臺灣博碩士論文加值系統

利用單體BisAPAF(2,2-Bis.1,3-amino-4-hydroxy- phenyl hexafluoro- propane)、IC(Isophthaloyl chloride)與BBTD(1,3-Bis(4- butyryl chloride) tetramethyldisiloxane)，在無水極性溶劑DMAc (Dimethylacetamide)中進行聚縮合反應，成功地合成出新型的PBOc『Polybenzoxazole copolymer』系列共聚物之可溶性前趨物：PHAc『Polyhydroxyamide copolymer』系列共聚物，再經由高溫環化反應形成PBOc系列共聚物。以同樣方式用BisAPAF與IC可合成出PBO。各系列聚合物之固有黏度為0.13~ 0.47dL/g，其結構可由FT-IR、1H-NMR圖譜及元素分析中得到鑑定。
各系列共聚物皆為非晶質結構，其玻璃轉移溫度、熱安定性皆隨著BBTD含量增加而降低，但亦能應用於短暫400℃之製程；其前驅物於許多常用溶劑中之溶解度甚佳，而環化後之共聚合物則表現出良好之耐化學性質。將各系列於矽晶圓上之薄膜以ASTM D3359, Method B進行黏著測試，皆有良好之附著力；經沸水滾煮測試後再進行黏著測試，以具有5B等級之PBOc10『BisAPAF-90%IC-10%BBTD』其附著力為最佳。且PBOc10亦具有非常低之吸水性，特別適合應用於現今要求低吸水性之電子產品上。

將PBOc10之前驅物PHAc10加入Naphthoquinone diazide(DNQ)系列之感光劑：2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzo- phenone (PIC-3)，亦成功地製備出正型鹼性水溶液顯影之感光材料。將感光配方以0.6% TMAH水溶液為顯影液進行微影製程之圖案轉移，其解析度皆可達到5μm左右，而其光敏感度與對比度分別為223 mJ/cm2與1.34。由光學顯微鏡及場發射掃描式電子顯微鏡觀察，其圖案皆十分完整。

Two novel series of positive working aqueous base developable photosensitive poly(benzoxazole) copolymer based on poly(hydroxyamide) copolymers (PHAcs), and 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5- sulfonyloxy)-benzophenone(PIC-3) photosensitive compound were developed. The PHAcs were prepared by the condensation polymeriaztion of 2,2-Bis. 1,3-amino-4-hydroxy-phenyl hexafluoro-propane(BisAPAF), Isophthaloyl chloride(IC) and 1,3-Bis(4- butyryl chloride) tetra- methyldisiloxane(BBTD) in DMAc. PHAcs were successfully converted into PBOcs by thermal treatment. The structures of PHAcs and PBOcs were characterized by FT-IR, 1H-NMR and elemental analysis(EA). The Glass transition temperature and thermal stabilities of the PBOcs decreased as the content of BBTD increased, but can still be applied to microelectronics. Furthermore, the PBOc10 (BisAPAF-90%IC-10%BBTD) received a rating of 5B by a tape peeling test, after cooking in boiling water for 24 hr at 1 atm. The photosensitive PBO precursor containing 30 wt % PIC-3 showed a sensitivity of 223 mJ/cm2 and a contrast of 1.34 when it was exposed to broad-band light, and developed with a 0.6 wt% aqueous tetramethylammonium hydroxide(TMAH) solution at room temperature. A fine positive image featuring about 5μm line and space patterns was observed on the film of the photoresist exposed to 285 mJ/cm2 ultraviolet light at 436 nm(G-line) by the contact mode.

總目錄
中文摘要..............................................................I
英文摘要..............................................................III
致謝..................................................................IV
總目錄................................................................VI
表目錄................................................................XIII
結構目錄..............................................................XV
圖目錄................................................................XVI

第一章 緒論...........................................................1
1-1前言...............................................................1
1-2研究動機...........................................................2

第二章 文獻回顧與原理.................................................3
2-1聚苯噁唑的發展與相關介紹...........................................3
2-1-1耐高溫高分子的發展與簡介.........................................3
2-1-2聚苯噁唑的發展與簡介.............................................4
2-2感光性高分子的簡介與應用...........................................10
2-2-1感光性高分子的簡介...............................................10
2-2-2正型感光性聚苯噁唑的簡介.........................................14
2-2-3感光性高分子的應用...............................................16
2-3微影成像技術及原理.................................................19
2-3-1表面清洗(Surface Cleaning).......................................20
2-3-2塗底(Adhesion Promotion).........................................21
2-3-3光阻旋塗(Spin Coating)...........................................21
2-3-4軟烤(Soft bake)..................................................25
2-3-5曝光(Exposure)...................................................25
2-3-6光罩(Mask).......................................................28
2-3-7光源(Light Source)...............................................28
2-3-8顯影(Development)................................................28
2-3-9硬烤(Hard Bake)..................................................29
2-3-10蝕刻(Etching)...................................................29
2-3-11光阻剝除(Stripping).............................................30
2-4光阻特性...........................................................31
2-4-1特性曲線(Characteristic Curve)...................................31
2-4-2感光度(Sensitivity)..............................................32
2-4-3對比度(Contrast).................................................35
2-4-4解析度(Reasolution)..............................................35
2-4-5熱穩定性(Thermal Stability)......................................36
2-4-6附著性(Adhesion) ................................................36
2-5光阻與基材間之附著力...............................................37
2-5-1新穎高分子之設計.................................................38
2-5-2黏著測試.........................................................41

第三章 實驗方法與步驟.................................................43
3-1實驗用藥品與儀器...................................................43
3-1-1實驗藥品.........................................................43
3-1-2實驗儀器.........................................................44
3-2 BBTD單體合成......................................................46
3-3實驗步驟...........................................................47
3-3-1 PBO前驅物PHA之合成 (BisAPAF-IC系統).............................47
3-3-2 PBOc05前驅物PHAc05之合成 (BisAPAF-95%IC-5%BBTD系統).............49
3-3-3 PBOc10前驅物PHAc10之合成 (BisAPAF-90%IC-10%BBTD系統)............51
3-4薄膜的製備.........................................................52
3-4-1 PBO薄膜製備(BisAPAF-IC系統).....................................52
3-4-2 PBOc05薄膜製備(BisAPAF-95%IC-5%BBTD系統)........................53
3-4-3 PBOc10薄膜製備(BisAPAF-90%IC-10%BBTD系統).......................54
3-5結構鑑定與分析.....................................................55
3-5-1紅外線吸收光譜分析...............................................55
3-5-2核磁共振光譜分析.................................................55
3-5-3元素分析.........................................................55
3-5-3 X光繞射分析.....................................................56
3-6物理性質測定.......................................................56
3-6-1固有黏度測定.....................................................56
3-6-2凝膠滲透層析儀測定...............................................57
3-6-3溶解度測試.......................................................57
3-6-4吸濕性測試.......................................................57
3-7熱性質分析.........................................................58
3-7-1熱重分析儀分析...................................................58
3-7-2微差掃描熱分析儀分析.............................................58
3-8黏著測試...........................................................59
3-8-1沸水滾煮測試.....................................................59
3-8-2百格膠帶測試.....................................................59
3-9微影製程...........................................................61
3-9-1矽晶圓表面處理...................................................61
3-9-2前驅物感光配方的配製.............................................61
3-9-3旋轉塗佈.........................................................62
3-9-4軟烤.............................................................63
3-9-5紫外-可見光光譜分析..............................................63
3-9-6曝光.............................................................64
3-9-7顯影液濃度之選擇.................................................64
3-9-8感光物質含量之選擇...............................................64
3-9-9環化熱處理.......................................................65
3-9-10感光配方環化前後之重量變化......................................65
3-9-11特性曲線的製作..................................................65
3-9-12圖案的觀察......................................................66

第四章 結果與討論.....................................................60
4-1 PBOc前驅物製備....................................................67
4-2結構鑑定與分析.....................................................69
4-2-1 BisAPAF-IC系統..................................................69
4-2-2 BisAPAF-95%IC-5%BBTD系統........................................71
4-2-3 BisAPAF-90%IC-10%BBTD系統.......................................73
4-3物理性質分析.......................................................75
4-3-1固有黏度測定與分析...............................................75
4-3-2凝膠滲透層析儀測定與分析.........................................76
4-3-3溶解度測試與分析.................................................77
4-3-4吸濕性測試與分析.................................................78
4-4熱性質分析.........................................................79
4-4-1熱重分析儀分析...................................................79
4-4-2微差掃描熱分析儀分析.............................................81
4-5黏著測試結果與分析.................................................82
4-5-1沸水滾煮測試結果.................................................82
4-5-2百格膠帶測試結果.................................................82
4-6感光性高分子光阻特性分析...........................................85
4-6-1薄膜厚度、旋塗速率與固含量之關係.................................85
4-6-2軟烤溫度之選擇...................................................86
4-6-3紫外-可見光光譜分析..............................................87
4-6-4顯影液濃度之選擇.................................................88
4-6-5感光物質含量之選擇...............................................90
4-6-6感光配方環化前後之厚度變化.......................................92
4-6-7特性曲線之製作...................................................93
4-6-8光學顯微鏡之圖案觀察.............................................94
4-6-9掃描式電子顯微鏡之圖案觀察.......................................94

第五章 結論...........................................................131

參考文獻..............................................................132

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