电子科学技术 Electronic Science & Technology [6-7] [8] - [9] [10] [11] [12] [13] [14] [10, 15] 实验部分 CuSO 4 80 NaHCO CO rpm15min

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1 电子科学技术第期卷第 01 期 2015 年 1 月 Electronic 肖定军等 Science & Technology : 用于电镀液使 HDI 板孔金属化的电子级氧化铜研究 Vol.02 No.01 Jan.2015 用于电镀液使 HDI 板孔金属化的电子级氧化铜研究肖定军, 谭泽, 刘彬云 ( 广东光华科技股份有限公司, 汕头,515000) 摘要 : 高密度互连 HDI 中的微盲孔技术对于印制电路板的发展是十分重要的聚合多孔微板型的电子级氧化铜是通过碱式碳酸铜的热分解法来制备的所得的多孔氧化铜粒度分布范围为 m 溶解速率为 9s 纯度达 99.87% 将氧化铜用于带不溶性阳极的电镀体系中能对铜离子浓度进行有效补充将电子级氧化铜粉末应用于电镀铜工艺能使高厚径比的通孔微盲孔以及 HDI 板上组合的通孔与微盲孔形成高性能的铜镀层关键词 : 氧化铜电沉积通孔微盲孔 HDI 中图分类号 : O69 文献标识码 :A 文章编号 : (2015) 电子科学技术 URL: http// DOI: /j.issn Studies of Electronic-grade Copper Oxide and its Application to Copper Electroplating Solution for Via Metallization of HDI Printed Circuit Board Dingjun Xiao, Ze Tan, Binyun Liu (Guangdong Guanghua Sci-Tech Co., Ltd.,Shantou, , China) Abstract: Microvias for high-density interconnection (HDI) are important for the development of printed circuit boards. Electronic-grade copper oxide with aggregated porous microplates was prepared from thermal decomposition of basic copper carbonate. Porous copper oxide exhibited a particulate distribution mainly ranging from 25μm to 88μm. Copper oxide exhibited a high dissolution rate of 9s and a purity of 99.87wt%. Copper oxide was employed to complement the concentration of cupric ions in a plating system with insoluble anode. Electronic-grade copper oxide could be used for copper electrodeposition to form high-performance metallization of through holes with a high aspect ratio, microvias, and combination of through holes and microvias in HDI printed circuit boards. Key words: Copper oxide; Electrodepostion; Through hole; Microvia, HDI 引言 PCB HDI [1-2] [3-5] 43

电子科学技术 Electronic Science & Technology [6-7] [8] - [9] [10] [11] [12] [13] [14] [10, 15] 400 450 1 实验部分 CuSO 4 80 NaHCO 3 70 80 CO 2 1000 2000rpm15min 400 450 R1 R2 R1 2CuSO 4 +4NaHCO 3 = CuCO 3

2 电子科学技术 Electronic Science & Technology [6-7] [8] - [9] [10] [11] [12] [13] [14] [10, 15] 实验部分 CuSO 4 80 NaHCO CO rpm15min R1 R2 R1 2CuSO 4 +4NaHCO 3 = CuCO 3 Cu(OH) 2 +2Na2SO 4 +3CO 2 +H 2 O R2 CuCOv Cu(OH) 2 = 2CuO+CO 2 +H 2 O SEM X XRD ICP-AES 4.2g80mL 12.5% v/v Autolab 2015 年 1mm SSE PCB SEMEDS s 2 结果与讨论 2.1 氧化铜的表征 1a 1b-d CO 2 CO 2 1 a b-d SEM 2 50nm 100μm 50% 25 88μm 20% 1 10μm 44

3 第 01 期肖定军等 : 用于电镀液使 HDI 板孔金属化的电子级氧化铜研究 1d 2.2 氧化铜的应用 12.5%v/v 4 0.9s 0.9s 1.4s-0.496V V 9.5s V 0.9s H+ H+ 2 XRD 3 [10,13] [16] 3 XRD [0 0 2] [1 1 1] ICP 99.87% 10ppm 9ppm Cl Fe Pb Zn Ni Mn Ca Mg 10ppm 3ppm 5ppm 1ppm 1ppm 1ppm 5ppm 5ppm XRD ICP %V/V H 2 SO s H 2 SO 4 CuSO μm 由可溶性氧化铜形成的镀铜层的性能 3 XRD TP 92% TP 70μm 125μm 45

4 电子科学技术 Electronic Science & Technology 95% 6μm 15μm 25μm 29μm 2015 年 1 0.8:1 2:1 3.2:1 TP 92% 77% 72% 2 : 70μm : 70μm : 70μm : 85μm : 100μm : 125μm : 150μm : 100μm (Dimple) 12 μm 6 μm 12 μm 9 μm TP 90% 95% 89% 92% 3 5a EDS 5b 6 HDI 5 SEM a EDS b 46

第 01 期肖定军等 : 用于电镀液使 HDI 板孔金属化的电子级氧化铜研究 6 3 结论 SEM XRD ICP Autolab SEM EDS 25μm 88μm 99.87%wt 25 9s TP dimple HDI 基金项目 No.2012A090100009 参考文献 [3] [4] [5] [6] [7] [8] [9] Society 152.6, pp.

5 第 01 期肖定军等 : 用于电镀液使 HDI 板孔金属化的电子级氧化铜研究 6 3 结论 SEM XRD ICP Autolab SEM EDS 25μm 88μm 99.87%wt 25 9s TP dimple HDI 基金项目 No.2012A 参考文献 [3] [4] [5] [6] [7] [8] [9] Society 152.6, pp. C425-C434, Q. Huanga, B. C. Baker-O Neala, C. Parksb, M. Hopstakena, A. Fluegelc, C. Emnetc, M. Arnoldc and D. Mayerc. Leveler Effect and Oscillatory Behavior during Copper Electroplating. Journal of The Electrochemical Society, 159.9, pp. D526-D531, S. K. Kang, S. L. Buchwalter, N. C. LaBianca, J. Gelorme, K. Papathomas and M. Poliks. Development of conductive adhesive materials for via fill applications.ieee Transactions on Components and Packaging Technologies, 24.3, pp , R. Kisiel, J. Felba, J. Borecki and A. Moscicki. Problems of PCB microvias filling by conductive paste.microelectronics Reliability, 47(2), pp , J. Barthelmes. Acid Copper Plating with Insoluble Anodes-A Novel Technology in PCB Manufacturing.TRANSACTIONS- INSTITUTE OF METAL FINISHING, 78(4), pp , X. Xu, H. Liu, W. Li and L. Zhu. A novel corrosion selfprotective copper/liquid microcapsule composite coating. Materials Letters, 65(4), pp , J. B. Haydu, E. H. Too and R. W. Hurtubise. Copper metallization of silicon wafers using insoluble anodes: U.S. Patent 6,024, M. A. Gondal, T. F. Qahtan, M. A. Dastageer, T. A. Salehb, Y. W. Magandaa and D.H. Anjum. Effects of oxidizing medium on the composition, morphology and optical properties of copper oxide nanoparticles produced by pulsed laser ablation.applied [1] W. P. Dow, C. C. Li, Y. C. Su, S. P. Shen, C. C. Huang, C. Lee, Surface Science, 286, pp , B.Hsu and S. Hsu. Microvia filling by copper electroplating [10] Z. Hong, Y. Cao and J. Deng. A convenient alcohothermal using diazine black as a leveler.electrochimica Acta, 54(24), approach for low temperature synthesis of CuO nanoparticles. pp , Materials letters, 52(1), pp , [2] W. P. Dow, H. Huang, M. Y. Yen and H. C. Huang. Influence of [11] R. V. Kumar, Y. Diamant and A. Gedanken. Sonochemical convection-dependent adsorption of additives on microvia filling synthesis and characterization of nanometer-size transition metal by copper electroplating.journal of The Electrochemical oxides from metal acetates.chemistry of Materials, 12(8), pp. 47

电子科学技术 Electronic Science & Technology 2015 年 2301-2305, 2000. [12] H. Wang, J. Z. Xu, J. J. Zhu and H. Y. Chen. Preparation of CuO nanoparticles by microwave irradiation.

6 电子科学技术 Electronic Science & Technology 2015 年 , [12] H. Wang, J. Z. Xu, J. J. Zhu and H. Y. Chen. Preparation of CuO nanoparticles by microwave irradiation.journal of crystal growth, 244(1):, pp , [13] X. Jiang, T. Herricks and Y. Xia. CuO nanowires can be synthesized by heating copper substrates in air.nano Letters, 2(12), pp , [14] C. Y. Chiang, K. Aroh, N. Franson, V. R. Satsangi, S. Dass and S. Ehrman. Copper oxide nanoparticle made by flame spray pyrolysis for photoelectrochemical water splitting Part II. Photoelectrochemical study.international Journal of Hydrogen Energy, 36(24), pp , 作者简介 : 肖定军 (1970-) 2002 年毕业于中山大学化学与化学工程学院有机化学专业获博士学位 2005 年加入广东光华科技股份有限公司一直从事电子化学品方面的研究开发工作 xiaodj@gic.ac.cn 48

ph ph ph Langmuir mg /g Al 2 O 3 ph 7. 0 ~ 9. 0 ph HCO - 3 CO 2-3 PO mg /L 5 p

ph ph ph Langmuir mg /g Al 2 O 3 ph 7. 0 ~ 9. 0 ph HCO - 3 CO 2-3 PO mg /L 5 p 1 2 1 2 3 1 2 1. 100054 2. 100054 3. 100036 ph ph ph Langmuir 166. 67 mg /g Al 2 O 3 ph 7. 0 ~ 9. 0 ph HCO - 4 5. 00 mg /L 5 ph doi 10. 13928 /j. cnki. wrahe. 2017. 03. 017 TV213. 4 + TU991. 26 + 6 A 1000-0860