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姓名	蘇凡鈞(Fan-jun Su)  查詢紙本館藏	畢業系所	化學工程與材料工程學系
論文名稱	混摻均聚物對團鏈共聚物微胞有序之影響 (Effects of Blending Homopolymers on Spatial Ordering of Block Copolymer Micelles)
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摘要(中)	本研究旨在探討透過混摻不同分子量的均聚物聚苯乙烯 (hPS) 來調控團鏈共聚物聚苯乙烯－聚4乙烯吡啶 (PS-b-P4VP) 微胞在四氫呋喃 (THF) 蒸氣中進行溶劑退火的側向有序性及微胞大小。我們發現短鏈長的hPS可以有效緩解PS-b-P4VP微胞－微胞間以及微胞－基材間受拉伸造成的自由能上升，且使PS-b-P4VP更趨向於球狀微胞結構，而此效果隨著鏈長的增加而降低，在長鏈長的hPS混摻下，由於長鏈上更喜好自糾纏而不喜參與微胞的組成，無法潤濕的乾毛刷將與PS-b-P4VP形成巨觀相分離，造成微胞由差排造成的有序性下降。而尾端皆有羫基的聚苯乙烯 (hPS-OH) 因其在矽基材 (SiOx/Si) 上具有更好的潤濕性能有效緩解基材與PS-b-P4VP鏈間拉伸所造成的自由能上升，因此在混摻相近分子量下的hPS-OH皆較混摻hPS有更低的缺陷密度和更高的有序性。 混摻均聚物對微胞結構重組的效應可分為三個階段： (1) 膨潤初期均聚物僅影響微胞的擴散速率造成有序性的變化，微胞大小影響並不明顯； (2) 膨潤充足後，均聚物才逐漸改變微胞的的大小； (3) 當退火結束的快速乾燥過程中，均聚物影響鏈的收縮亦影響到乾燥誘導微胞的有序性。透過KTHNY理論及GI-SAXS的量測可得混摻小分子量的HPs下長程方位有序以及近長程的平移有序，大範圍掃描所呈現的摩爾紋則發現在1個小時的THF退火下便可達到8*8 μm2的有序陣列。
摘要(英)	In this study, we aim to blend polystyrene homopolymerss (hPS) of various molar masses with PS-b-P4VP block copolymers (BCPs) to control the spatial ordering of spherical micelles on top of bare (SiOx/Si) during solvent vapour annealing (SVA) processes in THF vapour. Small amounts of hPS added into the PS-b-P4VP block copolymer easily induce the formation of spherical nanodomains with long-range spatial order and, on the other hand, added hPS and its derivatives with hydroxylic chain ends (hPS-OH) could interact with the substrate to relax the packing frustration of the PS-b-P4VP spherical micelles at planar interfaces, which further destroyed the packing order via a two-stage melting process. We find that blending shorter chains of hPS can more effectively bring about long-range orientational order and quasi-long range translational order of PS-b-P4VP micellar films. Also we find that the hydroxyl chain ends of hPS-OH preferentially reside at the substrate-film interface so as to improve wettability of the micelle films on the bare and PS-grafted substrates. As result, an 8 * 8 μm2 long-range order of arrays of PS-b-P4VP/PS micelles could be achieved by SVA under THF vapor.
關鍵字(中)	★ 團鏈共聚物 ★ 溶劑退火 ★ 有序 ★ KTHNY理論	關鍵字(英)	★ Block copolymer ★ Solvent vapor annealing ★ Ordering ★ KTHNY theory
論文目次	摘要 i Abstract ii 目錄 iv 圖目錄 vi 表目錄 xv 第一章 緒論 1 1-1 雙親性團鏈共聚物 1 1-1-1 雙親性團鏈共聚物的退火處理 3 1-1-2 雙親性團鏈共聚物的誘導自組裝 6 1-3 有序 – 無序相變化 12 1-3-1 徑向交互作用能勢 Pair Interaction Potential 12 1-3-2 KTHNY理論 19 1-4 混摻效應 27 1-4-1 薄膜中BCPs / HPs 混摻誘導之微胞構型演變 27 1-4-2 混摻之應用 30 1-6 實驗動機 32 第二章 實驗方法 34 2-1 實驗藥品 34 2-2 樣品製備 36 2-2-1 基材清潔 36 2-2-2 基材改質 36 2-2-3 薄膜成膜及溶劑退火 36 2-4 使用儀器 38 2-4-1 顯微影像觀察 38 2-4-2 X光散射分析 38 2-4-3 臨場觀察溶劑退火過程 40 第三章 結果與討論 41 3-1 PS-b-P4VP微胞型態 41 3-1-1 PS-b-P4VP微胞退火中的聚變－裂變行為 41 3-1-2 混摻HPs對PS-b-P4VP微胞之影響 44 3-1-3 不同退火時間下之演變 49 3-2 混摻hPS或hPS-OH對PS-b-P4VP微胞之有序性分析 58 3-2-1 摩爾紋分析 58 3-2-2 KTHNY理論分析 61 3-2-3 GI-SAXS分析 69 第四章 結論 87 參考資料 89 附錄 108 附錄1 Matlab code - 徑向分佈函數g(r) 108 附錄2 Matlab code - 方位關聯函數 g6(r) 110 附錄3 Matlab code - 平移關聯函數 gT(r) 113 附錄4 Matlab code - HNC Approximation 115
參考文獻	[1] Fontana, R. E.; Katine, J.; Rooks, M.; Viswanathan, R.; Lille, J.; MacDonald, S.; Kratschmer, E.; Tsang, C.; Nguyen, S.; Robertson, N.; Kasiraj, P. "E-beam writing: a next-generation lithography approach for thin-film head critical features." Magnetics, IEEE Transactions on 2002, 38，(1), 95-100. [2] Watt, F.; Bettiol, A. A.; Van Kan, J. A.; Teo, E. J.; Breese, M. B. H. "Ion Beam Lithography And Nanofabrication: A Review." International Journal of Nanoscience 2005, 04，(03), 269-286. [3] Cui, H.; Chen, Z.; Zhong, S.; Wooley, K. L.; Pochan, D. J. "Block Copolymer Assembly via Kinetic Control." Science 2007, 317，(5838), 647-650. [4] Segalman, R. A. "Patterning with block copolymer thin films." Materials Science and Engineering: R: Reports 2005, 48，(6), 191-226. [5] Hu, H.; Gopinadhan, M.; Osuji, C. O. "Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter." Soft Matter 2014, 10，(22), 3867-3889. [6] Lynd, N. A.; Meuler, A. J.; Hillmyer, M. A. "Polydispersity and block copolymer self-assembly." Prog. Polym. Sci. 2008, 33，(9), 875-893. [7] Gu, W.; Xu, J.; Kim, J.-K.; Hong, S. W.; Wei, X.; Yang, X.; Lee, K. Y.; Kuo, D. S.; Xiao, S.; Russell, T. P. "Solvent-Assisted Directed Self-Assembly of Spherical Microdomain Block Copolymers to High Areal Density Arrays." Adv. Mater. 2013, 25，(27), 3677-3682. [8] Cheng, J. Y.; Ross, C. A.; Chan, V. Z. H.; Thomas, E. L.; Lammertink, R. G. H.; Vancso, G. J. "Formation of a cobalt magnetic dot array via block copolymer lithography." Adv. Mater. 2001, 13，(15), 1174-1178. [9] Luo, M.; Epps, T. H. "Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication." Macromolecules 2013, 46，(19), 7567-7579. [10] Bates, C. M.; Maher, M. J.; Janes, D. W.; Ellison, C. J.; Willson, C. G. "Block Copolymer Lithography." Macromolecules 2013, 47，(1), 2-12. [11] Ruiz, R.; Kang, H.; Detcheverry, F. A.; Dobisz, E.; Kercher, D. S.; Albrecht, T. R.; de Pablo, J. J.; Nealey, P. F. "Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly." Science 2008, 321，(5891), 936-939. [12] Hazut, O.; Huang, B.-C.; Pantzer, A.; Amit, I.; Rosenwaks, Y.; Kohn, A.; Chang, C.-S.; Chiu, Y.-P.; Yerushalmi, R. "Parallel p-n Junctions across Nanowires by One-Step ex-situ Doping." ACS Nano 2014. [13] Kim, S. H.; Misner, M. J.; Xu, T.; Kimura, M.; Russell, T. P. "Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation." Adv. Mater. 2004, 16，(3), 226-231. [14] Kim, T. H.; Huh, J.; Hwang, J.; Kim, H. C.; Kim, S. H.; Sohn, B. H.; Park, C. "Ordered Arrays of PS-b-P4VP Micelles by Fusion and Fission Process upon Solvent Annealing." Macromolecules 2009, 42，(17), 6688-6697. [15] Sinturel, C.; Vayer, M.; Morris, M.; Hillmyer, M. A. "Solvent Vapor Annealing of Block Polymer Thin Films." Macromolecules 2013, 46，(14), 5399-5415. [16] Yokoyama, H.; Kramer, E. J. "Self-Diffusion of Asymmetric Diblock Copolymers with a Spherical Domain Structure." Macromolecules 1998, 31，(22), 7871-7876. [17] Lodge, T. P.; Blazey, M. A.; Liu, Z.; Hamley, I. W. "Asymmetric block copolymers in neutral good solvents: self-diffusion through the ordering transition." Macromol. Chem. Phys. 1997, 198，(4), 983-995. [18] Li, Y.; Wang, X.; Sanchez, I. C.; Johnston, K. P.; Green, P. F. "Ordering in asymmetric block copolymer films by a compressible fluid." J. Phys. Chem. B 2007, 111，(1), 16-25. [19] Peng, J.; Kim, D. H.; Knoll, W.; Xuan, Y.; Li, B.; Han, Y. "Morphologies in solvent-annealed thin films of symmetric diblock copolymer." J. Chem. Phys. 2006, 125，(6), 64702. [20] Paik, M. Y.; Bosworth, J. K.; Smilges, D. M.; Schwartz, E. L.; Andre, X.; Ober, C. K. "Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An in Situ GISAXS Study." Macromolecules 2010, 43，(9), 4253-4260. [21] Gotrik, K. W.; Hannon, A. F.; Son, J. G.; Keller, B.; Alexander-Katz, A.; Ross, C. A. "Morphology Control in Block Copolymer Films Using Mixed Solvent Vapors." ACS Nano 2012, 6，(9), 8052-8059. [22] She, M.-S.; Lo, T.-Y.; Ho, R.-M. "Controlled Ordering of Block Copolymer Gyroid Thin Films by Solvent Annealing." Macromolecules 2013, 47，(1), 175-182. [23] Jeong, J. W.; Park, W. I.; Kim, M. J.; Ross, C. A.; Jung, Y. S. "Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine-b-dimethylsiloxane) Block Copolymer." Nano Lett. 2011, 11，(10), 4095-4101. [24] Albert, J. N. L.; Bogart, T. D.; Lewis, R. L.; Beers, K. L.; Fasolka, M. J.; Hutchison, J. B.; Vogt, B. D.; Epps, T. H. "Gradient Solvent Vapor Annealing of Block Copolymer Thin Films Using a Microfluidic Mixing Device." Nano Lett. 2011, 11，(3), 1351-1357. [25] Seppala, J. E.; Lewis, R. L.; Epps, T. H. "Spatial and Orientation Control of Cylindrical Nanostructures in ABA Triblock Copolymer Thin Films by Raster Solvent Vapor Annealing." ACS Nano 2012, 6，(11), 9855-9862. [26] Albert, J. N. L.; Young, W. S.; Lewis, R. L.; Bogart, T. D.; Smith, J. R.; Epps, T. H. "Systematic Study on the Effect of Solvent Removal Rate on the Morphology of Solvent Vapor Annealed ABA Triblock Copolymer Thin Films." Acs Nano 2012, 6，(1), 459-466. [27] Gu, X.; Gunkel, I.; Hexemer, A.; Gu, W.; Russell, T. P. "An In Situ Grazing Incidence X-Ray Scattering Study of Block Copolymer Thin Films During Solvent Vapor Annealing." Adv. Mater. 2014, 26，(2), 273-281. [28] Smilgies, D. M.; Busch, P.; Papadakis, C. M.; Posselt, D. "Characterization of polymer thin films with small‐angle X‐ray scattering under grazing incidence (GISAXS)." Synchrotron Radiation News 2002, 15，(5), 35-42. [29] Papadakis, C. M.; Di, Z.; Posselt, D.; Smilgies, D.-M. "Structural Instabilities in Lamellar Diblock Copolymer Thin Films During Solvent Vapor Uptake." Langmuir 2008, 24，(24), 13815-13818. [30] Di, Z.; Posselt, D.; Smilgies, D.-M.; Papadakis, C. M. "Structural Rearrangements in a Lamellar Diblock Copolymer Thin Film during Treatment with Saturated Solvent Vapor." Macromolecules 2009, 43，(1), 418-427. [31] Di, Z. Y.; Posselt, D.; Smilgies, D. M.; Li, R. P.; Rauscher, M.; Potemkin, I. I.; Papadakis, C. M. "Stepwise Swelling of a Thin Film of Lamellae-Forming Poly(styrene-b-butadiene) in Cyclohexane Vapor." Macromolecules 2012, 45，(12), 5185-5195. [32] Kim, E.; Ahn, H.; Park, S.; Lee, H.; Lee, M.; Lee, S.; Kim, T.; Kwak, E.-A.; Lee, J. H.; Lei, X.; Huh, J.; Bang, J.; Lee, B.; Ryu, D. Y. "Directed Assembly of High Molecular Weight Block Copolymers: Highly Ordered Line Patterns of Perpendicularly Oriented Lamellae with Large Periods." ACS Nano 2013, 7，(3), 1952-1960. [33] Zhang, X.; Harris, K. D.; Wu, N. L. Y.; Murphy, J. N.; Buriak, J. M. "Fast Assembly of Ordered Block Copolymer Nanostructures through Microwave Annealing." ACS Nano 2010, 4，(11), 7021-7029. [34] Borah, D.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. "Sub-10 nm Feature Size PS-b-PDMS Block Copolymer Structures Fabricated by a Microwave-Assisted Solvothermal Process." ACS Appl. Mater. & Inter. 2013, 5，(6), 2004-2012. [35] Park, W. I.; Kim, K.; Jang, H. I.; Jeong, J. W.; Kim, J. M.; Choi, J.; Park, J. H.; Jung, Y. S. "Directed Self-Assembly with Sub-100 Degrees Celsius Processing Temperature, Sub-10 Nanometer Resolution, and Sub-1 Minute Assembly Time." Small 2012, 8，(24), 3762-3768. [36] Gotrik, K. W.; Ross, C. A. "Solvothermal Annealing of Block Copolymer Thin Films." Nano Lett. 2013, 13，(11), 5117-5122. [37] Jin, C.; Murphy, J. N.; Harris, K. D.; Buriak, J. M. "Deconvoluting the Mechanism of Microwave Annealing of Block Copolymer Thin Films." ACS Nano 2014, 8，(4), 3979-3991. [38] Borah, D.; Senthamaraikannan, R.; Rasappa, S.; Kosmala, B.; Holmes, J. D.; Morris, M. A. "Swift Nanopattern Formation of PS-b-PMMA and PS-b-PDMS Block Copolymer Films Using a Microwave Assisted Technique." ACS Nano 2013, 7，(8), 6583-6596. [39] Zhang, X.; Murphy, J. N.; Wu, N. L. Y.; Harris, K. D.; Buriak, J. M. "Rapid Assembly of Nanolines with Precisely Controlled Spacing from Binary Blends of Block Copolymers." Macromolecules 2011, 44，(24), 9752-9757. [40] Knoll, A.; Horvat, A.; Lyakhova, K. S.; Krausch, G.; Sevink, G. J.; Zvelindovsky, A. V.; Magerle, R. "Phase behavior in thin films of cylinder-forming block copolymers." Phys. Rev. Lett. 2002, 89，(3), 035501. [41] Tsarkova, L. "Distortion of a Unit Cell versus Phase Transition to Nonbulk Morphology in Frustrated Films of Cylinder-Forming Polystyrene-b-polybutadiene Diblock Copolymers." Macromolecules 2012, 45，(19), 7985-7994. [42] Luo, M.; Seppala, J. E.; Albert, J. N. L.; Lewis, R. L.; Mahadevapuram, N.; Stein, G. E.; Epps, T. H. "Manipulating Nanoscale Morphologies in Cylinder-Forming Poly(styrene-b-isoprene-b-styrene) Thin Films Using Film Thickness and Substrate Surface Chemistry Gradients." Macromolecules 2013, 46，(5), 1803-1811. [43] Knoll, A.; Tsarkova, L.; Krausch, G. "Nanoscaling of Microdomain Spacings in Thin Films of Cylinder-Forming Block Copolymers." Nano Lett. 2007, 7，(3), 843-846. [44] Stein, G. E.; Cochran, E. W.; Katsov, K.; Fredrickson, G. H.; Kramer, E. J.; Li, X.; Wang, J. "Symmetry Breaking of In-Plane Order in Confined Copolymer Mesophases." Phys. Rev. Lett. 2007, 98，(15), 158302. [45] Stein, G. E.; Kramer, E. J.; Li, X.; Wang, J. "Layering Transitions in Thin Films of Spherical-Domain Block Copolymers." Macromolecules 2007, 40，(7), 2453-2460. [46] Mishra, V.; Hur, S.-m.; Cochran, E. W.; Stein, G. E.; Fredrickson, G. H.; Kramer, E. J. "Symmetry Transition in Thin Films of Diblock Copolymer/Homopolymer Blends." Macromolecules 2010, 43，(4), 1942-1949. [47] Segalman, R. A.; Yokoyama, H.; Kramer, E. J. "Graphoepitaxy of spherical domain block copolymer films." Adv. Mater. 2001, 13，(15), 1152-1155. [48] Park, S.; Lee, D. H.; Xu, J.; Kim, B.; Hong, S. W.; Jeong, U.; Xu, T.; Russell, T. P. "Macroscopic 10-Terabit–per–Square-Inch Arrays from Block Copolymers with Lateral Order." Science 2009, 323，(5917), 1030-1033. [49] Hong, S. W.; Voronov, D. L.; Lee, D. H.; Hexemer, A.; Padmore, H. A.; Xu, T.; Russell, T. P. "Controlled Orientation of Block Copolymers on Defect-Free Faceted Surfaces." Adv. Mater. 2012, 24，(31), 4278-4283. [50] Hong, S. W.; Huh, J.; Gu, X. D.; Lee, D. H.; Jo, W. H.; Park, S.; Xu, T.; Russell, T. P. "Unidirectionally aligned line patterns driven by entropic effects on faceted surfaces." Proc. Natl. Acad. Sci. U.S.A. 2012, 109，(5), 1402-1406. [51] Detcheverry, F. o. A.; Liu, G.; Nealey, P. F.; de Pablo, J. J. "Interpolation in the Directed Assembly of Block Copolymers on Nanopatterned Substrates: Simulation and Experiments." Macromolecules 2010, 43，(7), 3446-3454. [52] Moon, H.-S.; Shin, D. O.; Kim, B. H.; Jin, H. M.; Lee, S.; Lee, M. G.; Kim, S. O. "Large-area, highly oriented lamellar block copolymer nanopatterning directed by graphoepitaxially assembled cylinder nanopatterns." J. Mater. Chem. 2012, 22，(13), 6307-6310. [53] Yang, J. K. W.; Jung, Y. S.; Chang, J.-B.; Mickiewicz, R. A.; Alexander Katz, A.; Ross, C. A.; Berggren, K. K. "Complex self-assembled patterns using sparse commensurate templates with locally varying motifs." Nat. Nano 2010, 5，(4), 256-260. [54] Tavakkoli K. G., A.; Gotrik, K. W.; Hannon, A. F.; Alexander-Katz, A.; Ross, C. A.; Berggren, K. K. "Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films." Science 2012, 336，(6086), 1294-1298. [55] Kulkarni, M. M.; Yager, K. G.; Sharma, A.; Karim, A. "Combinatorial Block Copolymer Ordering on Tunable Rough Substrates." Macromolecules 2012, 45，(10), 4303-4314. [56] Sivaniah, E.; Hayashi, Y.; Matsubara, S.; Kiyono, S.; Hashimoto, T.; Kukunaga, K.; Kramer, E. J.; Mates, T. "Symmetric diblock copolymer thin films on rough substrates. Kinetics and structure formation in pure block copolymer thin films." Macromolecules 2005, 38，(5), 1837-1849. [57] Chang, C.-Y.; Lee, Y.-C.; Wu, P.-J.; Liou, J.-Y.; Sun, Y.-S.; Ko, B.-T. "Micellar Transitions in Solvent-Annealed Thin Films of an Amphiphilic Block Copolymer Controlled with Tunable Surface Fields." Langmuir 2011, 27，(23), 14545-14553. [58] Chang, C. Y.; Wu, P. J.; Sun, Y. S. "Kinetically controlled self-assembly of monolayered micelle films of P(S-b-4VP) on bare and PS-grafted substrates." Soft Matter 2011, 7，(19), 9140-9147. [59] Park, S.; Kim, B.; Xu, J.; Hofmann, T.; Ocko, B. M.; Russell, T. P. "Lateral Ordering of Cylindrical Microdomains Under Solvent Vapor." Macromolecules 2009, 42，(4), 1278-1284. [60] Chang, C. Y.; Lee, Y. C.; Wu, P. J.; Liou, J. Y.; Sun, Y. S.; Ko, B. T. "Micellar Transitions in Solvent-Annealed Thin Films of an Amphiphilic Block Copolymer Controlled with Tunable Surface Fields." Langmuir 2011, 27，(23), 14545-14553. [61] Tracz, A.; Jeszka, J. K.; Watson, M. D.; Pisula, W.; Müllen, K.; Pakula, T. "Uniaxial Alignment of the Columnar Super-Structure of a Hexa (Alkyl) Hexa-peri-hexabenzocoronene on Untreated Glass by Simple Solution Processing." JACS 2003, 125，(7), 1682-1683. [62] Hashimoto, T.; Bodycomb, J.; Funaki, Y.; Kimishima, K. "The Effect of Temperature Gradient on the Microdomain Orientation of Diblock Copolymers Undergoing an Order−Disorder Transition." Macromolecules 1999, 32，(3), 952-954. [63] Angelescu, D. E.; Waller, J. H.; Adamson, D. H.; Register, R. A.; Chaikin, P. M. "Enhanced Order of Block Copolymer Cylinders in Single-Layer Films Using a Sweeping Solidification Front." Adv. Mater. 2007, 19，(18), 2687-2690. [64] Berry, B. C.; Bosse, A. W.; Douglas, J. F.; Jones, R. L.; Karim, A. "Orientational Order in Block Copolymer Films Zone Annealed below the Order−Disorder Transition Temperature." Nano Lett. 2007, 7，(9), 2789-2794. [65] Yager, K. G.; Fredin, N. J.; Zhang, X.; Berry, B. C.; Karim, A.; Jones, R. L. "Evolution of block-copolymer order through a moving thermal zone." Soft Matter 2010, 6，(1), 92-99. [66] Singh, G.; Yager, K. G.; Smilgies, D.-M.; Kulkarni, M. M.; Bucknall, D. G.; Karim, A. "Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing." Macromolecules 2012, 45，(17), 7107-7117. [67] Singh, G.; Batra, S.; Zhang, R.; Yuan, H.; Yager, K. G.; Cakmak, M.; Berry, B.; Karim, A. "Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films." ACS Nano 2013, 7，(6), 5291-5299. [68] Singh, G.; Yager, K. G.; Berry, B.; Kim, H.-C.; Karim, A. "Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films." ACS Nano 2012, 6，(11), 10335-10342. [69] Yokoyama, H.; Mates, T. E.; Kramer, E. J. "Structure of asymmetric diblock copolymers in thin films." Macromolecules 2000, 33，(5), 1888-1898. [70] Sakamoto, N.; Hashimoto, T.; Han, C. D.; Kim, D.; Vaidya, N. Y. "Order−Order and Order−Disorder Transitions in a Polystyrene-block-Polyisoprene-block-Polystyrene Copolymer." Macromolecules 1997, 30，(6), 1621-1632. [71] Yokoyama, H.; Kramer, E. J.; Rafailovich, M. H.; Sokolov, J.; Schwarz, S. A. "Structure and diffusion of asymmetric diblock copolymers in thin films: A dynamic secondary ion mass spectrometry study." Macromolecules 1998, 31，(25), 8826-8830. [72] Han, C. D.; Vaidya, N. Y.; Kim, D.; Shin, G.; Yamaguchi, D.; Hashimoto, T. "Lattice disordering/ordering and demicellization/micellization transitions in highly asymmetric polystyrene-block-polyisoprene copolymers." Macromolecules 2000, 33，(10), 3767-3780. [73] Sakamoto, N.; Hashimoto, T. "Ordering dynamics of cylindrical and spherical microdomains in polystyrene-block-polyisoprene-block-polystyrene. 1. SAXS and TEM observations for the grain formation." Macromolecules 1998, 31，(24), 8493-8502. [74] Sakamoto, N.; Hashimoto, T.; Han, C. D.; Kim, D.; Vaidya, N. Y. "Order-order and order-disorder transitions in a polystyrene-block-polyisoprene-block-polystyrene copolymer." Macromolecules 1997, 30，(6), 1621-1632. [75] Adams, J. L.; Graessley, W. M.; Register, R. A. "Rheology and the Microphase Separation Transition in Styrene-Isoprene Block-Copolymers." Macromolecules 1994, 27，(21), 6026-6032. [76] Adams, J. L.; Quiram, D. J.; Graessley, W. W.; Register, R. A.; Marchand, G. R. "Ordering dynamics of compositionally asymmetric styrene isoprene block copolymers." Macromolecules 1996, 29，(8), 2929-2938. [77] Schwab, M.; Stuhn, B. "Thermotropic transition from a state of liquid order to a macrolattice in asymmetric diblock copolymers." Phys. Rev. Lett. 1996, 76，(6), 924-927. [78] Schwab, M.; Stuhn, B. "Asymmetric diblock copolymers - Phase behaviour and kinetics of structure formation." Colloid. Polym. Sci. 1997, 275，(4), 341-351. [79] Bates, F. S.; Fredrickson, G. H. "Block Copolymer Thermodynamics - Theory and Experiment." Annu. Rev. Phys. Chem. 1990, 41, 525-557. [80] Dormidontova, E. E.; Lodge, T. P. "The order-disorder transition and the disordered micelle regime in sphere-forming block copolymer melts." Macromolecules 2001, 34，(26), 9143-9155. [81] McQuarrie, D. A., Statistical mechanics. University Science Books: Sausalito, Calif., 2000. [82] Stirpe, D.; Tompson, C. W. "Diffraction of X Rays by Liquid Neon." J. Chem. Phy. 1962, 36，(2), 392-398. [83] McConnell, G. A.; Gast, A. P. "Predicting disorder-order phase transitions in polymeric micelles." Phys. Rev. E 1996, 54，(5), 5447-5455. [84] McConnell, G. A.; Gast, A. P.; Huang, J. S.; Smith, S. D. "Disorder-order transitions in soft sphere polymer micelles." Phys. Rev. Lett. 1993, 71，(13), 2102-2105. [85] Robbins, M. O.; Kremer, K.; Grest, G. S. "Phase diagram and dynamics of Yukawa systems." J. Chem. Phy. 1988, 88，(5), 3286-3312. [86] McEwan, M. E.; Egorov, S. A.; Ilavsky, J.; Green, D. L.; Yang, Y. "Mechanical reinforcement of polymer nanocomposites: theory and ultra-small angle X-ray scattering (USAXS) studies." Soft Matter 2011, 7，(6), 2725-2733. [87] Korgel, B. A.; Fitzmaurice, D. "Small-angle x-ray-scattering study of silver-nanocrystal disorder-order phase transitions." Phys. Rev. B: Condens. Matter 1999, 59，(22), 14191-14201. [88] Kosterlitz, J. M.; Thouless, D. J. "Long range order and metastability in two dimensional solids and superfluids. (Application of dislocation theory)." J. Phy. C: Sol. Sta. Phy. 1972, 5，(11), L124. [89] Kosterlitz, J. M.; Thouless, D. J. "Ordering, metastability and phase transitions in two-dimensional systems." J. Phy. C: Sol. Sta. Phy. 1973, 6，(7), 1181. [90] Halperin, B. I.; Nelson, D. R. "Theory of Two-Dimensional melting." Phys. Rev. Lett. 1978, 41，(2), 121-124. [91] Nelson, D. R.; Halperin, B. I. "Dislocation-mediated melting in two dimensions." Phys. Rev. B 1979, 19，(5), 2457-2484. [92] Young, A. P. "Melting and the vector Coulomb gas in two dimensions." Phys. Rev. B 1979, 19，(4), 1855-1866. [93] Marcus, A. H.; Rice, S. A. "Phase transitions in a confined quasi-two-dimensional colloid suspension." Phys. Rev. E 1997, 55，(1), 637-656. [94] Schweigert, I. V.; Schweigert, V. A.; Peeters, F. M. "Radial-Fluctuation-Induced Stabilization of the Ordered State in Two-Dimensional Classical Clusters." Phys. Rev. Lett. 2000, 84，(19), 4381-4384. [95] Kalia, R. K.; Vashishta, P. "Interfacial colloidal crystals and melting transition." J. Phy. C: Sol. Sta. Phy. 1981, 14，(22), L643. [96] Kalia, R. K.; Vashishta, P.; de Leeuw, S. W. "Melting of a two-dimensional electron lattice." Phys. Rev. B 1981, 23，(9), 4794-4797. [97] Bedanov, V. M.; Gadiyak, G. V.; Lozovik, Y. E. "Melting in a two dimensional system with dipole interaction." Phys. Lett. A 1982, 92，(8), 400-402. [98] Li, M.; Johnson, W. L.; Goddard, W. A. "Evidence of hexatic phase formation in two-dimensional Lennard-Jones binary arrays." Phys. Rev. B 1996, 54，(17), 12067-12072. [99] Bagchi, K.; Andersen, H. C.; Swope, W. "Observation of a two-stage melting transition in two dimensions." Phys. Rev. E 1996, 53，(4), 3794-3803. [100] Jaster, A. "Computer simulations of the two-dimensional melting transition using hard disks." Phys. Rev. E 1999, 59，(3), 2594-2602. [101] Strandburg, K. J. "Two-dimensional melting." Rev. Mod. Phys. 1988, 60，(1), 161-207. [102] Marcus, A. H.; Rice, S. A. "Observations of first-order liquid-to-hexatic and hexatic-to-solid phase transitions in a confined colloid suspension." Phys. Rev. Lett. 1996, 77，(12), 2577-2580. [103] Murray, C. A.; Sprenger, W. O.; Wenk, R. A. "Comparison of Melting in 3 and 2 Dimensions - Microscopy of Colloidal Spheres." Phys. Rev. B 1990, 42，(1), 688-703. [104] Murray, C. A.; Vanwinkle, D. H.; Wenk, R. A. "Digital Imaging Studies of Submicron Colloidal Spheres Confined into a Single Layer between 2 Smooth Glass Plates - 2-Dimensional Melting." Phase Transitions 1990, 21，(2-4), 93-126. [105] Murray, C. A.; Van Winkle, D. H. "Experimental observation of two-stage melting in a classical two-dimensional screened Coulomb system." Phys. Rev. Lett. 1987, 58，(12), 1200-1203. [106] Van Winkle, D. H.; Murray, C. A. "Layering in colloidal fluids near a smooth repulsive wall." J. Chem. Phy. 1988, 89，(6), 3885-3891. [107] Segalman, R. A.; Hexemer, A.; Hayward, R. C.; Kramer, E. J. "Ordering and melting of block copolymer spherical domains in 2 and 3 dimensions." Macromolecules 2003, 36，(9), 3272-3288. [108] Segalman, R. A.; Hexemer, A.; Kramer, E. J. "Effects of lateral confinement on order in spherical domain block copolymer thin films." Macromolecules 2003, 36，(18), 6831-6839. [109] Segalman, R. A.; Hexemer, A.; Kramer, E. J. "Edge effects on the order and freezing of a 2D array of block copolymer spheres." Phys. Rev. Lett. 2003, 91，(19), 196101. [110] Stein, G. E.; Kramer, E. J.; Li, X.; Wang, J. "Single-crystal diffraction from two-dimensional block copolymer arrays." Phys. Rev. Lett. 2007, 98，(8). [111] Sohn, B.-H.; Choi, J.-M.; Yoo, S. I.; Yun, S.-H.; Zin, W.-C.; Jung, J. C.; Kanehara, M.; Hirata, T.; Teranishi, T. "Directed Self-Assembly of Two Kinds of Nanoparticles Utilizing Monolayer Films of Diblock Copolymer Micelles." JACS 2003, 125，(21), 6368-6369. [112] Peng, Q.; Tseng, Y.-C.; Darling, S. B.; Elam, J. W. "A Route to Nanoscopic Materials via Sequential Infiltration Synthesis on Block Copolymer Templates." ACS Nano 2011, 5，(6), 4600-4606. [113] de Gennes, P. G. "Conformations of Polymers Attached to an Interface." Macromolecules 1980, 13，(5), 1069-1075. [114] Leibler, L.; Orland, H.; Wheeler, J. C. "Theory of critical micelle concentration for solutions of block copolymers." J. Chem. Phy. 1983, 79，(7), 3550-3557. [115] Semenov, A. N. "Theory of diblock-copolymer segregation to the interface and free surface of a homopolymer layer." Macromolecules 1992, 25，(19), 4967-4977. [116] Pépin, M. P.; Whitmore, M. D. "Monte Carlo and Mean Field Study of Diblock Copolymer Micelles." Macromolecules 2000, 33，(23), 8644-8653. [117] Cavallo, A.; Müller, M.; Binder, K. "Monte Carlo Simulation of a Homopolymer−Copolymer Mixture Interacting with a Surface: Bulk versus Surface Micelles and Brush Formation." Macromolecules 2008, 41，(13), 4937-4944. [118] Shull, K. R.; Kramer, E. J.; Hadziioannou, G.; Tang, W. "Segregation of block copolymers to interfaces between immiscible homopolymers." Macromolecules 1990, 23，(22), 4780-4787. [119] Retsos, H.; Terzis, A. F.; Anastasiadis, S. H.; Anastassopoulos, D. L.; Toprakcioglu, C.; Theodorou, D. N.; Smith, G. S.; Menelle, A.; Gill, R. E.; Hadziioannou, G.; Gallot, Y. "Mushrooms and Brushes in Thin Films of Diblock Copolymer/Homopolymer Mixtures." Macromolecules 2001, 35，(3), 1116-1132. [120] Winey, K. I.; Thomas, E. L.; Fetters, L. J. "Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight." Macromolecules 1991, 24，(23), 6182-6188. [121] Shull, K. R.; Winey, K. I.; Thomas, E. L.; Kramer, E. J. "Segregation of block copolymer micelles to surfaces and interfaces." Macromolecules 1991, 24，(10), 2748-2751. [122] Whitmore, M. D.; Noolandi, J. "Theory of phase equilibria in block copolymer-homopolymer blends." Macromolecules 1985, 18，(12), 2486-2497. [123] Chen, X. C.; Yang, H.; Green, P. F. "Tethered-Polymer Structures in Thin Film Polymer Melts." Macromolecules 2011, 44，(14), 5758-5763. [124] Chen, X. C.; Yang, H.; Green, P. F. "Micellar Formation and Organization in Thin Film Polymer Blends." Macromolecules 2012, 45，(9), 3993-4000. [125] Oslanec, R.; Costa, A. C.; Composto, R. J.; Vlcek, P. "Effect of Block Copolymer Adsorption on Thin Film Dewetting Kinetics." Macromolecules 2000, 33，(15), 5505-5512. [126] Kim, B.; Ryu, D. Y.; Pryamitsyn, V.; Ganesan, V. "Dewetting of PMMA on PS−Brush Substrates." Macromolecules 2009, 42，(20), 7919-7923. [127] Lee, H.; Ahn, H.; Naidu, S.; Seong, B. S.; Ryu, D. Y.; Trombly, D. M.; Ganesan, V. "Glass Transition Behavior of PS Films on Grafted PS Substrates." Macromolecules 2010, 43，(23), 9892-9898. [128] Yang, J.; Wang, Q.; Yao, W.; Chen, F.; Fu, Q. "Effect of added homopolymer on structures of thin films of PS-b-PDMS/PS mixture under solvent vapor annealing." Appl. Surf. Sci. 2011, 257，(11), 4928-4934. [129] Hammond, M. R.; Cochran, E.; Fredrickson, G. H.; Kramer, E. J. "Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers." Macromolecules 2005, 38，(15), 6575-6585. [130] Son, J. G.; Gotrik, K. W.; Ross, C. A. "High-Aspect-Ratio Perpendicular Orientation of PS-b-PDMS Thin Films under Solvent Annealing." ACS Macro Letters 2012, 1，(11), 1279-1284. [131] de Gennes, P. G. "Wetting: statics and dynamics." Rev. Mod. Phys. 1985, 57，(3), 827-863. [132] van Hardeveld, R. M.; Gunter, P. L. J.; van Ijzendoorn, L. J.; Wieldraaijer, W.; Kuipers, E. W.; Niemantsverdriet, J. W. "Deposition of inorganic salts from solution on flat substrates by spin-coating: theory, quantification and application to model catalysts." Appl. Surf. Sci. 1995, 84，(4), 339-346. [133] Zhang, X.; Lee, F. K.; Tsui, O. K. C. "Wettability of End-Grafted Polymer Brush by Chemically Identical Polymer Films." Macromolecules 2008, 41，(21), 8148-8151. [134] Sun, Y.-S.; Chen, Y.-C.; Liou, J.-Y.; Su, F.-J. "Film Instability and Dewetting of Amphiphilic Block Copolymer Micelle Assemblies." ASAP. [135] Grim, P. C. M.; Nyrkova, I. A.; Semenov, A. N.; ten Brinke, G.; Hadziioannou, G. "The Free Surface of Thin Diblock Copolymer Films: Experimental and Theoretical Investigations on the Formation and Growth of Surface Relief Structures." Macromolecules 1995, 28，(22), 7501-7513. [136] Heier, J.; Sivaniah, E.; Kramer, E. J. "Anisotropic Coarsening of Two-Dimensional Surface Domains in Copolymer Thin Films." Macromolecules 1999, 32，(26), 9007-9012. [137] Lodge, T. P.; Dalvi, M. C. "Mechanisms of Chain Diffusion in Lamellar Block Copolymers." Phys. Rev. Lett. 1995, 75，(4), 657-660. [138] Khanna, V.; Kim, B. J.; Hexemer, A.; Mates, T. E.; Kramer, E. J.; Li, X.; Wang, J.; Hahn, S. F. "Chain architecture effects on the diffusion of cylinder-forming block copolymers." Macromolecules 2007, 40，(7), 2443-2452. [139] Barton, A. F. M. "Solubility parameters." Chem. Rev. 1975, 75，(6), 731-753. [140] Henkee, C.; Thomas, E.; Fetters, L. "The effect of surface constraints on the ordering of block copolymer domains." J Mater Sci 1988, 23，(5), 1685-1694. [141] Roe, R. J., Methods of X-ray and neutron scattering in polymer science. Oxford University Press: New York, 2000; p 155. [142] Kline, S. R. "Reduction and analysis of SANS and USANS data using IGOR Pro." J. Appl. Crystallogr. 2006, 39, 895-900. [143] Glatter, O.; Kratky, O., Small angle x-ray scattering. Academic Press: London ; New York, 1982; p 515. [144] Helfand, E.; Tagami, Y. "Theory of the Interface between Immiscible Polymers. II." J. Chem. Phy. 1972, 56，(7), 3592-3601. [145] Jopp, J.; Yerushalmi-Rozen, R. "Autophobic Behavior of Polymers at the Melt−Elastomer Interface." Macromolecules 1999, 32，(21), 7269-7275. [146] Hexemer, A.; Stein, G. E.; Kramer, E. J.; Magonov, S. "Block Copolymer Monolayer Structure Measured with Scanning Force Microscopy Moiré Patterns." Macromolecules 2005, 38，(16), 7083-7089. [147] Renaud, G.; Lazzari, R.; Leroy, F. "Probing surface and interface morphology with Grazing Incidence Small Angle X-Ray Scattering." Surf. Sci. Rep. 2009, 64，(8), 255-380. [148] Liou, J. Y.; Sun, Y. S. "Monolayers of Diblock Copolymer Micelles by Spin-Coating from o-Xylene on SiOx/Si Studied in Real and Reciprocal Space." Macromolecules 2012, 45，(4), 1963-1971. [149] Lee, B.; Park, I.; Yoon, J.; Park, S.; Kim, J.; Kim, K.-W.; Chang, T.; Ree, M. "Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering." Macromolecules 2005, 38，(10), 4311-4323. [150] Borukhov, I.; Leibler, L. "Enthalpic Stabilization of Brush-Coated Particles in a Polymer Melt." Macromolecules 2002, 35，(13), 5171-5182. [151] Yokoyama, H.; Kramer, E. J.; Hajduk, D. A.; Bates, F. S. "Diffusion in Mixtures of Asymmetric Diblock Copolymers with Homopolymers." Macromolecules 1999, 32，(10), 3353-3359.
指導教授	孫亞賢(Ya-sen Sun)	審核日期	2014-8-28
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