化学镀钴过程中添加剂糖精对结晶取向的调控

doi:10.61558/2993-074X.3533

摘要/Abstract

摘要：

在化学镀钴过程中，我们发现添加剂糖精的加入可明显改变化学镀钴层表面的形貌、织构取向及镀层的导电性。研究表明，当糖精添加量为3 mg·L^-1时，钴镀层由无序大晶粒转变为蜂巢状结构，具有密排六方（HCP）钴晶体的（002）择优取向，其电阻率降低至14.4 μΩ·cm，经过热处理后，电阻率进一步降低至10.7 μΩ·cm，这对于其在芯片中的应用具有重要价值。当糖精浓度升高时，晶粒逐渐细化，呈现“石林”状结构，择优取向不变，而糖精的加入在一定程度上提高了镀钴膜的纯度。通过密度泛函理论对钴镀层结晶行为的研究表明，糖精分子可吸附于钴密排晶面的特定c位点，抑制abc堆积方式生长，诱导晶体按ab堆积方式生长，从而实现HCP（002）晶面的择优生长。

关键词: 化学镀钴, 添加剂, 糖精, 结晶行为

Abstract:

In the process of electroless cobalt plating, the saccharin additive can significantly change the surface morphology, texture orientation, and conductivity of the cobalt coating layer. When the amount of saccharin was 3 mg·L^-1, the cobalt coating transformed from disordered large grains to a honeycomb structure, with a preferred orientation of (002) facet on hexagonal close-packed (HCP) cobalt crystals. The resistivity of the cobalt film decreased to 14.4 μΩ·cm, and further decreased to 10.7 μΩ·cm after the annealing treatment. When the concentration of saccharin was increased, the grain size was gradually refined and a “stone forest” structure was observed, with the preferred orientation remaining unchanged. The addition of saccharin also slightly improves the purity of cobalt coating to a certain extent. Through the study of the crystallization behavior of cobalt electroless plating, saccharin molecules can adsorb to specific c-sites on the cobalt dense crystal plane, inhibiting the growth of abc stacking arrangement and inducing the crystal growth in ab stacking mode, thereby achieving optimal growth of HCP (002) texture.

Key words: Electroless cobalt plating, Additives, Saccharin, Crystallization behavior

罗雨欣, 王静静, 王露, 闫子一, 马艺, 薄鑫, 党静霜, 王增林. 化学镀钴过程中添加剂糖精对结晶取向的调控[J]. 电化学（中英文）, 2025, 31(8): 2412231.

Luo Yu-Xin, Wang Jing-Jing, Wang Lu, Yan Zi-Yi, Ma Yi, Bo Xin, Dang Jing-Shuang, Wang Zeng-Lin. Effect of Saccharin on Crystallization Behavior of Electroless Cobalt Plating[J]. Journal of Electrochemistry, 2025, 31(8): 2412231.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3533

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I8/2412231

图/表 8

参考文献 36

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Step	Content	Condition
Degreasing	NaOH 80 g·L^-1, NaCO₃ 15 g·L^-1, Na₃PO₄ 30 g·L^-1	80 °C, 15 min
Swelling	NMP 100 ml·L^-1, NaOH, 90 g·L^-1, DGBE 20 ml·L^-1	60 °C, 10 min
Micro-etching	H₂SO₄ 12.3 mol·L^-1, MnO₂, 30 g·L^-1	70 °C, 20 min
Neutralization	98% H₂SO₄ 100 ml·L^-1, OA 28.2 g·L^-1	60 °C, 10 min
Presoak	OPC-SALT 250 g·L^-1	Room Temp., 2 min
Activation	35% HCl 30 ml·L^-1, OPC-SALT 170 g·L^-1, OPC-80 50 ml·L^-1	Room Temp., 6 min
Sensitization	5% HCl 100 ml·L^-1	Room Temp., 10 min