Copper foil, a thin layer of high-purity metallic copper, having excellent conductivity, ductility, and corrosion resistance, is extensively applied in various electronic applications. Thiolated (SH-containing) chemical additives (i.e., accelerator and inhibitor) in copper electroplating solution are known to be critical for optimizing the copper foil manufacturing processes. Due to the high ionic strength and acidity of copper electroplating solution, proper and accurate characterization of the thiolated chemical additives is a critical concern. In this study, a facile, accurate approach is developed for quantitative characterization of thiolated additives in the copper electroplating solution. Firstly, gold nanoparticles (AuNPs) were employed as an adsorbent for separating the thiolated chemical additives, namely, poly(ethylene glycol) methyl ether thiol (PEG-SH) as inhibitor, and 3-mercaptopropionic acid (MPA) as accelerator from other interfering chemicals present in the copper electroplating solution. Subsequently, quantitative analysis of the AuNPs in the form of thin particle film was performed using attenuated total reflection-Fourier transform infrared spectroscopy. Electrospray-differential mobility analyzer was employed orthogonally for the quantitative analysis of the amount of thiolated additives adsorbed on AuNP. Interestingly, the results indicated that the detection concentration ranges of 5 μM–100 μM for PEG-SH and 10 μM–200 μM for MPA, respectively. Overall, this work demonstrates a successful separation and analysis methodology for the thiolated chemical additives in copper electroplating solution which enables the precise control over the copper foil manufacturing process.

中文翻译：

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量化铜电镀过程中的硫醇化化学添加剂

铜箔是一层薄薄的高纯度金属铜，具有优异的导电性、延展性和耐腐蚀性，广泛应用于各种电子领域。众所周知，电镀铜溶液中的硫醇化（含SH）化学添加剂（即促进剂和抑制剂）对于优化铜箔制造工艺至关重要。由于铜电镀溶液的高离子强度和酸性，硫醇化化学添加剂的正确和准确的表征是一个关键问题。在本研究中，开发了一种简便、准确的方法来定量表征铜电镀溶液中的硫醇添加剂。首先，采用金纳米颗粒（AuNPs）作为吸附剂，将硫醇化化学添加剂（即作为抑制剂的聚乙二醇甲醚硫醇（PEG-SH）和作为促进剂的3-巯基丙酸（MPA））与其他干扰物分离。铜电镀液中存在的化学物质。随后，使用衰减全反射-傅立叶变换红外光谱法对薄膜形式的AuNPs进行定量分析。采用电喷雾-微分迁移率分析仪正交定量分析AuNP 上吸附的硫醇添加剂的量。有趣的是，结果表明，PEG-SH 的检测浓度范围为 5 μM–100 μM，MPA 的检测浓度范围为 10 μM–200 μM。总的来说，这项工作展示了一种成功的铜电镀溶液中硫醇化化学添加剂的分离和分析方法，可以精确控制铜箔制造过程。