溶劑退火法調控雙團鏈共聚物薄膜梯田狀表面浮凸物與奈米微結構

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：7

、訪客IP：3.137.171.121

姓名

郭鎮源(Chen-Yuan Kuo) 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

溶劑退火法調控雙團鏈共聚物薄膜梯田狀表面浮凸物與奈米微結構
(Surface Relief Terraces and Nanostructures in Solvent-annealed Thin Block Copolymer Films)

相關論文

★ 利用高分子模版製備具有表面增強拉曼訊號之奈米銀陣列基板	★ 新穎硬桿-柔軟雙嵌段共聚物與高分子混摻之介觀形貌
★ 超分子側鏈型液晶團鏈共聚物自組裝薄膜	★ 利用溶劑退火法調控雙團鏈共聚物奈米薄膜之自組裝結構
★ 溶劑退火誘導聚苯乙烯聚4-乙烯吡啶薄膜不穩定性現象之研究	★ 光化學法調控嵌段共聚物有序奈米結構薄膜及其模板之應用
★ 製備具可調控孔洞大小的奈米結構碳材用於增強拉曼效應之研究	★ 結合嵌段共聚物自組裝及微乳化法製備三維侷限多層級結構
★ 嵌段共聚物/多巴胺混摻體自組裝製備三維多尺度孔隙模板	★ 弱分離嵌段共聚物與均聚物雙元混合物在薄膜中的相行為
★ 摻雜效應對聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸紫外光照-導電度刺激響應之影響與其應用	★ 可撓式聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸熱電裝置研究：微結構調控增進熱電性質
★ 由嵌段共聚物膠束模板化的多層級孔洞碳材：從膠束(微胞)組裝到電化學應用	★ 聚苯乙烯聚4-乙烯吡啶共聚物微胞薄膜之聚變與裂變動態結構演化之研究
★ 除潤現象誘導非對稱型團鏈共聚物薄膜之層級結構	★ 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

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

摘要(中)

本研究討論聚苯乙烯聚氧化乙烯(poly(styrene-block-ethylene oxide, P(S-b-EO))團鏈共聚合物在矽基材上之薄膜，藉由混合溶劑退火(甲苯/丁醇)與退火時間的關係，誘導其薄膜產生梯田狀結構和微觀相分離結構。受溶劑退火期間，薄膜為了滿足膜厚相稱性而產生梯田狀結構。在短時間內 (溶劑退火12小時)，薄膜表面之梯田狀結構是由三種不同大小之圓球以兩類型的六角陣列依磊晶方式所構成。個別的六角陣列有其對應之相對薄膜厚度。在長時間中 (溶劑退火16和 20小時)，圓球狀微觀相分離結構經由融合成長為平行基材方向之圓柱狀結構。也因為非潤濕現象讓薄膜產生擾動，而梯田狀結構則會進一步形成以圓柱狀微觀相分離結構所構成之多層薄膜厚度，並且探討P(S-b-EO)薄膜受混合溶劑退火誘導之相轉變機制。最後，本論文進一步探討膜厚效應、基材界面受PS鏈段改質以及混合溶劑種類對P(S-b-EO)的薄膜奈米微結構之影響。

摘要(英)

In this study, we have investigated the temporal evolution of relief terraces and microphase-separated nanodomains in poly(styrene-block-ethylene oxide) P(S-b-EO) on silicon substrates (SiOx/Si) annealed under toluene/butanol vapors. For thin films, solvent annealing causes the formation of relief terraces. With solvent annealing for 12 h, hexagonal arrays of nanospheres of three sizes are dominant over the surface morphology of relief-terraced microstructures with epitaxial packing. The coexistence of nanospheres of three sizes is ascribed to a morphology triggered by the constraint of the film thickness. Upon exposure to toluene/butanol vapors for 16 and 20 h, these nanospheres become metastable and grow further into nanocylinders lying on the surface. During dewetting, the undulations of the local thickness and the nanodomain transitions are inseparable, consequently forming relief terraces comprising multiple layers of lying nanocylinders. The mechanisms and causes of nanodomain transitions of varied routes in solvent-annealed P(S-b-EO) films are analyzed and discussed. Finally, the influences of film thickness, PS-grafted substrates and binary mixed vapors of nonpolar (toluene) and polar solvents (water, methanol, ethanol or propanol) on the nanodomains of P(S-b-EO) were investigated.

關鍵字(中)

★ 雙團鏈共聚物
★ 相轉變
★ 低掠角小角度X光散射儀
★ 高分子薄膜
★ 溶劑退火法

關鍵字(英)

★ solvent annealing
★ thin films
★ GISAXS
★ phase transitions
★ block copolymers

論文目次

摘要 ............................................................................................................ i
Abstract ........................................................................................................ iiContents .............................................................................................................. iii
Figure Captions ................................................................................................. vi
Table Captions .................................................................................................. xii
Chapter 1. Introduction ................................................................................. 1
1-1 Phase Behavior of Block Copolymers ................................................... 1
1-2 Bulk State ................................................................................................. 2
1-3 Thin Film State ........................................................................................ 3
1-3-1 Confinement ..................................................................................... 4
1-3-2 Surface Effects ................................................................................. 5
1-4 Applications ............................................................................................. 7
1-4-1 Templates ......................................................................................... 8
1-4-2 Membranes ...................................................................................... 9
1-4-3 Nanolithography ............................................................................ 11
1-5 Preparation of block Copolymer Films ............................................... 12
1-5-1 Microdomain Orientation ............................................................ 12
A. Electric Field Alignment ............................................................... 12
B. Surface Modification ..................................................................... 13
1-5-2 Microdomain Lateral Ordering ................................................... 14
A. Chemical Pattern ........................................................................... 14
B. Graphoepitaxy ............................................................................... 15
1-5-3 Morphologies of Microdomain .................................................... 16
1-6 Solvent-induced phase separation ....................................................... 17
1-6-1 Rate of Solvent Removal ............................................................... 17
1-6-2 Annealing Time ............................................................................. 18
1-6-3 Solvent Vapor Pressure ................................................................ 19
1-6-4 Solvent Selectivity .......................................................................... 21
1-7 The Phenomena of Dewetting and Stability wthin Films .................. 23
1-7-1 Preparation Films via Spin-coating ............................................. 23
1-7-2 Dewetting ........................................................................................ 23
1-8 Motivations ............................................................................................ 25
Chapter 2. Materials and Experimental Methods .................................... 26
2-1 Materials ................................................................................................ 26
2-1-1 Polymer .......................................................................................... 26
2-1-2 Solutions ......................................................................................... 27
2-2 Experimental Section ............................................................................ 28
2-2-1 Cleaning up Substrate................................................................... 28
2-2-2 Surface Modification ..................................................................... 28
2-2-3 Thin Film Preparation .................................................................. 28
2-2-4 Characterizations .......................................................................... 29
2-3 Experiment Equipment ........................................................................ 31
2-4 Instrumental Analysis ........................................................................... 32
2-4-1 Optical Microscopy, OM .............................................................. 32
2-4-2 Atomic Force Microscope, AFM .................................................. 33
2-4-3 Transmission Electron Microscopy, TEM .................................. 34
2-4-4 Grazing Incidence Small Angle X-ray Scattering, GISAXS ..... 35
Chapter 3. Results and Discussion .............................................................. 36
3-1 Microscale Surface Features of P(S-b-EO) Thin Film .................. 37
3-2 Nanoscale Surface Morphology of P(S-b-EO) Thin Film ............. 40
A. The Short Time Interval of Solvent Annealing .......................... 40
B. The Long Time Interval of Solvent Annealing ........................... 52
3-3 The Factors of Microphase Separation ........................................... 56
A. The Effect of Film Thickness ....................................................... 56
B. The Effect of Different Substrates ............................................... 59
Chapter 4. Conclusions ................................................................................ 62
Chapter 5. References .................................................................................. 63
Chapter 6. Future Work .............................................................................. 76
Chapter 7. Appendix .................................................................................... 77

參考文獻

1. P. Alexandridis and J. F. Holzwarth, “Block Copolymers”, Curr. Opin. Colloid Interface Sci., 5, 312 (2000).
2. F. S. Bates, M. A. Hillmyer, T. P. Lodge, C. M. Bates, K. T. Delaney, G. H. Fredrickson, “Multiblock Polymers: Panacea or Pandora’’s Box?”, Science 336, 434 (2012).
3. M. W. Matsen, F. S. Bates, “Unifying Weak- and Strong-Segregation Block Copolymer Theories”, Macromolecules, 29, 1091 (1996).
4. I. W. Hamley, “The Physics of Block Copolymers”, Oxford Science Publications, Oxford University Press, USA, 1998.
5. A. K. Khandpur, S. Forster, F. S. Bates, I. W. Hamley, A. J. Ryan, W. Bras, K. Almdal, K. Mortennsen, “Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition”, Macromolecules, 28, 8796 (1995).
6. R. A. Farrell, N. Petkov, M. A. Morris, J. D. Holmes, “Self-assembled templates for the generation of arrays of 1-dimensional nanostructures: From molecules to devices”, Journal of Colloid and Interface Science, 349, 449 (2010).
7. A. Knoll, A. Horvat, K. S. Lyakhova, G. Krausch, G. J. A. Sevink, A.V. Zvelindovsky, R. Magerle, “Phase Behavior in Thin Films of Cylinder- Forming Block Copolymers”, Phys. Rev. Lett., 89, 035501 ( 2002).
8. A. Horvat, K. S. Lyakhova, G. J. A. Sevink, and A. V. Zvelindovsky, R. Magerle, “Phase behavior in thin films of cylinder-forming ABA block copolymers: Mesoscale modeling”, J. Chem. Phys., 120, 1117 (2004).
9. K. S. Lyakhova, G. J. A. Sevink, A. V. Zvelindovsky, A. Horvat, R. Magerle, “Role of dissimilar interfaces in thin films of cylinder-forming block copolymers”, J. Chem. Phys., 120, 1127 (2004).
10. S. Ludwigs, G. Krausch, R. Magerle, “Phase Behavior of ABC Triblock Terpolymers in Thin Films: Mesoscale Simulations”, Macromolecules, 38, 1859 (2005).
11. H. P. Huinink, J. C. M. Brokken-Zijp, M. A. van Dijk, G. J. A. Sevink, “Asymmetric block copolymers confined in a thin film”, J. Chem. Phys. 112, 2452 (2000).
12. L. Tsarkova, A. Knoll, G. Krausch, R. Magerle, “Substrate-Induced Phase Transitions in Thin Films of Cylinder-Forming Diblock Copolymer Melts”, Macromolecules, 39, 3608 (2006).
13. K. Fukunaga, T. Hashimoto, H. Elbs, G. Krausch, “Self-Assembly of a Lamellar ABC Terpolymer Thin Film. Effect of Substrates”, Macromolecules, 36, 2852 (2003).
14. H. I. Smith, M. L. Schattenberg, S. D. Hector, J. Ferrera, E. E. Moon, I. Y. Yang, M. Burkhardt, “X-ray nanolithography: Extension to the limits of the lithographic process”, Microelctronic Engineering, 32, 143 (1996).
15. D. V. Nicolau, T. Taguchi, H. Taniguchi, S. Yoshikawa, “Negative and Positive Tone Protein Patterning on E-Beam/Deep-UV Resists”, Langmuir, 15, 3845 (1999).
16. R. D. Piner, J. Zhu, F. Xu, S. Hong, C. A. Mirkin, “"Dip-Pen" Nanolithography”, Science, 283, 661 (1999).
17. S. Hong, C. A. Mirkin, “A Nanoplotter with Both Parallel and Serial Writing Capabilities”, Science, 288, 1808 (2000).

18. J. Xu, S. Park, S. Wang, T. P. Russell, B. M. Ocko, A. Checco, “Directed Self-Assembly of Block Copolymers on Two-Dimensional Chemical Patterns Fabricated by Electro-Oxidation Nanolithography”, Adv. Mater., 22, 2268 (2010).
19. J. Chai, F. Huo, Z. Zheng, L. R. Giam, W. Shim, C. A. Mirkin, “Scanning probe block copolymer lithography”, PNAS, 107, 20202 (2010).
20. S. Kramer, R. R. Fuierer, C. B. Gorman, “Scanning Probe Lithography Using Self-Assembled Monolayers”, Chem. Rev., 103, 4367 (2003).
21. B. Basnar, I. Willner, “Dip-Pen-Nanolithographic Patterning of Metallic, Semiconductor, and Metal Oxide Nanostructures on Surfaces”, Small, 5, 28 (2009).
22. S. Y. Chou, P. R. Krauss, P. J. Renstrom, “Imprint Lithography with 25-Nanometer Resolution”, Science, 272, 85 (1996).
23. X. Man, D. Andelman, H. Orland, P. Thebault, P.-H. Liu, P. Guenoun, J. Daillant, S. Landis, “Organization of Block Copolymers using NanoImprint Lithography : Comparison of Theory and Experiments”, Macromolecules, 44, 2206 (2012).
24. C. Parka, J. Yoonb, E. L. Thomas, “Enabling nanotechnology with self-assembled block copolymer patterns”, Polymer, 44, 6725 (2003).
25. R. A. Segalman, “Patterning with block copolymer thin films”, Materials Science and Engineering: R: Reports, 48, 191 (2005).
26. S.B. Darling, “Directing the self-assembly of block copolymers”, Progress in Polymer Science, 32, 1152 (2007).
27. I.W. Hamley, “Ordering in thin films of block copolymers: Fundamentals to potential applications”, Progress in Polymer Science, 34, 1161 (2009).

28. J. K. Kim, S. Y. Yang, Y. Lee, Y. Kim, “Functional nanomaterials based on block copolymer self-assembly”, Progress in Polymer Science, 35, 1325 (2010).
29. S. Park, B. Kim, J.-Y. Wang, T. P. Russell, “Fabrication of Highly Ordered Silicon Oxide Dots and Stripes from Block Copolymer Thin Films”, Adv. Mater., 20, 681 (2008).
30. H. Cho, H. Park, T. P. Russell, S. Park, “Precise placements of metal nanoparticles from reversible block copolymer nanostructures”, J. Mater. Chem., 20, 5047 (2010).
31. C. D. Rosa, F. Auriemma, R. D. Girolamo, G. P. Pepe, T. Napolitano, R. Scaldaferri, “Enabling Strategies in Organic Electronics Using Ordered Block Copolymer Nanostructures”, Adv. Mater., 22, 5414 (2010).
32. Y. Hu, D. Chen, S. Park, T. Emrick, T. P. Russell, “Guided Assemblies of Ferritin Nanocages : Highly Ordered Arrays of Monodisperse Nanoscopic Elements”, Adv. Mater., 22, 2583 (2010).
33. J. I. Lee, S. H. Cho, S.-M. Park, J. K. Kim, J. K. Kim, J.-W. Yu, Y. Chul Kim, T. P. Russell, “Highly Aligned Ultrahigh Density Arrays of Conducting Polymer Nanorods using Block Copolymer Templates”, Nano Lett., 8, 2315 (2008).
34. J. G. Son, W. K. Bae, H. Kang, P. F. Nealey, K. Char, “Placement Control of Nanomaterial Arrays on the Surface-Reconstructed Block Copolymer Thin Films”, ACS Nano, 3, 3927 (2009).
35. Y. S. Jung, J. H. Lee, J. Y. Lee, C. A. Ross, “Fabrication of Diverse Metallic Nanowire Arrays Based on Block Copolymer Self-Assembly”, Nano Lett., 10, 3722 (2010).

36. J. Bai, X. Zhong, S. Jiang, Y. Huang, X. Duan, “Graphene nanomesh”, Nature Nanotechnology, 5, 190 (2010).
37. M. Kim, N. S. Safron, E. Han, M. S. Arnold, P. Gopalan, “Fabrication and Characterization of Large-Area, Semiconducting Nanoperforated Graphene Materials”, Nano Lett., 10, 1125 (2010).
38. D. O. Shin, D. H. Lee, H.-S. Moon, S.-J. Jeong, J. Y. Kim, J. H. Mun, H. Cho, S. Park, S. O. Kim, “Sub-Nanometer Level Size Tuning of a Monodisperse Nanoparticle Array Via Block Copolymer Lithography”, Adv. Funct. Mater., 21, 250 (2011).
39. S. Y. Yang, I. Ryu, H. Y. Kim, J. K. Kim, S. K. Jang, T. P. Russell, “Nanoporous Membranes with Ultrahigh Selectivity and Flux for The Filtration of Viruses”, Adv. Mater., 16, 709 (2006).
40. S. Y. Yang, J. Park, J. Yoon, M. Ree, S. K. Jang, J. K. Kim,“Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance”, Adv. Mater., 18, 1371 (2008).
41. S. Y. Yang, J.-A Yang, E.-S. Kim, G. Jeon, E. J. Oh, K. Y. Choi, S. K. Hahn, J. K. Kim, “Single-File Diffusion of Protein Drugs through Cylindrical Nanochannels”, ACS Nano, 4, 3817 (2010).
42. W. A. Phillip, M. Amendt, B. O’Neill, L. Chen, M. A. Hillmyer, E. L. Cussler, “Diffusion and Flow Across Nanoporous Polydicyclopentadiene- Based Membranes”, ACS Appl. Mater. Interfaces, 1, 472 (2009).
43. W. A. Phillip, B. O’Neill, M. Rodwogin, M. A. Hillmyer, E. L. Cussler, “Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes”, Applied Material and Interfaces, 2, 847 (2010).
44. E. A. Jackson, M. A. Hillmyer, “Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration”, ACS Nano, 4, 3548 (2010).
45. W. Joo, M. S. Park, J. K. Kim, “Block copolymer film with sponge-like nanoporous strucutre for antireflection coating”, Langmuir, 22, 7960 (2006).
46. W. Joo, H. J. Kim, J. K. Kim, “Broadband antireflection coating covering from visible to near infrared wavelengths by using multilayered nanoporous block copolymer films” Langmuir, 26, 5110 (2010).
47. H.-Y. Hsueh, H.-Y. Chen, M.-S. She, C.-K. Chen, R.-M. Ho, S. Gwo, H. Hasegawa, E. L. Thomas, “Inorganic Gyroid with Exceptionally Low Refractive Index from Block Copolymer Templating”, Nano Lett., 10, 4994 (2010).
48. X. Li, Y. Han, “Tunable wavelength antireflective film by non-solvent-induced phase separation of amphiphilic block copolymer micelle solution”, J. mater. Chem., 21, 18024 (2011).
49. M. Park, C. Harrison, P. M. Chaikin, R. A. Register, D. H. Adamson, “Block Copolymer Lithography: Periodic Arrays of ~1011 Holes in 1 Square Centimeter”, Science, 276, 1401 (1997).
50. T. Thurn-Albrecht, J. Schotter, G. A. Kastle, N. Emley, T. Shibauchi, L. Krusin-Elbaum, K. Guarini, C. T. Black, M. T. Tuominen, T. P. Russell, “Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates”, Science, 290, 2126 (2000).
51. T. Thurn-Albrecht, J. DeRouchey, T. P. Russell, H. M. Jaeger, “Overcoming Interfacial Interactions with Electric Fields”, Macromolecules, 33, 3250 (2000).

52. T. Thurn-Albrecht, J. DeRouchey, T. P. Russell, R. Kolb, “Pathways toward Electric Field Induced Alignment of Block Copolymers”, Macromolecules, 35, 8106 (2002).
53. T. Xu, Y. Zhu, S. P. Gido, T. P. Russell, “Electric Field Alignment of Symmetric Diblock Copolymer Thin Films”, Macromolecules, 37, 2625 (2004).
54. P. Mansky, Y. Liu, E. Huang, T. P. Russell, C. Hawker, “Controlling Polymer-Surface Interactions with Random Copolymer Brushes”, Science, 275, 1458 (1997).
55. K. W. Guarini, C. T. Black, E. Huang, S. H. I. Yeung, “Optimization of Diblock Copolymer Thin Film Self Assembly”, Adv. Mater., 14, 1290 (2002).
56. E. Han, K. O. Stuen, Y.-H. La, P. F. Nealey, P. Gopalan, “Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains”, Macromolecules, 41, 9090 (2008).
57. S. O. Kim, H. H. Solak, M. P. Stoykovich, N. J. Ferrier, J. J. de Pablo, P. F. Nealey, “Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates”, Nature, 424, 411 (2003).
58. S.-J. Jeong, H.-S. Moon, B. H. Kim, J. Y. Kim, J. Yu, S. Lee, M. G. Lee, H. Y. Choi, S. O. Kim, “Ultralarge-Area Block Copolymer Lithography Enabled by Disposable Photoresist Prepatterning”, ACS Nano, 4, 5181 (2011).
59. S.-J. Jeong, S. O. Kim, “Ultralarge-area block copolymer lithography via soft graphoepitaxy”, J. Mater. Chem., 21, 5856 (2011).

60. H. Jung, D. Hwang, E. Kim, B.-J. Kim, W. B. Lee, J. E. Poelma, J. Kim, C. J. Hawker, J. Huh, D. Y. Ryu, J. Bang, “Three-Dimensional Multilayered Nanostructures with Controlled Orientation of Microdomains from Cross-Linkable Block Copolymers”, ACS Nano, 5, 6164 (2011).
61. J. Xu, T. P. Russell, B. M. Ockob, A. Checco, “Block copolymer self-assembly in chemically patterned squares”, Soft Matter, 7, 3915 (2011).
62. R. A. Segalman, H. Yokoyama, E. J. Kramer, “Graphoepitaxy of Spherical Domain Block Copolymer Films”, Adv. Mater., 13, 1151 (2001).
63. S. Park, D. H. Lee, J. Xu, B. Kim, S. W. Hong, U. Jeong, T. Xu, T. P. Russell, “Macroscopic 10-Terabit–per–Square-Inch Arrays from Block Copolymers with Lateral Order”, Science, 323, 1030 (2009).
64. S. Park, D. H. Lee, T. P. Russell, “Self-Assembly of Block Copolymers on Flexible Substrates”, Adv. Mater., 22, 1882 (2010).
65. A. Tavakkoli K. G., K. W. Gotrik, A. F. Hannon, A. Alexander-Katz, C. A. Ross, K. K. Berggren, “Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films”, Science, 336, 1294 (2012).
66. J. Y. Cheng, C. A. Ross, E. L. Thomas, H. I. Smith, G. J. Vancso, “Templated Self-Assembly of Block Copolymer : Effect of Substrate Topography”, Adv. Mater., 15, 1599 (2003).
67. I. Bita, J. K. W. Yang, Y. S. Jung, C. A. Ross, E. L. Thomas, K. K. Berggren, “Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates”, Science, 321, 939 (2008).
68. S.-M. Park, M. Dong, C. T. Rettner, D. S. Dandy, Q. Wang, H.-C. Kim, “Bending of Lamellar Microdomains of Block Copolymers on Nonselective Surfaces”, Macromolecules, 43, 1665 (2010).

69. P. Muller-Buschbaum, J. S. Gutmann, M. Wolkenhauer, J. Kraus, M.Stamm, D. Smilgies, W. Petry, “Solvent-Induced Surface Morphology of Thin Polymer Films”, Macromolecules, 34, 1369 (2001).
70. E. B. Gowd, M. Böhme, M. Stamm, “Thin Films Morphologies of ABC Triblock Copolymers Prepared From Solution”, Macromolecules, 35, 5570 (2002).
71. E. B. Gowd, M. Böhme, M. Stamm, “In Situ GISAXS Study on Solvent Vapour Induced Orientation Switching in PS-b-P4VP Block Copolymer Thin Films”, Materials Science and Engineering, 14, 012015 (2010).
72. J. Zhang, X. Yu, P. Yang, J. Peng, C. Luo, W. Huang, Y. Han, “Microphase Separation of Block Copolymer Thin Films”, Macromol. Rapid Commun., 31, 591 (2010).
73. J. N. L. Albert, T. H. Epps, III, “Self-assembly of block copolymer thin films”, Materials Today, 13, 24 (2010).
74. J. N. L. Albert, J. D. Kim, C. M. Stafford, T. H. Epps, III, “Controlled vapor deposition approach to generating substrate surface energy/chemistry gradients”, Rev. Sci. Instrum., 82, 065103 (2011).
75. R. Roy, J. K. Park, W.-S. Young, S. E. Mastroianni, M. S. Tureau, T. H. Epps, III, “Double-Gyroid Network Morphology in Tapered Diblock Copolymers”, Macromolecules, 44, 3910 (2011).
76. R.-M. Ho, W.-H. Tseng, H.-W. Fan, Y.-W. Chiang, C.-C. Lin, B.-T. Ko, B.-H. Huang, “Solvent-induced microdomain orientation in polystyrene- b-poly(L-lactide) diblock copolymer thin films for nanopatterning”, Polymer, 46, 9362 (2005).

77. G. Kim, M. Libera, “Morphological Development in Solvent-Cast Polystyrene-Polybutadiene-Polystyrene (SBS) Triblock Copolymer Thin Films”, Macromolecules, 31, 2569 (1998).
78. S. Park, B. Kim, J. Xu, T. Hofmann, B. M. Ocko, T. P. Russell, “Lateral Ordering of Cylindrical Microdomains Under Solvent Vapor”, Macromolecules, 42, 1278 (2009).
79. B. Kim, S. W. Hong, S. Park, J. Xu, S.-K. Hongc, T. P. Russell, “Phase transition behavior in thin films of block copolymers by use of immiscible solvent vapors”, Soft Matter, 7, 443 (2011).
80. Y. S. Jung, J. B. Chang, E. Verploegen, K. K. Berggren, C. A. Ross, “A Path to Ultranarrow Patterns Using Self-Assembled Lithography”, Nano Lett., 10, 1000 (2010).
81. J. Bang, B. J. Kim, G. E. Stein, T. P. Russell, X. Li, J. Wang, E. J. Kramer, C. J. Hawker, “Effect of Humidity on the Ordering of PEO-Based Copolymer Thin Films”, Macromolecules, 40, 7019 (2007).
82. Y. S. Jung, C. A. Ross, “Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns”, Adv. Mater., 21, 2540 (2009).
83. J. N. L. Albert, T. D. Bogart, R. L. Lewis, K. L. Beers, M. J. Fasolka, J. B. Hutchison, B. D. Vogt, T. H. Epps, III, “Gradient Solvent Vapor Annealing of Block Copolymer Thin Films Using a Microfluidic Mixing Device”, Nano Lett., 11, 1351 (2011).
84. Y. Xuan, J. Peng, L. Cui, H. Wang, B. Li, Y. Han, “Morphology Development of Ultrathin Symmetric Diblock Copolymer Film via Solvent Vapor Treatment”, Macromolecules, 37, 7301 (2004).

85. J. W. Jeong, W. I. Park, M.-J. Kim, C. A. Ross, Y. S. Jung, “Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine-b-dimethylsiloxane) Block Copolymer”, Nano Lett., 11, 4095 (2011).
86. S.-P. Hsu, Y.-S. Sun, “Controls over Microdomain in Diblock Copolymer Thin Films by Polar/Nonpolar Cosolvent Annealing”, 國立中央大學化學工程研究所碩士論文 (2010).
87. M.-S. Lin, Y.-S. Sun, “Fabrication of block copolymer thin films with hierarchical ordering upon solvent annealing combined with micro-contact printing”, 國立中央大學化學工程研究所碩士論文 (2011).
88. 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 (2001).
89. G. Reiter, A. Sharma, A. Casoli, M.-O. David, R. Khanna, P. Auroy, “Thin Film Instability Induced by Long-Range Forces”, Langmuir, 15, 2551 (1999)
90. J. C. Meredith, A. P. Smith, A. Karim, E. J. Amis, “Combinatorial Materials Science for Polymer Thin-Film Dewetting”, Macromolecules, 33, 9747 (2000).
91. S. H. Lee, P. J. Yoo, S. J. Kwon, H. H. Lee, “Solvent-driven dewetting and rim instability”, J. Chem. Phys., 121, 4346 (2004).
92. P. Muller-Buschbaum, E. Bauer, O. Wunnicke, 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).
93. J. Peng, Y. Han, W. Knoll, D. H. Kim, “Development of Nanodomain and Fractal Morphologies in Solvent Annealed Block Copolymer Thin Films”, Macromol. Rapid Commun., 28, 1422 (2007).
94. T. H. Kim, J. Hwang, W. S. Hwang, J. Huh, H.-C. Kim, S. H. Kim, J. M. Hong, E. L. Thomas, C. Park, “Hierarchical Ordering of Block Copolymer Nanostructures by Solvent Annealing Combined with Controlled Dewetting”, Adv. Mater., 20, 522 (2008).
95. C. Harrison, M. Park, P. Chaikin, R. A. Register, D. H. Adamson, N. Yao, “Depth Profiling Block Copolymer Microdomains”, Macromolecules, 31, 2185 (1998).
96. K. Fukunaga, H. Elbs, R. Magerle, G. Krausch, N. Yao, “Large-Scale Alignment of ABC Block Copolymer Microdomains via Solvent Vapor Treatment”, Macromolecules, 33, 947 (2000).
97. M. Konrad, A. Knoll, G. Krausch, R. Magerle, “Volume Imaging of an Ultrathin SBS Triblock Copolymer Film”, Macromolecules, 33, 5518 (2000).
98. S. Ludwigs, K. Schmidt, C. M. Stafford, E. J. Amis, M. J. Fasolka, A. Karim, R. Magerle, G. Krausch, “Combinatorial Mapping of the Phase Behavior of ABC Triblock Terpolymers in Thin Films: Experiments”, Macromolecules, 38, 1850 (2005).
99. K. S. Lyakhova, A. Horvat, A. V. Zvelindovsky, G. J. A. Sevink, “Dynamics of Terrace Formation in a Nanostructured Thin Block Copolymer film”, Langmuir, 22, 5848 (2006).

100. A. Horvat, A. Knoll, G. Krausch, L. Tsarkova, K. S. Lyakhova, G. J. A. Sevink, A. V. Zvelindovsky, R. Magerle, “Time Evolution of Surface Relief Structures in Thin Block Copolymer Films”, Macromolecules, 40, 6930 (2007).
101. C. Neto, M. James, A. M. Telford, “On the Composition of the Top Layer of Microphase Separated Thin PS-PEO Films”, Macromolecules, 42, 4801 (2009).
102. G. Coulon, T. P. Russell, V. R. Deline, P. F. Green, “Surface-induced orientation of symmetric, diblock copolymers: a secondary ion mass-spectrometry study”, Macromolecules, 22, 2581 (1989).
103. J. Brandrup, E. H. Immergut, E. A. Grulke, Polymer Handbook, 4/e., John Wiley & Sons, New York, 1999.
104. M. W. Davidson, M. Abramowitz, “OPTICAL MICROSCOPY”, Online PDF resource, 1999.
105. J. E. Lennard-Jones, “Cohesion”, Proceedings of the Physical Society, 43, 461 (1931).
106. P.B. Hirsch, A. Howie, R. B. Nicholson, D.W. Pashley, M. J.Whelan, “Electron Microscopy of Thin Crystals”, Kriger, Huntington, NY, 1977.
107. P. Müller-Buschbaum, “A Basic Introduction to Grazing Incidence Small-Angle X-Ray Scattering”, Lect. Notes Phys., 776, 61 (2009).

指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2012-7-5

推文