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Nonchemically-amplified Resists Based on Photosensitive Oxime Ester Functionalized Polystyrene
- Acta Polymerica Sinica Vol. 55, Issue 10, Pages: 1313-1324(2024)
- 作者机构：
1.中国科学院理化技术研究所 光化学转换与功能材料重点实验室 北京 100190
2.中国科学院大学 北京 100049
- 作者简介：
Jin-ping Chen, E-mail: chenjp@mail.ipc.ac.cn
Yi Li, E-mail: yili@mail.ipc.ac.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2024.24065
CLC：Published：20 October 2024，
Published Online：11 June 2024，
Received：02 March 2024，
Accepted：03 April 2024
- 稿件说明：
移动端阅览
安惠雯, 廉鹏, 陈金平, 于天君, 曾毅, 李嫕. 基于羧酸肟酯光敏基团的非化学放大型聚合物光刻胶. 高分子学报, 2024, 55(10), 1313-1324
An, H. W.; Lian, P.; Chen, J. P.; Yu, T. J.; Zeng, Y.; Li, Y. Nonchemically-amplified resists based on photosensitive oxime ester functionalized polystyrene. Acta Polymerica Sinica, 2024, 55(10), 1313-1324
安惠雯, 廉鹏, 陈金平, 于天君, 曾毅, 李嫕. 基于羧酸肟酯光敏基团的非化学放大型聚合物光刻胶. 高分子学报, 2024, 55(10), 1313-1324 DOI： 10.11777/j.issn1000-3304.2024.24065.
An, H. W.; Lian, P.; Chen, J. P.; Yu, T. J.; Zeng, Y.; Li, Y. Nonchemically-amplified resists based on photosensitive oxime ester functionalized polystyrene. Acta Polymerica Sinica, 2024, 55(10), 1313-1324 DOI： 10.11777/j.issn1000-3304.2024.24065.
摘要
合成了2种羧酸肟酯光敏基团修饰的苯乙烯类单体2
2
2-三氟-1-(4'-乙烯基-[1
1'-联苯
]
-4-基)乙-1-酮-
O
-(3-甲基苯甲酰基)肟(OXE-P)和2
2
2-三氟-1-(4'-乙烯基-[1
1'-联苯
]
-4-基)乙烷-1-酮-
O
-噻吩-2-甲酰肟(OXE-S)通过核磁共振氢谱(
1
H-NMR)、高分辨率质谱(HRMS)表征了单体分子结构. 采用可逆加成-断裂链转移(RAFT)聚合方法制备得了2种新型聚合物POXE-P和POXE-S，使用凝胶渗透色谱(GPC)表征了聚合物分子量大小及其分布. 结果表明，聚合物具有良好的溶解性、热稳定性和成膜性，满足作为光刻胶材料的要求. 将聚合物分别溶于光刻胶溶剂，形成非化学放大型光刻胶. 通过电子束光刻测
试了POXE-P非化学放大型光刻胶的光刻性能，结果表明，POXE-P光刻胶可获得50 nm HP (half-pitch)的光刻图案. 红外光谱(FTIR)和原位产物分析研究POXE-P光刻胶的曝光机理，表明肟酯结构在曝光后发生分解，形成了羰基化合物、二氧化碳等分子. 聚合物侧链的结构变化以及聚合物链间可能存在的自由基交联反应使得聚合物在曝光前后发生了溶解度转变，显影后形成负性光刻图案.
Abstract
Two styrene derivatives 2
2
2-trifluoro-1-(4'-vinyl-[1
1'-biphenyl
]
-4-yl)ethan-1-one-
O
-(3-methylbenzoyl) oxime (OXE-P) and 2
2
2-trifluoro-1-(4'-vinyl-[1
1'-biphenyl
]
-4-yl)ethan-1-one-
O
-thiophene-2-carbonyl oxime
OXE-S) modified by photosensitive oxime ester group were synthesized. They were characterized by
1
H nuclear magnetic resonance (
1
H-NMR) spectroscopy and high-resolution mass spectrometry (HRMS). New polymers (POXE-P and POXE-S) were prepared by the reversible addition-fragmentation transfer (RAFT) polymerization
and were further characterized by gel permeation chromatography (GPC)
giving molecular weights (
M
w
) of 8.3 kDa and 7.2 kDa
and polydispersites (
Đ
) of 1.1. Both polymers possess good solubility
thermal stability and film-forming capability
which meet the requirements of resist
materials. The polymers were dissolved separately in the propylene glycol methyl ether acetate (PGMEA) to form nonchemically-amplified resists (n-CARs). The lithographic performance of the POXE-P resist was examined by e-beam lithography
giving a 50 nm HP (half-pitch) lithographic pattern. The mechanism of POXE-P resist during exposure was investigated by Fourier transform infrared spectrometer (FTIR) and
in situ
outgassing analysis. It showed that the oxime ester group decomposed during exposure to form carbonyl compounds
CO
2
and other small molecules. The cleavage of side chains and the possible crosslinking led to the solubility switch of the polymer
resulting in negative lithographic patterns.
关键词
非化学放大型光刻胶可逆加成-断裂链转移(RAFT)聚合羧酸肟酯电子束光刻机理
Keywords
Nonchemically-amplified resistReversible addition-fracture chain transfer (RAFT) polymerizationOxime esterElectron beam lithographyMechanism
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