利用臨場及不同入射角低掠角小角度X光散射研究對稱型嵌段共聚物與均聚物混摻之表面浮凸薄膜的結構演變：均聚物分散係數之影響

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姓名

楊昕潼(Shin-Tung Yang) 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

利用臨場及不同入射角低掠角小角度X光散射研究對稱型嵌段共聚物與均聚物混摻之表面浮凸薄膜的結構演變：均聚物分散係數之影響
(Structural Evolution in Terraced Films of Block Copolymer/Homopolymer Blends Studied by In-Situ and Angle-Dependence Grazing Incidence Small-Angle X-ray Scattering：Effects of Chain Length Disparity)

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至系統瀏覽論文 (2026-7-25以後開放)

摘要(中)

本研究使用對稱型嵌段共聚物—聚苯乙烯-b-聚（甲基丙烯酸甲酯）混摻聚苯乙烯均聚物（PS21k-b-PMMA21k/PS6k），在不同的混摻比例、均聚物的分散係數（PDI）和熱回火溫度下，我們可以獲得不同奈米結構。為了去除表面潤濕層並增加 PS 和 PMMA 之間的對比度，我們使用了氧氣等離子體蝕刻。並利用光學顯微鏡（OM）、原子力顯微鏡（AFM）、掃描電子顯微鏡（SEM）、掠入射小角 X 射線散射（GISAXS）深入分析薄膜形態。
透過臨場（in-situ）可以探討在熱回火之自組裝行為，在量測不同入射角之方式（angle-dependent）可以研究結構及晶面特徵。透過均聚物PDI的不同，在PDI = 1.05及1.33可以獲得水平圓柱（Parallel cylinders, Cs//）的形貌，但PDI 1.5在70/30的混摻比例下結構會有所改變，並受到溫度的牽制。當溫度230 ℃會在薄膜表面形成單層穿孔層（Perforated layers, PLs //）結構，而內部維持水平圓柱，在270 ℃則會形成完整雙連續螺旋（Bicontinuous Double Gyroids, DG）結構。透過公式擬和水平圓柱的散射峰，能夠量化入射角、臨界角、q⊥方向貢獻以及穿透光與反射光之路徑，準確判斷晶面貢獻以及域間間距，更深入了解薄膜之結構。

摘要(英)

We have demonstrated the symmetric weakly separated block copolymer, polystyrene-block-poly（methyl methacrylate）blended with homopolystyrene（PS21k-b-PMMA21k/PS6k）. By using different blending ratios, homopolymer’s dispersity（PDI）and annealing temperatures, we obtained several nanostructures. To remove the surface wetting layer and to increase the contrast between PS and PMMA segments, we used oxygen plasma etching. Optical microscopy（OM）, atomic force microscopy（AFM）, scanning electron microscopy（SEM）, grazing-incidence small-angle X-ray scattering（GISAXS）were also used for in-depth morphological analysis of thin films.
Through in-situ GISAXS, the self-assembly behavior during thermal annealing can be investigated. The structures and crystal facet characteristics can be studied by angle-dependent GISAXS. Through quantitative analysis of angle-dependence GISAXS, we found that blend films favor a morphology of parallel cylinders（Cs//）when PS homopolymers of PDI=1.05 and 1.33 were mixed with the PS-b-PMMA at weight fractions of 70/30, 60/40 and 50/50. For PDI=1.5, perforated layers（PLs //) and bicontinuous double gyroids（DG）were obtained in blend films of P（S-b-MMA） and hPS of a weight fraction of 70/30. At 230 ℃, a surface layer of perforations formed on top of parallel cylinders. At 270 ℃, bicontinuous double gyroids formed. By fitting the q-scattering peaks of the horizontal cylinders through the formula, it is possible to quantify the incident angles, critical angles and diffraction spots along the q⊥ direction, thus allowing us to accurately determine the crystal plane contribution and interdomain spacing.

關鍵字(中)

★ 低掠角小角度X光散射
★ 分散係數
★ 嵌段共聚物

關鍵字(英)

★ GISAXS
★ Disparity
★ Block Copolymer

論文目次

摘要 i
Abstract ii
致謝 iii
目錄 iv
圖目錄 vi
表目錄 xiii
第1章緒論 1
1-1 前言 1
1-2 嵌段共聚物 3
1-3 塊材系統之自組裝 5
1-4 薄膜系統之自組裝 8
1-4-1 厚度效應 8
1-4-2 表面場作用力 10
1-4-3 空間侷限效應與膜厚相稱性 12
1-5 嵌段共聚物和均聚物之混摻系統 15
1-5-1 均聚物之濃度及分子量對結構變化的影響 17
1-5-2 薄膜層數對結構變化的影響 20
1-6 聚合物分散係數（Polydispersity Index, PDI） 22
1-7 研究背景與動機 24
第2章實驗 25
2-1 實驗材料 25
2-1-1 高分子材料 25
2-1-2 溶劑 26
2-1-3 基材 26
2-2 實驗儀器 26
2-3 實驗設計與樣品製備 27
2-3-1 基材前處理 27
2-3-2 高分子薄膜製備 27
2-3-3 移除潤濕層之方法—氧氣離子電漿蝕刻 29
2-3-4 低掠角小角度X 光散射樣品in-situ 量測 30
2-4 儀器原理 31
2-4-1 光學顯微鏡（OM） 31
2-4-2 原子力顯微鏡（AFM） 32
2-4-3 掃描式電子顯微鏡（SEM） 34
反射式膜厚儀（Optical interferometer） 37
2-4-4 低掠角小角度X光散射儀（GISAXS） 38
2-4-4-1 圓柱（Cylinders, Cs） 43
2-4-4-2 穿孔層（Perforated Layers, PLs//） 49
2-4-4-3 雙連續螺旋（bicontinuous Double Gyroids, DG） 51
第3章結果與討論 53
3-1 臨場（in-situ）實驗之特徵峰探討 53
3-1-1 樣品表面之觀察 54
3-1-2 GISAXS 2D圖特徵之探討 56
3-1-3 混摻效應對結構之影響 59
3-1-4 PDI效應對結構之影響 63
3-1-5 截斷棒（Truncation Rods）之晶面擬合 65
3-2 不同入射角（Angle-dependent）實驗之特徵峰探討 68
3-2-1 厚邊效應 69
3-2-2 PDI = 1.05之定性分析 74
3-2-3 PDI = 1.05之定量分析 75
3-2-4 PDI效應 84
3-2-4-1 PDI = 1.33 84
3-2-4-2 PDI = 1.50 87
3-2-5 雙連續螺旋之結構探討 92
第4章結論 98
第5章參考文獻 100
第6章附錄 107

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指導教授

李岱洲孫亞賢(Tai-Chou Lee Ya-Sen Sun)

審核日期

2023-7-26

推文