聚(氘化苯乙烯-b-甲基丙烯酸甲酯)薄膜於紫外光改質聚苯乙烯層之熱退火期間型態轉變探討

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楊濰甄(Wei-Chen 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

聚(氘化苯乙烯-b-甲基丙烯酸甲酯)薄膜於紫外光改質聚苯乙烯層之熱退火期間型態轉變探討
(Morphological Evolution of Thermal Annealed Deuterated Polystyrene-block-Poly(methyl methacrylate) Thin Films on a UV-Treated Polystyrene Layer)

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摘要(中)

本研究主要藉由原子力顯微鏡、穿透式電子顯微鏡、低掠射小角度X-光散射和中子反射探討聚(氘化苯乙烯-b-甲基丙烯酸甲酯) (Deuterated Polystyrene-block-Poly(methyl methacrylate), dPS-b-PMMA)薄膜在具有中性表面之改質聚苯乙烯層(Polystyrene, PS)，於熱回火效應對微相分離結構有序性及排向性的結構影響。

首先利用紫外光在充滿氮氣環境中(手套箱)照射交聯，而中性層的產生則是在空氣下照射紫外光獲得，再利用紫外光於空氣中照光，製備具有中性表面之PS層，再利用旋轉塗佈法將dPS-b-PMMA薄膜旋鍍於以紫外光照射交聯及中性化改質之PS層上，接著在真空環境中進行210-280 oC恆溫熱回火。其結果發現在低於270 oC下熱回火，dPS-b-PMMA表面容易形成一層dPS潤濕層，這是由於在此溫度條件下，dPS鏈段及PMMA鏈段之自由表面能()並未相同(即dPSPMMA，非中性表面)。在270 oC恆溫回火，可抑制dPS潤濕層，顯示在此條件下dPSPMMA。此外我們發現在270 oC恆溫回火不同時間，短時間熱回火則形成垂直取向的層板狀結構，而隨著回火時間增加，垂直層板狀轉變為垂直奈米柱狀，最後形成穿孔層狀奈米結構，在此論文中，我們將針對相轉變之機制做深入探討及解釋。

摘要(英)

In this study, the structural evolution of deuterated polystyrene-block-poly (methyl methacrylate) (dPS-b-PMMA) thin films with thermal annealing of various durations on a layer of UV-irradiated polystyrene were studied by means of atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incident small-angle X-ray scattering (GISAXS) and neutron reflectivity (NR). Upon exposure to UV light in a glove box and in air, the PS layer was cross-linked and neutralized. dPS-b-PMMA thin films supported on the cross-linked/neutralized PS layer were prepared by spin coating and then the specimens were isothermally annealed at 210280∘C under vacuum. We found that thermal annealing at a temperature below 270 oC would preferentially grew a wetting layer of dPS on top. The formation of the preferential wetting layer is due to the fact that the surface energy (dPS) of the dPS block was not equal to that (PMMA) of the PMMA block. In other words, below 270 oC, the free surface of the dPS-b-PMMA was not neutral. When annealed at 270 oC, dPS-b-PMMA would have a neutral free surface. Besides, we found that 270 oC-thermal annealing of a short period first led to the formation of perpendicular-oriented lamellae. Nevertheless, prolonged thermal annealing produced phase transitions from standing lamellae to vertical nanocylinders and finally to perforated-layer-like nanostructures. In this thesis, we would propose possible mechanisms about the morphology evolution.

關鍵字(中)

★ 嵌段共聚物
★ 中子反射
★ 聚(氘化苯乙烯-b-甲基丙烯酸甲酯)
★ 相轉變

關鍵字(英)

★ Block Copolymer
★ Neutron Reflectivity
★ dPS-b-PMMA
★ Phase Transition

論文目次

摘要(v)
Abstract(vi)
致謝(vii)
目錄(ix)
圖目錄(xii)
表目錄(xvi)
第1章簡介(1)
一、高分子團鏈共聚物(1)
1-1.團鏈共聚物(1)
1-2.團鏈共聚物之自組裝行為(2)
1-3.自洽平均場理論(4)
1-4.高分子薄膜內之微相分離結構(5)
1-5.高分子薄膜之空間侷限效應及界面/表面能的影響(5)
1-6.高分子薄膜之濕潤與非潤濕(7)
二、控制高分子薄膜的有序性結構之排向(9)
2-1.表面改質-化學接枝法(9)
2-2.表面改質-石墨稀法(11)
2-3.表面改質-化學官能基交聯法(12)
2-4.表面改質-光化學交聯法(13)
三、研究背景與動機(15)
第2章實驗(16)
一、實驗材料(16)
二、實驗儀器(18)
三、實驗製備與設計(20)
3-1.矽晶基材清洗(20)
3-2.改質前聚苯乙烯薄膜製備(20)
3-3.紫外光改質聚苯乙烯薄膜(21)
3-4.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)有序結構製備(22)
3-5.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)熱穩定性量測(22)
3-6.薄膜樣品低掠角小角度X光散射測量(23)
3-7.塊材樣品之穿透式小角度X光散射儀測量(24)
3-8.光電子能譜分析(24)
3-9.薄膜中子反射儀量測(25)
四、中子科學之特性(27)
4-1.中子源的特點(27)
4-2.中子技術的優點(28)
五、儀器原理(30)
5-1.原子力顯微鏡(30)
5-2.低掠角式小角度X光散射儀(31)
5-3.X光反射率掃描量測(33)
5-4.中子反射儀(34)
第3章結果與討論(36)
3-1.聚苯乙烯表面改質之探討(36)
3-2.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)之退火溫度探討(41)
3-3.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)之相轉變行為(44)
3-4.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)不同膜厚之結構探討(50)
3-5.聚(氘化苯乙烯-b-甲基丙烯酸甲酯)之相轉變因素之探討(52)
3-6.利用中子反射探討相轉變(55)
第4章結論(62)
第5章參考文獻(64)

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2018-7-9

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