SnAgCu系钎料的合金组织和力学性能

研究了Cu含量对SnAgCu系钎料合金显微组织及其与化学镀Ni基板钎焊接头力学性能的影响。结果表明:高Cu含量SnAgCu合金会产生较多的(CuxNi1-x)6Sn5金属间化合物,从而减少镀Ni层的消耗,进一步提高钎焊接头的剪切强度。与Sn-3.0Ag-0.3Cu相比,Sn-3.0Ag-1.0Cu钎焊接头剪切强度提高了6.78%。经过150℃时效1000h后,界面Ni3(P,Sn)层的增长率从Sn-3.0Ag-0.3Cu合金的约66%降低到Sn-3.0Ag-1.0Cu合金的约40%。     

Ga元素含量对305钎料组织及性能的影响

通过在Sn-3Ag-0.5Cu钎料中添加不同含量的Ga，并采用差示扫描量热法（DSC）、万能试验机测试方法配制合金材料的熔化特性曲线、力学性能、金相结构、焊接润湿扩展率等性质，研究Ga含量对Sn-3Ag-0.5Cu钎料的熔化过程、焊接润湿扩展性以及组织和力学性能方面的影响。结果表明，Sn-3Ag-0.5Cu钎料中加入Ga元素以后，随着Ga增加，钎料的熔点显著降低，熔程也逐渐增大；适量的Ga元素可以改善Sn-3Ag-0.5Cu钎料的润湿性能；当Ga元素的添加量质量分数达到0.5%时，Sn-3Ag-0.5Cu钎料的组织均匀，晶粒明显细化，钎料的力学性能最佳，但Ga元素含量进一步增加时，在晶界处析出黑色富Ga相，对钎料力学性能产生了不利影响。     

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。     

Sn-58Bi-0.5Ce/Cu界面金属间化合物的性能研究

研究了Sn-58Bi-0.5Ce/Cu钎焊接头在120℃时效过程中界面组织形貌及金属间化合物层(IMC)的厚度变化。结果表明:在Sn-58Bi-0.5Ce/Cu钎焊接头界面处形成了较为平坦的双层金属间化合物,靠近钎料的上层为Cu6Sn5相,邻近Cu基板的下层为Cu3Sn相。等温时效处理后,IMC层逐渐凸起,且随着时效时间的增加,IMC层不断增厚。通过对实验数据进行拟合,得到钎焊接头界面IMC层的生长速度常数为5.77×10–17m2/s。     

Sn-3.0Ag-0.5Cu/Cu焊点可靠性研究

采用铺展面积法研究了Sn-3.0Ag-0.5Cu无铅钎料在不同温度下的润湿性能,同时探讨了150℃等温时效对Sn-3.0Ag-0.5Cu/Cu焊点界面组织及力学性能的影响。结果表明,随着钎焊温度的升高,Sn-3.0Ag-0.5Cu钎料的润湿性能明显增加。焊后钎料/Cu界面处对应的金属间化合物为Cu6Sn5相,经150℃时效,界面层的形貌由原来的齿状逐渐转化为层状,且厚度随着时效时间的增加而增加。发现界面层金属间化合物厚度与时效时间的二次方根成线性关系。对焊点在时效过程中的力学性能进行分析,发现Sn3.0Ag0.5Cu/Cu焊点的力学性能随着时效时间的增加逐渐降低,时效初期,焊点的力学性能下降较快,后期趋于平缓。     

Ce对SnAgCu系无铅焊锡力学性能的影响

通过向Sn-3Ag-2.8Cu钎料合金中添加微量稀土Ce,利用扫描电子显微镜(SEM)研究了不同稀土含量对Sn-3Ag-2.8Cu合金的力学性能的影响,同时对显微组织进行了分析.实验结果表明,微量的Ce稀土可以显著提高Sn-3Ag-2.8Cu钎料的延伸率、延长其焊接接头在室温下的蠕变断裂寿命,尤其是当稀土的质量分数为0.1%时,其蠕变断裂寿命可以达到Sn-3Ag-2.8Cu钎料的9倍以上,当稀土的质量分数超过0.1%时,接头的蠕变断裂寿命呈下降趋势.综合考虑,最佳的稀土质量分数为0.05%～0.10%.     

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。     

回流焊对SnAgCu焊点IMC及剪切强度的影响

研究了回流焊次数对Sn-0.3Ag-0.7Cu-xNi/Cu(x=0,0.05)焊点的界面反应及其剪切强度的影响。结果表明:随着回流焊次数的增加,界面金属间化合物(IMC)Cu6Sn5和(Cu1-xNix)6Sn5的厚度均增加。在钎料中添加w(Ni)为0.05%,可有效抑制IMC的生长,与回流焊次数无关。回流焊次数对Sn-0.3Ag-0.7Cu/Cu和Sn-0.3Ag-0.7Cu-0.05Ni/Cu的剪切强度影响都不大,五次回流焊后剪切强度略有下降,剪切强度分别为21MPa和25MPa。发现断裂面部分在钎料中,部分在钎料和IMC之间。     

内生无铅复合钎料在不同工艺条件下的制备及性能研究

通过采用不同工艺的内生法在Sn-3.5Ag共晶钎料基体中引入弥散分布的Cu6Sn5颗粒,制得了内生无铅复合钎料。研究了不同工艺条件对该钎料力学性能及电迁移行为的影响。结果表明,在冷却速度(0.1℃/s)较慢时制备的钎料,其内生Cu6Sn5颗粒细小,分布最均匀,且团聚程度较轻,另外,其钎焊接头力学性能最好;通5 A电流384 h后,其正负极金属间化合物层厚度的差异保持在约1.2μm,说明Cu6Sn5颗粒的引入提高了钎料的抗电迁移性能。     

Sn-Cu、Sn-Ag-Cu系无铅钎料的钎焊特性研究

制备了Sn-0.7Cu、Sn-3.5Ag-0.6Cu钎料,用润湿平衡法测量了钎料对铜的润湿曲线,研究了温度、钎剂活性、钎焊时间对润湿行为的影响,并与Sn-37Pb钎料进行了比较。结果表明:升高温度能显著改善无铅钎料对铜的钎焊性。当温度<270℃时,Sn-0.7Cu的钎焊性明显低于Sn-3.5Ag-0.6Cu钎料;而当温度≥270℃时,两种钎料对铜都会显示较好的润湿性,而Sn-0.7Cu略优于Sn-3.5Ag-0.6Cu钎料。提高钎剂活性能显著增强钎料对铜的润湿性,其卤素离子的最佳质量分数均为0.4%左右。随着浸渍时间的延长,熔融钎料与铜的界面间产生失润现象。无铅钎料的熔点和表面张力较高,是钎焊性较差的根本原因。     

Intermetallic reactions in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes

The intermetallic compounds (IMCs) formed during the reflow and aging of Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes were investigated. After reflow, the thickness of (Cu, Ni, Au)₆Sn₅ interfacial IMCs in Sn3Ag0.5Cu0.06Ni0.01Ge was similar to that in the Sn3Ag0.5Cu specimen. The interiors of the solder balls in both packages contained Ag₃Sn precipitates and brick-shaped AuSn₄ IMCs. After aging at 150°C, the growth thickness of the interfacial (Ni, Cu, Au)₃Sn₄ intermetallic layers and the consumption of the Ni surface-finished layer on Cu the pads in Sn3Ag0.5Cu0.06Ni0.01Ge solder joints were both slightly less than those in Sn3Ag0.5Cu. In addition, a coarsening phenomenon for AuSn₄ IMCs could be observed in the solder matrix of Sn3Ag0.5Cu, yet this phenomenon did not occur in the case of Sn3Ag0.5Cu0.06Ni0.01Ge. Ball shear tests revealed that the reflowed Sn3Ag0.5Cu0.06Ni0.01Ge packages possessed bonding strengths similar to those of the Sn3Ag0.5Cu. However, aging treatment caused the ball shear strength in the Sn3Ag0.5Cu packages to degrade more than that in the Sn3Ag0.5Cu0.06Ni0.01Ge packages.     

不同加载速率对SAC/Cu焊点剪切强度的影响

通过对Sn0.3Ag0.7Cu/Cu和Sn3.0Ag0.5Cu/Cu焊点进行剪切测试结果表明:两种钎料焊点的剪切强度与加载速率有着明显的相关性,即焊点的剪切强度都随着加载速率的增加而增加。当加载速率为0.01 mm/s时,断裂模式为韧脆混合断裂,随着加载速率的增加,两种钎料焊点断口的韧窝数量不断增加,呈现韧性断裂特征,断口以韧窝为主。另外在相同加载速率下,Sn3.0Ag0.5Cu/Cu焊点断口的韧窝数量和分布情况都优于Sn0.3Ag0.7Cu/Cu焊点,即其韧性断裂的趋势更加明显,剪切强度更大。     

Intermetallic formation in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with immersion Ag surface finish

The intermetallic compounds formed in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Ag/Cu pads are investigated. After reflow, scallop-shaped η-Cu₆Sn₅ and continuous planar η-(cu_0.9Ni_0.1)₆Sn₅ intermetallics appear at the interfaces of the Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder joints, respectively. In the case of the Sn3Ag0.5Cu specimens, an additional ε-Cu₃Sn intermetallic layer is formed at the interface between the η-Cu₆Sn₅ and Cu pads after aging at 150°C, while the same type of intermetallic formation is inhibited in the Sn3Ag0.5Cu0.06Ni0.01Ge packages. In addition, the coarsening of Ag₃Sn precipitates also abates in the solder matrix of the Sn3Ag0.5Cu0.06Ni0.01Ge packages, which results in a slightly higher ball shear strength for the specimens.     

Pb-free Sn/3.5Ag electroplating bumping process and under bump metallization (UBM)

Pb-free solder is one of the biggest issues in today's electronic packaging industry. This paper introduces a newly developed Sn/3.5Ag alloy plating process for wafer level bumping. The effects of Under Bump Metallization (UBM) on the process, interfacial reaction, and mechanical strength have been investigated. Four different types of sputtering-based UBM layers-TiW/Cu/electroplated Cu, Cr/CrCu/Cu, NiV/Cu, and TiW/NiV-were fabricated with eutectic Pb/63Sn and Sn/3.5Ag solder. The result shows that the Sn/Ag solder gains Cu or Ni from UBM's and becomes Sn/Ag/Cu or Sn/Ag/Ni during reflow process. Sn/Ag solder has higher reactivity with Cu and Ni than Pb/63Sn. The Intermetallic Compound (IMC) spalling from the interface between UBM/solder has been observed on Cr/CrCu/Cu and TiW/NiV UBM's. However, the IMC spalling phenomena did not decrease the bump shear strength with a bump size of 110 /spl mu/m, whereas a size of 60 /spl mu/m brought a decrease in shear value and failure mode change.     

Constitutive and Aging Behavior of Sn3.0Ag0.5Cu Solder Alloy

We describe double-lap shear experiments on Sn3.0Ag0.5Cu solder alloy, from which fits to Anand's viscoplastic constitutive model, power-law creep model, and to time-hardening primary-secondary creep model are derived. Results of monotonic tests for strain rates ranging from 4.02E-6 to 2.40E-3 s^-1, and creep response at stress levels ranging from 19.5 to 45.6 MPa are reported. Both types of tests were conducted at temperatures of 25degC, 75degC , and 125degC. Following an earlier study where Anand model and time hardening creep parameters for Sn3.8Ag0.7Cu and Sn1.0Ag0.5Cu solder alloys were reported, here we report power law model parameters so as to enable a comparison between all three alloys. Primary creep in Sn3.0Ag0.5Cu solder alloy is shown to be significant and are considered in addition to secondary creep and monotonic behavior. Aging influence on behavior is also shown to be significant. On the basis of experimental data, the following four aspects are discussed: 1) difference between testing on bulk versus joint specimen; 2) consistency between the creep and monotonic behaviors; 3) comparison against behaviors of Sn1.0Ag0.5Cu and Sn3.8Ag0.7Cu alloys as well as aganist Sn40Pb, 62Sn36Pb2Ag and 96.5Sn3.5Ag alloys; and 4) comparison of Sn3.0Ag0.5Cu and Sn3.8Ag0.7Cu relative to their aging response.     

Comparative study of microstructures and properties of three valuable SnAgCuRE lead-free solder alloys

Lead-free solders with excellent material properties and low cost are essential for the electronics industry. It has been proved that mechanical properties of SnAgCu alloys can be remarkably improved with a minute addition of rare earth (RE) elements. For comparison and optimization, three valuable solder candidates, Sn3.8Ag0.7Cu0.05RE, Sn3Ag0.5Cu0.05RE, and Sn2.9Ag1.2Cu0.05RE, were chosen due to the excellent properties of their own SnAgCu basic alloys. Wetting properties, melting temperature, bulk tensile properties, and joint tensile and shear properties were investigated. In addition, the microstructures of solder joints were observed and the effects of microstructure on mechanical properties were analyzed. Experimental results indicated that the tensile and shear strengths of solder joints were decreased from Sn3.8Ag0.7Cu0.05RE, Sn2.9Ag1.2Cu0.05RE, to Sn3Ag0.5Cu0.05RE, in order. Such difference in mechanical properties could be attributed to the influence of slightly coarse or strong Cu₆Sn₅ scallops in the reaction layer as well as superior eutectic network and large volume percentage of large primary intermetallic compounds (IMCs) inside the solder joints. It is also suggested that the size and volume percentage of large primary IMCs inside the solder be controlled. In addition, serration morphology was observed at the edge of large primary and eutectic IMCs in the three solder joints, which could be related to the content of Ag, Cu, and RE. The serration morphology was proved to be beneficial to mechanical properties theoretically. Furthermore, the three alloys investigated possessed similar wetting properties, melting temperatures, and bulk tensile properties.     

La对Sn3.5Ag0.5Cu钎料界面组织和性能的影响

通过SEM和EDAX等,研究了La添加量对Sn3.5Ag0.5Cu钎料与Cu基体焊合界面IMC微观组织及性能的影响。结果表明:添加不同量的La均对Sn3.5Ag0.5Cu与Cu基体焊合后的组织有细化作用并增强其力学性能。其中以w(La)达到0.05%时最优,剪切强度可提高10.7%。材料热力学理论计算结果表明,La具有"亲Sn"倾向,添加少量La到Sn3.5Ag0.5Cu钎料中,可减小Cu6Sn5/Cu界面Sn的活度,降低IMC的长大驱动力。     

Effect of small Sn–3.5Ag–0.5Cu additions on the structure and properties of Sn–9Zn solder in ball grid array packages

Sn–9Zn with various additions of Sn–3.5Ag–0.5Cu powder was prepared by mechanically dispersing different weight percentages (1, 3, 5 and 7) of Sn–Ag–Cu powder into Sn–9Zn solder paste. In the Sn–Zn solder, scallop-shaped AuZn₃ intermetallic compound was found at the interfaces. On the other hand, in the Sn–3.5Ag–0.5Cu content solders, an additional ε-AgZn₃ intermetallic compound layer was found to be well adhered on the top surface of the AuZn₃ layer and the ε-AgZn₃ layer thickness increased with the number of reflow cycles. In addition, fine spherical-shaped ε-AgZn₃ intermetallic compound particles as well as an acicular-shaped Zn-rich phase was clearly observed in the β-Sn matrix. On increasing the Sn–Ag–Cu content, the shear load was increased from 1.80 to 2.03 kg after one reflow cycle. In the Sn–3.5Ag–0.5Cu content solders, the fracture surfaces exhibited typical ductile behavior with very rough dimpled surfaces while the fracture surface in the Sn–Zn solder gave fractures with a brittle appearance. In the fracture surface of the Sn–3.5Ag–0.5Cu content solders, some dimples were clearly observed associated with the formation of spherical-shaped ε-AgZn₃ intermetallic compound particles.     

Interfacial reactions and shear strengths between Sn-Ag-based Pb-free solder balls and Au/EN/Cu metallization

The morphological and compositional evolutions of intermetallic compounds (IMCs) formed at three Pb-free solder/electroless Ni-P interface were investigated with respect to the solder compositions and reflow times. The three Pb-free solder alloys were Sn3.5Ag, Sn3.5Ag0.75Cu, and Sn3Ag6Bi2In (in wt.%). After reflow reaction, three distinctive layers, Ni₃Sn₄ (or Ni-Cu-Sn for Sn3.5Ag0.75Cu solder), NiSnP, and Ni₃P, were formed on the electroless Ni-P layer in all the solder alloys. For the Sn3.5Ag0.75Cu solder, with increasing reflow time, the interfacial intermetallics switched from (Cu,Ni)₆Sn₅ to (Cu,Ni)₆Sn₅+(Ni,Cu)₃Sn₄, and then to (Ni,Cu)₃Sn₄ IMCs. The degree of IMC spalling for the Sn3.5Ag0.75Cu solder joint was more than that of other solders. In the cases of the Sn3.5Ag and Sn3Ag6Bi2In solder joints, the growth rate of the Ni₃P layer was similar because these two type solder joints had a similar interfacial reaction. On the other hand, for the Sn3.5Ag0.75Cu solder, the thickness of the Ni₃P and Ni-Sn-P layers depended on the degree of IMC spalling. Also, the shear strength showed various characteristics depending on the solder alloys and reflow times. The fractures mainly occurred at the interfaces of Ni₃Sn₄/Ni-Sn-P and solder/Ni₃Sn₄.     

Effects of Cu, Ag and Sb on the creep-rupture strength of lead-free solder alloys

The materials used in the present research are pure Sn metal and Sn-0.5% Cu, Sn-3.5%Ag, Sn-0.3%Sb, and Sn-3.5%Ag-0.5%Cu alloys. Effects of Cu, Ag and Sb on the creep-rupture strength of lead-free solder alloys have been investigated. Creep tests are performed at the stress and temperature range of 3 to 12 MPa and 378 to 403 K, respectively. A 3.5% addition of Ag had the largest contribution to the creep-rupture strength of Sn metal among the single addition of 0.5%Cu, 3.5%Ag, and 0.3%Sb. The combined addition of 3.5%Ag and 0.5%Cu makes the largest creep-rupture strength. The effects of these elements on the microstructure of the lead-free alloys are also investigated with optical microscope (OM) and transmission electron microscope (TEM) observations.