使用聚苯乙烯製備垂直嵌段共聚物薄膜 奈米結構及交聯密度探討

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：56

、訪客IP：18.217.242.39

姓名

吳崧豪(Song-Hao Wu) 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

使用聚苯乙烯製備垂直嵌段共聚物薄膜奈米結構及交聯密度探討
(Effects of Cross-linking density of UV Irradiated Polystyrene Chains on Domain Orientation and Spatial Order of Block Copolymer Thin 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	★ 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
★ 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

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]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

本實驗使用聚苯乙烯(PS)薄膜當作改質層，藉由聚苯乙烯薄膜上的化學反應，改變原始聚苯乙烯薄膜的性質，在製作表面改質薄膜過程上，我們藉由紫外光的照射的環境不同來調整薄膜的表面能，表面能控制在中性條件下，可以得到垂直排列的雙嵌段高分子(PS-b-PMMA)結構的範圍。本實驗和眾多團隊的不同之處為，取代原始的隨機共聚物的改質方法，並探討交聯密度的強度對應雙嵌段高分子結構的有序程度，以及在不同薄膜厚度下，對退火溫度的移動力變化，和其熱穩定性性質的不同，透過不同的儀器來探測介面間的相互影響對結構的變化。
希望能透過此一製程相較簡單、有效率以及材料取得容易的幾個特點來取代隨機共聚物和其他製成繁瑣的表面改質技術，由於改質上僅需要塗佈以及紫外光曝曬的製成，若能應用在放大製程上面規模生產的難度會比其他改質方法低許多，另外可以藉由聚苯乙烯的特性，調控不同的照光強度、照光的持續時間，藉此控制不同交聯程度，透過此一特點改變改質膜的強度。

摘要(英)

In this study, we demonstrate a novel strategy to control the orientation of microdomains in block copolymer thin films through surface modification by PS thin film. The PS thin film were crosslinked by UV lamp exposure to precisely tune the interfacial interaction between the poly(styrene-b-methyl methacrylate)(PS-b-PMMA) and substrate interface. We are able to obtain nanopattern with vertical hexagonal and lamellae structure.
Since the film is made of PS, which is the most general plastics, cumbersome and multiple steps of polymer synthesis are unnecessary, making possible the mass production of surface modification over varied substrates.
PS layer after UV lamp treated , produced non preferential condition for upper BCP(PS-b-PMMA) and produced perpendicular oriented cylinders and lamellae, UVIN produce enough strength for crosslinking , UVIA produce oxide layer , both process are necessary to make the neutral condition,

關鍵字(中)

★ 高分子

關鍵字(英)

★ BCP

論文目次

摘要 iii
Abstract iv
致謝 v
目錄 vi
圖目錄 ix
表目錄 xiv
第1章簡介 1
一、團鏈共聚物之自組裝行為 1
1-1 自組裝的機制 1
1-2 自洽平均場理論 3
1-3 薄膜內之微相分離 7
二、控制高分子有序結構 8
2-1 電場引導高分子有序性 9
2-2 表面改質 11
2-3 化學圖案改質 12
2-3-1基材圖形導向 13
2-4 溶劑退火改變高分子導向 14
三、研究背景與動機 16
第2章實驗 17
一、實驗材料 17
二、實驗儀器 19
三、試片製備 20
3-1 基材製備 20
3-2 薄膜製備 22
3-3 紫外光照射 22
3-4 雙嵌段共聚物的自組裝 23
四、實驗設計 23
4-1 以聚苯乙烯做基材改質 23
4-2 不同分子量的聚苯乙烯做基材改質 23
4-3 不同基材上的垂直結構製備 24
4-4 不同膜厚的聚苯乙烯做基材改質 24
4-5不同膜厚的聚(苯乙烯-b-甲基丙烯酸甲酯)結構製備 25
五、儀器原理 26
5-1 光學顯微鏡 26
5-2 原子力顯微鏡 27
5-3 低掠角小角度X光散射 28
5-4 X光反射率掃描量測 30
第3章結果與討論 32
一、使用聚苯乙烯為基底之表面改質 32
1-1 以聚苯乙烯取代隨機共聚物之表面改質 32
1-2 聚苯乙烯薄膜之製作及化學反應 37
1-3 聚苯乙烯之交聯及氧化反應 37
二、聚苯乙烯交聯密度的控制及其對形貌影響 42
2-1 PS薄膜溶劑抵抗性之觀察 43
2-2 交聯密度之量化 46
2-3 使用熱退火將聚(苯乙烯-b-甲基丙烯酸甲酯)自組裝 50
2-4 交聯密度對熱退火後表面結構影響 51
2-5 控制照光時間對高分子表面形貌影響 61
三、製備後之高分子結構測定 67
3-1 氧電漿法測定高分子縱向的有序排列 67
3-2 GISAXS-小角度低掠角X光量測 71
3-3 XRR觀察高分子鏈擴散效應及厚度量測 80
3-4 SEM測定橫切面 85
四、聚苯乙烯改質層延伸探討 90
4-1 聚苯乙烯應用在不同基材 90
4-2 聚苯乙烯改質層厚度變化 93
第4章結論 95
第5章參考文獻 97

參考文獻

1. Sun, Ya-Sen, Ching-Tun Wang, and Jiun-You Liou. "Tuning polymer-surface chemistries and interfacial interactions with UV irradiated polystyrene chains to control domain orientations in thin films of PS-b-PMMA." Soft matter 12.11 (2016): 2923-2931.
2. Han, Eungnak, et al. "Perpendicular orientation of domains in cylinder-forming block copolymer thick films by controlled interfacial interactions." Macromolecules 42.13 (2009): 4896-4901.
3. Ham, S., Shin, C., Kim, E., Ryu, D. Y., Jeong, U., Russell, T. P., & Hawker, C. J. (2008). Microdomain orientation of PS-b-PMMA by controlled interfacial interactions. Macromolecules, 41(17), 6431-6437.
4. Sparnacci, K., Antonioli, D., Gianotti, V., Laus, M., Ferrarese Lupi, F., Giammaria, T. J., ... & Perego, M. (2015).Ultrathin random copolymer-grafted layers for block copolymer self-assembly. ACS applied materials & interfaces, 7(20), 10944-10951.
5. Ferrarese Lupi, F., Giammaria, T. J., Seguini, G., Vita, F., Francescangeli, O., Sparnacci, K., ... & Perego, M. (2014). Fine tuning of lithographic masks through thin films of PS-b-PMMA with different molar mass by rapid thermal processing. ACS applied materials & interfaces, 6(10), 7180-7188.
6. Zhao, Y., Sivaniah, E., & Hashimoto, T. (2008). SAXS Analysis of the Order− Disorder Transition and the Interaction Parameter of Polystyrene-block-poly (methyl methacrylate). Macromolecules, 41(24), 9948-9951.
7. Mansky, P., Russell, T. P., Hawker, C. J., Mays, J., Cook, D. C., & Satija, S. K. (1997). Interfacial segregation in disordered block copolymers: effect of tunable surface potentials. Physical review letters, 79(2), 237.
8. Kim, Sangwon, et al. "Order–disorder transition in thin films of horizontally-oriented cylinder-forming block copolymers: thermal fluctuations vs. preferential wetting." Soft Matter 12.27 (2016): 5915-5925.
9. Seguini, G., Giammaria, T. J., Lupi, F. F., Sparnacci, K., Antonioli, D., Gianotti, V., ... & Francescangeli, O. (2014). Thermally induced self-assembly of cylindrical nanodomains in low molecular weight PS-b-PMMA thin films. Nanotechnology, 25(4), 045301.
10. Frascaroli, J., Seguini, G., Spiga, S., Perego, M., & Boarino, L. (2015). Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO2 substrates. Nanotechnology, 26(21), 215301.
11. Gianotti, V., Antonioli, D., Sparnacci, K., Laus, M., Giammaria, T. J., Ferrarese Lupi, F., ... & Perego, M. (2013). On the thermal stability of PS-b-PMMA block and P (S-r-MMA) random copolymers for nanopatterning applications. Macromolecules, 46(20), 8224-8234.
12. Ceresoli, M., Lupi, F. F., Seguini, G., Sparnacci, K., Gianotti, V., Antonioli, D., ... & Perego, M. (2014). Evolution of lateral ordering in symmetric block copolymer thin films upon rapid thermal processing. Nanotechnology, 25(27), 275601.
13. Mishra, V., Fredrickson, G. H., & Kramer, E. J. (2012). Effect of film thickness and domain spacing on defect densities in directed self-assembly of cylindrical morphology block copolymers. ACS nano, 6(3), 2629-2641.
14. Son, J. G., Kang, H., Kim, K. Y., Lee, J. S., Nealey, P. F., & Char, K. (2011). Orientation Change of Diblock Copolymer Thin Films by the Addition of Amphiphilic Surfactants: Effect of Film Thickness and Surfactant Concentration. Macromolecules, 45(1), 150-158.
15. Huang, E., Pruzinsky, S., Russell, T. P., Mays, J., & Hawker, C. J. (1999). Neutrality conditions for block copolymer systems on random copolymer brush surfaces. Macromolecules, 32(16), 5299-5303.
16. Xia, Z., Patchan, M., Maranchi, J., Elisseeff, J., & Trexler, M. (2013). Determination of crosslinking density of hydrogels prepared from microcrystalline cellulose. Journal of Applied Polymer Science, 127(6), 4537-4541.
17. Chang, Chih-Yao, Pin-Jiun Wu, and Ya-Sen Sun. "Kinetically controlled self-assembly of monolayered micelle films of P (S-b-4VP) on bare and PS-grafted substrates." Soft Matter 7.19 (2011): 9140-9147.
18. Pandav, G., Durand, W. J., Ellison, C. J., Willson, C. G., & Ganesan, V. (2015). Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes. Soft matter, 11(47), 9107-9114.
19. Vu, T., Mahadevapuram, N., Perera, G. M., & Stein, G. E. (2011). Controlling domain orientations in thin films of AB and ABA block copolymers. Macromolecules, 44(15), 6121-6127.
20. Mahadevapuram, N., Mitra, I., Bozhchenko, A., Strzalka, J., & Stein, G. E. (2016). In‐plane and out‐of‐plane defectivity in thin films of lamellar block copolymers. Journal of Polymer Science Part B: Polymer Physics, 54(2), 339-352.
21. Li, L., Chen, C., Zhang, A., Liu, X., Cui, K., Huang, J., ... & Han, Z. (2009). Fabrication of robust honeycomb polymer films: A facile photochemical cross-linking process. Journal of colloid and interface science, 331(2), 446-452.
22. Yan, M., & Harnish, B. (2003). A simple method for the attachment of polymer films on solid substrates. Advanced Materials, 15(3), 244-248.
23. Zisman, Wm A. "Relation of the equilibrium contact angle to liquid and solid constitution." 1964. 1-51.
24. Kwok, Daniel Y., and August W. Neumann. "Contact angle measurement and contact angle interpretation." Advances in colloid and interface science 81.3 (1999): 167-249.
25. Ham, S., Shin, C., Kim, E., Ryu, D. Y., Jeong, U., Russell, T. P., & Hawker, C. J. (2008). Microdomain orientation of PS-b-PMMA by controlled interfacial interactions. Macromolecules, 41(17), 6431-6437.
26. Matsen, M. W., and Frank S. Bates. "Unifying weak-and strong-segregation block copolymer theories." Macromolecules 29.4 (1996): 1091-1098.
27. Ginzburg, Valeriy V., et al. "Modeling chemoepitaxy of block copolymer thin films using self-consistent field theory." Journal of Photopolymer Science and Technology 26.6 (2013): 817-823.
28. Son, J. G., Gotrik, K. W., & Ross, C. A. (2012). High-aspect-ratio perpendicular orientation of PS-b-PDMS thin films under solvent annealing. ACS Macro Letters, 1(11), 1279-1284.
29. Maher, M. J., Bates, C. M., Blachut, G., Sirard, S., Self, J. L., Carlson, M. C., ... & Ellison, C. J. (2014). Interfacial design for block copolymer thin films. Chemistry of Materials, 26(3), 1471-1479.
30. Peters, R., & Dalnoki-Veress, K. (2012). Film thickness dependent ordering dynamics of lamellar forming diblock copolymer thin films. European Physical Journal E--Soft Matter, 35(12).
31. Liedel, Clemens, et al. "Beyond orientation: the impact of electric fields on block copolymers." Macromolecular Chemistry and Physics 213.3 (2012): 259-269.
32. Goldberg-Oppenheimer, Pola, et al. "Hierarchical orientation of crystallinity by block-copolymer patterning and alignment in an electric field." Chemistry of Materials 25.7 (2013): 1063-1070.
33. Han, Eungnak, et al. "Graphoepitaxial assembly of symmetric block copolymers on weakly preferential substrates." Advanced Materials 22.38 (2010): 4325-4329.
34. Tsai, Hsinyu, et al. "Two-dimensional pattern formation using graphoepitaxy of PS-b-PMMA block copolymers for advanced FinFET device and circuit fabrication." ACS nano 8.5 (2014): 5227-5232.
35. Frascaroli, J., Seguini, G., Spiga, S., Perego, M., & Boarino, L. (2015). Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO2 substrates. Nanotechnology, 26(21), 215301.

指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2017-7-27

推文