本研究之重點在於製備大範圍有序垂直排向之六角圓柱陣列，所以從選擇溶解雙團鏈共聚物聚苯乙烯聚氧乙烯(PS-b-PEO)的溶劑、塗佈成膜、並以極性/非極性混合溶劑蒸氣在不同混合比例下退火處理，希望從這三道程序當中分別找出最適當的條件。首先以四種不同揮發速率的溶劑溶解PS-b-PEO，再以滴鍍(drop casting)的方式成膜，結果顯示溶劑揮發速率快慢會影響圓柱結構排列的有序性，其中以揮發速率最慢的甲苯在高分子濃度為2wt%時形成的垂直圓柱陣列最好，但缺點是薄膜表面相當不平整以及達到有序陣列的時間較長。改以旋鍍改善薄膜平整度，但其高轉速反而加速溶劑揮發的速率，使的垂直圓柱陣列相當無序。因此我們利用浸鍍可大幅改善這些問題，並進一步以不同的拖曳速率調控圓柱結構的排向，在低速拖曳時溶劑揮發主導圓柱排向為垂直式，而在高速拖曳時慣性力主導圓柱排向為水平式。最後，綜合上述結果我們選用甲苯當作溶劑配製2wt%的高分子溶劑以1mm/s的拖曳速率浸鍍成膜後，利用非極性溶劑甲苯混合極性溶劑(水或醇類溶劑)以不同的混合比例共溶劑蒸氣下溶劑退火處理，我們成功地在甲苯/乙醇混合比例為95：5製備出大範圍有序垂直的六角圓柱陣列，並在甲苯/乙醇混合比例為60：40發現圓柱結構會轉變成Fddd，以及甲苯/正丙醇混合比例為85：15發現圓柱結構和雙連續相(Double Gyroid)共存，証實PS-b-PEO以適當的比例混合選擇性溶劑(selective solvent)退火能夠誘導相轉變的發生。

I have systematically studied the morphology and orientation of microstructures in thin films of an asymmetric poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer after the thin films were subjected to solvent annealing in various vapors of nonpolar/polar cosolvents. In the first part of the thesis, I dissolved PS-b-PEO into the four solvents: toluene, benzene, tetrahydrofuran and chloroform. Each of the four solvents has a different evaporation rate. Therefore, I investigated the effect of the evaporation rate on the microphase-separated microdomains and their spatial ordering. Toluene has the slowest solvent rate. As a result, the evaporation of toluene led to hexagonal arrays of cylinders with a perpendicular orientation. On the other hand, I prepared thin films by drop casting and spin coating. It was found that drop casting couldn’t yield uniform thin films due to the coffee ring effect and that spin coating couldn’t generate microstructures with long-range ordering. Therefore, I used another coating approach, dip-coating, to prepare thin films instead. The low withdrawing rate (0.5 mm/s) induced to cylinders with a perpendicular orientation, and the high withdrawing rate (1.25 mm/s) induced to cylinders with a parallel orientation. In the second part of the thesis, I studied the morphologies in thin films after those films were subjected to solvent annealing in various solvent vapors (in mixed vapors of nonpolar/polar cosolvents). The various polar solvents in the mixed vapors were water, methanol, ethanol, 1-propanol, 1-butanol and 1-hexanol whereas the nonpolar solvent was toluene. PS-b-PEO thin films were first deposited on SiOx/Si by dip-coating at 1 mm/s from a 2 wt% toluene solution. I successfully fabricated the long range hexagonal arrays of perpendicularly-oriented cylinders upon solvent annealing thin films in the toluene/ethanol vapor of the volumetric fraction of 95/5. In addition, controling the mixed ratio of nonpolar/polar cosolvents led to complicated microphase-separated morphologies, such as the Fddd structure in the thin film with exposure to the toluene/ethanol vapor of 60/40 and the coexistence of double-gyroids and cylinders in the thin film with solvent annealing in the toluene /1-propanol vapor of the fraction of 85/15.

[1] M. W. Matsen, and F. S. Bates, “Unifying Weak- and Strong-Segregation Block Copolymer Theories,” Macromolecules, 29, 1091-1098 (1996).
[2] A. K. Khandpur, S. Forster, F. B. Bates, I. W. Hamley, A. J. Ryan, W. Bras, K. Almdal, and K. Mortensen, “Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition,” Macromolecules, 28, 8796-8806 (1995).
[3] 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).
[4] 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).
[5] M. Park, C. Harrison, P. M. Chaikin, R. A. Register, and D. H. Adamson, “Block Copolymer Lithography: Periodic Arrays of ~1011 Holes in 1 Square Centimeter,” Science, 276, 1401-1404 (1997).
[6] P. Mansky, Y. Liu, E. Huang, T. P. Russell, and C. Hawker, “Controlling Polymer-Surface Interactions with Random Copolymer Brushes,” Science, 275, 1458-1460 (1997).
[7] K. Naito, H. Hieda, M. Sakurai, Y. Kamata, and K. Asakawa, “2.5-inch Disk Patterned Media Prepared by an Artificially Assisted Self-assembling Method,” IEEE Trans. on Magnetics, 38, 1949-1951 (2002).
[8] S. Y. Yang, I. Ryu, H. Y. Kim, J. K. Kim, S. K. Jang, and T. P. Russell, “Nanoporous Membranes with Ultrahigh Selectivity and Flux for the Filtration of Viruses,” Adv. Mater., 18, 709-712 (2006).
[9] D. H. Kim, K. H. A. Lau, J. W. F. Robertson, O. J. Lee, U. Jeong, J. I. Lee, C. J. Hawker, T. P. Russell, J. K. Kim, and W. Knoll, “Thin Films of Block Copolymers as Planar Optical Waveguides,” Adv. Mater., 17, 2442-2446 (2005).
[10] C. T. Black, K. W. Guarini, Y. Zhang, H. Kim, J. Benedict, E. Sikorski, I. V.Babich, and K. R.Milkove, “High-capacity,Self-assembled Metal
-Oxide-Semiconductor Decoupling Capacitors,” IEEE Electron Device Lett., 25, 622-624 (2004).
[11] T. L. Morkved, M. Lu, A. M. Urbas, E. E. Ehrichs, H. M. Jaeger, P. Mansky, and T. P. Russell, “Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields,” Science, 273, 931-933 (1996).
[12] P. Mansky, J. DeRouchey, T. P. Russell, J. Mays, M. Pitsikalis, T. Morkvedand, and H. Jaeger, “Large-area Domain Alignment in Block Copolymer Thin Films Using Electric Fields,” Macromolecules, 31, 4399–4401 (1998).
[13] E. Han, I. In, S. M. Park, Park Y. H. La, Y. Wang, P. F. Nealey, and P. Gopalan, “Photopatternable Imaging Layers for Controlling Block Copolymer Microdomain Orientation,” Adv. Mater., 19, 4448-4452 (2007).
[14] S. Ji, G. Liu, F. Zheng, G. S. W. Craig , F. J. Himpsel , and P. F. Nealey, “Preparation of Neutral Wetting Brushes for Block Copolymer Films from Homopolymer Blends”, Adv. Mater., 20, 3054-3060 (2008).
[15] R. A. Segalman, H. Yokoyama, and E. J. Kramer, “Graphoepitaxy of Spherical Domain Block Copolymer Films,” Adv. Mater., 13, 1152-1155 (2001).
[16] J. Y. Cheng, C. A. Ross, E. L. Thomas, H. I. Smith, and G. J. Vancso, “Fabrication of Nanostructures with Long-Range Order Using Block Copolymer Lithography,” Appl. Phys. Lett., 81, 3657-3659 (2002).
[17] S. O. Kim, H. H. Solak, M. P. Stoykovich, N. J. Ferrier, J. J. de Pablo, and P. F. Nealey, “Epitaxial Self-Assembly of Block Copolymer on Lithographically Defined Nanopatterned Substrates,” Nature, 424, 411-414 (2003).
[18] J. Y. Cheng, F. Zhang, V. P. Chuang, A. M. Mayes, and C. A. Ross, “Self-Assembled One-Dimensional Nanostructure Arrays,” Nano Lett., 6, 2099-2103 (2006).
[19] L. Rockford, Y. Liu, P. Mansky, T. P. Russell, M. Yoon, and S. G. J. Mochrie, “Polymers on Nanoperiodic, Heterogeneous Surfaces,” Phys. Rev. Lett., 82, 2602-2605 (1999).
[20] X. M. Yang, R. D. Peters, P. F. Nealey, H. H. Solak, and F. Cerrina, “Guided Self-Assembly of Symmetric Diblock Copolymer Films on Chemically Nanopatterned Substrates,” Macromolecules, 33, 9575-9582 (2000).
[21] S. M. Park, G. S. W. Craig, Y. H. La, and P. F. Nealey, “Morphological Reconstruction and Ordering in Films of Sphere-Forming Block Copolymers on Striped Chemically Patterned Surfaces,” Macromolecules, 41, 9124-9129 (2008).
[22] G. Kim, and M. Libera, “Morphological Development in Solvent-Cast Polystyrene– Polybutadiene−Polystyrene (SBS) Triblock Copolymer Thin Films,” Macromolecules, 31, 2569-2577, (1998).
[23] G. Kim, and M. Libera, “Kinetic Constraints on the Development of Surface Microstructure in SBS Thin Films,” Macromolecules, 31, 2670-2672 (1998).
[24] Q. Zhang, O. K. C. Tsui, B. Du, F. Zhang, T. Tang, and T. He, “Observation of Inverted Phases in Poly(styrene-b-butadiene-b-styrene) Triblock Copolymer by Solvent-Induced Order−Disorder Phase Transition,” Macromolecules, 33, 9561-9567 (2000).
[25] J. Bang, U. Jeong, D. Y. Ryu, T. P. Russell, and C. J. Hawker, “Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns,” Adv. Mater., 21, 1-24(2009).
[26] J. Bang, S. H. Kim, E. Drockenmuller, M. J. Misner, T. P. Russell, and C. J. Hawke, “Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers,” J. Am. Chem. Soc., 128, 7622-7629 (2006).
[27] S. Park, D. H. Lee, J. Xu, B. Kim, S. W. Hong, U. Jeong, T. Xu, and T. P. Russell, “Macroscopic 10-Terabit per Square-Inch Arrays from Block copolymer with lateral order,” Science, 323, 1030-1033 (2009).
[28] S. Ludwigs, K. Schmidt, C. M. Stafford, E. J. Amis, M. J. Fasolka, A. Karim, R. Magerle, and G. Krausch, “Combinatorial Mapping of the Phase Behavior of ABC Triblock Terpolymers in Thin Films: Experiments,” Macromolecules, 38, 1850-1858 (2005).
[29] Y. S. Jung, and C. A. Ross, “Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns,” Adv. Mater., 21, 1-6 (2009).
[30] D. Bornside, C.W. Macosko, and L. E. Scriven, “On the modeling of spin coating,” J. maging Technol., 13, 122-130 (1987).
[31] 范慧雯，「剪切力誘導PS-PLLA團聯共聚物奈米微結構定向-奈米圖案成形之製備」，國立中興大學化學工程研究所碩士論文 (2003)。
[32] W.J. Daughton, and F. L.Givens, “An Investigation of the Thickness Variation of Spun-on Thin-films Commonly with the Semiconductor Inhdustry,” J. Electrochem. Soc., 129, 173-179 (1982).
[33] F. L. Givens, and W.J. Daughton, “On the Uniformity of Films:a New Technique Applied to Polyimides,” J. Electrochem. Soc., 126, 269-276 (1979).
[34] K. E. Strawhecker, S. K. Kumar, J. F. Douglas, and A. Karim, “The Critical Role of Solvent Evaporation on the Roughness of Spin-Cast Polymer Films,” Macromolecules, 34, 4669-4672 (2001).
[35] R. D. Deegan, O. Bakajin, T. F. Dupont, G. Huber, S. R. Nagel, and T. A. Witten, “Capillary Flowasthe Cause of Ring Stains From Dried Liquid Drops,” Nature, 389, 827-829 (1997).
[36] L. Landau, and B. Levich, “Dragging of a Liquid by a Moving Plate,” Acta Physicochimi URSS., 17, 42-54 (1942).
[37] R. Limary, P. F. Green, and K. R. Shull, “Influence of Surface Ordering on the Wetting of Structured Liquids,” Eur. Phys. J. E, 8,103-110 (2002).
[38] I. W. Hamley, “Ordering in Thin Films of Block Copolymers: Fundamentals to Potential Applications,” Progress in Polymer Science, 34, 1161-1210 (2009)
[39] K. D. F. Wensink, and B. Jérôme, “Dewetting Induced by Density Fluctuations,” Langmuir, 18, 413-416 (2002).
[40] S. H. Lee, P. J. Yoo, S. J. Kwon, and H. H. Lee, “Solvent-Driven Dewetting and Rim Instability,” J. Chem. Phys., 121, 4346-4351 (2004).
[41] P. Müller-Buschbaum, E. Bauer, O. Wunnicke, and M. Stamm, “The Control of Thin Film Morphology by the Interplay of Dewetting, Phase Separation and Microphase Separation,” J. Phys.: Condens. Matter, 17, S363-S386 (2005).
[42] J. Peng, Y. Xuan, H. Wang, B. Li, and Y. Han, “Solvent Vapor Induced Dewetting in Diblock Copolymer Thin Films,” Polymer, 46, 5767-5772 (2005).
[43] G. Reiter, A. Sharma, A. Casoli, M. O. David, R. Khanna, and P. Auroy, “Thin Film Instability Induced by Long-Range Forces,” Langmuir 15, 2551-2558 (1999).
[44] R. Xing, C. Luo, Z. Wang, C. Luo, Z. Wang, and Y. Han, “Dewetting of Polymethyl Methacrylate on the Patterned Elastomer Substrate by Solvent Vapor Treatment,” Polymer, 48, 3574-3583 (2007).
[45] J. P. Spatz, S. Sheiko, and M. Möller, “Substrate-Induced Lateral Micro-Phase Separation of a Diblock Copolymer,” Adv. Mater., 8, 513-517 (1996).
[46] P. J. Flory, Principles of Polymer Chemistry, 3/e, Cornell University Press, USA, 1989.
[47] R. W. Carpick, and M. Salmeron, “Scratching the Surface: Fundamental Investigations of Tribology with Atomic Force Microscopy,” Chem. Rev., 97, 1163-1194 (1997).
[48] D. K. Bowen and B. K. Tanner, High Resolution X-ray Diffractometry and Topography, Taylor & Francis, UK, 2002.
[49] 鄭有舜，「X-光小角度散射在軟物質研究上的應用」，物理雙月刊，廿六卷二期，416-424，93年4月。
[50] R. M. Ho, W. H. Tseng, H. W. Fan, Y. W. Chiang, C. C. Lin, B. T. Ko, and B. H. Huang, “Solvent-Induced Microdomain Orientation in Polystyrene-b-Poly(l-lactide) Diblock Copolymer Thin Films for Nanopatterning,” Polymer, 46, 9362-9377 (2005).
[51] V. Khanna, E. W. Cochran, A. Hexemer, G. E. Stein, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang, S. F. Hahn, “Effect of Chain Architecture and Surface Energies on the Ordering Behavior of Lamellar and Cylinder Forming Block Copolymers,” Macromolecules, 39, 9346-9356 (2006).
[52] S. Walheim, M. Böltau, J. Mlynek, G. Krausch, and U. Steiner, “Structure Formation via Polymer Demixing in Spin-Cast Films,” Macromolecules, 30, 4955-5003 (1997).
[53] H. Elbs, K. Fukunaga, R. Stadler, G. Sauer, R. Magerle, and G. Krausch, “Microdomain Morphology of Thin ABC Triblock Copolymer Films,” Macromolecules, 32, 1204-1211 (1999).
[54] K. A. Cavicchi, K. J. Berthiaume, and T. P. Russell, “Solvent Annealing Thin Films of Poly(isoprene-b-lactide),” Polymer, 46, 11635-11639 (2005).
[55] M. Takenaka, T. Wakada, S. Akasaka, S. Nishitsuji, K.Saijo, H. Shimizu, and H. Hasegawa, “Orthorhombic Fddd Network in Diblock Copolymer Melts,” Macromolecules, 40, 4399-4402 (2007).
[56] M. I. Kim, T. Wakada, S. Akasaka, S. Nishitsuji, K. Saijo, H. Hasegawa, K. Ito, and M. Takenaka, “Determination of the Fddd Phase Boundary in Polystyrene-block-Polyisoprene Diblock Copolymer Melts,” Macromolecules, 42, 5266-5271 (2009).
[57] J. Jung, H. W. Park, S. Lee H. Lee, T. Chang, K. Matsunaga, and H. Jinnai, “Effect of Film Thickness on the Phase Behaviors of Diblock Copolymer Thin Film,” ACS NANO, 4, 3109-3116 (2010).
[58] H. Mao, and M. A. Hillmyer, “Macroscopic Samples of Polystyrene with Ordered Three-Dimensional Nanochannels, ” Soft Matter, 2, 57-59 (2006).
[59] F. Haken, and J. Lal, “Polyelectrolyte-like Behavior of Poly(ethylene-oxide) solutions with added monovalent salt,” Europhys. Lett., 64, 204-210 (2003).
[60] T. P. Lodge, K. J. Hanley, B. Pudil, and V. Alahapperuma, “Phase Behavior of Block Copolymers in a Neutral Solvent,” Macromolecules, 36, 816-822 ( 2003).
[61] C. Lai, W. B. Russell, and R. A. Register, “Phase Behavior of Styrene-Isoprene Diblock Copolymers in Strongly Selective Solvents,” Macromolecules, 35, 841-849 ( 2002).
[62] P. J. Flory, “Thermodynamics of High Polymer Solutions,” J. Chem. Phys., 10, 51-62(1942).
[63] J. Hildebrand and R. L. Scott, The Solubility of Nonelectrolytes, 3/e, Reinhold, New York, 1950.
[64] M. L. Huggins, “Theory of Solutions of High Polymers,” J. Am. Chem. Soc., 64, 1712-1719(1942).
[65] J. H. Hildebrand, “Solubility. XII. Regular Solutions,”J. Am. Chem. Soc., 51, 66-80(1929).