以異山梨醇基生質透明聚醯亞胺開發低介電負型光阻

Abstract

近年來，由石油及塑膠材料所造成的自然資源枯竭和環境污染引起了全球對此議題的關注，因此生質聚合物的開發逐漸受到矚目。預計將來生質聚合物即可在各種工業中廣泛地應用，因此學術和工業研究人員必須從生質或可再生資源中開發新材料。為了有效且經濟地利用這些生質聚合物，對於新型生質聚合物的開發以及改進其材料特性的方法仍然存在挑戰。聚醯亞胺具有出色的熱穩定性、耐化學性、機械耐久性以及良好且穩定的介電性能等，讓生質聚合物有望應用於工業中。本篇論文預計引入葡萄糖衍生之異山梨醇做為生質來源，期望透過開發及引入此生質單體達到未來生質材料廣泛應用的目標。 本研究第二章透過設計單體結構開發生質高透明聚醯亞胺，包括引入脂肪族雙胺單體 DDA、CHDA，以及二酐ODPA、6FDA對透明度及薄膜性質之探討。最終利用二胺3SODA 強拉電子的特性削弱電荷轉移效應及6FDA 大立體障礙的設計提升聚醯亞胺之透明性，並透過使用化學閉環的方式成功得到一高透明生質聚醯亞胺，此高透明生質聚醯亞胺仍具有一定水準的熱性質，具有256 oC的玻璃轉化溫度以及65ppm/K 的熱膨脹係數。另一方面，我們透過引入僵硬之二酯基結構設計出一低介電生質聚醯亞胺，在10 GHz之高頻下其介電常數達2.88，介電損失為 0.003。 本研究第三章延續第二章使用生質材料的概念，透過導入感光型材料開發高生質含量之聚醯亞胺，期望應用於感光光阻與覆蓋膜。經過引入不同官能基之單體調控其膜材性質，包括氟酯、二酯基、氟醚等結構，最終將異山梨醇之低碳二胺 (ISBA)與含氟醚基之BAPHF以及二酐 (ISBESA)單體導入聚醯胺酸搭配合成肉桂酸型光鹼釋出劑(PBG)，在曝光後烘烤150 oC 下5分鐘，開發出具有介電常數(Dk)及消散因子(Df)低於2.8、0.008 (10 GHz以上)以及3.0、0.01 (20 GHz以上)，以及熱膨脹係數(CTE)低於50 ppm/K及破裂應變(εb)大於10%之感光型聚醯亞胺膜材，並應用於低溫負型光阻(< 200 oC)，達成可圖案化功能並達成L/S 10/10 μm解析度。基於上述兩章之研究內容，本篇研究為生質材料之功能開發及應用提供了一個可行的範本，期望未來可應用在低碳排之產業應用中。

The issue of environmental contamination and the depletion of natural resources caused by the usage of petroleum and plastic materials have been of great concern. Therefore, the invention of a bio-based polymer that can be regenerable and massively utilized is the most feasible solution to the environmental and resource problem. However, it is still full of challenges to effectively and economically utilize the bio-source and to find out a way to improve the durability and functionality of bio-based polymer. Polyimide (PI) has excellent performances in thermal stability, chemical resistance, mechanical durability, and reasonable dielectric properties, making bio-based polymer expect to be utilized in industries. To achieve the goal of biomaterials being used widely and massively, we used a glucose derived isosorbide as bio-source to design a usable polyimide. In Chapter 2, a bio-based polyimide with high optical transparency and low dielectric constant/dissipation factor was designed. Through the introduction of monomers including aliphatic diamine DDA, CHDA, and dianhydride ODPA, 6FDA, the effect of structure and process on the film transparency and properties were investigated. Eventually, a diamine SODA with a strong electron-withdrawing group and a dianhydride 6FDA with a large free volume were copolymerized with ISBA, and gained a bio-based high transparent polyimide, PI (ISBA-50% 3SODA-6FDA), which presented a T400 of 86.6% and YI of 1.2 was obtained. Also, a low dielectric bio-based polyimide, PI (ISBA-50% ABHQ-TAHQ), with a Dk of 2.88 and Df of 0.003 was gained. In Chapter 3, we extend the concept of bio-based material, a bio-based and low dielectric constant/dissipation factor photosensitive polyimide (PSPI) used as photo-resist is designed. We introduced fluorine-ester, fluorine-ether, and symmetric ester groups into ISBA-ISBESA to produce a PSPI that possesses a low dielectric constant of 2.73 and 2.66, low dissipation factor of 0.0072 and 0.0089, at 10 GHz and 20 GHz, respectively. Through the evaluation of the photolithography process, including PBG content, PEB temperature, PEB time to the dissolution rate, and the degree of imidization, PAA (50% ISBA-50% BAPHF-ISBESA) formulated with cinnamic-derived photo-base generator underwent an optimized process condition of PB 100 ℃, 5 min, 10wt% PBG addition, PEB at 150 ℃ for 5 min, and obtained a PSPI pattern with L/S resolution of 10/10μm. In conclusion, we use a glucose-derived bio-source, ISB, to synthesize a highly transparent bio-based polyimide. On the other hand, to simplify the manufacturing process and also achieve the goal of reducing pollution, we designed a bio-based photo-resist possessing a low dielectric property. Hoping that this thesis provided a good example of designing bio-based polyimide, and one day can achieve the goal of net zero emissions.