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电化学(中英文) ›› 2022, Vol. 28 ›› Issue (6): 2104531.  doi: 10.13208/j.electrochem.210453

• 综述 • 上一篇    下一篇

酸性镀铜添加剂开发及应用技术

邹浩斌1, 谭超力1, 熊伟1, 席道林2, 刘彬云3,*()   

  1. 1.光华科学技术研究院(广东)有限公司, 广东 广州 510288
    2.广东东硕科技有限公司, 广东 广州 510288
    3.广东光华科技股份有限公司, 广东 汕头 515021
  • 收稿日期:2022-02-28 修回日期:2022-06-09 出版日期:2022-06-28 发布日期:2022-06-12
  • 通讯作者: 刘彬云 E-mail:beston@ghtech.com

Introduction of Development and Application Technology of Organic Additives for Acid Copper Electroplating

Hao-Bin Zou1, Chao-Li Tan1, Wei Xiong1, Dao-Lin Xi2, Bin-Yun Liu3,*()   

  1. 1. Guanghua Institute of Sci-Tech(Guangdong) Co., Ltd, Guangzhou, Guangdong 510288, China
    2. Guangdong Toneset Sci-Tech Co., Ltd., Guangzhou, Guangdong 510288, China
    3. Guangdong Guanghua Sci-Tech Co., Ltd., Shantou, Guangdong 515021, China
  • Received:2022-02-28 Revised:2022-06-09 Published:2022-06-28 Online:2022-06-12
  • Contact: Bin-Yun Liu E-mail:beston@ghtech.com

摘要:

酸性镀铜是积层法多层板制造工艺中的关键技术,是实现基板内部任意层间互连与高密度互连的重要技术方法。本文介绍了酸性镀铜添加剂的主要研究重点、场景化电镀技术开发以及相关应用技术研究,主要使用计时电位法与线性扫描伏安法研究了不同结构类型整平剂在铜电沉积过程中的电流-电压关系曲线,用于定性判断添加剂的吸、脱附情况及阴极极化能力,结合凝胶色谱技术研究自主合成聚合物包括整平剂与抑制剂的分子量与分布系数,并概括了已经成熟商品化的不同场景下的填孔电镀技术类型及其优势,同时针对填孔电镀工艺中常见的应用技术的问题进行了简要阐述,以供业界参考与借鉴。

关键词: 积层法多层板, 酸性镀铜, 填孔, 整平剂, 竞争吸附, 电化学

Abstract:

Acid copper electroplating is one of the key technologies in buildup multilayer PCB (BUM-PCB) manufacture process and the most important technique to achieve electrical interconnection between any layer and high-density interconnection in a substrate. This article introduces the research focus of organic additives used in acid copper electroplating, and developing different kinds of micro-via filling copper electroplating technique applied in various scenarios, and some other technical problems from applications. First of all, according to the chronopotentiometric (CP) experiment results, the levelers with different polymeric molecular structures exhibited various responses of cupric deposition potential along with their increased concentrations, which is the critical information for studying the absorption and desorption behaviors of organic additives, and provides reasonable advices for additives formula design. Linear sweeping voltammetric (LSV) study is very helpful for studying the absorption behavior of organic additives under different potentials and quantitatively describing the degree of current change because of potential polarization that helps evaluate the stability of micro-via filling performance of particular additive formular. Secondly, with the use of gel permeation chromatography (GPC) we have widely studied polymer molecular structure in the aspect of molecular weight and polydispersity, which includes carrier and leveler. The precise information of polymeric molecular structure obtained from experiments can greatly enhance comprehension of the absorption mechanism of polymer additives. Corresponding electrochemical experiment results show that there is obvious correlation between molecular weight of carrier and its suppression effect. Examples of polymerization reaction of some levelers with novel molecular structure are presented, which aims at studying the influence of steric hindrance on electrochemical or electroplating performance by adjusting the length of carbon chain between two aminos and the number of heteroatom, like oxygen atom. Thirdly, different kinds of micro-via filling copper electroplating technique applied in various scenarios have been developed, which includes high-speed micro-via filling copper electroplating technique, ultrathin thickness controlled micro-via filling copper electroplating technique, highly uniform pattern line and micro-via filling copper electroplating technique, through hole and micro-via filling copper electroplating technique and through hole filling copper electroplating technique. Finally, technical problems from application of additives are simply introduced here. Copper plating equipment is the workplace for plating solution and its structure design and process parameters will profoundly affect the micro-via filling performance in the aspect of flow field and electric field. Large void is very easy to be formed inside micro-via under improper convection and deposition velocity. Virgin make-up solution (VMS) components also affect micro-via filling performance obviously in coordination with organic additives by changing overpotential of cupric reduction reaction. Precise determination of organic additives in aged plating solution is very challengeable because byproducts accumulated during manufacture have completely different absorption mechanisms compared to fresh plating solution.

Key words: build up multilayer printed circuit board, acid copper electroplating, via filling, leveler, competitive adsorption, electrochemistry