This work is supported by Guangdong Basic and Applied Basic Research Fund (2019A1515110771, 2019A1515110469)
纳米孪晶铜具有高强高导高韧的优异性能，使其成为近年来电子封装领域的研究热点。众所 周知，添加剂在直流电镀过程中对镀层质量起着至关重要的作用。亚甲基蓝作为一种常用的染料型添 加剂，在电镀铜行业中被广泛使用。该研究在直流电镀过程中，将不同浓度的亚甲基蓝添加到纳米孪 晶铜电解液中，并进一步研究纳米孪晶铜的微观组织和力学性能与亚甲基蓝添加浓度的关系。随着亚 甲基蓝浓度的增加，镀膜的生长速度缓慢下降，晶粒逐渐细化。当亚甲基蓝浓度为 2 mg/L 时，可以看 到自底向上生长的柱状晶，且存在高密度孪晶结构。使用动态热机械分析仪对其力学性能进行测试发 现，此浓度下薄膜的拉伸强度可达到 194 MPa，约为粗晶铜的 2 倍(约 110 MPa)；薄膜表面维氏硬度可 以达到 1.6 GPa，优于普通粗晶铜硬度。
Nanotwinned copper has excellent properties of high strength, high conductivity and high toughness, which makes it a research hotspot in the field of electronic packaging in recent years. During the electrodeposit procedure, the additives play a vital role in the quality and property of nanotwinned copper. Among these additive, methylene blue is commonly used in the direct-current (DC) electroplating regular copper industry. In this study, the effect of methylene blue on the microstructure and mechanical property of nanotwinned copper was investigated. It was found that the microscopic morphology and mechanical properties of nanotwinned copper are closely related to the concentration of methylene blue. As the concentration increases, the growth rate of electrodeposits shows a decreasing tendency, demonstrating a strong grain refinement effect. When the methylene blue concentration is 2 mg/L, columnar grains start growing from the bottom substrate to upper surface, and there exists a high-density twin structure within the columnar grains. What’s more, the tensile strength of the film at this concentration is 194 MPa, which is almost twice as that of regular coarse-grain copper (about 110 MPa) as measured by the dynamic thermomechanical analyzer (DMA). The surface hardness of the film can reach 1.6 GPa, which is also higher than the hardness of coarse-grained copper.
黄 静,李忠国,高丽茵,李 晓,李 哲,刘志权,孙 蓉.亚甲基蓝对直流电镀纳米孪晶铜组织及 力学性能的影响 [J].集成技术,2021,10(1):55-62
HUANG Jing, LI Zhongguo, GAO Liyin, LI Xiao, LI Zhe, LIU Zhiquan, SUN Rong. Effect of Methylene Blue on the Microstructure and Mechanical Properties of Nanotwinned Copper during DC Electroplating[J]. Journal of Integration Technology,2021,10(1):55-62