新型光刻胶及玻璃刻蚀应用研究
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摘要
本论文是关于环氧树脂改性超支化感光聚合物的合成、以该感光树脂制备厚型光刻胶极其在玻璃刻蚀加工方面的应用研究。以偏苯三酸酐、环氧氯丙烷和甲基丙烯酸缩水甘油酯一步反应制备了羧基功能化的感光超支化聚酯，通过环氧树脂两端的环氧基与超支化聚酯的羧基反应制备了改性感光聚合物，改变反应物配比，合成了不同感光特性的树脂。GPC、DSC、TGA及力学性能结果表明：当改性环氧树脂用量为70％(官能团比)时，聚合物的性能最佳。通过残膜率—曝光时间曲线表征了以超支化感光树脂配制的光刻胶的感光特性。初始曝光时间T_0，残膜反差值γ_(gel)可以通过多种因素来调整，制得了初始曝光时间2．7s，残膜反差值达到2．8的光刻胶。在混合光源以及接触曝光的条件下分辨率达到2～3μm，且图像十分清晰，断面整齐。
研究了活性稀释剂及助剂对光刻胶性能的影响，确定了以超支化感光聚合物为基体树脂的厚型光刻胶的光刻工艺，研制了适宜的显影液。光刻工艺基本条件为：前烘温度为65℃，前烘时间为20～25分钟；曝光时间为5分钟；显影液为丙酮／乙醇=3(质量比)，显影时间为5分钟；后烘温度为70℃。研制的厚型光刻胶有效厚度约为100μm，极限透光深度为272μm。在接触曝光条件下，胶厚为80μm左右时，深宽比能达到1:1。
以环氧改性的感光树脂配制的光刻胶用于玻璃化学刻蚀的保护层，其耐刻蚀性能较传统光刻胶有明显提高。以HF酸为主体的玻璃刻蚀剂，研究了HCl、HNO_3以及氟化铵对玻璃化学刻蚀的影响，在HF：HNO_3：H_2O：NH_4F=1：3：6：0．74(质量比)时，所得的混合刻蚀剂对载玻片玻璃的刻蚀速度≥35μm／min；以环氧改性的超支化感光树脂为基体树脂的光刻胶形成玻璃刻蚀的单层掩膜，可得到线宽50μm的清晰刻蚀图样，玻璃的刻蚀深度超过38μm。
This work is about the synthesis of photo reactive hyperbranched polyesters modified with epoxy resin, the preparation of negative thick photoresists with these photo reactive polyesters, and application as the mask in the chemical etching for microfabrication of glass. Photo reactive hyperbranched polyesters terminated with-COOH were prepared by trmellitic anhydride, epichlorohydrin and grycidol methacrylate. The modification of the polyesters was performed through the reaction of the epoxy groups on the epoxy resin with the -COOH. A serios of photosensitive resins with difference in photosensitivity were prepared and was characterized by GPC, DSC and TGA. Photocuring behaviours of resin and the photoresists were studied. Sensitivity and contract of the photoresists were measured by gel content High sensitivity and high contract (T_(0, gel) andγ_(gel) were 2.71s and 2.802, respectively) were realized. Clear patterns with smooth surface and resolution reached to 2～3μm were prepared with the photoresists through contact exposure with mixed UV light.
Effects of reactive diluents and additives on the properties of the photosists were studied. The photolithographic conditions and the developing solution for the thick negative-tone UV photoresist were defined as: prebaking at 65℃for 20～25min, exposure time 5min; developed for 5 min in acetone/ethanol=3 (m/m) and post baking at 70℃. With single-layer coatings the thicknesses of the dried photoresist over 50μm was achieved, and over 100μm thicknesses was also achieved by mulicoating. The aspect ratio of thick (80μm) photoresist was about 1:1.
Photo masks for glass etching were prepared with the photoresists composed of the modified photoreactive resins. The wet chemical etching agents made of HF and HCl, HNO_3 exhibited high etching rate (≥35μm/min). Photoresists made of the modified photoreactive hyperbranched polyesters were patterned with line width of 50μm. Glass etching with depth for over 38μm was realized using the photoresist as the only mask.
研究了活性稀释剂及助剂对光刻胶性能的影响，确定了以超支化感光聚合物为基体树脂的厚型光刻胶的光刻工艺，研制了适宜的显影液。光刻工艺基本条件为：前烘温度为65℃，前烘时间为20～25分钟；曝光时间为5分钟；显影液为丙酮／乙醇=3(质量比)，显影时间为5分钟；后烘温度为70℃。研制的厚型光刻胶有效厚度约为100μm，极限透光深度为272μm。在接触曝光条件下，胶厚为80μm左右时，深宽比能达到1:1。
以环氧改性的感光树脂配制的光刻胶用于玻璃化学刻蚀的保护层，其耐刻蚀性能较传统光刻胶有明显提高。以HF酸为主体的玻璃刻蚀剂，研究了HCl、HNO_3以及氟化铵对玻璃化学刻蚀的影响，在HF：HNO_3：H_2O：NH_4F=1：3：6：0．74(质量比)时，所得的混合刻蚀剂对载玻片玻璃的刻蚀速度≥35μm／min；以环氧改性的超支化感光树脂为基体树脂的光刻胶形成玻璃刻蚀的单层掩膜，可得到线宽50μm的清晰刻蚀图样，玻璃的刻蚀深度超过38μm。
This work is about the synthesis of photo reactive hyperbranched polyesters modified with epoxy resin, the preparation of negative thick photoresists with these photo reactive polyesters, and application as the mask in the chemical etching for microfabrication of glass. Photo reactive hyperbranched polyesters terminated with-COOH were prepared by trmellitic anhydride, epichlorohydrin and grycidol methacrylate. The modification of the polyesters was performed through the reaction of the epoxy groups on the epoxy resin with the -COOH. A serios of photosensitive resins with difference in photosensitivity were prepared and was characterized by GPC, DSC and TGA. Photocuring behaviours of resin and the photoresists were studied. Sensitivity and contract of the photoresists were measured by gel content High sensitivity and high contract (T_(0, gel) andγ_(gel) were 2.71s and 2.802, respectively) were realized. Clear patterns with smooth surface and resolution reached to 2～3μm were prepared with the photoresists through contact exposure with mixed UV light.
Effects of reactive diluents and additives on the properties of the photosists were studied. The photolithographic conditions and the developing solution for the thick negative-tone UV photoresist were defined as: prebaking at 65℃for 20～25min, exposure time 5min; developed for 5 min in acetone/ethanol=3 (m/m) and post baking at 70℃. With single-layer coatings the thicknesses of the dried photoresist over 50μm was achieved, and over 100μm thicknesses was also achieved by mulicoating. The aspect ratio of thick (80μm) photoresist was about 1:1.
Photo masks for glass etching were prepared with the photoresists composed of the modified photoreactive resins. The wet chemical etching agents made of HF and HCl, HNO_3 exhibited high etching rate (≥35μm/min). Photoresists made of the modified photoreactive hyperbranched polyesters were patterned with line width of 50μm. Glass etching with depth for over 38μm was realized using the photoresist as the only mask.
引文
1．施文芳，黄宏，化学通报，1997，4：1
2. Blackford L, SRI Report on "Radiation Curable Coatings" June,1993
3. Giianinetto V, Rad Tech International North America ,Conference. Proceedings,1994,54:293
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7．夏伟如，章舒，夏敏．上海化工，2002，12
8．王文君，张改莲，王力元，余尚先．感光科学与光化学，2003，7
9．陈明，李元昌，洪啸吟．高等学校化学学报，2000，9
10．杨凌露，张改莲，余尚先．化学通报，2003，7
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14. Seok-Ho Hwang, Jae-Chang Jung .Polym Int 48:851±854 (1999)
15．崔铮 著．微钠米加工技术及其应用．高等教育出版社，2005
16．张帅，贾育秦．现代制造工程2005(9)
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28. Volker Schmidt, Winfried Arens, Ulrich Kriems. Micromachining and Microfabrieation Process Technology Ⅷ. Proceedings of SPIE. Vol. 4979 (2003)
29. Roberto CARASCO, Jan A. DZIUBAN□, Ignaeio MORENO,etc. Proceedings of SPIE Vol.5836
30. Chuanhua Wen Corresponding, Weihua Deng Secondauthor, Yuquan Li,Thirdauthor. Proceedings. of SPIE Vol. 5281.
31. H. Langen, V. Fascio, R. Wuthrich, D. Viquerat. Proceedings of SPIE Vol. 4568 (2001)
32. Jian Zhang, Thomas Haiqing Gong .Micromachining and Microfabrication Process Technology Ⅵ.Proceedings of SPIE Vol. 4174 (2000)
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34. C.Ilieseu et al, Surface and Coating Technology 192 (2005) 43-47
35. Junting Liu et al.Journal of Non-Crystalline Solides 342(2004) 110-115
36. Yu Liujiang, B. K. Tay ,D. Sheeja. Nanotechnology Proceedings of SPIE Vol. 5118 (2003)
37. J.H.M. Ten Thije Boortkkamp, J.K.M. Jansen. Journal of Engineering Mathematics 43:385-399, 2002.
38. Hiroyuki Niino et al, Fourth International Symposium on Laser Precision Microfabrication Proceedings of SPIE Vol. 5063
39．顾震宇．感光性高分子材料的发展及其在印刷业中的应用，印刷杂志，1999．7
40．FENG Zong-Cai(冯宗财)，WANG Yue-Chuan(王跃川)，Chin J Func Mater(功能材料)[J]，2002，33(1)：101
41．康锡惠，刘梅清编著．《光化学原理与应用》．天津大学出版社1995
42．谭惠民，罗运军编著．《超支化聚合物》北京化学工业出版社2005
43．罗铂靓，杜惊雷，唐雄贵等．Semiconductor Technology vol.30 no.7
44. Cui Z, Lawes R A. J.Micromech.Microeng., V7,p.125,1997
45. Zhong-geng Ling, Kun Lian, Linke Jian. Proceedings of SPIE Vol.3999 (2000)
46. 梁静秋．光机电信息, Vol.11, No.8 2000
47. P.C.Simpson, A.T.Woolley, R.A.Mathies, Biomedical Microdevices [J], 1998, 1:7
48. Thierry Corman ,Peter Enoksson ,GEran Stemmel, Journal of Micromechanics and Microengineering [J], 1998, 8:84
49. Axel Grosse, Matthias Grewe ,Henning Fouckhardt. Journal of Micromechanics and Microengineering[J], 2001,11:257
50. H. K. Jang et al, J. Vac. Sci. Technol. A 19(1), Jan/Feb 2001
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52．王承遇，陶瑛编著《玻璃表面处理技术》．化学工业出版社2004
2. Blackford L, SRI Report on "Radiation Curable Coatings" June,1993
3. Giianinetto V, Rad Tech International North America ,Conference. Proceedings,1994,54:293
4．肖啸，刘世杰，乐山师范学院学报，2004，19：26
5．陈用烈，曾兆华，杨建文编著．辐射固化材料及其应用．北京：化学工业出版社，2003
6．武玲，余尚先．感光材料，1994，4
7．夏伟如，章舒，夏敏．上海化工，2002，12
8．王文君，张改莲，王力元，余尚先．感光科学与光化学，2003，7
9．陈明，李元昌，洪啸吟．高等学校化学学报，2000，9
10．杨凌露，张改莲，余尚先．化学通报，2003，7
11. Reinhold Schwalm, Horst Binder, Dirk Funhofl. Journal of Applied Polymer Science, Vol.78, 208-216 (2000)
12. Heng peng Wu ,Kenneth E. Gonsalves. Adv. Funct. Mater. 2001, 11, No. 4, August
13. S.C.Fu, H.W.Lin, W.Y.Chou, L.A.Wang, K.H.Hsieh. Journal of Applied Polymer Science, Vol. 83, 1860-1869 (2002)
14. Seok-Ho Hwang, Jae-Chang Jung .Polym Int 48:851±854 (1999)
15．崔铮 著．微钠米加工技术及其应用．高等教育出版社，2005
16．张帅，贾育秦．现代制造工程2005(9)
17. Francis E H Tay, J A vanKan, F Watt, WO Choong. J. Micromech. Microeng. 11(2001)27-32
18. J O'Brien, P J Hughes, M Brunet, B O'Neill, J Alderman, B Lane, A O'Riordan and C O'Driscoll. J. Micromech. Microeng. 11(2001) 353-358
19. Chien-Hung Ho, Wensyang Hsu. J. Micromech. Microeng. 14 (2004) 356-364
20. Chii-Rong Yang, Gen-Wen Hsieh, Yu-Sheng Hsieh, Yu-Der Lee. J. Micromech. Microeng.14(2004) 1126-1134
21. Muralidhar K Ghantasala, Jason P Hayes, Erol C Harvey ,Dinesh K Sood. J. Micmmech. Microeng. 11(2001) 133-139
22. K D Vora, B Y Shew, E C Harvey, J P Hayes, A G Peele. J. Micromech. Microeng. 15 (2005) 978-983
23. Ewan H Conradie ,David F Moore. J. Micromech. Mieroeng. 12 (2002) 368-374
24. Bemd Loechel. J. Micromech. Mieroeng. 10 (2000) 108-115.
25. In-hyouk Song, Pratul K Ajmera. J. Micromech. Microeng. 13 (2003) 816-821
26. Elisabeth Verpoorte, Nicof. De rooij, Proceedings Of The IEEE, Vol. 91, no. 6, June 2003
27. Jong UkBu, Youngioo Yee, See-Hyung Lee, Jinhong Kim. The 121h Intemalianal Conference on Solid Sfale Sensors, Actualon and Mierosyslems, Boslon. June 8-12. 2003
28. Volker Schmidt, Winfried Arens, Ulrich Kriems. Micromachining and Microfabrieation Process Technology Ⅷ. Proceedings of SPIE. Vol. 4979 (2003)
29. Roberto CARASCO, Jan A. DZIUBAN□, Ignaeio MORENO,etc. Proceedings of SPIE Vol.5836
30. Chuanhua Wen Corresponding, Weihua Deng Secondauthor, Yuquan Li,Thirdauthor. Proceedings. of SPIE Vol. 5281.
31. H. Langen, V. Fascio, R. Wuthrich, D. Viquerat. Proceedings of SPIE Vol. 4568 (2001)
32. Jian Zhang, Thomas Haiqing Gong .Micromachining and Microfabrication Process Technology Ⅵ.Proceedings of SPIE Vol. 4174 (2000)
33. Volker Sehmidt, Winfried Arens,Ulrieh Kriems. Micromachining and Microfabrication Process Technology Ⅷ.Proceedings of SPIE Vol. 4979(2003)
34. C.Ilieseu et al, Surface and Coating Technology 192 (2005) 43-47
35. Junting Liu et al.Journal of Non-Crystalline Solides 342(2004) 110-115
36. Yu Liujiang, B. K. Tay ,D. Sheeja. Nanotechnology Proceedings of SPIE Vol. 5118 (2003)
37. J.H.M. Ten Thije Boortkkamp, J.K.M. Jansen. Journal of Engineering Mathematics 43:385-399, 2002.
38. Hiroyuki Niino et al, Fourth International Symposium on Laser Precision Microfabrication Proceedings of SPIE Vol. 5063
39．顾震宇．感光性高分子材料的发展及其在印刷业中的应用，印刷杂志，1999．7
40．FENG Zong-Cai(冯宗财)，WANG Yue-Chuan(王跃川)，Chin J Func Mater(功能材料)[J]，2002，33(1)：101
41．康锡惠，刘梅清编著．《光化学原理与应用》．天津大学出版社1995
42．谭惠民，罗运军编著．《超支化聚合物》北京化学工业出版社2005
43．罗铂靓，杜惊雷，唐雄贵等．Semiconductor Technology vol.30 no.7
44. Cui Z, Lawes R A. J.Micromech.Microeng., V7,p.125,1997
45. Zhong-geng Ling, Kun Lian, Linke Jian. Proceedings of SPIE Vol.3999 (2000)
46. 梁静秋．光机电信息, Vol.11, No.8 2000
47. P.C.Simpson, A.T.Woolley, R.A.Mathies, Biomedical Microdevices [J], 1998, 1:7
48. Thierry Corman ,Peter Enoksson ,GEran Stemmel, Journal of Micromechanics and Microengineering [J], 1998, 8:84
49. Axel Grosse, Matthias Grewe ,Henning Fouckhardt. Journal of Micromechanics and Microengineering[J], 2001,11:257
50. H. K. Jang et al, J. Vac. Sci. Technol. A 19(1), Jan/Feb 2001
51. H. K. ,Jang et al, J. Vac. Sci. Technol. A 18(5),Sep/Oct 2000
52．王承遇，陶瑛编著《玻璃表面处理技术》．化学工业出版社2004