本研究以兩種不同分子量的聚苯乙烯聚氧化乙烯(polystyrene-block-poly(ethylene oxide), PS-b-PEO)團鏈共聚合物，藉由混合溶劑退火方法，觀察其微觀相分離結構。藉由控制共溶劑組成成份，誘導PS-b-PEO薄膜內部形成有序微觀相分離結構與排向。然而，由於薄膜易受溶劑膨潤影響而產生非潤濕現象，使得PS-b-PEO薄膜無法維持均一的厚度而產生薄膜破裂，也造成微觀相分離結構無法形成大範圍有序陣列。因此，進一步將薄膜的非潤濕特性結合奈米模板，利用微接觸式壓印與溶劑退火製備具有層級結構之PS-b-PEO薄膜。首先，探討薄膜經由兩種不同極性的混合溶劑退火後，以原子力顯微鏡(AFM)與小角度X光散射儀(GISAXS)觀察及鑑定表面與內部之微相分離結構，其結果顯示，藉由不同混合溶劑的組成比例，可得到多樣性微相奈米結構之薄膜，如六角堆積柱狀結構、層板結構、雙連續相結構；值得一提的是，具有高分子量的PS-b-PEO薄膜在甲苯與丙醇溶劑退火後可形成多樣的微胞結構。經由微米接觸壓印將尾端接有氫氧基之聚苯乙烯均聚物預先以微米陣列方式接枝於基材上，接著將PS-b-PEO旋鍍於聚有微米陣列模板的基材上，可形成具有微米陣列的PS-b-PEO水滴形薄膜。經由溶劑退火後，水滴形薄膜內部的奈米結構受到膜厚與薄膜圓形弧面之影響，使得微相結構由柱狀轉變成非柱狀的結構。

In the study, I investigated microphase?separated structures of solvent annealed PS-b-PEO thin films of two types of molecular weight in mixed vapors of binary nonpolar/polar solvents. Ordered microphase-separated nanostructures were achieved by controlling solvent annealing conditions, in which one of the key parameters is the compositions of co-solvent vapors. However, the main drawback for solvent annealing is that block copolymer thin films often dewet on top of substrates during solvent annealing in solvent vapors. Thus, large scale microphase?seperated nanostructures with an ordered array could not generate since the thin films became inhomogenous in film thickness due to solvent-indueced dewetting. Moreover, I fabricated micro-patterned droplets that have ordered nanostructures at a nanometer scale by a combinationtorial approach of solvent annealing and micro-contact imprinting. First, I discussed that various morphologies were formed in thin films exposed to vapors of binary nonpolar/polar solvents of different compositions. By an tomic force microscopy (AFM) and grazing-incident small-angle X-ray scattering (GISAXS), I identified that the nanostructures were comprised of vertically-oriented cylinders with hexagonal packing, vertical lamellae and bicontinuous complex domains. Specially, various kinds of micelles were formed, after high-molecular-weight PS-b-PEO thin films were solvent annealed in co-solvent vapors of toluene and propanol. Finally, micro-patterned thin films were prepared by spin coating on substrates that were grafted by a pre-patternned layer of PS brushes by micro-contact imprinting. After solvent annealing, the thin films formed an array of spherical droplets at a microscopic scale. The nanostructures were generated within the spherical droplets. Due to the effect of thickness and radius curvature, the nanostructures transferred from cylinders to non-cylinders.

1. Matsen, M. W., Bates, F. S., “Unifying Weak- and Strong-Segregation Block Copolymer Theories”, Macromolecules, 29, 1091-1098 (1996)
2. Khandpur, A. K., Forster, S., Bates, F. B., Hamley, I. W., Ryan, A. J., Bras, W., Almdal, K., Mortennsen, K., “Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition”, Macromolecules, 28, 8796-8806 (1995)
3. Hamley, I. W., “Ordering in thin films of block copolymers: Fundamentals to potential applications”, Progress in Polymer Science, 34, 1161-1210 (2009)
4. A. Knoll, A. Horvat, K.S. Lyakhova, G. Krausch, G. J. A. Sevink, A. V. Zvelindovsky, and R. Magerle,“Phase behavior in thin films of cylinder-forming block copolymer,” Phys. Rev. Lett., 89, 035501/1-4 (2002)
5. A. Horvat, K. S. Lyakhova, G. J. A. Sevink , A. V. Zvelindovsky, and R. Magerle, “Phase behavior in thin films of cylinder-forming ABA block copolymers:Mesoscale modeling,” J. Chem. Phys., 120, 1117-1126 (2004)
6. Park, M., Harrison, C., Chaikin, P. M., Register, R. A., Adamson, D. H., “Block Copolymer Lithography: Periodic Arrays of ~1011 Holes in 1 Square Centimeter”, Science, 276, 1401-1404(1997).
7. Misner, M. J., Skaff, H., Emrick, T., Russell, T. P., “Directed Deposition of Nanoparticles Using Diblock Copolymer Templates”, Adv. Mater., 15, 221-224(2003).
8. Shin, K., Leach, K. A., Goldbach, J. T., Kim, D. H., Jho, J. Y., Tuominen, M., Hawker, C. J., Russell, T. P., “A Simple Route to Metal Nanodots and Nanoporous Metal Films”, Nano Lett., 2, 933-936(2002)
9. Park, S., Kim, B., Wang, J.-Y., Russell, T. P., “Fabrication of Highly Ordered Silicon Oxide Dots and Stripes from Block Copolymer Thin Films”, Adv. Mater., 20, 681-685(2008)
10. Lopes, W. A., Jaeger, H. M., “Hierarchical self-assembly of metal nanostructures on diblock copolymer scaffolds”, Nature, 414, 735-738(2001)
11. Aizawa, M.; Buriak, J. M. “Block Copolymer-Templated Chemistry on Si, Ge, InP, and GaAs Surfaces”, J. Am. Chem. Soc., 127, 8932-8933(2005)
12. Gowd, E. B.; Nandan, B.; Vyas, M. K.; Bigall, N. C.; Eychmüller, A.; Schlörb, H.; Stamm, M. “Highly Ordered Palladium Nanodots and Nanowires from Switchable Block Copolymer Thin Films”, Nanotechnology, 20, 415302_1-415302_10(2009)
13. Yang, S. Y., Ryu, I., Kim, H. Y., Kim, J. K., Jang, S. K., Russell, T. P., “Nanoporous Membranes with Ultrahigh Selectivity and Flux for The Filtration of Viruses”, Adv. Mater., 16, 709-712(2006)
14. Yang, S. Y., Park, J., Yoon, J., Ree, M., Jang, S. K., Kim, J. K.,“Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance”, Adv. Mater., 18, 1371-1377(2008)
15. Peinemann, K.-V., Abetz, V., Simon, P. F. W., “Asymmetric superstructure formed in a block copolymer via phase separation”, Nature Materials, 6, 992-996(2007)
16. Yang, S. Y., Yang, J.-A, Kim, E.-S., Jeon, G., Oh, E. J., Choi, K. Y., Hahn, S. K., Kim, J. K. “Single-File Diffusion of Protein Drugs through Cylindrical Nanochannels”, ACS Nano, 4, 3817-3822(2010)
17. Phillip, W. A., O’Neill, B., Rodwogin, M., Hillmyer, M. A., Cussler, E. L., “Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes”, Applied Material and Interfaces, 2, 847-853(2010)
18. Kim, D. H., Lau, K. H. A., Robertson, J. W. F., Lee, O.-J., Jeong, U., Lee, J. I., Hawker, C. J., Russell, T. P., Kim, J. K., Knoll, W., “Thin Films of Block Copolymers as Planar Optical Waveguides”, Adv. Mater., 17, 2442-2446 (2005)
19. Hsueh, H.-Y., Chen, H.-Y., She, M.-S., Chen, C.-K., Ho, R.-M., S., Gwo, Hasegawa, H., Thomas, E. L., “Inorganic Gyroid with Exceptionally Low Refractive Index from Block Copolymer Templating” Nano Lett., 10, 4994-5000(2010)
20. Crossland, E. J. W., Kamperman, M., Nedelcu, M., Ducati, C., Wiesner, U., Smilgies, D.-M., Toombes, G. E. S., Hillmyer, M. A., Ludwigs, S., Steiner, U., Snaith, H. J., “A Bicontinuous Double Gyroid Hybrid Solar Cell”, Nano Lett., 9, 2807-2812(2009)
21. Crossland, E. J. W., Kamperman, M., Nedelcu, M., Ducati, C., Wiesner, U., Smilgies, D.-M., Toombes, G. E. S., Hillmyer, M. A., Ludwigs, S., Steiner, U., Snaith, H. J., “A Bicontinuous Double Gyroid Hybrid Solar Cell”, Nano Lett., 9, 2807-2812(2009)
22. Batrakova, E. V., Kabanov, A. V., “Pluronic Block Copolymers: Evolution of Drug Delivery Concept from Inert Nanocarriers to Biological Response Modifiers”, Polymer, 130, 98-106(2008)
23. Thurn-Albrecht, T, Schotter, J., Ka¬stle, G. A., Emley, N., Shibauchi, T., Krusin-Elbaum, L., Guarini, K., Black, C. T., Tuominen, M. T., Russell, T. P. “Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates”, Science, 290, 2126-2129(2000)
24. Thurn-Albrecht, T., DeRouchey, J., Russell, T. P., Jaeger, H. M. “Overcoming Interfacial Interactions with Electric Fields”, Macromolecules, 33, 3250-3253(2000)
25. Thurn-Albrecht, T., DeRouchey, J., Russell, T. P., Kolb, R. “Pathways toward Electric Field Induced Alignment of Block Copolymers”, Macromolecules, 35, 8106-8110(2002)
26. Xu, T., Zhu, Y., Gido, S. P., Russell, T. P. “Electric Field Alignment of Symmetric Diblock Copolymer Thin Films”, Macromolecules, 37, 2625-2629(2004)
27. Mansky, P., Liu, Y., Huang, E., Russell, T. P., Hawker, C., “Controlling Polymer-Surface Interactions with Random Copolymer Brushes”, Science, 275, 1458-1460(1997)
28. Guarini, K. W., Black, C. T., Huang, E., Yeung, S. H. I., “Optimization of Diblock Copolymer Thin Film Self Assembly”, Adv. Mater., 14, 1290-1294(2002)
29. Ham, S., Shin, C., Kim, E., Ryu, D. Y., Jeong, U., Russell, T. P., Hawker, C. J., “Microdomain Orientation of PS-b-PMMA by Controlled Interfacial Interactions”, Macromolecules, 41, 6431-6437 (2008)
30. Kim, S. O., Solak, H. H., Stoykovich, M. P., Ferrier, N. J., de Pablo, J. J., Nealey, P. F., “Epitaxial Self-Assembly of Block Copolymers on Lithographically Defined Nanopatterned Substrates”, Nature, 424, 411-414(2003)
31. Rockford L., Liu Y., Mansky P., Russell T. P., Yoon M., Mochrie S. G. J., “Polymers on Nanoperiodic, Heterogeneous Surfaces”, Phys. Rev. Lett., 82, 2602-2605(1999)
32. Yang, X. M., Peters, R. D., Nealey, P. F., Solak, H. H., Cerrina, F., “Guided Self-Assembly of Symmetric Diblock Copolymer Films on
Chemically Nanopatterned Substrates”, Macromolecules, 33, 9575-9582(2000)
33. Ruiz, R., Kang, H. M., 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, 321, 936-939(2008)
34. Stoykovich M. P., Mueller M., Kim S. O., Solak H. H., Edwards E. W., de Pablo J. J., Nealey P. F., “Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures”, Science, 308, 1442-1446(2005)
35. Yang, X. M., Peters, R. D., Nealey, P. F., Solak, H. H., Cerrina, F., “Long-Range Order and Orientation of Cylinder-Forming Block Copolymers on Chemically Nanopatterned Striped Surfaces”, Macromolecules, 39, 3598-3607(2006)
36. Stoykovich M. P., Kang H., Daoulas K. C., Liu G., Liu C.-C., de Pablo J. J., Mueller M., Nealey P. F., “Directed Self-Assembly of BlockCopolymers for Nanolithography: Fabrication of Isolated Features andEssential Integrated Circuit Geometries”,ACS Nano, 1, 168-175(2007)
37. A. M. Welander, H. Kang, K. O. Stuen, H. H. Solak, M. Mueller, J. J. de Pablo, P. F. Nealey, “Rapid Directed Assembly of Block Copolymer Films at Elevated Temperatures”, Macromolecules, 41, 2759-2761(2008)
38. Segalman, R. A., Yokoyama, H., Kramer, E. J., “Graphoepitaxy of Spherical Domain Block Copolymer Films”, Adv. Mater., 13, 1152-1155(2001)
39. Cheng, J. Y., Ross, C. A., Thomas, E. L., Smith, H. I., Vancso, G. J., “Templated Self-Assembly of Block Copolymers: Effect of Substrate Topography”, Adv. Mater., 15, 1599-1602(2003)
40. Bita, I., Yang, J. K. W., Jung, Y. S., Ross, C. A., Thomas, E. L., Berggren, K. K., “Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates”, Science, 321, 939-943(2008)
41. Park, S. M., Berry, B. C., Dobisz, E., Kim, H.-C., “Observation of Surface Corrugation-Induced Alignment of Lamellar Microdomains in PS-b-PMMA Thin Films”, Soft Matter, 5, 957-961(2009)
42. 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, 323, 1030-1033(2009)
43. Kim, G., Libera, M., “Morphological Development in Solvent-Cast Polystyrene-Polybutadiene-Polystyrene (SBS) Triblock Copolymer Thin Films”, Macromolecules, 31, 2569-2577(1998)
44. Kim, G., Libera, M., “Kinetic Constraints on the Development of Surface Microstructure in SBS Thin Films”, Macromolecules, 31, 2670-2672(1998)
45. Ho, R.-M., Tseng, W.-H., Fan, H.-W.,Chiang, Y.-W., Lin, C.-C., Ko, B.-T., Huang B.-H., “Solvent-Induced Microdomain Orientation in Polystyrene-b-poly(L-lactide) Diblock Copolymer Thin Films for Nanopatterning”, Polymer, 46, 9362-9377(2005)
46. Jung, Y. S., Chang, J. B., Verploegen, E., Berggren, K. K., Ross, C. A., “A Path to Ultranarrow Patterns Using Self-Assembled Lithography”, Nano Lett., 10,1000-1015(2010)
47. 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., 11, 1351-1357(2011)
48. Park, S., Kim, B., Xu, J., Hofmann, T., Ocko, B. M., Russell, T. P., “Lateral Ordering of Cylindrical Microdomains Under Solvent Vapor”, Macromolecules, 42, 1278-1284(2009)
49. Xuan, Y., Peng, J., Cui, L., Wang, H., Li, B., Han, Y., “Morphology Development of Ultrathin Symmetric Diblock Copolymer Film via Solvent Vapor Treatment”, Macromolecules, 37, 7301-7307(2004)
50. Bang, J., Kim, S. H., Drockenmuller, E., Misner, M. J., Russell, T. P., Hawker, C. J., “Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers”, J. Am. Chem. Soc., 128, 7622-(2006)
51. Bang, J., Kim, B. J., Stein, G. E., Russell, T. P., Li, X., Wang, J., Kramer, E. J., Hawker C. J., “Effect of Humidity on the Ordering of PEO-Based Copolymer Thin Films”, Macromolecules, 40, 7019-7025(2007)
52. Jung, Y. S., Ross, C. A., “Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns”, Adv. Mater., 21, 2540-2545(2009)
53. Bhargava, P., Tu, Y., Zheng, J. X., Xiong, H., Quirk, R. P., S. Cheng, Z. D., “Temperature-Induced Reversible Morphological Changes of Polystyrene-block-Poly(ethylene Oxide) Micelles in Solution”, J. Am. Chem. Soc., 129, 1113-1121(2007)
54. Abbas, S., Li, Z., Hassan, H., Lodge, T. P., “Thermoreversible Morphology Transitions of Poly(styrene-b-dimethylsiloxane) Diblock Copolymer Micelles in Dilute Solution”, Macromolecules, 40, 4048-4052(2007)
55. Geng, Y., Ahmed, F., Bhasin, N., Discher, D. E., “Visualizing Worm Micelle Dynamics and Phase Transitions of a Charged Diblock Copolymer in Water”, J. Phys. Chem. B, 109, 3772-3779(2005)
56. Shen, H., Zhang, L., Eisenberg, A., “Multiple pH-Induced Morphological Changes in Aggregates of Polystyrene-block-poly(4-vinylpyridine) in DMF/H2O Mixtures”, J. Am. Chem. Soc., 121, 2728-2740(1999)
57. Ouarti, N., Viville, P., Lazzaroni, R., Minatti, E., Schappacher, M., Deffieux, A., Borsali, R., “Control of the Morphology of Linear and Cyclic PS-b-PI Block Copolymer Micelles via PS Addition”, Langmuir, 21, 1180-1186(2005)
58. Zupancich J. A., Bates F. S., Hillmyer M. A., “Aqueous Dispersions of Poly(ethyleneoxide)-b-poly(ç-methyl-E-caprolactone) Block Copolymers”, Macromolecules, 39, 4286-4288(2006)
59. Zhang, L., Eisenberg, A., “Multiple Morphologies and Characteristics of “Crew-Cut” Micelle-like Aggregates of Polystyrene-b-poly(acrylic acid) Diblock Copolymers in Aqueous Solutions”, J. Am. Chem. Soc., 118, 3168-3181(1996)
60. Yu Y., Eisenberg, A., “Control of Morphology through Polymer-Solvent Interactions in Crew-Cut Aggregates of Amphiphilic Block Copolymers”, J. Am. Chem. Soc., 119, 8383-8384(1997)
61. Yu Y., Zhang L., Eisenberg A., “Morphogenic Effect of Solvent on Crew-Cut Aggregates of Apmphiphilic Diblock Copolymers”, Macromolecules, 31, 1144-1154(1998)
62. Bhargava, P., Zheng, J. X., Li, P., Quirk, R. P., Harris, F. W., Cheng, S. Z. D., “Self-Assembled Polystyrene-block-poly(ethylene oxide) Micelle Morphologies in Solution”, Macromolecules, 39, 4880-4888(2006)
63. Bang, J., Jain, S., Li, Z., Lodge, T. P., “Sphere, Cylinder, and Vesicle Nanoaggregates in Poly(styrene-b-isoprene) Diblock Copolymer Solutions”, Macromolecules, 39, 1199-1208(2006)
64. Du H., Zhu J., Jiang W., “Study of Controllable Aggregation Morphology of ABA Amphiphilic Triblock Copolymer in Dilute Solution by Changing the Solvent Property”, J. Phys. Chem. B, 111, 1938-1945(2007)
65. Bang, J., Jain, S., Li, Z., Lodge, T. P., “Sphere, Cylinder, and Vesicle Nanoaggregates in Poly(styrene-b-isoprene) Diblock Copolymer Solutions”, Macromolecules, 39, 1199-1208(2006)
66. Njikang, G., Han, D., Wang, J., Liu, G., “ABC Triblock Copolymer Micelle-Like Aggregates in Selective Solvents for A and C”, Macromolecules, 41, 9727-9735(2008)
67. R. Limary, P. F. Green, K. R. Shull, “Influence of surface ordering on the wetting of structured liquids” , Eur. Phys. J. E., 8,103–110 (2002)
68. Wensink, K. D. F., Jérôme, B., “Dewetting Induced by Density Fluctuations” , Langmuir, 18, 413-416 (2002)
69. Lee, S. H., Yoo, P. J., Kwon, S. J., Lee, H. H., “Solvent-driven dewetting and rim instability”, J. Chem. Phys., 121, 4346-4351 (2004)
70. Müller-Buschbaum, P., Bauer, E., Wunnicke, O., Stamm, M., “The control of thin film morphology by the interplay of dewetting, phase separation and microphase separation”, J. Phys.: Condens. Matter, 17, S363-S386 (2005)
71. Peng, J., Xuan, Y., Wang, H., Li, B., Han, Y., “Solvent vapor induced dewetting in diblock copolymer thin films,” Polymer, 46, 5767-5772 (2005)
72. Reiter, G., Sharma, A., Casoli, A., David, M.-O., Khanna, R., Auroy P., “Thin Film Instability Induced by Long-Range Forces,” Langmuir 15, 2551-2558 (1999)
73. Sehgal, A., Ferreiro, V., Douglas, J. F., Amis, E. J., Karim, A., “Pattern-Directed Dewetting of Ultrathin Polymer Films”, Langmuir, 18, 7041-7048(2002)
74. Julthongpiput, D., Zhang, Z., Douglas, J. F., Karim, A., Faasolka, M. J., “Pattern-Directed to Isotropic Dewetting Transition in Polymer Films on Micropatterned Surfaces with Differential Surface Energy Contrast”, Soft Matter, 3,613-618(2007)
75. Farrell, R. A., Kehagias, N., Shaw, M. T., Reboud, V., Zelsmann, M., Holmes, J. D., Torres, C. M. S., Morris, M. A., “Surface-Directed Dewetting of a Block Copolymer for Fabricating Highly Uniform Nanostructured Microdroplets and Concentric Nanorings”, ACS NANO, 5, 1073-1085(2011)
76. Kim, T. H., Hwang, J., Hwang, W. S., Huh, J., Kim, H.-C., Kim S. H., Hong J. M., Thomas E. L., Park C., “Hierarchical Ordering of Block Copolymer Nanostructures by Solvent Annealing Combined with Controlled Dewetting”, Adv. Mater., 20, 522-527(2008)
77. Kim, T. H., Huh, J., Park, C., “Micropatterns of Hierarchical Self-Assembled Block Copolymer Droplets with Solvent-Assisted Wetting of Brush Monolayers”, Macromolecules, 43, 5352-5357(2010)
78. Farrell, R. A., Kehagias, N., Shaw, M. T., Reboud, V., Zelsmann, M., Holmes, J. D., Torres, C. M. S., Morris, M. A., “Surface-Directed Dewetting of a Block Copolymer for Fabricating Highly Uniform Nanostructured Microdroplets and Concentric Nanorings”, ACS NANO, 5, 1073-1085(2011)
79. 徐士平，「極性/非極性共溶劑退火法調控雙團鏈共聚物薄膜奈米微結構」，國立中央大學化學工程研究所碩士論文 (2010)
80. Tureau, M. S., Epps III, Thomas H., “Nanoscale Networks in Poly[isoprene-blockstyrene- block-(methyl methacrylate)] Triblock Copolymers”, Macromol. Rapid. Commun., 30, 1751-1755(2009)
81. Jain, S., Dyrdahl, M. H. E., Gong, X., Scriven, L. E., Bates, F. S., “Lyotropic Phase Behavior of Poly(ethylene oxide)-Poly(butadiene) Diblock Copolymers: Evolution of the Random Network Morphology”, Macromolecules, 41, 3305-3316(2008)
82. J. Brandrup, E. H. Immergut, E. A. Grulke, Polymer Handbook, 4/e., John Wiley & Sons, New York, 1999