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研究生：	林佳儀 Lin, Chia-Yi
論文名稱：	正型水性顯影聚苯噁唑/黏土奈米感光複合材料之研究 Photosensitive poly(benzoxazole)/organoclay nanocomposites
指導教授：	許聯崇 Hsu, Lien-Chung
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2004
畢業學年度：	92
語文別：	中文
論文頁數：	107
中文關鍵詞：	奈米複合材、黏土、感光性高分子、正型、聚苯噁唑
外文關鍵詞：	PBO, clay, nanocomposite, photosensitive
相關次數：	點閱：62 下載：2
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　　本研究以添加有機黏土於聚苯噁唑(polybenzoxazole，PBO)的前驅物-聚羥醯胺(polyhydroxyamide，PHA)中形成PHA/clay奈米複合材料，以降低聚苯噁唑薄膜之熱膨脹係數(CTE)，並將其製備成正型鹼性水溶液顯影感光性PHA/clay之光阻配方，以研究其微影成像之特性。首先經由有機胺鹽和鈉蒙脫土(Na+-mentmorillonite)進行離子交換反應，製成膨潤化有機黏土(organoclay)。同時利用4,4-oxybis(benzoic acid)與thionyl chloride行氯化反應後之產物4,4’-oxydibenzoyl chloride，再與BisAPAF單體進行縮合聚合反應，合成出PHA樹脂，其固有黏度(inherent viscosity) 為0.3dL/g。將PHA與有機黏土製備出PHA/clay薄膜，經350℃環化後形成PBO/clay薄膜。經由X-ray 繞射分析顯示，DOA-Clay添加至5wt %時，呈脫層型分散，當添加量至7wt %時，黏土開始出現聚集或插層分散。TEM 分析也顯示添加3wt %及5wt % 黏土時，呈奈米分散，但添加7wt %黏土時，開始呈現聚集的情形。熱機械分析(TMA)指出，PBO/clay奈米複合材料的熱膨脹係數隨黏土添加量的增加而降低，添加5wt % 黏土時，薄膜之熱膨脹係數可以降低33%，此外，添加有機黏土，可增進PBO薄膜之熱性質(Tg、熱裂解溫度、恆溫耐熱性)。由PBO /clay薄膜試片的機械性質分析得知，有機黏土可以增加PBO的彈性模數，添加至5wt % 黏土時彈性模數增加了42%，顯示有機黏土有很好的補強效果。由吸水性實驗可看出添加黏土可降低PBO的吸水率，添加5wt % 黏土時吸水率更降低了62%。將PHA/clay和2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)–benzophenone
(PIC-3) 感光劑配製成感光性樹脂配方，經由適當控制微影成像(microlithography)參數，其解析度皆可達到5μm左右。此外，光敏感度(sensitivity)及對比值(contrast)並不會因添加有機黏土而受到影響。

　　A project was carried out aimed at reducing the coefficient of thermal expansion (CTE) of photositive polybenzoxazole formulations (photoresists) through the incorporation of an organoclay. The organoclay was formed by a cation exchange reaction between a Na+-montmorillonite clay and an ammonium salt of dodecylamine (DOA). The polybenzoxazole (PBO) precursor polyhydroxyamide (PHA) was made by polycondensation reaction between 2,2-bis(3-amino-4-hydroxyphenol) hexafluoropropane (BisAPAF) and 4,4-oxydibenzoyl chloride (ODC) with an inherent viscosity of 0.3dL/g.The PHA/clay was subsequently thermal cured to PBO/clay film. Both x-ray diffraction (XRD) and transmission electron microscope (TEM) analyses showed that when containing 5wt % organoclay, the clay was dispersed in PBO matrix in a nanosacle. The CTE of PBO/clay film which contained 5wt % organoclay was decreased 33% compared to the pure PBO film. Besides, the PHA/clay nanocomposite films displayrd higher thermal stability, elastic modulus and water resistance than similar PBO films that do not contain clay. The photosensitive resin/clay formulations were prepared from PHA/ 5wt % organoclay and DNQ (PIC-3) photosensitive compound . The photosensitive PHA/clay nanocomposite showed a line/space pattern with a resolution of 5 µm was . Because the organoclay were well dispersed in the photosensitive PHA/clay nanocomposites, the sensitivity, contrast and photolithographic performance of the photoresist are not ignificantly
affected.

目錄
摘要............................................ I
Abstract.......................................III
誌謝............................................IV
目錄.............................................V
圖目錄...........................................X
表目錄....................................... XIII
第一章緒論.......................................1
1-1 前言.........................................1
1-2 研究動機.....................................3
第二章文獻回顧及原理.............................4
2-1 聚苯噁唑(Polybenzoxazole，PBO)的發展與應用...4
2-2 感光性高分子.................................6
2-2-1 感光性高分子的發展與應用...................6
2-2-2 感光性聚苯噁唑(PSPBO)的應用................9
2-3 高分子/黏土奈米複合材料的發展與應用.........11
2-3-1 黏土之簡介............................... 11
2-3-2 高分子/黏土奈米複合材料之製備方法.........14
2-3-3 高分子/黏土奈米複合材料之型態.............16
2-3-4 高分子/黏土奈米複合材料之發展趨勢.........18
2-4 微影成像技術（Microlithography）及原理......20
2-4-1 表面清洗..................................20
2-4-2 塗底......................................21
2-4-3 上光阻....................................23
2-4-4 軟烤......................................23
2-4-5 曝光......................................25
2-4-6 曝後烤....................................26
2-4-7 顯影......................................28
2-4-8 硬烤......................................28
2-4-9 蝕刻......................................28
2-4-10 光阻剝除.................................29
2-5 光阻特性....................................29
2-5-1 感度......................................32
2-5-2 對比(Contrast) ...........................33
2-5-3 解析度(Resolution)........................34
2-5-4 熱穩定性(Thermal stability)...............34
2-5-5 接著性(Adhesion)..........................34
第三章實驗步驟..................................35
3-1 實驗用藥品與儀器............................35
3-1-1 藥品......................................35
3-1-2 實驗儀器..................................36
3-2 實驗步驟....................................37
3-2-1 黏土改質..................................37
3-2-2 聚苯噁唑前驅物-聚羥醯胺之合成.............38
3-2-3 感光性聚苯噁唑/黏土奈米複合材料之合成.....40
3-3 結構鑑定與分析..............................44
3-3-1 固有黏度(Inherent viscosity) 之測定.......44
3-3-2 紅外線光譜儀(FTIR) 分析...................44
3-3-3 核磁共振光譜(1H-NMR) 分析.................44
3-3-4 元素分析儀................................45
3-3-5 X-ray 繞射(XRD) 分析......................45
3-3-6 穿透式電子顯微鏡(TEM)觀察.................46
3-3-7 熱重損失分析(TGA) ........................46
3-3-8 微差掃描熱(DSC) 分析......................46
3-3-9 熱機械分析(TMA) ..........................47
3-3-10 穿透度分析...............................47
3-3-11 紫外-可見光吸收光譜分析..................47
3-3-12 吸濕性測試...............................48
3-3-13 溶解度測試...............................48
3-3-14 薄膜機械性質分析.........................48
3-4 微影製程....................................48
3-4-1 矽晶片表面處理............................48
3-4-2 配製光阻劑................................49
3-4-3 旋轉塗佈..................................49
3-4-4 預烤......................................49
3-4-5 曝光......................................50
3-4-6 顯影......................................50
3-4-7 PHA 環化反應..............................50
3-4-8 圖案的觀察................................50
3-4-9 溶解速率的計算............................50
3-4-10 特性曲線的製作...........................51
第四章結果與討論................................52
4-1 聚苯噁唑( PBO )的合成與性質鑑定.............52
4-1-1 聚苯噁唑(PBO)及前驅物-聚羥醯胺(PHA)之合成.52
4-1-2 前驅物聚羥醯胺(PHA) 之鑑定................53
(a) 固有黏度測定(Inherent viscosity)............53
(b) 傅立葉紅外線光譜( FT-IR )之鑑定.............53
(c) 核磁共振光譜( 1H-NMR )之鑑定................53
4-1-3 聚苯噁唑(PBO) 之鑑定......................54
(a) 元素分析....................................54
(b) 傅立葉紅外線光譜( FT-IR )之分析.............54
4-2 奈米複合材料之製備與分析....................55
4-2-1 奈米複合材料之製備........................55
4-2-2 有機黏土之分析............................55
(a) 傅立葉紅外線光譜( FT-IR )之分析.............55
(b) 熱重損失分析................................56
(c) X-ray 繞射分析..............................56
4-2-2 PBO/clay 奈米複合材料之分析...............57
(a) X-ray 繞射分析..............................57
(b) 穿透式電子顯微鏡(TEM)之分析.................57
4-3 熱性質分析..................................58
4-3-1 熱膨脹係數之分析..........................58
4-3-2 玻璃轉移溫度之分析........................59
4-3-3 熱重損失分析..............................60
4-3-4 恆溫耐熱性分析............................61
4-4 機械性質分析................................61
4-5 吸濕性測試..................................62
4-6 溶解度量測..................................63
4-7 感光性聚苯噁唑/黏土之特性分析...............64
4-7-1 UV-Visible 光譜分析.......................65
(a) 穿透光譜分析................................65
(b) 吸收光譜分析................................65
4-7-2 微影特性..................................66
(a) 不同固含量之膜厚與轉速的關係................66
(b) 預烤溫度與時間之選擇........................66
(c) 顯影液濃度之選擇............................67
(d) PIC-3 含量之選擇............................67
(e) 特性曲線的製作..............................68
(f) OM之圖案觀察................................69
(g) SEM 之圖案觀察..............................69
第五章結論.................................... 102
參考文獻...................................... 104

                                    

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