不同位置 27 圖 2-5-2 P(S-r-BCB-r-MMA) 合成與交聯反應示意圖 27 圖 2-5-3 P(S-b-MMA) 在不同表面上之形態 28 圖 2-5-4 P(S-b-MMA) 在改質後的基板上由SEM所觀測到的影像 29 圖 2-5-5 UV/ozone方式清洗矽晶圓表面之P(S-b-MMA)薄膜形態 29 圖 2-5-6 高分子鏈以UV照射方式交聯示意圖 30 圖 2-5-7 PS-b-PMMA在厚的薄膜上所觀察到垂直於基板的結構 30 圖 2-5-8 PS-b-P2VP薄膜在不同組成比例下改質後的表面形態 31 圖 3-2-1 反射光光譜曲線 41 圖 3-2-2 AFM三種操作模式在原子位能圖的分佈示意圖 41 圖 3-2-3 GISAXS 量測示意圖 42 圖 3-2-4 GISAXS 散射峰與方向性之關係 42 圖 3-3-1 合成無規則共聚物之反應流程圖 48 圖 3-3-2 無規則共聚物薄膜熱交聯裝置示意圖 49 圖 3-3-3 常溫溶劑退火裝置示意圖 49 圖 4-1-1 單體4-Vinylbenzocyclobutene 1H NMR分析圖譜 50 圖 4-1-2 單體4-Vinylpyridine 1H NMR分析圖譜 51 圖 4-1-3 單體styrene 1H NMR分析圖譜 52 圖 4-1-4 PB-4VP 1H NMR圖譜分析 53 圖 4-1-5 PB-97 1H NMR圖譜分析 54 圖 4-1-6 PB-13 1H NMR圖譜分析 55 圖 4-1-7 PB-30 1H NMR圖譜分析 56 圖 4-1-8 PB-33 1H NMR圖譜分析 56 圖 4-1-9 PB-45 1H NMR圖譜分析 57 圖 4-1-10 PB-56 1H NMR圖譜分析 57 圖 4-1-11 PB-64 1H NMR圖譜分析 58 圖 4-1-12 PB-70 1H NMR圖譜分析 58 圖 4-1-13 PB-88 1H NMR圖譜分析 59 圖 4-2-1 無規則共聚物DSC圖譜分析 62 圖 4-2-2 無規則共聚物TGA分析 62 圖 4-3-1 無規則共聚物薄膜之接觸角 64 圖 4-4-1 PS(20,000)-b-P4VP(17,000) 塊材TEM影像 68 圖 4-4-2 PS(20,000)-b-P4VP(17,000) 薄膜在未改質的矽晶圓表面之形態 68 圖 4-4-3 PS(20,000)-b-P4VP(17,000) 薄膜表面改質後之形態 69 圖 4-4-4 PS(20,000)-b-P4VP(17,000) 薄膜島與洞之分析 70 圖 4-4-5 改變PS-b-P4VP薄膜厚度在PB-56改質後基板後之形態 71 圖 4-4-6 PS(20,000)-b-P4VP(17,000)薄膜在PB-56表面改質 GISAXS 結果 72 圖 4-4-7 PS(20,000)-b-P4VP(17,000)薄膜在PB-64表面改質 GISAXS 結果 73 圖 4-4-8 PS(48,000)-b-P4VP(20,300) 塊材TEM影像 76 圖 4-4-9 PS(48,000)-b-P4VP(20,300) 薄膜在未改質的矽晶圓表面之形態 76 圖 4-4-10 PS(48,000)-b-P4VP(20,300) 薄膜表面改質後之形態 77 圖 4-5-1 PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜之形態 80 圖 4-5-2 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜中自組裝結構示意圖 81 圖 4-5-3 PS(20,000)-b-P4VP(17,000)(PDP)1.0 薄膜中自組裝結構示意圖 81 圖 4-5-4 PS(20,000)-b-P4VP(17,000)(PDP)0.5 GISAXS分析結果 82 圖 4-5-5 PS(20,000)-b-P4VP(17,000)(PDP)0.8 GISAXS分析結果 83 圖 4-5-6 PS(20,000)-b-P4VP(17,000)(PDP)1.0 GISAXS分析結果 84 圖 4-5-7 PS(20,000)-b-P4VP(17,000)(PDP)x 在PB-4VP改質後基板上形態 88 圖 4-5-8 PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜以AFM不同敲擊模式觀察薄 膜表面之形態 89 圖 4-5-9 改變PS(20,000)-b-P4VP(17,000)(PDP)0.5薄膜厚度在PB-4VP改質後基板上之形態 90 圖 4-5-10 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜在PB-4VP基板改質後側面TEM影像 91 圖 4-5-11 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜在PB-4VP基板改質後之PL 形態示意圖 91 圖 4-5-12 PS(20,000)-b-P4VP(17,000)(PDP)x 以PB-4VP改質後形態為平躺於基 板示意圖 92 圖 4-5-13 PS(20,000)-b-P4VP(17,000)(PDP)x 以PB-4VP改質後形態為垂直於基板示意圖 92 圖 4-5-14 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜在PB-4VP表面改質後GISAXS結果 93 圖 4-5-15 PS(20,000)-b-P4VP(17,000)(PDP)0.8 薄膜在PB-4VP表面改質後GISAXS結果 94 圖 4-5-16 PS(20,000)-b-P4VP(17,000)(PDP)1.0 薄膜在PB-4VP表面改質後GISAXS結果 95 圖 4-5-17 PS(20,000)-b-P4VP(17,000)(PDP)1.5 薄膜在PB-4VP表面改質後GISAXS結果 96 圖 4-5-18 PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜在PB-97改質後之形態 100 圖 4-5-19 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜在PB-97表面改質之形態示意圖 101 圖 4-5-20 PS(20,000)-b-P4VP(17,000)(PDP)1.0 薄膜在PB-97表面改質之形態示意圖 101 圖 4-5-21 PS(20,000)-b-P4VP(17,000)(PDP)0.5 薄膜在PB-97表面改質後GISAXS結果 102 圖 4-5-22 PS(20,000)-b-P4VP(17,000)(PDP)0.8 薄膜在PB-97表面改質後GISAXS結果 103 圖 4-5-23 PS(20,000)-b-P4VP(17,000)(PDP)1.0 薄膜在PB-97表面改質後GISAXS結果 104 圖 4-5-24 PS(20,000)-b-P4VP(17,000)(PDP)1.5 薄膜在PB-97表面改質後GISAXS結果 105 圖 4-5-25 PS(20,000)-b-P4VP(17,000)(PDP)x 超薄膜以PB-97表面改質後之形態 106 表目錄 表 3-3-1 合成無規則共聚物反應物所加入之重量及莫耳數 48 表 4-1-1 無規則共聚物性質分析 60 表 4-5-1 PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜改質前後週期之比較 97 表 4-5-2 PS(20,000)-b-P4VP(17,000)(PDP)x 薄膜改質前後形態之比較 99 | |
| dc.language.iso | zh-TW | |
| dc.subject | TEMPO | zh_TW |
| dc.subject | 超分子 | zh_TW |
| dc.subject | 表面改質 | zh_TW |
| dc.subject | 無規則共聚物 | zh_TW |
| dc.subject | 薄膜 | zh_TW |
| dc.subject | 嵌段式共聚物 | zh_TW |
| dc.subject | substrate modification | en |
| dc.subject | TEMPO | en |
| dc.subject | block copolymer | en |
| dc.subject | supramolecule | en |
| dc.subject | thin film | en |
| dc.subject | random copolymer | en |
| dc.title | 無規則共聚物表面改質對嵌段式共聚物及其超分子薄膜結構之影響 | zh_TW |
| dc.title | Cross-Linked Random Copolymer Mats for Controlling the Orientation of Block Copolymers and their Supramolecules in Thin Films | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 99-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 廖文彬(Wen-Bin Liau),邱文英(Wen-Yen Chiu) | |
| dc.subject.keyword | 嵌段式共聚物,超分子,表面改質,無規則共聚物,薄膜,TEMPO, | zh_TW |
| dc.subject.keyword | TEMPO,block copolymer,supramolecule,thin film,random copolymer,substrate modification, | en |
| dc.relation.page | 114 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2011-08-19 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 高分子科學與工程學研究所 | |
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