- Previous Article
- Next Article
- Table of Contents
Polymer(Korea), Vol.26, No.6, 701-709, November, 2002
감광성 DMNB 기를 함유한 새로운 포지형 감광성 폴리이미드의 합성 및 물성
Synthesis and Characterization of New Positive Photosensitive Polyimide Having Photocleavable 4,5-Dimethoxy-2-nitrobenzyl (DMNB) Groups
E-mail:
초록
새로운 포지티브형 감광성 폴리이미드 전구체를 합성하기 위하여, 폴리아믹산의 일부 카르복시산 기를 K2CO3/HMPA 조건 하에서 광분해성 감광성 기인 4,5-dimethoxy-2-nitrobenzyl bromide와 반응시켜 에스테르를 형성하고 나머지 카르복시산 기를 화학적 이미드화시켜 poly[imide-co-(amic ester)]를 합성하였다. 합성된 고분자의 구조는 FT-IR, 1H-NMR 등으로 확인하였고, DSC와 TGA를 이용하여 열적 특성을 확인하였다. 또한 이 고분자에 자외선을 조사하면 감광성 기인 4,5-dimethoxy-2-nitrobenzyl 기가 분해되어 카르복시산 기를 형성함에 따라 고분자가 알칼리 현상액에 대해 용해하였으며, 이를 이용하여 포지티브 패턴을 형성할 수 있었다. 여러가지 4,5-dimethoxy-2-nitrobenzyl ester 농도를 갖는 poly[imide-co-(amic ester)]의 겔분율 실험을 통하여 감광곡선을 얻었으며, 이를 통해 이 고분자의 감광특성을 조사하였다. 그 결과 감도는 4000~6000 mJ/cm(2) 이었으며, 조도는 3.1~4.9 정도인 것으로 확인되었다.
To synthesize a new positive photosensitive polyimide precursor, parts of carboxylic acid groups in poly(amic acid) were esterified with 4,5-dimethoxy-2-nitrobenzyl bromide in the presence of K2CO3/HMPA followed by the chemical imidization of residual carboxylic acid units. The chemical structure of resulting polymer was characterized by 1H-NMR, UV/vis and FT-IR spectroscopic methods, and its thermal properties were examined by DSC and TGA. Upon UV irradiation, 4,5-dimethoxy-2-nitrobenzyl moiety underwent the photodegradation. As a result, the polymer became soluble in alkaline developer due to the formation of carboxylic acid moiety, which was used to make a micron-sized positive pattern. Sensitivity curves were obtained from the gel fraction experiments with respect to the various 4,5-dimethoxy-2-nitrobenzyl ester contents. From those curves, the sensitivity was ranged from 4000 to 6000 mJ/cm(2), and the contrast was measured to be from 3.1 to 4.9.
Keywords:polyimides;photosensitive polymer;positive type;micro-lithography;poly[imide-co-(amic ester)]
- Lee DH, Polym.(Korea), 11(3), 206 (1987)
- Yoda N, Hiramoto H, J. Macromol. Sci.-Chem., A21, 1641 (1984)
- Rubner R, Ahne H, Kuhn E, Photograph. Sci. Eng., 23, 303 (1997)
- Pfeifer J, Rohde O, "Proceedings of Second International Conference on Polyimides: Synthesis, Characterization and Application," p. 130, Marcel Dekker, New York (1985)
- Reiser A, "Photoreactive Polymers-The Science and Technology of Resist," Wiley, New York (1989)
- Schlitz A, IEEE Trans. Compon. Hybrides Manuf. Technol., 15, 226 (1992)
- Chakravorty KK, Chien CP, Cech JM, IEEE Trans. Compon. Hybrides Manuf. Technol., 13, 200 (1990)
- Kerwin RE, Goldrick MR, Polym. Eng. Sci., 11, 426 (1971)
- Lee MH, Chong YS, J. Korean Soc. Imaging Sci. Tech., 5, 34 (1999)
- Lee MH, Ryu Y, J. Korean Soc. Imaging Sci. Tech., 5, 27 (1999)
- Kubota S, Moriwaki T, ando T, Fukami A, J. Macromol. Sci.-Chem., A24, 1497 (1987)
- Kubota S, Yamawaki Y, Moriwaki T, Eto S, Polym. Eng. Sci., 29, 950 (1989)
- Kubota S, Tanaka Y, Moriwaki T, Eto S, J. Electrochem. Soc., 138, 1080 (1991)
- Pillai VNR, Synthesis, 1980, 1 (1980)
- Park JW, Lee M, Lee MH, Liu JW, Kim SD, Chang JY, Rhee SB, Macromolecules, 27(13), 3459 (1994)
- Rhee SB, Park J, Moon BS, Lee MH, Chang JY, Macromol. Chem. Phys., 196, 691 (1995)
- Lee MH, Park J, Rhee SB, Abstract of 36th IUPAC International Symposium on Macromolecules, p. 116, Aug. 4-9, 1996, Seoul, Korea (1996)
- Lee MH, Park J, Rhee SB, U.S. Patent, Appl. 08/558,597 (1995)
- Lee MH, Park J, Rhee SB, Japan Patent, appl. 95-283268 (1995)
- Lee MH, Park J, Rhee SB, Korea Patent, Appl. 94-28242 (1994)
- Baltrop JA, Plant PJ, Schofield P, J. Chem. Soc.-Chem. Commun., 22, 823 (1966)