Hanzawa Masaki, Ogura Taku, Akamatsu Masaaki, Sakai Kenichi, Sakai Hideki
NIKKOL GROUP Nikko Chemicals Co., Ltd., 3-24-3 Hasune, Itabashi, Tokyo 174-0046, Japan.
Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
Langmuir. 2023 Oct 17;39(41):14670-14679. doi: 10.1021/acs.langmuir.3c02034. Epub 2023 Oct 5.
Organic photoresist coatings, primarily composed of resins, are commonly used in the electronics industry to protect inorganic underlayers. Conventional photoresist strippers, such as amine-type agents, have shown high removal performance but led to environmental impact and substrate corrosiveness. Therefore, this trade-off must be addressed. In this study, we characterized the removal mechanism of a photoresist film using a nonionic triblock Pluronic surfactant [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] in a ternary mixture of ethylene carbonate (EC), propylene carbonate (PC), and water. In particular, the removal dynamics determined by using a quartz crystal microbalance with dissipation monitoring was compared with those determined by performing confocal laser scanning microscopy and visual observation to analyze the morphology, adsorption mass, and viscoelasticity of the photoresist film. In the absence of the Pluronic surfactant, the photoresist film in the ternary solvent exhibited a three-step process: (i) film swelling caused by the penetration of a good solvent (EC and PC), (ii) formation of photoresist particles through dewetting, and (iii) particle aggregation on the substrate. This result was correlated to the Hansen solubility parameters. The addition of the Pluronic surfactant not only prevented photoresist aggregation in the third step but also promoted desorption from the substrate. This effect was dependent on the concentration of the Pluronic surfactant, which influenced diffusion to the interface between the photoresist and the bulk solution. Finally, we proposed a novel photoresist stripping mechanism based on the synergy between dewetting driven by an EC/PC-to-water mixture and adsorption by the Pluronic surfactant.
有机光刻胶涂层主要由树脂组成,常用于电子工业中保护无机底层。传统的光刻胶剥离剂,如胺类试剂,具有较高的去除性能,但会对环境造成影响并导致基板腐蚀。因此,必须解决这种权衡问题。在本研究中,我们表征了在碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和水的三元混合物中使用非离子三嵌段普朗尼克表面活性剂[聚(环氧乙烷)-聚(环氧丙烷)-聚(环氧乙烷)]去除光刻胶膜的机理。特别是,将使用具有耗散监测功能的石英晶体微天平测定的去除动力学与通过共聚焦激光扫描显微镜和目视观察测定的动力学进行比较,以分析光刻胶膜的形态、吸附质量和粘弹性。在没有普朗尼克表面活性剂的情况下,三元溶剂中的光刻胶膜呈现出三步过程:(i)由良溶剂(EC和PC)渗透引起的膜膨胀,(ii)通过去湿形成光刻胶颗粒,以及(iii)颗粒在基板上聚集。该结果与汉森溶解度参数相关。添加普朗尼克表面活性剂不仅在第三步中防止了光刻胶聚集,还促进了从基板上的解吸。这种效果取决于普朗尼克表面活性剂的浓度,其影响向光刻胶与本体溶液之间界面的扩散。最后,我们基于EC/PC与水的混合物驱动的去湿和普朗尼克表面活性剂的吸附之间的协同作用,提出了一种新型的光刻胶剥离机理。