李立清,安文娟,王义.MPS和氯离子在电镀铜盲孔填充工艺中的作用机理[J].表面技术,2018,47(5):122-129.
LI Li-qing,AN Wen-juan,WANG Yi.Action Mechanism of MPS and Chloride Ions in Electroplating Copper Microvia Filling[J].Surface Technology,2018,47(5):122-129 |
| MPS和氯离子在电镀铜盲孔填充工艺中的作用机理 |
| Action Mechanism of MPS and Chloride Ions in Electroplating Copper Microvia Filling |
| 投稿时间：2018-01-22 修订日期：2018-05-20 |
| DOI：10.16490/j.cnki.issn.1001-3660.2018.05.018 |
| 中文关键词: MPS 氯离子 电镀 盲孔 作用机理 |
| 英文关键词:MPS chloride ion electroplating microvia mechanism |
| 基金项目:中国博士后基金（2016M592118）；江西省博士后基金（2015KY11，2015RC17）；江西省杰出人才基金（20171BCB23065） |
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| 中文摘要: |
| 目的 揭示MPS（3-巯基-1-丙烷磺酸钠）和氯离子在电镀铜盲孔填充中的作用，并获得相应的机理模型。方法 在既定的电镀铜基础液中添加MPS和氯离子，研究其对TP值（盲孔率）的影响，并用金相显微镜观察。通过测定阴极极化曲线和计时电流曲线，分析其对反应过程中氧化还原性质的影响。结果 在MPS单一体系中，MPS会与Cu+形成-S-Cu+络合物和-SO 3-Cu+络合物，且MPS质量浓度在6 mg/L时抑制作用达到最好，MPS加入到基础液后会使阴极电流密度正移、平衡电位负移，表明MPS此时起到了抑制铜离子沉积的作用。在MPS-氯离子复合体系中，MPS能够形成MPS-Cu+-Cl络合物，当MPS质量浓度为6 mg/L、氯离子质量浓度为60 mg/L时，加速作用达到最大，由于氯离子的存在，MPS加入到基础液后会使阴极电流密度负移、平衡电位正移，表明MPS此时起到了加速铜离子沉积的作用。结论 MPS在没有氯离子时会形成-S-Cu+和-SO 3-Cu+络合物而起到抑制作用，在有氯离子时会形成MPS-Cu+-Cl-络合物而起到加速作用。同时提出了这些络合物都会以“单分子层”形式吸附于盲孔底部的理论模型，这能很好地解释实验过程。 |
| 英文摘要: |
| The work aims to study the effect of MPS (Sodium 3-mercapto-1-propanesulfonate) and Cl in electroplating copper microvia filling and obtain the corresponding action mechanism model. MPS and Cl were added into prepared electrocoppering liquid to study the effects on TP value (microvia rate) and observed by metalloscope. The effects of oxidation-reduction property during reaction were studied by measuring cathodic polarization curve and design current curve. MPS and Cu+ in single MPS system formed compounds of -S-Cu+ and -Cu+ and the inhibition effect reached the best when MPS concentration was 6 mg/L. MPS added into basic liquid caused positive shift of cathode-current density and negative shift of equilibrium potential and inhibited the disposition of Cu+. In MPS-Cl compound system, MPS formed compounds of MPS-Cu+-Cl and the acceleration reached the maximum when MPS concentration was 6 mg/L and Cl was 60 mg/L. Due to Cl, MPS added into basic liquid caused positive shift of cathode-current density and negative shift of equilibrium potential and accelerated the disposition of Cu+. MPS can inhibit the deposition when forming compounds of -S-Cu+ and -SO 3-Cu+ due to lack of Cl, but can accelerate the desposition when formimg compounds of MPS-Cu+-Cl with Cl. The theoretical model for compounds adsorbing at microvia bottom in form of “single molecular layer” can explain the experiment process clearly. |
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