Yin X, Hong L, Chen B-H, Ko T-M
Department of Chemical and Environmental Engineering, National University of Singapore, 10 Kent Ridge Crescent, 119260 Singapore.
J Colloid Interface Sci. 2003 Jun 1;262(1):89-96. doi: 10.1016/S0021-9797(03)00191-7.
Electroless nickel (EN) plating is a process in which Ni2+ ions are reduced by hydrogen atoms adsorbed at a fresh Ni surface. However, detaching of a handful of tiny Ni metal particles from a substrate causes the entrance of these particles into the plating solution. The metal particles offer very reactive surfaces for the reduction of Ni2+ ions, which in turn aggravates the detachment, causing a self-accelerated cycle. Eventually the plating solution will be subject to an overwhelming precipitation of Ni black. This paper proposes a one-dimensional diffusion model to explain the dependence of the bath stability on the plating time under different bath loadings. This mathematical model contains Vd, defined as the decomposition volume, a measure to judge chemical stability of a plating solution. To obtain Vd experimentally, a PdCl2 solution was purposely introduced into a model solution (the addition leads to immediate generation of metal particles) until the very moment of onset of massive deposition of colloidal Ni. The Vd data from the experiment were then used to perform simulation in order to complete the model proposed. Other than the effects of bath loadings and plating time, an adsorption model was also created to describe the temperature effect. To coordinate the adsorption model, l-cysteine was used as an adsorbate that plays a deactivation role. The under bump metallization process on patterned silicon wafers has been used to support the main theme of this study.
化学镀镍(EN)是一个通过吸附在新鲜镍表面的氢原子将Ni2+离子还原的过程。然而,从基底上分离出少量微小的镍金属颗粒会导致这些颗粒进入镀液。这些金属颗粒为Ni2+离子的还原提供了非常活泼的表面,这反过来又加剧了颗粒的分离,从而导致一个自我加速的循环。最终,镀液会出现大量黑色镍沉淀。本文提出了一个一维扩散模型来解释在不同镀液负载下镀液稳定性对镀覆时间的依赖性。这个数学模型包含Vd,即分解体积,它是判断镀液化学稳定性的一个指标。为了通过实验获得Vd,特意将PdCl2溶液引入到模型溶液中(该添加会立即产生金属颗粒),直到胶体镍大量沉积开始的那一刻。然后利用实验得到的Vd数据进行模拟,以完善所提出的模型。除了镀液负载和镀覆时间的影响外,还创建了一个吸附模型来描述温度效应。为了配合吸附模型,使用了L-半胱氨酸作为起失活作用的吸附质。在图案化硅片上的凸点下金属化工艺被用于支持本研究的主题。