Effect of Basicity of Amino Group at Side Chain in Diallylamine-Type Copolymer Additive on Via-Filling by Copper
Effect of Basicity of Amino Group at Side Chain in Diallylamine-Type Copolymer Additive on Via-Filling by Copper
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二烯丙胺型共聚物添加剂侧链氨基碱性对铜填孔的影响
DOI：
10.1149/2.021312jes
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
and K. Kondo
中科院分区：
文献类型：
--
作者：
M. Takeuchi;Y. Yamada;M. Bunya;S. Okada;N. Okamoto;T. Saito;and K. Kondo
在以前的研究中，我们实现了自下而上的通孔填充铜电沉积过程中使用一个单一的二烯丙基胺型共聚物添加剂，而不是传统的四种类型的添加剂。然而，我们还没有建立这种单一添加剂的功能和聚合物结构之间的关系。为了研究添加剂的功能和聚合物添加剂的碱性的强度，我们合成了一系列在聚合物侧链上具有两个氨基的二烯丙基胺型共聚物，将它们作为单一添加剂添加到碱性酸性硫酸铜浴中，进行电沉积，并使用光学显微镜（OM）观察通孔横截面。我们还进行了基于石英晶体微天平（QCM）和线性扫描伏安法（LSV）测量的电化学分析。通过比较侧链末端的氨基和靠近主链的氨基，发现后者的碱性较弱，这是由于邻基效应。然而，当这两个氨基之间的距离较长时，靠近主链的氨基的碱性较强。在主链附近具有强氨基的聚合物添加剂的使用具有抑制通孔外部的电沉积并实现良好的自下而上填充的效果。
In a previous study, we achieved the bottom-up via-filling during copper electrodeposition using a single diallylamine-type copolymer additive instead of the conventional four types of additives. However, we have not yet established the relation between the function of this single additive and the polymer structure. To investigate the additive function and the strength of the polymer additive's basicity, we synthesized a series of diallylamine-type copolymers having two amino groups on the polymer side chain, added them to a basic acid copper sulfate bath as a single additive, performed the electrodeposition, and observed the via cross sections using an optical microscope (OM). We also performed an electrochemical analysis based on quartz crystal microbalance (QCM) and linear sweep voltammetry (LSV) measurements. By comparing the amino group at the end of the side chain with the one near the main chain, it was found that the basicity of the latter is weak due to the neighboring group effect. However, when the distance between these two amino groups is long, the basicity of the amino group near the main chain is strong. The use of a polymer additive with a strong amino group near the main chain had the effect of suppressing the electrodeposition outside the via and achieving a good bottom-up filling.