光刻胶中金属离子的去除和定量分析  

Removal and Quantitative Analysis of Metal Ions in Photoresist

作　　者：张卫杰 陈金平[1] 于天君[1] 曾毅[1,3] 郭旭东 王双青[2] 杨国强[2,3] 李嫕[1,3] ZHANG Wei-Jie;CHEN Jin-Ping;YU Tian-Jun;ZENG Yi;GUO Xu-Dong;WANG Shuang-Qing;YANG Guo-Qiang;LI Yi(CAS Key Laboratory of Photochemical Conversion and Optoelectronic Materials,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences,Beijing 100190,China;CAS Key Laboratory of Photochemistry,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;University of Chinese Academy of Sciences,Beijing 100039,China)

机构地区：[1]中国科学院理化技术研究所,中国科学院光化学转换与功能材料重点实验室,北京100190 [2]中国科学院化学研究所,中国科学院光化学重点实验室,北京100190 [3]中国科学院大学,北京100039

出　　处：《分析化学》2021年第10期1750-1757,共8页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.22090012,U20A20144);中国科学院仪器研制项目(No.YZQT020)资助。

摘　　要：采用巯基树脂为金属离子吸附剂,分析了巯基树脂对光刻胶主体材料中残留的金属催化剂Pd的吸附热力学和动力学行为。在不同温度下,将巯基树脂对Pd的吸附实验数据进行动力学模型拟合,结果表明,巯基树脂对光刻胶中Pd的吸附过程符合拟二级动力学模型,说明此吸附过程受化学吸附控制,光刻胶中的Pd和巯基基团化学螯合作用对吸附起重要作用。等温吸附结果符合Langmuir等温吸附方程,表明光刻胶中Pd在巯基树脂表面倾向于单分子层吸附。在实验温度范围内,随着吸附温度升高,巯基树脂对Pd的最大吸附量由12.68 mg/g提高到17.49 mg/g,表明适当提高吸附温度有助于提高巯基树脂的吸附效率。对光刻胶中的金属离子的综合去除实验结果表明,巯基树脂对光刻胶中Li、Na、Mg、Al、K、Ca、Cr、Mn、Fe、Ni、Cu、Zn、Pd和Sn等金属均有良好的吸附效果,可以使纯化后光刻胶中大部分金属离子达到μg/L量级,与进口金属离子去除系统相比,巯基树脂对光刻胶中Pd的纯化效果更显著,含量从5.9 mg/L降低到0.4μg/L,对于Na和Ca等高丰度金属离子,可分别降低到11.8和13.0μg/L,纯化效果有待进一步优化和改进。Thiol resin was used as an adsorbent to remove metal ions in organic photoresists.The thermodynamics and kinetics of the adsorption of Pd in photoresists were investigated extensively by inductively coupled plasma-mass spectrometry(ICP-MS).The adsorption data of Pd ion under different temperatures followed pseudo-second-order kinetic model,indicating that the adsorption process was controlled by chemical interactions of Pd and thiol groups.The results of isothermal adsorption were fitted well with Langmuir isothermal adsorption model,indicating that Pd in photoresist tended to adsorb monolayer on the surface of thiol resin.With the temperature increased,the maximum adsorption capacity of thiol resin for Pd increased from 12.68 mg/g to 17.49 mg/g,suggesting that appropriately increasing the adsorption temperature was helpful to improve the adsorption efficiency.The comprehensive purification results showed that thiol resin could be considered as a promising adsorbent for removal of Li,Na,Mg,Al,K,Ca,Cr,Mn,Fe,Ni,Cu,Zn,Pd and Sn ions in the photoresist.Most of the metal ions could be removed,with residual concentration down to 1.0μg/L level.Compared with the Pall purification system,thiol resin was more effective for Pd purification,decreasing the content of Pd from 5.9 mg/L to 0.4μg/L.However,for abundant metal ions such as Na and Ca with reducing limitation to 11.8μg/L and 13.0μg/L,respectively,the purification needs to be further optimized.

关 键 词：光刻胶 金属离子去除 巯基树脂 吸附动力学 等温吸附 

分 类 号：O647.3[理学—物理化学] TN405[理学—化学]