三种典型Sn-Ag-Cu无铅钎料的组织和性能研究

对比研究了三种典型标称成分的Sn-Ag-Cu钎料(即日本JEIDA推荐的Sn-3.0Ag-0.5Cu、欧盟IDEALS推荐的Sn-3.8Ag-0.7Cu和美国NEMI推荐的Sn-3.9Ag-0.6Cu)的显微组织特征、熔化特性、润湿性以及钎焊接头微焊点的力学性能等。结果表明,三种钎料的组织和性能非常接近。然而从性价比等方面综合考虑,Sn-3.0Ag-0.5Cu为三种钎料中最具优势的替代传统Sn-Pb钎料(共晶和近共晶钎料)的无铅合金。     

Generation of Tin(II) Oxide Crystals on Lead-Free Solder Joints in Deionized Water

The effect of the anode and cathode on the electrochemical corrosion behavior of lead-free Sn-Ag-Cu and Sn-Ag-Cu-Bi solder joints in deionized water was investigated. Corrosion studies indicate that SnO crystals were generated on the surfaces of all lead-free solder joints. The constituents of the lead-free solder alloys, such as Ag, Cu, and Bi, did not affect the corrosion reaction significantly. In contrast to lead-free solders, PbO _x was formed on the surface of the traditional 63Sn-37Pb solder joint in deionized water. A cathode, such as Au or Cu, was necessary for the electrochemical corrosion reaction of solders to occur. The corrosion reaction rate decreased with reduction of the cathode area. The formation mechanism of SnO crystals was essentially a galvanic cell reaction. The anodic reaction of Sn in the lead-free solder joints occurred through solvation by water molecules to form hydrated cations. In the cathodic reaction, oxygen dissolved in the deionized water captures electrons and is deoxidized to hydroxyl at the Au or Cu cathode. By diffusion, the anodic reaction product Sn²⁺ and the cathodic reaction product OH⁻ meet to form Sn(OH)₂, some of which can dehydrate to form more stable SnO·xH₂O crystals on the surface of the solder joints. In addition, thermodynamic analysis confirms that the Sn corrosion reaction could occur spontaneously.     

无铅焊料的选择与对策（未完待续）

通过大量的数据信息分析了各研究机构在无铅焊料方面的研究成果，在目前流行使用的无铅焊料的基础上，进一步研究并比较了其中的Sn-Cu系列与具有专利限制的SnAgCu系列焊料在消费类电子产品组装的波峰焊工艺中使用的可靠性，同时研究并比较Sn-Ag系列焊料与SnAgCu系列焊料在回流焊工艺使用的情况。结果表明，Sn-Cu共晶焊料在消费类电子产品组装的波峰焊工艺中完全可以取代Sn-Ag-Cu系列焊料，同时满足使用要求；而同样技术成熟的Sn-Ag共晶焊料也完全可以取代SnAgCu系列焊料在回流焊工艺使用，焊点的可靠性与成本可以媲美SnAgCu焊料。而且该二元合金在使用维护以及回收利用方面具有相当的优势。     

A reliability study of the lead-free solder connections of miniature chip components on hybrid circuits

The results of the influence of lead-free solder paste, design and process parameters on the attachment reliability of chip surface-mounted components (SMCs) on thick-film conductor pads are presented. The purpose of the investigation was to compare the quality of the soldered joints made with new solder pastes that do not contain lead with joints soldered with standard SnPb solders. The miniature zero-ohm chip resistors were soldered with selected lead-free solder pastes. The visual appearance of the solder joint according to the standards of lead-free soldered components was compared with components soldered with SnPb solders. On the test sample with soldered chip resistors connected in series, the solder-joint resistance was measured before and after temperature cycling. On the same test sample the solder-joint resistance changes were measured with impedance spectroscopy. After temperature cycling the damaged samples were analysed with SEM and EDS. The reliability test results after temperature cycling indicate two lead-free solder pastes that are the most convenient for chip-component soldering on thick-film conductor pads with the reliability of the joints being equal or better than solder joints with Pb-containing solder paste.     

电子组装用高温无铅钎料的研究进展

分析了国内外电子组装用高温无铅钎料的研究现状。指出目前常用的高温钎料仍然是高Pb焊料或80Au-20Sn钎料,导致焊料含Pb而污染环境,或者含质量分数为80%的Au而使焊料成本奇高。指明了Bi-Ag系钎料具有潜力替代高Pb焊料或80Au-20Sn钎料。未来的研究将在成分设计及可靠性等方面进行探索,以最终找到既经济又可替代传统高铅钎料的高温无铅钎料。     

Evaluation of Lead- Free Solder Joints in Electronic Assemblies

The feasibility of printed circuit board assembly with lead-free solder alloys was investigated. Studies were conducted with two baseline eutectic binary alloys, SnBi and SnAg, and three new lead-free solder formulations: (1) 91.8Sn-4.8Bi-3.4Ag (wt%) developed at Sandia Laboratories, (2) 77.2Sn-20In-2.8Ag developed at Indium Corp. of America, and (3) 96.2Sn-2.5Ag-0.8Cu-0.5Sb provided by AIM Inc. The basic physical properties (melting temperature, wetting, mechanical strength) pertinent to each of the newly developed alloys are described. The feasibility of 0.4 mm pitch assembly was established with each of the lead-free solder alloys investigated, although the processing windows were generally found to be narrower. All solder joints exhibited good fillets, in accordance with the workmanship standards. Wetting of the lead-free solders was significantly improved on immersion tin vs imidazole finished circuit boards. The laminates did not suffer thermal degradation effects, such as warpage, delamination, or severe discoloration (reflow was performed under an inert atmosphere). It is thus concluded that the manufacturability performance of the new solder formulations is adequate for surface mount applications.     

The effect of solder paste composition on the reliability of SnAgCu joints

As the electronics industry is moving towards lead-free manufacturing processes, more effort has been put into the reliability study of lead-free solder materials. Various tin–silver–copper-based solders have become widely accepted alternatives for tin–lead solders. In this study, we have tested three different SnAgCu solder compositions. The first consisted of a hypoeutectic 96.5Sn/3.0Ag/0.5Cu solder, the second of a eutectic 95.5Sn/3.8Ag/0.7Cu solder, and the third of a hypereutectic 95.5Sn/4.0Ag/0.5Cu solder. A eutectic SnPb solder was used as a reference. The test boards were temperature-cycled (−40 to +125 °C) until all samples failed. The results of the temperature cycling test were analyzed, and cross-section samples were made of the failed joints. Scanning electron and optical microscopy were employed to analyze the fracture behavior and microstructures of the solder joints. The reliability of lead-free solders and the effect of microstructures on joint reliability are discussed.     

JIS Z 3198无铅钎料试验方法简介与评述

JIS Z 3198是关于无铅钎料及其接合部性能测试的工业标准,由日本焊接协会提出初始提案,经日本工业标准调查会审议,最终由日本经济产业省于2003年6月20日并发布.标准涵盖了无铅钎料熔化温度范围测试、机械特性测试、铺展性测试、润湿性测试、接头的拉伸与剪切强度测试、QFP引线软钎焊接头拉引测试、片式元件软钎焊接头的剪切测试7个方面.依据JIS Z 3198 1-7原文对该标准各部分进行介绍,拟推进我国电子封装与组装的无铅化进程.     

稀土元素对无铅钎料微观结构及性能的影响

添加适量的稀土元素可以有效提高无铅钎料(如SnAgCu,SnZn)的性能,尤其是添加稀土的SnAgCu钎料的蠕变断裂寿命是未添加时的7倍.针对添加微量稀土元素对无铅钎料润湿性、力学性能、蠕变性能以及电迁移行为的影响,特别是对钎料微观结构的变化规律进行了综述,并指出了新型钎料的应用及发展前景.     

三种高Sn无铅钎料的表面张力和润湿性能研究

采用悬滴法测量了3种无铅钎料合金(Sn-3.0Ag-0.5Cu、Sn-0.7Cu与Sn-9.0Zn)在260℃时的表面张力,分别为525.5,534.8和595.4 mN/m;同时采用座滴法测量了其在260℃熔融状态下与Cu基板的接触角,分别为24.5°、28.0°和102.5°,并且与传统Sn-37.0Pb钎料进行了比较研究。结果表明,无铅钎料合金的表面张力与接触角均大于Sn-37.0Pb钎料。结合Young-Dupre公式讨论了钎料合金表面张力与其润湿性能的相关性,认为Sn基钎料合金在Cu基板上的润湿性能主要取决于其表面张力。     

无铅焊料的蠕变行为研究进展

无铅焊料已经逐渐代替锡铅焊料广泛应用于电子产品连接技术。但其在环境中的物理和机械性能,尤其是蠕变性能却低于锡铅焊料合金,成为无铅焊料可靠性的主要问题。综述了近些年来无铅焊料蠕变性能的研究,包括蠕变机制、蠕变本构方程、焊点尺寸、无铅合金成分、金属间化合物以及微观组织结构对蠕变性能影响等主要研究热点,并对此领域的发展做出了展望。     

无铅电子封装材料及其焊点可靠性研究进展

随着2006年7月1日RoHS法令实施的最后期限的来临,无铅焊料的研究与应用又掀起了新一轮的热潮。由于封装材料与封装工艺的改变,给焊点可靠性带来了一系列相关问题。笔者就近年来国内外开发的无铅焊料、焊点的失效模式、焊点可靠性评价方法和焊点的主要缺陷进行了综述;对今后该领域的研究前景及方向进行了展望。     

高温高铅焊料无铅化的研究进展

微电子封装工业中应用于高温领域的高铅焊料的无铅化是一个国际化难题。对目前高温无铅焊料的研究进展进行了综述,包括80Au-20Sn、Bi基合金、Sn-Sb基合金和Zn-Al基合金。从各种焊料的熔化行为、力学性能、导电导热性能、润湿性、界面反应和可靠性等方面,总结了这些高温无铅焊料的特性以及在应用中各自存在的问题。通过比较,认为Sn-Sb基合金在高温领域取代高铅焊料将有很大的应用前景。     

Development of nano-composite lead-free electronic solders

Inert, hybrid inorganic/organic, nano-structured chemicals can be incorporated into low melting metallic materials, such as lead-free electronic solders, to achieve desired levels of service performance. The nano-structured materials technology of polyhedral oligomeric silsesquioxanes (POSS), with appropriate organic groups, can produce suitable means to promote bonding between nano-reinforcements and the metallic matrix. The microstructures of lead-free solder reinforced with surface-active POSS tri-silanols were evaluated using scanning electron microscopy (SEM). Wettability of POSS-containing lead-free solders to copper substrate was also examined. Steady-state deformation of solder joints made of eutectic Sn-Ag solder containing varying weight fractions of POSS of different chemical moieties were evaluated at different temperatures (25°C, 100°C, and 150°C) using a rheometric solids analyzer (RSA-III). Mechanical properties such as shear stress versus simple shear-strain relationships, peak shear stress as a function of rate of simple shear strain, and testing temperature for such nano-composite solders are reported. The service reliability of joints made with these newly formulated nano-composite solders was evaluated using a realistic thermomechanical fatigue (TMF) test profile. Evolution of microstructures and residual mechanical property after different extents of TMF cycles were evaluated and compared with joints made of standard, unreinforced eutectic Sn-Ag solder.     

氮气保护无铅波峰焊焊接质量分析

相对于传统的Sn-Pb焊料,无铅焊料更容易氧化,润湿性较差,从而影响波峰焊接质量.N2保护可以降低无铅焊料的氧化,提高无铅焊料的润湿性,从而提高波峰焊接质量.从润湿性的机理分析了N2保护提高无铅焊料润湿性的原因,并通过润湿性实验和波峰焊接试验证实了N2保护的优越性.     

无铅波峰焊接设备特点

相对于传统的Sn—Pb焊料，无铅焊料需要较高的焊接温度，而且润湿性差，另外免清洗助焊剂和水溶性助焊剂的固体含量低，活性温度高和活性区间窄。无铅焊料和助焊剂的特性决定了无铅波峰焊设备在结构和材料选用上有很大不同。本文通过对无铅波峰焊设备的各个部分的特点进行分析，为传统的旧波峰焊设备的改造提供参考。     

Mechanical characterization of Sn–Ag-based lead-free solders

Recently, preventing environmental pollutions, lead-free (Pb-free) solders are about to replace tin–lead (Sn–Pb) eutectic solders. However, the mechanical properties of Pb-free solders have not been clarified. Hence, the following study was conducted; first, a rate-dependent plasticity was characterized to represent the inelastic deformation behavior for Sn–Ag-based lead-free solders. The material parameters in a constitutive model were determined in a direct method combining both rate-dependent and rate-independent plastic strains. The constitutive model unifies both rate-dependent creep behavior and rate-independent plastic behavior occurring concurrently at the same time in the solders. Secondly, the strength of solders with a variety of plating materials was studied. Intermetallic compounds (IMC) between solder and electrical pads are formed during reflow process and gradually grow in service. By using the Cu-plates on which Cu or Ni or Ni/Au plating was deposited, the specimens of solder joints were fabricated with Sn–Ag-based lead-free solders. After aging the specimens in an isothermal chamber, tensile tests were performed. From scanning electron microscope (SEM) microscope observation and EDX microprobe analysis, the growth and components of the IMC layer were also examined. Based on the experimental tests, the relations between solder joint strength and the aging period were discussed. Furthermore, the validation of fracture strength of solder joints resulting from the tensile tests was verified with package-mounted board level reliability tests.     

Effects of thermomechanical cycling on lead and lead-free (SnPb and SnAgCu) surface mount solder joints

Accelerated reliability tests have been performed on leadless and leaded lead-free and lead containing SMT component assemblies. Results so far have shown that lead-free reflow soldering is a viable alternative for conventional lead based reflow soldering. The selected ternary eutectic solder alloy SnAg3.8Cu0.7 requires higher processing temperatures which could restrict the use of certain board and component types, but other than that no major modifications seem necessary. Although better SnAg3.8Cu0.7 bulk mechanical properties were obtained compared to the near eutectic lead bearing bulk solder properties, reflowed solder joints did not reflect this difference. In general, quite similar reliability results were obtained as found for the lead based solders. Dependent on board and component metallisations and use environment, the reliability of the lead-free solders could perform better or worse than the lead based solders. Temperature dependent aspects such as solderability and mechanical behaviour of the lead-free assemblies could play a role in this. Although microstructural differences can be seen between the lead-free and lead bearing solder joints, similar joint failure mechanisms occur. Resistor solder joint cracks propagate from underneath the component through either transgranular (lead-free) grains or along intergranular (lead) grain boundaries between lead-rich and tin-rich areas and into coarsened regions near the component terminations. Gullwing lead cracks were seen propagating from the heel fillet along the lead/solder interfacial intermetallic mostly (some cracks started in the heel fillet and propagated through the solder body dispersed with coarsened spherical Ag₃Sn intermetallic particles). Package design and leadframe material seem to play a more important role in the fatigue mechanism than the change in microstructure of the solder joint.     

无铅波峰焊设备的特点

相对于传统的Sn-Pb焊料,无铅焊料需要较高的焊接温度,而且润湿性差,另外免清洗助焊剂和水溶性助焊剂的固体含量低,活性温度高和活性区间窄。无铅焊料和助焊剂的特性决定了无铅波峰焊设备在结构和材料选用上有很大不同。通过对无铅波峰焊设备的各个部分的特点进行分析,为传统的旧波峰焊设备的改造提供参考。     

Stress–Strain Characteristics of Tin-Based Solder Alloys for Drop-Impact Modeling

The stress–strain properties of eutectic Sn-Pb and lead-free solders at strain rates between 0.1 s⁻¹ and 300 s⁻¹ are required to support finite-element modeling of the solder joints during board-level mechanical shock and product-level drop-impact testing. However, there is very limited data in this range because this is beyond the limit of conventional mechanical testing and below the limit of the split Hopkinson pressure bar test method. In this paper, a specialized drop-weight test was developed and, together with a conventional mechanical tester, the true stress–strain properties of four solder alloys (63Sn-37Pb, Sn-1.0Ag-0.1Cu, Sn-3.5Ag, and Sn-3.0Ag-0.5Cu) were generated for strain rates in the range from 0.005 s⁻¹ to 300 s⁻¹. The sensitivity of the solders was found to be independent of strain level but to increase with increased strain rate. The Sn-3.5Ag and the Sn-3.0Ag-0.5Cu solders exhibited not only higher flow stress at relatively low strain rate but, compared to Sn-37Pb, both also exhibited higher rate sensitivity that contributes to the weakness of these two lead-free solder joints when subjected to drop impact loading.