本研究結合由“top-down”微影製程所得到不同形貌的奈米模板以及“bottom-up”的嵌段共聚物自組裝方法來得到一個大面積且具有序性的奈米結構。
在第一版奈米模板中，我們以沉積硬遮罩取代光阻、調整蝕刻氣體參數以及事先成長蝕刻終點的方式，得到擁有垂直側壁、平坦底部以及改善微溝渠現象的奈米模板；而在奈米模板尺寸及圖形的優化上，第二版奈米模板利用電子束微影系統搭配製程的垂直整合得到週期為250奈米的奈米光柵結構，第三版奈米模板則是透過多重曝光的方式改善正方形及六角形結構的角落圓滑現象。

In this study, we combine the “top-down” lithography process and “bottom-up” self-assembly of block copolymer approach to generate nano-structure with well-oriented periodic arrays over large area.
The first nano-template is a periodic Si grating made by dry etching, where a SiO2 layer is used as a hard mask to define the grating structure. We modify the concentration of process gases during etching, a steep sidewall and flat surface at the bottom of trenches is achieved. The second nano-template is with a grating feature size down to 50 nm, which is fabricated by e-beam lithography and a sidewall coating technique. The 3rd nano-template is square and hexagonal sharp-angle wells fabricated through multi-step photolithography. Then we take a process similar to making the second nano-template to get the final structure.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1.1 前言 1
1.2 文獻回顧 2
1.3 研究動機 5
1.4 論文架構 6
第二章 理論背景 7
2.1 嵌段共聚物的自組裝現象 7
2.2 嵌段共聚物的成核機制 10
2.3 奈米模板的侷限效應 12
第三章 奈米模板製作與嵌段共聚物填充流程 14
3.1 奈米模板設計與製作 14
3.1.1 第一版奈米模板製作流程 15
3.1.2 第二版奈米模板製作流程 16
3.1.3 第三版奈米模板製作流程 17
3.2 製程步驟詳細說明 19
3.2.1 第一版奈米模板 19
3.2.2 第二版奈米模板 25
3.2.3 第三版奈米模板 31
3.3 嵌段共聚物填充流程 35
第四章 奈米模板與嵌段共聚物於奈米模板中之自組裝現象量測 37
4.1 奈米模板之量測 37
4.1.1 第一版奈米模版之量測 37
4.1.2 第二版奈米模版之量測 40
4.1.3 第三版奈米模版之量測 42
4.2 嵌段共聚物於奈米模板中之自組裝現象 45
4.2.1 嵌段共聚物於第一版奈米模板中之自組裝現象 46
4.2.2 嵌段共聚物於第二版奈米模板中之自組裝現象 47
4.2.3 嵌段共聚物於第三版奈米模板中之自組裝現象 48
第五章 結論 49
參考文獻 53
附錄 奈米模板製作流程 56

[1] 陳家俊、藍榮煌, “奈米科技的發展與應用” 半導體科技, 2001,台北市: 亞格數位
[2] Roper, C.S., et al., “Single crystal silicon nanopillars, nanoneedles and nanoblades with precise positioning for massively parallel nanoscale device integration.” Nanotechnology, 2012. 23(22): p. 10.
[3] Latu-Romain, E., et al., “A generic approach for vertical integration of nanowires.” Nanotechnology, 2008. 19(34): p. 6.
[4] Mita, K., et al., “Cylindrical Domains of Block Copolymers Developed via Ordering under Moving Temperature Gradient: Real-Space Analysis.” Macromolecules, 2008. 41(22): p. 8789-8799.
[5] Hashimoto, T., et al., “The effect of temperature gradient on the microdomain orientation of diblock copolymers undergoing an order-disorder transition.” Macromolecules, 1999. 32(3): p. 952-954.
[6] Morkved, T.L., et al., “Local control of microdomain orientation in diblock copolymer thin films with electric fields.” Science, 1996. 273(5277): p. 931-933.
[7] Peters, R.D., et al., “Wetting behavior of block copolymers on self assembled films of alkylchlorosiloxanes: Effect of grafting density. Langmuir”, 2000. 16(24): p. 9620-9626.
[8] Peters, R.D., et al., “Using self-assembled monolayers exposed to X-rays to control the wetting behavior of thin films of diblock copolymers.” Langmuir, 2000. 16(10): p. 4625-4631.
[9] Han, E., et al., “Photopatternable imaging layers for controlling block copolymer microdomain orientation.” Advanced Materials, 2007. 19(24): p. 4448-+.
[10] Segalman, R.A., E.J. Kramer, and H. Yokoyama, “Graphoepitaxy of Spherical Domain Block Copolymer Films.” Advanced Materials, 2001. vol. 13: p. 1152.
[11] Tavakkoli, K.G.A., et al., “Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films.” Science, 2012. 336(6086): p. 1294-1298.
[12] Whitesides, G.M. and B. Grzybowski, “Self-assembly at all scales.” Science, 2002. 295(5564): p. 2418-2421.
[13] Philp, D. and J.F. Stoddart, “Self-Assembly in Natural and Unnatural Systems.” Angewandte Chemie International Edition in English, 1996. 35(11): p. 1154-1196.
[14] Forster, S. and T. Plantenberg, “From self-organizing polymers to nanohybrid and biomaterials.” Angewandte Chemie-International Edition, 2002. 41(5): p. 689-714.
[15] Gast, A.P., C.K. Hall, and W.B. Russel, “POLYMER-INDUCED PHASE SEPARATIONS IN NON-AQUEOUS COLLOIDAL SUSPENSIONS.” Journal of Colloid and Interface Science, 1983. 96(1): p. 251-267.
[16] Park, S., et al., “Macroscopic 10-Terabit-per-Square- Inch Arrays from Block Copolymers with Lateral Order.” Science, 2009. 323(5917): p. 1030-1033.
[17] Leibler, L., “Theory of Microphase Separation in Block Copolymers.” Macromolecules, 1980. 13(6): p. 1602-1617.
[18] Traiphol, R., et al., “Spectroscopic Study of Photophysical Change in Collapsed Coils of Conjugated Polymers:  Effects of Solvent and Temperature.” 2006. 39: p. 1165–1172.
[19] Matsen, M.W. and F.S. Bates, “Unifying Weak- and Strong-Segregation Block Copolymer Theories.” Macromolecules, 1996. 29(4): p. 1091-1098.
[20] Hamley, I.W., “Ordering in thin films of block copolymers: Fundamentals to potential applications.” Progress in Polymer Science, 2009. 34(11): p. 1161-1210.
[21] 蕭宏, “雙重、三重和多重圖案化技術” 半導體製程技術導論, 2013, 新北市: 全華圖書.
[22] Wu, H.-Y. Canon FPA-3000i5+ Stepper.
[23] Vitale, S.A., H. Chae, and H.H. Sawin, “Silicon etching yields in F-2, Cl-2, Br-2, and HBr high density plasmas.” Journal of Vacuum Science & Technology a-Vacuum Surfaces and Films, 2001. 19(5): p. 2197-2206.
[24] Hoekstra, R.J., et al., “Microtrenching resulting from specular reflection during chlorine etching of silicon.” Journal of Vacuum Science & Technology B, 1998. 16(4): p. 2102-2104.
[25] 梁曉堯, “矽積體光學晶片應用於光收發雙向多工器模組” 2011, 新竹市: 國立清華大學光電所.
[26] Merlos, A., et al., “TMAH/IPA ANISOTROPIC ETCHING CHARACTERISTICS.” Sensors and Actuators a-Physical, 1993. 37-8: p. 737-743.
[27] 巫清景, “製作奈米模板並探討嵌段共聚物於奈米模板下之自組裝現象” 2015, 新竹市: 國立清華大學光電所.