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Effect of Reverse Pulse on Additives Adsorption and Copper Filling for Through Silicon Via
Journal of The Electrochemical Society ( IF 3.9 ) Pub Date : 2018-08-07 , DOI: 10.1149/2.0021901jes
Q. S. Zhu 1 , X. Zhang 1 , C. Z. Liu 2 , H. Y. Liu 3
Affiliation  

In order to develop the suitable Cu electrolyte for TSV filling using period pulse reverse (PPR) electroplating, the operating mechanism of reverse pulse on the adsorption of additives within TSV was systematically investigated. Whether the promotion or reduction of the adsorption of polyethylene glycol (PEG), bis (sodiumsulfopropyl) disulfide (SPS) and Janus Green B (JGB) by reverse pulse was determined by the charge of the formed complex of this additive with Cu+ and Cl. The charge of formed complex was dependent on the Cl concentration. The reverse pulse had no significant effect on the adsorption of single JGB. In comparison, the composite JGB-PEG inhibitor could be repelled by reverse pulse at the microvia bottom. For the composite PEG-SPS or PEG-JGB-SPS, since the preferentially adsorbed Cu+-Cl-PEG dense layer could effectively block the transportation of Cl, few sites of Cl were left for the SPS adsorption and then mainly formed positively charged SPS-Cu+, which accounted for the detachment of SPS by anodic pulse current at microvia entrance in the presence of PEG. Based on the change of the additives coverage surface by reverse pulse, the microvia filling performances in PPR plating compared to those in DC plating could be well explained.

中文翻译:

反向脉冲对硅通孔中添加剂吸附和铜填充的影响

为了开发适用于周期性脉冲反向(PPR)电镀TSV填充的Cu电解液,系统地研究了反向脉冲对TSV内添加剂吸附的作用机理。反向脉冲是促进还是降低聚乙二醇(PEG),双(磺丙基丙基)二硫化物(SPS)和Janus Green B(JGB)的吸附,取决于该添加剂与Cu +和Cl形成的配合物的电荷-。电荷形成的复合物是依赖于氯-专注。反向脉冲对单个JGB的吸附没有显着影响。相比之下,复合JGB-PEG抑制剂可被微孔底部的反向脉冲排斥。对于复合PEG-SPS或PEG-JGB-SPS中,由于优先吸附的Cu + -Cl - -PEG致密层可以有效地阻断Cl组成的交通- ,氯的几个网站-被留为SPS吸附,然后主要形成带正电的SPS-Cu +,这是由于存在PEG时微孔入口处的阳极脉冲电流导致SPS脱离的原因。基于反向脉冲改变的添加剂覆盖表面,可以很好地解释PPR镀层与DC镀层相比的微孔填充性能。
更新日期:2018-08-07
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