A One-Component Negative Photoresist Based on an Epoxy Terpolymer Containing Oxime-Urethane Groups as a Photobase Generator

Kyu Ho Chae; Jin Hee Park

Macromolecular Research, Vol.12, No.4, 352-358, August, 2004

Kyu Ho Chae^†, and Jin Hee Park

Department of Applied Chemistry and The Polymer Science and Technology Research Center, Chonnam National University, Gwangju 500-757, Korea

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For their application as one-component photoresists, we prepared epoxy terpolymers containing oxime-urethane and benzophenone groups by the radical polymerization of glycidyl methacrylate (GMA), methacryloxyethyl benzophenoneoxime urethane (MBU), and N-(4-benzoyl)phenylmaleimide (BPMI). The terpolymer composition was optimized to provide the most photosensitive photoresist. The photo-decomposition reaction of the oxime-urethane groups in the terpolymer was monitored by UV absorption spectroscopy, and the photo-crosslinking reaction of the epoxy terpolymer was observed by measuring the normalized thickness. The photosensitivity of the epoxy terpolymer increased as the amount of BPMI and MBU units increased up to 16 and 24 mol%, respectively. Among the terpolymers we prepared, terpolymer T-II(contents of GMA, MBU, BPMI are 75, 19, 6.1 mole%, respectively) exhibited the highest photosensitivity (Dc 0.5 = 430mJ/cm2) and had a moderate contrast ( γp = 1.23). Negative-tone micropatterns having a line width of ca. 10 μm were obtained by developing the system with chloroform.

Keywords:photoresist;photocrosslinking;photobase generator;terpolymer;micropattern formation.

[References]

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Roteman J, US Patent 3,988,152 (1976)
Chae KH, Macromol. Rapid Commun., 1, 19 (1998)
Hwang H, Jang DJ, Chae KH, J. Photochem. Photobiol. A-Chem., 37, 126 (1999)
Chae KH, Song HB, Polym. Bull., 40(6), 667 (1998)
Chae KH, Song HB, Sun HY, Chang JY, Bull. Korean Chem. Soc., 21, 690 (2002)
Chae KH, SUng KH, J. Polym. Sci. A: Polym. Chem., 41, 975 (2004)
Nishikubo T, Takehara E, Kaneyama A, J. Polym. Sci. A: Polym. Chem., 31, 3013 (1993)
Katogi S, Yusa M, J. Polym. Sci. A: Polym. Chem., 40(22), 4045 (2002)
Tachi H, Yamamoto T, Shirai M, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 39(9), 1329 (2001)
Ito KI, Nishimura M, Sashio M, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 32(9), 1793 (1994)
Lto K, Shigeru Y, Kawata Y, Ito K, Tsnooka M, Can. J. Chem., 73, 1924 (1995)
Kutal C, Willson CG, J. Electrochem. Soc., 134, 2280 (1987)
Mejiritski A, Ssrker AM, Wheaton B, Neckers DC, Chem. Mater., 9, 1488 (1997)
Chae KH, Jang HJ, J. Polym. Sci. A: Polym. Chem., 40(8), 1200 (2002)
Allen NS, Salleh NG, J. Photochem. Photobiol. A-Chem., 99, 161 (1996)
Wolf MW, Legg KD, Brown RE, Singer LA, Park JH, J. Am. Chem. Soc., 97, 4490 (1975)
Ahn KD, Koo JS, Chung CM, J. Polym. Sci. A: Polym. Chem., 34(2), 183 (1996)
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Shirai M, Kinoshita H, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 31, 451 (1993)

[Referenced By]

[Related Articles]

[1] Yasuyo H, GB Patent 2,206,351 (1989)

[2] Yuichiro M, Akira M, Takao K, Minoru Y, JP Patent 2001192431 (2001)

[3] Nobuyuki I, Takafumi O, JP Patent 2001040052 (2001)

[4] Junya Y, Kenji M, Kenji S, JP Patent 2001033959 (2001)

[5] Takao O, Tatsuya K, Ichiro M, Naoya K, JP Patent 2001026624 (2001)

[6] Roteman J, US Patent 3,988,152 (1976)

[7] Chae KH, Macromol. Rapid Commun., 1, 19 (1998)

[8] Hwang H, Jang DJ, Chae KH, J. Photochem. Photobiol. A-Chem., 37, 126 (1999)

[9] Chae KH, Song HB, Polym. Bull., 40(6), 667 (1998)

[10] Chae KH, Song HB, Sun HY, Chang JY, Bull. Korean Chem. Soc., 21, 690 (2002)

[11] Chae KH, SUng KH, J. Polym. Sci. A: Polym. Chem., 41, 975 (2004)

[12] Nishikubo T, Takehara E, Kaneyama A, J. Polym. Sci. A: Polym. Chem., 31, 3013 (1993)

[13] Katogi S, Yusa M, J. Polym. Sci. A: Polym. Chem., 40(22), 4045 (2002)

[14] Tachi H, Yamamoto T, Shirai M, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 39(9), 1329 (2001)

[15] Ito KI, Nishimura M, Sashio M, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 32(9), 1793 (1994)

[16] Lto K, Shigeru Y, Kawata Y, Ito K, Tsnooka M, Can. J. Chem., 73, 1924 (1995)

[17] Kutal C, Willson CG, J. Electrochem. Soc., 134, 2280 (1987)

[18] Mejiritski A, Ssrker AM, Wheaton B, Neckers DC, Chem. Mater., 9, 1488 (1997)

[19] Chae KH, Jang HJ, J. Polym. Sci. A: Polym. Chem., 40(8), 1200 (2002)

[20] Allen NS, Salleh NG, J. Photochem. Photobiol. A-Chem., 99, 161 (1996)

[21] Wolf MW, Legg KD, Brown RE, Singer LA, Park JH, J. Am. Chem. Soc., 97, 4490 (1975)

[22] Ahn KD, Koo JS, Chung CM, J. Polym. Sci. A: Polym. Chem., 34(2), 183 (1996)

[23] Hanson JE, Reichmanis E, Houlihan FM, Neenan TX, Chem. Mater., 4, 837 (1992)

[24] Shirai M, Kinoshita H, Tsunooka M, J. Polym. Sci. A: Polym. Chem., 31, 451 (1993)