臺灣博碩士論文加值系統

本研究利用分子結構設計、聚合反應製程及配方組成調控等步驟，分別
開發一般型 PSPI 及低溫型 PSPI 材料，利用旋轉塗佈法將其塗在 wafer 上，經蝕刻及顯影等製程得到微米級線寬的圖案。並分別探討一般型 PSPI 及低溫型PSPI 樹脂在聚合反應後的材料特性和對光電特性的影響。
在聚合反應部分，一般型 PSPI 利用 pyridine 添加量的提升，可提高聚合後樹脂的固有黏度值(IV)，才能達到製膜所需的機械強度，並透過水洗的方式純化，以降低樹脂中離子含量。而在低溫型 PSPI 中，導入壓克力系的感光單體，並透過 1H-NMR 進行分子結構鑑定，及利用 TGA 與萬能拉力機進行材料熱性質與機械強度測試。
在配方組成設計方面，利用光起始劑、交聯劑及偶合劑等配方篩選，調
整最佳的固含量濃度及溶劑的黏度，使其可透過旋轉塗佈方式塗在wafer 上，並透過百格刀測試發現當組成中含有與 wafer 相同的 Si 成分時，PSPI 與 wafer有最佳之黏著性。本研究並進一步探討光起始劑對解析度之影響，及旋轉塗布轉速對膜厚之影響。
在光電特性量測部分，藉由熱烘烤製程、曝光量及交聯溫度/時間等參數的調控，再經顯影劑的篩選、顯影時間等黃光製程控制，可成功完成顯影
蝕刻製程，經 SEM 檢測結果，得到解析度為微米級線寬的圖形。

Despite having a full range of semiconductor manufacturing and application system,Taiwan is lagging behind in the development of photosensitive resin material. IC material specifications are the key to determining end product quality and this prevents domestic suppliers from providing product with stable specifications and extending their
application into high end products in the future. This program is aimed at developing photosensitive resin technology for low temperature 3D IC applications to improve product performance at the molecular level, including the following: Key material
synthesis technologies: Monomer synthesis, low temperature photosensitive resin molecular design and synthesis production process. High performance photosensitive production film formulation and production: Film coating uniformity and technology
development and materialization/mechanical/electric inspection and analysis/Lithographic process material verification. Establish semiconductor component photoelectric property verification and precision product testing technology. Thus, we plan to accelerate the development of advanced key semiconductor materials that not only comply with the trend for compact and light weight 3C product development, but are also cost effective, replacing conventional packaging materials.

一、緒論…………………………………………………………………………12

1.1 前言………………………………………………………………………....13

1.2 研究背景與動機……………………………………………….…………...13

1.3 研究目的………………….……………………………………………..…17

二、理論基礎與文獻探討………………………………………………….....20

2.1 感光性聚醯亞胺樹脂簡介………………………………………...….…...21

2.2 低溫型 PSPI 樹脂簡介……………………………………………..…...…21

2.3 低溫型 PSPI 文獻與專利分析………………………………………...…..22

三、低實驗方法與步驟…………………………………………………….....26

3.1 實驗規劃與流程圖……………………………………………………...…26

3.2 實驗材料…………………………………………………………………...27

3.3 實驗步驟……………………………………………………………..…….27

3.3.1 一般型 PSPI 樹脂製備………………………………………...…..…….28

3.3.2 低溫型 PSPI 樹脂製備……………………...……………………..…….29

3.4 實驗儀器介紹…………………………………………….…………….….30

3.4.1 樹脂分子結構驗證方法….…………….………………………………..31

3.4.2 聚醯亞胺聚合度分析………….…………………………………….…..32

3.4.3 樹脂熱穩定性(Tg)驗證方法………………………………………...…..33

3.4.4 樹脂耐熱性(Td)驗證方法…………………………………………....…..33

3.4.5 機械性質(tensile strength)驗證方法……………………….................. …..34

3.4.6 應力量測(residual stress)驗證方法……………………....................... …...35

四、結果與討論………................................................................... …………...38

4.1 一般型 PSPI 實驗結果...................................... ………………………….....38

4.1.1 整體實驗流程與構.................................. …………………………….....38

4.1.2 一般型 PSPI 聚合反應........... ………………………………………….....39

4.1.3 PSPI 樹脂與基材黏著性測試…………………………………................. 43

4.1.4 PSPI 樹脂性質與純化方法………………………..................................... 45

4.1.5 配方調控與證……….............................................................................. 46

4.1.6 顯影蝕刻與光電性質測.......................................................................... 52

4.2 低溫型 PSPI 實驗結果................................................................................... 53

4.2.1 整體實驗流程與構.................................................................................. 54

4.2.2 分子結構設計與合.................................................................................. 55

4.2.3 耐熱性及機械性質試.............................................................................. 58

4.2.4 1H-NMR 結構鑑定...................................................................................... 63

4.2.5 光起始劑設計與選.................................................................................. 64

4.2.6 應力量測估.............................................................................................. 66

4.2.7 Lab 級低溫感光樹脂製程驗證法........................................................... 67

五、結論………………………………………………………………...……….73

參考文獻……………………………………………………………………….75

1. R. A. Meyers, J. Polym. Sci.：Part Al, 7(10), p2757(1969).

2. N. Bilow, A. L. Landis and L. J. Miller, U.S. Patent 3,845,018，(1974).

3. M. K. Ghosh and K. L. Mittal, Polyimides：Fundamentals and Applications, Marcel Dekker, New York, p7(1996).

4. H. D. Stenzenberger, Brit. Polym. J., 15(1979).

5. R. W. Lauver, J. Appl. Polym. Sci, 17(8), p2529(1979).

6. J. V. Crivello, J. Polym. Sci, 11(6), p1185, (1973).

7. N. Bilow, A. L. Landis and L. J. Miller, U.S. Patent 3,845,018，(1974).

8. A. V. Rami. Reddy and P. Sreenivasulu Reddy, J. Appl. Polym. Sci., 58,p1935(1995).

9. Alexander A Kuznetsov, High Perform. Polym., 12, p445(2000).

10. K. Y. Choi and S. K. Choi, J. Polym. Sci.：Part A：20, p1107(1982).

11. M. Bruma, B.Schulz,T. Kopnick and J. Robinson, High Perform. Polym., 12, p429(2000).

12. C. Jung, T. Aoyama, T. Wada, H. Sasabe, M. Jikei and M. Kakimoto, High Perform. Polym., 12, p205(2000).

13. M. Pasmanaban, M. Kakimoto and Y. Imai, J. Polym. Sci.：Part A.:28, p1569(1990).

14. Y. Yamada, High Perform. Polym., 10, p92(1998).

15. M. K. Ghosh and K. L. Mittal, Polyimides：Fundamentals and Applications, Marcel Dekker, New York, p15(1996).

16. R. E. Kerwin and M. R. Goldrick, Polym. Engng. Sci., 2, p426(1971).

17. R. Rubner, Siemens Forsch Entwickl Ber, 5, p92(1976).

18. R. Rubner, B. Barter and G. Bald, Siemens Forsch Entwickl Ber, 5, p235(1976).

19. H. J. Merrem, R. Klug and H. Hartner, Polyimide: Synthesis, Characteristic, Application, 2, p919(1984).

20. J. S. Li, Z. B. Li and P. K. Zhu, J. Appli. Polym. Sci., 77, p943(2000).

21. U. Mitsuru and N. Tomonari, Macromolecules, 29, p6427(1996).

22. Y. Naoya and H. Hiramoto, J. Macrol. Scl-Chem., A21, p1641(1984).

23. K. H. Kim, S. Jang and F. W. Harris, Macromolecules, 34, p8925(2001).

24. H. A. Kang, I. S. Chung, M. Kakimoto and S. Y. Kim, Polym. Journal, 33, p284(2001).

25. R. Runber, US patent 4040831, (1977).

26. U. Geissler, US patent 5182187, (1993)

27. H. George, US patent 5766808, (1998).

28. L. Minnema, J. M. Zande, Polym. Engng. Sci. 28(12), p815(1988).

29. R. Rubner, H. Ahne, E. Kuhn and G. Kolodziej, Photogr. Sci, Eng., 23(5), p303(1979).

30. N. Yoda and H. Hiramoto, J. Macromol. Sci.(Chem.), A21(13＆14), p1641(1984).

31. A. A. Lin, V. R. Sastri, G. Tesoro and A. Reiser, Macromolecules, 21(4), p1165(1988).

32. M. G. Moss, R. M. Cuzmer and T. Brewer, Proc. SPIE, 1086, p396 (1989).

33. P. M. Hergenrother and S. T. Havens, Macromolecules, 27, p4659 (1994).

34. I. S. Chung and S. Y. Kim, Macromolecules, 33, p3190 (2000).

35. Oish, Y.; Onodera, S.; Oravec, J.; Mori, K.; Ando, S.; Terui, Y.;Maeda, K. J Photopolymer Sci Technol,16,p 263(2003).

36. Akimoto, S.; Jikei, M.; Kakimoto, M. High Perform Polym,12, p177(2000).

37. Sasaki, A.; Miyasaka, M.; Hiro, M.; Kaji, M. J Photopolym SciTech, 15, p16(2002)