RAFT聚合法合成甲基丙烯酸酯共聚物及其在负性光致抗蚀剂中的应用

doi:10.7517/j.issn.1674-0475.2016.04.371

影像科学与光化学 ›› 2016, Vol. 34 ›› Issue (4): 371-379.DOI: 10.7517/j.issn.1674-0475.2016.04.371

RAFT聚合法合成甲基丙烯酸酯共聚物及其在负性光致抗蚀剂中的应用

林立成¹, 徐文佳¹, 刘敬成¹, 刘仁¹, 穆启道², 刘晓亚¹

1. 江南大学化学与材料工程学院, 江苏无锡 214122;
2. 苏州瑞红电子化学品有限公司, 江苏苏州 215124

收稿日期:2015-12-24 修回日期:2016-03-15 出版日期:2016-07-15 发布日期:2016-07-15
通讯作者: 刘敬成
基金资助:
国家重大科技专项(2010ZX02304)、江苏省产学研前瞻性联合研究项目(BY2015019-14)和中央高校基本科研业务费专项资金(JUSRP11514)资助

Synthesis of Methacrylate Copolymer via RAFT Polymerization and Their Application in Negative Photoresist

LIN Licheng¹, XU Wenjia¹, LIU Jingcheng¹, LIU Ren¹, MU Qidao², LIU Xiaoya¹

1. School of Chemical & Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu,P.R.China;
2. Suzhou Rui Hong Electronic Chemicals Co., Ltd., Suzhou 215124, Jiangsu, P.R.China

Received:2015-12-24 Revised:2016-03-15 Online:2016-07-15 Published:2016-07-15

摘要/Abstract

摘要：

以甲基丙烯酸(MAA)、甲基丙烯酸苄基酯(BZMA)、甲基丙烯酸羟乙酯(HEMA)和丙烯酸正丁酯(BA)为共聚单体,偶氮二异丁腈(AIBN)为引发剂,2-(十二烷基三硫代碳酸酯基)-2-甲基丙酸(DMP)为链转移试剂,采用可逆加成-断裂链转移聚合(RAFT)制备了甲基丙烯酸酯共聚物(PMBBH)。利用傅立叶红外光谱(FT-IR)、核磁共振氢谱(¹HNMR)和凝胶渗透色谱(GPC)对共聚物的结构进行了表征。以共聚物PMBBH为基体树脂制备了负性光致抗蚀剂,考察了PMBBH的分子量对光致抗蚀剂分辨率的影响。结果表明,以数均分子量为5.45×10³ g/mol,重均分子量为7.79×10³ g/mol的PMBBH-2作为基体树脂时,该光致抗蚀剂得到的图像轮廓清晰,图形分辨率可达50 μm。

关键词: 可逆加成-断裂链转移聚合(RAFT), 甲基丙烯酸酯共聚物, 光致抗蚀剂

Abstract:

A series of methacrylate copolymers PMBBH were synthesized through reversible addition-fragmentation chain tansfer polymerization (RAFT). Methacrylic acid (MAA), benzyl methacrylate (BZMA), and hydroxyethyl methacrylate (HEMA) were used as comonomers. Azobisisobutyronitrile (AIBN) was used as an initiator and 2-(dodecylsulfanylthiocarbonylsulfanyl)-2-methylpropionic acid(DMP) as the chain transfer agent. The structure and properties of polymers were characterized by fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (¹HNMR) and gel permeation chromatography (GPC). Negative photoresist based on PMBBH was prepared. Effect of molecular weight on the resolution of photoresist had been examined. The results showed that photoresist based on PMHBB-2 with the number-average molecular weight of 5.45×10³ g/mol and the weight-average molecular weight of 7.79×10³ g/mol exhibited the best performance with sub-50 μm resolution.

Key words: reversible addition-fragmentation chain transfer polymerization (RAFT), methacrylate copolymer, photoresist

林立成, 徐文佳, 刘敬成, 刘仁, 穆启道, 刘晓亚. RAFT聚合法合成甲基丙烯酸酯共聚物及其在负性光致抗蚀剂中的应用[J]. 影像科学与光化学, 2016, 34(4): 371-379.

LIN Licheng, XU Wenjia, LIU Jingcheng, LIU Ren, MU Qidao, LIU Xiaoya. Synthesis of Methacrylate Copolymer via RAFT Polymerization and Their Application in Negative Photoresist[J]. Imaging Science and Photochemistry, 2016, 34(4): 371-379.

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RAFT聚合法合成甲基丙烯酸酯共聚物及其在负性光致抗蚀剂中的应用

Synthesis of Methacrylate Copolymer via RAFT Polymerization and Their Application in Negative Photoresist

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