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

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姓名

陳鈺忠(Yu-chung Chen) 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

溶劑退火誘導聚苯乙烯聚4-乙烯吡啶薄膜不穩定性現象之研究
(Film Instability in Solvent-Annealed Block Copolymer Thin Films)

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摘要(中)

本研究在探討雙團鏈高分子PS-b-P4VP薄膜旋鍍在矽基材SiOx/Si以及透過表面改質的聚苯乙烯毛刷基材PS-SiOx/Si，利用THF溶劑蒸氣退火刺激後，其除潤現象、奈微米結構對於薄膜不穩定性間的相依關係。首先PS-b-P4VP團鏈共聚高分子在基材效應的實驗中，在親水性的矽基材上，由於極性基材易吸附P4VP鏈段，造成在退火過程中，該鏈段受到基材錨定作用而形成潤濕層，部分微胞移動受限於錨定影響，聚變過程發生緩慢，薄膜穩定度高。相對於極性基材，對於接有毛刷層的改質基板上，此毛刷層扮演著阻隔層的角色，隔絕極性基材對於P4VP鏈段間的吸引力。在溶劑蒸氣退火下，微胞聚變過程中所釋出的間隙將會在薄膜上造成孔洞，孔洞形成造成薄膜上洞與鄰近地區薄膜以及大小洞間有壓力差存在，使得薄膜上為趨於表面能最小，洞與洞間的彼此融合或增長驅使薄膜推擠而形成梯田式堆疊，同時微胞上PS與接枝層PS同種鏈段間自除潤發生，驅使液滴形貌的形成。結合影像定量分析統整出對於薄膜上的孔洞覆蓋率變化之趨勢，階段性地呈現薄膜除潤行為的演化過程。最後探討在溶劑退火過程中，對稱型PS22k-b-P4VP22k及非對稱型PS19k-b-P4VP22k之PS鏈段分子量不同反映出迥然不同的表徵。將利用混掺不同分子量的PS均聚物修飾鏈長差異及提升毛刷層接枝密度以改善薄膜不穩定性之現象。

摘要(英)

In this study, I investigate PS-b-P4VP thin films spin-coated on bare (SiOx/Si) and PS-grafted(PS-SiOx/Si) silicon substrates and observe the relationship between film instability and internal nanostructures during solvent annealing in THF solvent vapor. The first experiment is to study the substrate effect. The hydrophilic of bare silicon substrates preferentially adsorbs P4VP segments in the annealing process, causing block copolymer chains to form a wetting layer at the substrate interface. At early stages, micellar movement is restricted by the anchoring effect, which induced slow fusion process. Hence, the film did not rupture. Compared to micellar films on polar substrates, fusion of PS-b-P4VP micelles on the PS-grafted substrate occurs quickly upon solvent annealing. This is because the PS-grafted brush layer obstructs the attractive interaction between SiOx/Si and P4VP chains. Furthermore, micellar fusion leads to micro-sized holes in the film. Because of the formation of holes, there exists pressure difference(Laplace pressure)between holes and their surrounding areas. In order to reduce the surface free energy, the holes grew by merging with their neighboring analog. At intermediate stages of solvent annealing, terraced structures start to form whereas at final stages droplets form. The driving force for film instability on PS-SiOx/Si is the auto phobic behavior between PS segments within micelles and the PS-grafted substrate. In addition, we find different molecular weights of PS segments between symmetric and asymmetric PS-b-P4VP induced different surface characterizations upon solvent annealing. Dewetting behavior of asymmetric PS-b-P4VP thin films is more serious than that of symmetric PS-b-P4VP ones. The last section, I attempt to improve the film instability of PS-b-P4VP by blending PS homopolymers of various molar masses.

關鍵字(中)

★ 團鏈共聚物
★ 溶劑退火
★ 薄膜不穩定性

關鍵字(英)

★ PS-b-P4VP
★ solvent annealing
★ film instability

論文目次

目錄
摘要 i
Abstract ii
目錄 iii
圖目錄 vii
表目錄 xv
第一章　緒　　論 1
第二章　簡　　介 3
2-1 雙親性團鏈共聚物 3
2-2 薄膜試樣的微觀相分離 7
2-2-1 外界效應誘導高分子薄膜型態變化 8
2-2-2 雙團鏈高分子薄膜微相分離型態 10
2-2-3 薄膜之膜厚相稱性與厚度效應 12
2-3 薄膜不穩定性 14
2-4均聚物薄膜的除潤行為 18
2-4-1分子間作用力 19
2-4-2 自除潤(亂度效應) 22
2-4-3 殘餘應力 24
2-5 團鏈共聚物薄膜除潤行為 25
2-5-1 團鏈共聚物薄膜內移動機制 26
2-6 異質成核與成長的薄膜除潤行為 30
2-7 混摻均聚物對於團鏈共聚物薄膜之影響 31
2-7-1 均聚物混摻於團鏈共聚物間的空間分布 31
2-7-2混摻均聚物降低packing frustration energy 33
2-8 實驗動機 35
第三章　實驗 36
3-1 高分子材料 36
3-2 溶劑藥品與基材 37
3-3 實驗儀器 37
3-4 樣品製備與實驗步驟 38
3-4-1 基材清洗 38
3-4-2 基材表面改質 38
3-4-3 薄膜的製備及退火處理 39
3-4-4 薄膜表面覆蓋率影像軟體分析 40
3-5 儀器分析 40
3-5-1 原子力顯微鏡 (AFM) 40
3-5-2 光學顯微鏡 (OM) 42
3-5-3小角度X光散射 (Small-angle X-ray scattering, SAXS) 44
第四章　結果與討論 45
4-1 旋鍍成膜後PS-b-P4VP微胞在溶劑退火過程型態變化 45
4-1-1 微胞的形成 45
4-1-2 聚苯乙烯-聚4乙烯吡啶之聚變/裂變 47
4-2 對稱型/非對稱型聚苯乙烯-聚4乙烯吡啶除潤現象 53
4-3聚苯乙烯-聚4乙烯吡啶薄膜表面變化定量分析 55
4-3-1 非對稱型PS-b-P4VP系統薄膜表面變化定量分析 55
4-3-2對稱型PS-b-P4VP系統薄膜表面變化定量分析 59
4-4非對稱系統之微胞濃度對於除潤結構演變的影響 61
4-4-1 高覆蓋率PS-b-P4VP薄膜系統 61
4-4-2 低覆蓋率PS-b-P4VP薄膜系統 66
4-5 基材對於薄膜穩定性的影響 67
4-5-1 矽基材上非對稱型PS-b-P4VP薄膜除潤行為 67
4-5-2 矽基材上非對稱型PS-b-P4VP薄膜表面變化定量分析 70
4-6 混摻均聚物後團鏈共聚物薄膜的除潤現象 71
4-6-1 混摻後之微胞形成 71
4-6-2 混摻均聚物重量比6.8%在溶劑退火過程中薄膜穩定度及型態變化 73
4-6-2-1 混摻均聚物在溶劑退火過程薄膜型態變化 73
4-6-2-2混摻均聚物在溶劑退火過程薄膜表面變化定量分析 76
4-6-3混摻均聚物重量比15%在溶劑退火過程薄膜穩定度及型態變化 78
4-6-3-1 混摻均聚物在溶劑退火過程薄膜型態變化 78
4-6-3-2混摻均聚物在溶劑退火過程薄膜表面變化定量分析 80
4-7基材對於混摻均聚物薄膜穩定性的影響 82
4-7-1重量比6.8%混摻系統在溶劑退火過程薄膜型態變化及表面定量分析 82
4-7-2重量比15%混摻系統在溶劑退火過程薄膜型態變化及表面定量分析 85
第五章　結　　論 88
參考文獻 90
附錄 102

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指導教授

孫亞賢(Ya-sen Sun)

審核日期

2013-7-31

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