SnAgCuGe钎料组织、熔化、润湿及界面的研究
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摘要
铅和铅的化合物对环境和人体健康有严重的危害。近年来随着微电子、表面组装技术(SMT)的发展,研制面向21世纪的绿色钎料产品以取代传统的锡铅钎料成为钎焊工业所面临的重要课题之一。通过近十年的研发,研究者们发现:在众多无铅钎料中,SnAgCu钎料最有可能成为SnPb铅料的替代品。
对无铅钎料,我国开展研究比较晚,与国外的产品还具有较大的差距。本文选择目前最为常用的Sn-Ag-Cu无铅钎料,通过向其中添加少量的Ge元素,研究了Ge对Sn-Ag-Cu无铅钎料组织、熔化特性和铺展润湿性能的影响,并分析了Ge的添加对Sn-Ag-Cu/Cu界面及对Sn-Ag-Cu/Cu接头老化的影响。
研究结果表明,在所研究的合金系列中,未出现低熔点共晶峰,表明微量锗的添加不会使Sn-Ag-Cu合金产生低熔点共晶成分,有利于在钎焊过程中形成可靠的连接焊点。添加少量锗对Sn-Ag-Cu钎料合金的熔化温度影响不大,熔点温度在217.642℃~218.622℃之间。通过铺展面积的测量得出:当Ge含量为0.5%时,该系钎料具有较大的铺展面积和较小的润湿角。
添加锗元素后,钎料组织中的Ag3Sn和Cu6Sn5相都得到了一定程度的细化,并且其分布状态均匀,使共晶组织中的金属间化合物排列趋于规则。研究了含Ge量不同的Sn-Ag-Cu-Ge钎料与Cu板的钎焊界面。锗含量为1.0%时界面平均厚度最小为2.165μm,并且界面最平坦;锗含量为0.5%时界面厚度最大可达2.37~3.75μm,并且界面整体看来参差不齐。
研究了在150℃的干燥箱中经100h时效后的钎焊接头,三个成分钎料形成的金属间化合物层都有不同程度的长大。Sn-2.5Ag-0.7Cu-1.0Ge/Cu的界面平均厚度最薄为3.94μm。而锗含量为Sn-2.5Ag-0.7Cu-0.5Ge/Cu的界面生长的厚度最大是4.71μm。不含锗的界面厚度为4.275μm。总体来说,在时效的100小时内,由基体向Cu-Sn界面层扩散铜原子的速度大于界面层向钎料扩散的速度,从而导致了界面层的长大。
Lead and its compounds are harmful to environment and human health. In recent years, with the development of microelectronic and Surface Mounted Technology, developing new green solders to replace tin lead solder is becoming one of the most important subjects. After ten years study, researcher found that among all of the lead free solders, SnAgCu solder is the most possible solder to replace tin lead solder.
As our research about lead free solder is latter, we have a great gap compared with abroad. This work choose the most popular solder (Sn-Ag-Cu lead free solder) as experimentl material, adding a small mount of Ge into in, to study the effect of Ge to its microstructure,melting characteristic and spreading wettability, and how Ge effect the interface of Sn-Ag-Cu/Cu, and its effect on Sn-Ag-Cu/Cu joint after aging.
The result shows that, there is no low-melting eutectic substance formed in the Sn-Ag-Cu alloy, because there is no low-melting eutectic peak in all the alloys. This can form reliable spot weld. Ge has small effect on Sn-Ag-Cu solder’s melting temperature. Its melting temperature is between 217.642℃and 218.622℃. According to measure the spreading area: when adding 0.5% Ge, the solder has lager spreading area and smaller wetting angle.
After adding Ge into the solder, the Ag3Sn phase and Cu6Sn5 phase are refined, and their distribution become homogeneous, and the arrangement of intermetallic compounds become more regulation.
Studied the interface of Sn-Ag-Cu-Ge solder and Cu plate. When the amount of Ge is 1.0%, the interface has the smallest thickness(2.165μm), and the interface is flattest. When the amount of Ge is 0.5%, the interface’s thickness is between 2.37~3.75μm, and the interface is unflat.
Studied the soldering joint after aging 100 hours at 150℃in drying cabinet, the intermetallic compounds in the three solders are all growed up. Sn-2.5Ag-0.7Cu-1.0Ge/Cu has the thinnest interface (3.94μm). Sn-2.5Ag-0.7Cu-0.5Ge/Cu has the thickest interface (4.71μm). Generally speaking, the speed of Cu atom from the basic body to the Cu-Sn boundary layer is higher than the speed of Cu atom from boundary layer to the solder, that makes the boundary layer grow up,when aging 100 hours.
对无铅钎料,我国开展研究比较晚,与国外的产品还具有较大的差距。本文选择目前最为常用的Sn-Ag-Cu无铅钎料,通过向其中添加少量的Ge元素,研究了Ge对Sn-Ag-Cu无铅钎料组织、熔化特性和铺展润湿性能的影响,并分析了Ge的添加对Sn-Ag-Cu/Cu界面及对Sn-Ag-Cu/Cu接头老化的影响。
研究结果表明,在所研究的合金系列中,未出现低熔点共晶峰,表明微量锗的添加不会使Sn-Ag-Cu合金产生低熔点共晶成分,有利于在钎焊过程中形成可靠的连接焊点。添加少量锗对Sn-Ag-Cu钎料合金的熔化温度影响不大,熔点温度在217.642℃~218.622℃之间。通过铺展面积的测量得出:当Ge含量为0.5%时,该系钎料具有较大的铺展面积和较小的润湿角。
添加锗元素后,钎料组织中的Ag3Sn和Cu6Sn5相都得到了一定程度的细化,并且其分布状态均匀,使共晶组织中的金属间化合物排列趋于规则。研究了含Ge量不同的Sn-Ag-Cu-Ge钎料与Cu板的钎焊界面。锗含量为1.0%时界面平均厚度最小为2.165μm,并且界面最平坦;锗含量为0.5%时界面厚度最大可达2.37~3.75μm,并且界面整体看来参差不齐。
研究了在150℃的干燥箱中经100h时效后的钎焊接头,三个成分钎料形成的金属间化合物层都有不同程度的长大。Sn-2.5Ag-0.7Cu-1.0Ge/Cu的界面平均厚度最薄为3.94μm。而锗含量为Sn-2.5Ag-0.7Cu-0.5Ge/Cu的界面生长的厚度最大是4.71μm。不含锗的界面厚度为4.275μm。总体来说,在时效的100小时内,由基体向Cu-Sn界面层扩散铜原子的速度大于界面层向钎料扩散的速度,从而导致了界面层的长大。
Lead and its compounds are harmful to environment and human health. In recent years, with the development of microelectronic and Surface Mounted Technology, developing new green solders to replace tin lead solder is becoming one of the most important subjects. After ten years study, researcher found that among all of the lead free solders, SnAgCu solder is the most possible solder to replace tin lead solder.
As our research about lead free solder is latter, we have a great gap compared with abroad. This work choose the most popular solder (Sn-Ag-Cu lead free solder) as experimentl material, adding a small mount of Ge into in, to study the effect of Ge to its microstructure,melting characteristic and spreading wettability, and how Ge effect the interface of Sn-Ag-Cu/Cu, and its effect on Sn-Ag-Cu/Cu joint after aging.
The result shows that, there is no low-melting eutectic substance formed in the Sn-Ag-Cu alloy, because there is no low-melting eutectic peak in all the alloys. This can form reliable spot weld. Ge has small effect on Sn-Ag-Cu solder’s melting temperature. Its melting temperature is between 217.642℃and 218.622℃. According to measure the spreading area: when adding 0.5% Ge, the solder has lager spreading area and smaller wetting angle.
After adding Ge into the solder, the Ag3Sn phase and Cu6Sn5 phase are refined, and their distribution become homogeneous, and the arrangement of intermetallic compounds become more regulation.
Studied the interface of Sn-Ag-Cu-Ge solder and Cu plate. When the amount of Ge is 1.0%, the interface has the smallest thickness(2.165μm), and the interface is flattest. When the amount of Ge is 0.5%, the interface’s thickness is between 2.37~3.75μm, and the interface is unflat.
Studied the soldering joint after aging 100 hours at 150℃in drying cabinet, the intermetallic compounds in the three solders are all growed up. Sn-2.5Ag-0.7Cu-1.0Ge/Cu has the thinnest interface (3.94μm). Sn-2.5Ag-0.7Cu-0.5Ge/Cu has the thickest interface (4.71μm). Generally speaking, the speed of Cu atom from the basic body to the Cu-Sn boundary layer is higher than the speed of Cu atom from boundary layer to the solder, that makes the boundary layer grow up,when aging 100 hours.
引文
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14 G. W. Handwerker. Americal Lead-Free Dynamical Research. J. Electron. Mater, 1998, 38(12): 968~971
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2 况延香.迈向新世纪的微电子封装技术.电子工艺技术,2001,(1):1~6
3 R. P. Prasad. Surface Mount Technology Principles and Practice. Van Nastrand Reinhold, 1989,17(4): 215~228
4 E. P. Wood, K. L. Nimmo. Lead-Free Solders for Electronic Packaging. J. Eloctron, 1994, 23(8): 709~714
5 C. E. Homer, H. C. Watkins. Reliability Inventigation and Interfacial Reaction of Ball-Grid-Array Packages Using the Lead-Free Sn-Cu solder. MetalInd, 1992, 26(2):364~366
6 M. R. Harrison, J. H. Vincent, Proc. 12th European Microelectronics & Packaging Conference. IMAPS Europe, 1999, 12(5): 98~104
7 Katsuaki Suganuma. The Current Status of Lead-free Soldering. NPL&ITRL Technology Report, 2001, 23(5): 67~69
8 薛松柏,钱乙余.创新、环保-21 世纪我国钎焊与扩散焊的发展方向.焊接,2000,(1):1~4
9 M. McCormack, S. Jin. New Lead-free Solder Alloy with Superior Mechanical Properties. Appl. Phys. Lett, 1993, 63(1): 15~18
10 庄鸿寿.无铅软钎料的新进展.电子工艺技术,2001,22(5):192~196
11 P. T. Vianco, J. A. Rejent. Properties of Ternary Sn-Ag-Bi Solder Alloys:Part I-thermal Properties and Microstructural Analysis. J. Electron. Mater, 1999, 28(10): 1127~1136
12 J. W. Moms. High Temperature Deformation of Polycrystalline Sn-Bi Solid of Structure. J. Electron. Mater, 1992, 8(21): 599~607
13 J. A. Glazer. Metalurgy of Low Temperature Pb-free Solders for Electronic Assembly. Int. Mater Rev, 1995, 40(2): 65~93
14 G. W. Handwerker. Americal Lead-Free Dynamical Research. J. Electron. Mater, 1998, 38(12): 968~971
15 J. W. Morris, L. F. Goldstein, Z. Mei. Microstructure and Mechanical Properties of Sn-In and Sn-Bi Solders. J. Electron. Mater, 1993, 9(23): 25~27
16 H. Kabassis, J. W. Rutter, W. C. Winegard. Phase Relationships in Bi-In-Sn Alloys Systems. Mater. Sci. Technol, 1986, 13(2): 985~988
17 G. Ghosh, M. Loomans, M. E. Fine. An Investigation of Phase Equilibria of Bi-Sb-Sn system. J. Electron. Mater, 1994, 17(23): 619~621
18 S. W. Yoon, B. S. Rho, H. M. Kim, et al. Sn2.5Ag0.5Cu Lead-Free Solder Balls with “Ge” and “Ni”. J. Electron. Mater, 1999, 24(30): 1503~1507
19 C. A. Mackay, W. D. Voss. The Interfacial Reaction between Sn-Zn-Ag-Ga-Al Solders and Metallized Cu Substrates. Mater. Sci. Technol, 1985, 24(10):57~59
20 W. J. Tomlinson. Residual Shear Strength of Sn-Ag and Sn-Bi Lead-free SMT Joints after Thermal Shock. J. Mater. Sci, 1992, 11(27): 557~559
21 J. M. Song. Microstructure and Tensile Properties of Sn-9Zn-xAg Lead-free Solder Alloys. Scripta Materialia, 2003, 9(48): 1047~1051
22 于大全,赵杰,王来.稀土元素对 Sn-9Zn 合金润湿性的影响.中国有色金属学报,2003,13(4):1001~1004
23 C. M. Wu, D. Q. Yu, L. Wang, The Wettability and Microstructure of Sn-Zn-RE Alloys. J. Electron. Mater, 2003, (32): 63~69
24 C. M. Wu, D. Q. Yu et al. The Properties of Sn-9Zn Lead-free Solder Alloys Doped with Trace Rare Earth Elements. J. Electronic. Mater, 2002, (31): 921~927
25 T. H. Chuang, S. F. Yen, M. D. Cheng. An Analysis of the Current Status of Lead-Free Soldering. NPL&ITRL Report, 1999, (8): 67~70
26 J. Seyyedi. Contact Angle Measyrements of Sn-Ag and Sn-Cu Lead-Free Solders on Copper Substrates. Soldering Surf. Mount Technol, 1993, 13(26): 82~85
27 J. L. Freer, J. W. Morns. Effect of Structural Transformation on the Creep Parameters of Sn-9.8In Alloy. J. Electron. Mater, 1992, 6(21): 647~649
28 H. Ohtani, K. Ishida. A Thermodynamic Study of the Phase Equilibria in the Bi-Sn-Sb System. J. Electron. Mater, 1994, 18(23): 747~749
29 J. Glazer. Metallurgy of Low Temperature Pb-free Solders for Electronic Assembly. Int. Mater. Rev, 1995, 40(2): 65~93
30 于大全.电子封装互连无铅钎料及其界面问题研究.大连理工大学博士论文,2004:6~8
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