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研究生：	陳琬琪 Chen, Wan-Chi
論文名稱：	正型鹼性水溶液顯影耐高溫感光性聚苯噁唑之研究 Novel Positive Photosensitive Polybenzoxazole Precursors for Microelectronic Applications
指導教授：	許聯崇 Hsu, Lien-Chung Steve
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：	2002
畢業學年度：	90
語文別：	中文
論文頁數：	107
中文關鍵詞：	感光性、聚苯噁唑、正型
外文關鍵詞：	photositive, PBO
相關次數：	點閱：66 下載：3
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中文摘要

本文研究利用被trimethylsilyl(TMS)部份保護及tetrahydropyranyl (THP)部份保護的聚苯噁唑的前驅物及以雙苯酚為基材的1,2-naphthoguinoldiazide-4sulfonate(DNQ-4)感光物質製成－可由鹼性水溶液顯影的正型感光材料。
聚苯噁唑前驅物是由2,2-bis( 3amino-4-hydroxy phenol )hexafiouoropropane(BisAPAF)和isophthaloyl chloride(IC)兩單體以低溫聚合反應製成，再和trimethylchlorosilane或3,4-Dihydro-2H-pyran反應形成部份氫氧基被保護的聚苯噁唑前驅物，此前驅物在350℃處熱處理會環化成聚苯噁唑。此前驅物的黏度為0.35dL/g環化後的聚苯噁唑的玻璃轉移溫度為309℃。在氮氣下，5 %重量損失的溫度為550℃。
由被TMS保護的聚苯噁唑前驅物和20 wt%的DNQ-4所製成的感光材料，經過曝光及用0.6 wt%四甲基氫氧化胺(TMAH)顯影後，得到解析度為5μm的圖案，其光敏感度為172 mJ/cm2，對比值為1.33。而被THP保護的聚苯噁唑前驅物和50 wt%的DNQ-4所製成的感光材料，經過曝光及用0.6 wt%四甲基氫氧化胺(TMAH)顯影後，得到解析度為5μm的圖案，其光敏感度為212mJ/cm2，對比值為1.44。此兩感光材料均可顯著的降低未曝光部份的膜損失(dark film loss)而可以做成厚膜光阻。

ABSTRACT

Positive working, aqueous base developable photosensitive polybenzoxazole (PBO) precursors composition based on a partially trimethylsilyl (TMS) and tetrahydropyranyl (THP) protected PBO precursors and a Bisphenol A based 1,2-naphthoquinone diazide-4-sulfonate (DNQ-4) photosensitive compound has been developed. The polymer was prepared from a low temperature polymerization of 2，2’-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) and isophthaloyl chloride (IC), following by reacting with trimethylchlorosilane or 3,4-Dihydro-2H-pyran. Subsequently, thermal cyclization of the PBO precursor at 350 oC produced the corresponding PBO. The inherent viscosity of the precursor polymer was 0.35 dL/g. The cyclized PBO showed a glass transition temperature (Tg) at 309 oC and a 5% weight loss temperature at 550 oC in nitrogen. The structure of the precursor polymer and the fully cyclized polymer were characterized by FTIR and 1H-NMR. The photosensitive polymer of TMS protected PBO precursor containing 20 wt % DNQ-4 photosensitive compound showed a sensitivity of 172 mJ/cm2 and a contrast of 1.33 in a 3μm film with a 0.6 wt % tetramethylammonium hydroxide (TMAH) developer. A pattern with a resolution of 5 μm was obtained from this composition. The photosensitive polymer protected by THP containing 50 wt % DNQ-4 photosensitive compound showed a sensitivity of 212 mJ/cm2 and a contrast of 1.44 in a 3μm film with a 0.6 wt % tetramethylammonium hydroxide (TMAH) developer. A pattern with a resolution of 5 μm was also obtained from this composition.The two novel PBO precursors photosensitive composition showed a significant improvement in dark film loss after development and could be used to make a thick film resist.

目錄

中文摘要…………………………………………………………………I
英文摘要………………………………………………………………...II
目錄……………………………………………………………………..IV
圖目錄…………………………………………………….…………..VIII
表目錄………………………………………….…………………….....XI
第一章	緒論………………………………………………………………1
1-1前言………………………………………….………….………1
1-2 研究動機………………………………………………….……3
第二章	原理與理論背景…………………………………………………5
2-1聚苯噁唑的發展與相關介紹……………….…………….……5
2-2感光性聚苯噁唑的應用…………………………….………….9
2-3微影成像技術及原理…………………………………………11
2-3-1光阻……………………………………………………11
2-3-2軟烤……………………………………………………12
2-3-3曝光法…………………………………………………13
2-3-4光罩……………………………………………………14
2-3-5光源..…………………………………………………..14
2-3-6顯影...………………………………………………….14
2-3-7硬烤....……….…..…………………………………….14
2-3-8蝕刻……………………………………...…………….15
2-3-9光阻剝除…………………………………...………….15
2-4感光性特性曲線………………………………………………15
2-4-1感光度…………………………………………………15
2-4-2對比度…………………………………………………16
2-4-3解析度…………………………………………………17
2-4-4顯像性…………………………………………………17
2-5感光劑…………………………………………………………17
2-6化學增幅法………………………………………………...….18
第三章	實驗……………………………………………………………..29
3-1藥品……………………………………………………………29
3-2儀器……………………………………………………………30
3-3實驗步驟………………………………………………………31
3-3-1 PBO precursor的合成…………………………………31
3-3-2 PBO precursor的改質…………………………………34
3-3-2-1以TMS為保護基………………………………34
3-3-2-2以THP為保護基………………………………36
3-3-3感光性化合物Bisphenol A-DNQ-4之合成……..38
3-4性質測試與分析………………………………………………39
    3-4-1紅外線光譜儀分析…………………………………….39
3-4-2核磁共振光譜儀分析………………………………….39
3-4-3紫外線光譜儀………………………………………….39
3-4-4熱重分析儀測試……………………………………….40
3-4-5差式掃描卡計分析…………………………………….40
3-4-6溶解度測試…………………………………………….40
3-4-7黏度測定……………………………………………….40
3-4-8 介電常數量測………………………………………....41
3-4-8-1矽晶片處理、旋轉塗佈、環化處理………………..41
3-4-8-2 膜厚量測、軟烤………………………………….41
3-4-8-3 曝光、顯影、硬烤、鍍金……………………….42
3-4-8-4 C-V曲線量………………………………………..42
3-4-9 TMA分析……………………………………………...42
3-5 PBO感光配方之微影製程……………………………...…….43
3-5-1矽晶片處理…………………………………………….43
3-5-2感光配方的配置……………………………………….43
3-5-3旋轉塗佈……………………………………………….43
3-5-4軟烤…………………………………………………….44
3-5-5曝光……………………………………...………….….44
3-5-6顯影………………………………………………....….44
3-5-7膜厚量測………………………………………...…..…44
3-5-8前驅物的環化熱處理……………………………….…44
3-5-9解析度觀察…………………………………...……..…45
第四章結果與討論……………………………………..………..….…..45
4-1前驅物的合成與分析………………………………..…...……46
4-1-1合成……………………………………………..….…..46
4-1-2鑑定與分析……………………………………...……..48
4-1-2-1 FT-IR分析………………..……...……………..48
4-1-2-2 1H-NMR分析…………..………………..….….48
4-1-2-3熱性質分析…………..……………….……...…48
4-1-2-4 UV譜儀測試………..………………...…...…...49
4-1-2-5 PBO前驅物環化分析..……………………..….49
4-1-3 PBO基本特性……………..……………………..…..49
4-2 感光性化合物（Bisphenol A-DNQ-4）的合成與分析…....50
4-2-1合成萘醌重氮化合物………………………………...50
4-2-1鑑定與分析……………………………………….…..53
4-2-1-1 FT-IR分析………….…………………….…...53
4-2-1-2 1H-NMR分析………………………………....53
4-2-1-3 UV光譜儀分析…………………………….....53
4-2-1-4 熱差性質分析……………………………...…54
4-3 以Chlorotrimethylsilane（TMS）保護PBO precursor ...….54
4-3-1 合成…………………………………………………...54
4-3-2 鑑定與分析…………………………………………...56
4-3-2-1 1H-NMR分析………………………………….56
4-3-2-2 FT-IR分析…………………………….……….56
4-3-2-3 UV光譜儀分析…………………………….….56
4-3-3 微影特性………………………………………….…..57
4-3-3-1 溶解速率……………….……………………...57
4-3-3-2 光化學特性…………………………………....59
4-3-3-3 顯像結果…………………………………..…..60
4-4 以Tetrahydropyranyl (THP)保護PBO precursor………..…..60
4-4-1 合成……………………………………………….…..60
4-4-2鑑定及分析……………………………………….……61
4-4-2-1 1H-NMR分析…………………………….…….61
4-4-2-2 FT-IR分析………………….……………..……62
4-4-2-3 UV光譜儀分析……………………………..….62
4-4-3 微影特性………………………………………….…..62
4-4-3-1溶解速率……………………………………….63
4-4-3-2 光化學特性……………………………………64
4-4-3-3 顯像結果………………………………………64
第五章 結論…………………………………………………..………103
參考文獻………………………………………………………………104



















圖目錄

圖1-1 傳統PI和感光型PI製程比較………………………….…….4
圖2-1光阻在微影成像製程的示意圖…………………………….…24
圖2-2 旋轉塗佈的示意圖…………………………………………....25
圖2-3 三種曝光方式的示意圖(a)接觸式(b)近接式(c)投影式…......26
圖2-4 濕蝕刻與乾蝕刻的比較圖……………………………….…...27
圖2-5 負型與正型光阻感光特性曲線……………………………....28
Fig.3-1 Synthesis of PBO precursor……………………………….…..32
Fig.3-2 Synthesis of TMS protected PBO precursor……………...…...35
Fig.3-3 Synthesis of THP protected PBO precursor………………..….36
Fig. 4-1 FT-IR spectra of PBO precursor…………………………...….65
Fig. 4-2 1H-NMR spectrum of PBO precursor………………………....66
Fig. 4-3 Thermogravimeteric curve of cured PBO by TGA (10℃/min) in nitrogen…………………...…………………………………..67
Fig. 4-4 DSC analysis curve of cured PBO………………………….….68
Fig. 4-5 TMA analysis curve of cured PBO……………………….……69
Fig. 4-6 UV spectrum of PBO precursor………………………….…….70
Fig. 4-7 FT-IR spectrum of cured PBO …...…………………...….……71
Fig. 4-8 FT-IR spectra of Bisphenol-DNQ-4 thin film expose and unexposed. ………………………………………………..…..72
Fig. 4--9 1H-NMR spectrum of Biphenol-DNQ-4……………….….…..73
Fig. 4-10 UV spectra of Bisphenol-DNQ-4 with various exposed time………………………………………………...……….…74
Fig. 4-11 Thermogravimeteric curve of Bisphenol-DNQ-4 by TGA        (10℃/min) in nitrogen…………………………………..….…75
Fig. 4-12 1H-NMR spectrum of 20% TMS protected PBO precursor…..76
Fig. 4-13 FT-IR spectra of (a) 20% TMS protected PBO precursor and
 (b) PBO precursor…………………………………………...…77
Fig. 4-14 UV spectra of PBO precursor and 20% TMS protected PBO precursor………………………………………………..……..78
Fig. 4-15 UV spectrum of 20% TMS protected PBO precursor with 20% Bisphenol-DNQ-4 film………………………………………..79
Fig. 4-16 The characteristic curve of 20% TMS protected PBO precursor……………………………………………..…….….80
Fig. 4-17 OM photographs of 20% TMS protected PBO precursor before cure (a) and after cure (b)…………...………………….…......81
Fig. 4-18 SEM photographs of 20% TMS protected PBO precursor …..82
Fig. 4-19 1H-NMR spectrum of 50% THP protected PBO precursor…..83
Fig. 4-20 FT-IR spectrum of 50% THP protected PBO precursor ……..84
Fig. 4-21 UV spectrum of 50% THP protected PBO precursor ………..85
Fig. 4-22 UV spectra of 50% THP protected PBO precursor with 20% Bisphenol-DNQ-4 before and after exposed……………..…..86
Fig. 4-23 The characteristic curve of 50% THP protected PBO precursor…………………………………………………...…87
Fig. 4-24 OM photographs of 50% THP protected PBO precursor before cure (a)and after cure(b)……………………………..…...…..88


表目錄

Table 2-1 PBO的基本特性……………………………………………..21
Table 2-2 感光性高分子的發展年表…………………………………..22
Table 2-3 Film Properties of PBO and Polyimide……………………….23
Table 4-1 Synthesis of PBO precursor…………………………….……..89
Table 4-2 Properties of PBO precursor…………………………….…….90
Table 4-3 Properties of PBO……………………………………………..91
Table 4-4 IR absorption of Bisphenol-DNQ-4 before and after exposed..92
Table 4-5 Dissolution rates of BisAPAF-IC PBO precursor, the 20% 
TMS protected BisAPAF-IC PBO precursor, the 20% TMS 
protected BisAPAF-IC PBO precursor/20% DNQ-4 before 
and after exposure …………………………………….……….93
Table 4-6 The dark film loss of PBO precursor and 20% TMS protected
 PBO precursor………………………………………………...94
Table 4-7 Curing shrinkage of 20% TMS protected PBO precursor...…..95
Table 4-8. Solubility of BisAPAF-IC PBO precursor, 20% TMS
 protected BisAPAF-IC PBO precursor and cured PBO………96
Table 4-9 Comparison of the dissolution rate of 20% TMS protected 
PBO precursor and 50% THP protected PBO precursor……...97
Table 4-10 The dissolution rate of 50% THP protected PBO 
precursor………………………………………………….….98
Table 4-11 Comparison of the dissolution rate of 20% TMS protected 
PBO precursor and 50% THP protected PBO precursor with Bisphenol-DNQ-4 exposed and un exposed………………….99
Table 4-12 Comparison of the drak film loss of PBO precursor and
20% TMS protected PBO precursor and 50% THP protected PBO precursor………………………………………………100
Table 4-13 The curing shrinkage of 50% THP protected PBO precursor………………………………………….…………101
Table 4-14.Solubility of BisAPAF-IC PBO precursor, 50% THP protected BisAPAF-IC PBO precursor and cured PBO……………….102





                                    

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