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研究生:許坤霖
研究生(外文):Kun-Lin Hsu
論文名稱:透明聚酯壓克力負型光阻之物性優質化及微影特性研究
論文名稱(外文):Study on Optimal Property and Photolithography of Negative-work and Transparent Photosensitive Polyester Acrylate
指導教授:鄭文桐
口試委員:李宗銘張棋榕
口試日期:2016-07-22
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2016
畢業學年度:104
語文別:中文
論文頁數:103
中文關鍵詞:透明感光性高分子聚酯壓克力樹脂硬度附著力田口方法光微影
外文關鍵詞:transparentphotosensitive polymerpolyester acrylatehardnessadhesionTaguchi methodphotolithography
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近年來全球智慧型電子產品的使用越來越深入生活,光電產業在觸控面板的技術上積極發展,其中單片式玻璃觸控面板 (one glass solution, OGS)的解決方案能讓複雜的模組堆疊結構轉為輕薄化,目前以透明負型感光性高分子薄膜作為絕緣材料的應用上還有物理性質上的不足,因此本研究決定以硬度及附著力作為目標,藉由田口品質工程找出最佳之配方條件及製程參數,本論文主要分為兩部分。
第一部分,感光性高分子系統中主要由乙酸丙二醇單甲基醚酯 (PGMEA)、聚酯壓克力樹脂、聚二季戊四醇五丙烯酸酯 (DPHA)、三丙烯乙二醇雙丙烯酸酯 (TPGDA)及光起始劑 (Irgacure 500)所組成,我們設計L9 (34)直交表,規劃不同單體之間的比例、光起始劑含量、曝光量及硬烤時間進行實驗,將鉛筆硬度及十字切割之附著力數值化後,透過權重比進行正規化,接著利用S/N比的計算及變異數分析 (ANOVA)找出最佳硬度及附著力雙目標之參數組合,將製備出的感光性高分子薄膜使用傅立葉轉換紅外光譜儀 (FTIR)及熱重分析儀 (TGA)分別進行光反應程度確認及耐熱性測試。
第二部分為了光微影特性需求,故將最適化配方進一步調整固含量,並透過微影曲線獲得負型光阻之光敏感度及計算出對比度,最後以光學顯微鏡 (OM)觀察圖案之線寬線距比,找出最佳之溶劑添加量。
從結果顯示,本研究獲得以下重要成果:
(1) 由田口方法可知,透明聚酯壓克力負型光阻配方之硬度及附著力的最適化參數為單體添加量DPHA/TPGDA (20phr/15phr)、光起始劑Irgacure 500 (2phr)、曝光量 (1200mJ/cm2)及硬烤溫度 (200℃),經紫外光聚合之感光性薄膜其鉛筆硬度為3H及十字切割附著力為5B。
(2) 由FTIR分析得知,本研究之感光性高分子膜厚為1µm時,其雙鍵轉化率達84%所需曝光能量為1800mJ/cm2。
(3) 本研究的透明感光性高分子之熱裂解溫度由TGA測試得知,在膜厚1µm下,當DPHA添加量由15phr增至20phr,從382℃提升至396℃及曝光量由600mJ/cm2增至1200mJ/cm2時,從379℃提升至396℃,因為交聯密度的提升有助於熱擴散抑制作用;然而,光起始劑含量由2phr增至6phr時,則從396℃降為366℃,此為過多的光起始劑殘餘導致交聯結構變質。
(4) 當光阻配方固含量由16.2wt.%提升至25.9wt.%時,在膜厚1µm下,無膜厚損失所需最低曝光能量從68 mJ/cm2增至90 mJ/cm2且對比度從1.26降至0.68,此為黏度增加時會使聚合速率降低所致。
(5) 當固含量為19.7wt.%,曝光能量600 mJ/cm2及以0.01wt.% KOH溶液顯影30秒後,經由OM觀察得知,本研究之光阻微影線寬線距比可達到1.1,其所需曝光量較高之原因推測為汙染物而導致光罩的光穿透率下降所致。


In recent years, the use of smart 3C product is tend to occupy our life in the global. Therefore, the development of the optoelectronics industry more and more focus on new touch panel technology. Among them, one glass solution (OGS) is a kind of outstanding method to overcome difficulties. It allows complex modules stacked structure turn to slim type. Currently, the physical properties of negative-tone photosensitive transparent insulation materials are still insufficient. In this study, we select hardness and adhesion properties as targets for Taguchi method to find the optimal formulation and process. The experiment is mainly divided into two parts in this study.
Firstly, we designed L9 (34) orthogonal array experiments to optimize the ratio of monomers, amount of photoinitiator, exposure dosages, and post baking temperature for the polymer solution composed from propylene glycol monomethyl ether acetate (PGMEA), polyester acrylate oligomer, photoinitiator (Irgacure 500), reactive monomers of dipentaerythritol hexaacrylate (DPHA) and tri (propylene glycol) diacrylate (TPGDA) to obtain the excellent hardness and adhesion of photopolymeric film through Taguchi method associated with analysis of variance (ANOVA). Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) are to be also employed to examine thermal resistance and degree of photo-polymerization, respectively, after casting film in this work.
Secondly, photolithography characteristics of the photoresist films under different solid content can be used to evaluate sensitivity and contrast. Also, the optical microscope (OM) was used to observe the pattern resolution of the line width.
As shown in results, the significant findings of this study could be remarked as below:
(1) The optimal conditions of formula and process are 20phr/15phr of DPHA/TPGDA, 2phr of Irgacure 500, 1200mJ/cm2 of UV dosage, and post baked temperature in furnace at 200℃ respectively, resulting in the transparent photosensitive polyester acrylate both with the pencil hardness of 3H and the cross-cut adhesion of 5B.
(2) The conversion of transparent photosensitive polyester acrylate film at 1µm reach 84% after irradiating with 1800 mJ/cm2 of UV light, as measured by FTIR.
(3) As measured by TGA, the thermal decomposition temperature of transparent photosensitive polyester acrylate film with thickness of 1µm will increase from 382℃ to 396℃ and from 379℃ to 396℃ but decrease from 396℃ to 366℃, as the content of DPHA was varied from 15phr to 20phr, the UV exposure was changed from 600mJ/cm2 to 1200mJ/cm2 , and amount of I500 was raised from 2phr to 6phr, which were caused by heat diffusion inhibition effect due to higher crosslinked density and residual photoinitiator resulted in deterioration effect after photo-polymerization respectively.
(4) When the solid content of the negative-work photoresist with thickness of 1µm was varied from 16.2wt.% to 25.9wt.%, for the film thickness without reduction, the requirement of exposure dosages would increase from 68 mJ/cm2 to 90 mJ/cm2, resulting in the contrast would be decreased from 1.26 to 0.68 due to the higher viscosity of photoresist to slow the polymerization rate.
(5) By OM observation, the ratio of line width to space for negative patterns with solid content of 19.7wt.% and film thickness of 1µm is 1.1 after irradiating by 600mJ/cm2 of exposure dosage, followed by development with 0.01wt.% KOH in de-ionic water for 30 seconds.


摘要 i
Abstract iii
目錄 v
表目錄 ix
圖目錄 x
第一章 緒論 1
1-1前言 1
1-2研究動機 2
1-3研究方法 3
1-4本文架構 5
第二章 理論基礎 6
2-1 感光性高分子物性相關文獻 6
2-2 光阻材料 12
2-2-1 光阻 12
2-2-2 寡聚物 14
2-2-3 反應性單體 16
2-2-4 光起始劑 18
2-3 影響紫外光聚合速率之因素 23
2-4 田口品質工程 27
2-4-1 參數設計 27
2-4-2 因子種類 28
2-4-3 直交表 30
2-4-4 訊號雜訊比 32
2-4-5 變異數分析 35
2-4-6 實驗確認 35
第三章 研究方法 36
3-1 感光性高分子優質化配方設計 36
3-1-1 田口品質工程實驗設計 36
3-1-2 變異數分析 39
3-1-3 感光性高分子製備方法 41
3-1-4 硬度測試 42
3-1-5 附著力測試 43
3-1-6 硬度及附著力數值化 45
3-2 負型光微影材料製備及性質分析 46
3-2-1 固含量測定 46
3-2-2 流變性質 47
3-2-3 旋轉塗佈曲線 48
3-2-4 微影特性曲線 49
3-2-5 光微影製程 50
3-3 儀器分析 51
3-3-1 傅立葉轉換紅外光譜儀 (Fourier transform infrared spectroscopy, FTIR) 51
3-3-2 熱重分析儀 (Thermogravimetric analysis, TGA) 52
3-3-3光學膜厚量測儀 54
3-4 實驗材料與儀器設備 57
3-4-1 實驗藥品 57
3-4-2 實驗儀器與設備 61
第四章 結果與討論 63
4-1 感光性高分子物性優質化 63
4-1-1 感光性高分子之軟烤特性 63
4-1-2反應性單體對硬度及附著力的影響 64
4-1-3最適化參數組合 65
4-1-4傅立葉轉換紅外光光譜 74
4-1-5 熱穩定性測試 77
4-2 光微影製程 81
4-2-1 固含量測定 81
4-2-2 流變性質 82
4-2-3 旋轉塗佈曲線 83
4-2-4 微影特性曲線 84
4-2-5 圖案線寬線距解析度 86
第五章 結論與未來方向 94
5-1 結論 94
5-2 未來方向 95
參考文獻 96


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