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

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姓名

洪嘉彣(Jia-Wen Hong) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

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
(Phase Behavior in Thin Films of Weakly-Segregated Block Copolymer/Homopolymer Binary Blends)

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摘要(中)

我們已經研究對稱型且弱分離的嵌段共聚物—聚苯乙烯-b-聚（甲基丙烯酸甲酯），及其與低分子量均聚物—聚苯乙烯的混合物在混摻比例下的薄膜相行為。通過熱退火過程，根據混合物中均聚物的不同含量，獲得了幾種形態。為了觀察薄膜的內部結構並增加PS和PMMA域之間的對比度，使用氧氣等離子體蝕刻選擇性地去除了PMMA塊和PS表層。借助光學顯微鏡（OM）、原子力顯微鏡（AFM）、掃描式電子顯微鏡（SEM）、低掠角小角度 X 光散射技術（GISAXS）仔細識別了薄膜結構。這些獲得的形態包含穿孔層（Perforated Layer, PL）、雙連續螺旋（bicontinuous Double Gyroids, DG）、圓柱（Cylinder, C）等結構。穿孔層和雙連續螺旋僅存在於一個狹窄的體積分率。除了PS混合比例以外，空間侷限效應和熱退火溫度也會影響穿孔層和雙連續螺旋之間的相穩定性。在薄膜中，聚苯乙烯-b-聚（甲基丙烯酸甲酯）和聚苯乙烯的複雜二元相混摻的存在可歸因於通過添加聚苯乙烯來減輕packing frustration。

摘要(英)

We have demonstrated the phase behavior in thin films of a symmetric weakly-segregated block copolymer, polystyrene-block-poly （methyl methacrylate）, PS-b-PMMA, and its mixtures with a low molecular weight homopolymer （polystyrene, PS） at different blending ratios. Through thermal annealing, several morphologies were obtained, depending on the different contents of homopolymer PS in the mixtures and annealing temperatures. To observe the inner structures in thin films and to increase the contrast between the PS and PMMA domains, oxygen plasma etching was used to selectively remove the PMMA block and PS skin layer. The thin film structures were carefully identified by means of optical microscopy（OM）, atomic force microscopy（AFM）, scanning electron microscope（SEM） and grazing-incidence small-angle X-ray scattering（GISAXS）. These obtained morphologies include perforated layers（PLs）, double gyroids（DGs）and cylinders（Cs）. PLs and DGs only existed in a narrow region. In addition to the blending ratios, spatial confinement effects and annealing temperatures also affected the phase stability between PLs and DGs. The presence of complex binary phases in thin blend films of PS-b-PMMA/PS is ascribed to alleviation of packing frustration through the addition of PS.

關鍵字(中)

★ 混摻
★ 薄膜
★ 嵌段共聚物
★ 相行為
★ 自組裝

關鍵字(英)

★ blend
★ thin film
★ block copolymer
★ phase behavior
★ self-assembly

論文目次

摘要 i
Abstract ii
致謝 iii
目錄 iv
圖目錄 vi
表目錄 xv
第一章簡介 1
1-1 共聚物之自組裝機制 1
1-2 塊材系統之自組裝 2
1-3 薄膜系統之自組裝 3
1-3-1 結構多樣性 4
1-3-2 奈米結構排向及梯田結構的形成 4
1-3-3 厚度效應引起之相轉換 6
1-3-4 厚度效應對晶格排列之影響 8
1-3-5自由鏈段在表面或界面聚集對奈米結構形態之影響 9
1-4 嵌段共聚物與均聚物之混摻系統 10
1-5 研究動機 15
第二章實驗 17
2-1 實驗材料 17
2-1-1高分子材料 17
2-1-2 溶劑 18
2-1-3 基材 18
2-2 實驗儀器 18
2-3 實驗製備與設計 19
2-3-1 基材之前處理 19
2-3-2 聚（苯乙烯-b-甲基丙烯酸甲酯）混摻聚苯乙烯均聚物之薄膜製備 19
2-3-3 移除潤濕層之方法—氧氣離子電漿蝕刻 20
2-3-4 增加嵌段共聚物對比之方法 20
2-4 儀器原理 21
2-4-1 光學顯微鏡（OM） 21
2-4-2 原子力顯微鏡（AFM） 22
2-4-3 掃描式電子顯微鏡（SEM） 23
2-4-4 低掠角小角度X光散射儀（GISAXS） 25
第三章結果與討論 34
3-1 組成效應對相行為之影響 34
3-2 厚度和溫度效應對相行為之影響 40
3-3 穿孔層和雙連續螺旋之臨界層數與厚度 48
3-4 穿孔層與雙連續螺旋之相轉變 50
3-4-1 兩相轉變之初步探討 50
3-4-2 雙連續螺旋轉變為穿孔層與否 54
3-4-3 低溫回火影響高溫回火 55
3-4-4 多邊形區塊的表面形貌 63
3-4-5 高溫回火影響低溫回火 65
3-5 在不同組成下之混摻物分子量效應 67
3-5-1 混摻比例75/25—穿孔層與雙連續螺旋相 67
3-5-2 混摻比例40/60—球狀結構 68
第四章結論 70
第五章參考文獻 72
第六章附錄 78

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2021-8-5

推文