Development of high strength Sn-0.7Cu solders with the addition of small amount of Ag and In

Nowadays, a major concern of Sn-Cu based solder alloys is focused on continuously improving the comprehensive properties of solder joints formed between the solders and substrates. In this study, the influence of Ag and/or In doping on the microstructures and tensile properties of eutectic Sn-0.7Cu lead free solder alloy have been investigated. Also, the effects of temperature and strain rate on the mechanical performance of Sn-0.7Cu, Sn-0.7Cu-2Ag, Sn-0.7Cu-2In and Sn-0.7Cu-2Ag-2In solders were investigated. The tensile tests showed that while the ultimate tensile strength (UTS) and yield stress (YS) increased with increasing strain rate, they decreased with increasing temperature, showing strong strain rate and temperature dependence. The results also revealed that with the addition of Ag and In into Sn-0.7Cu, significant improvement in YS (∼255%) and UTS (∼215%) is realized when compared with the other commercially available Sn-0.7 wt. % Cu solder alloys. Furthermore, the Sn-0.7Cu-2Ag-2In solder material developed here also exhibits higher ductility and well-behaved mechanical performance than that of eutectic Sn-0.7Cu commercial solder. Microstructural analysis revealed that the origin of change in mechanical properties is attributed to smaller β-Sn dendrite grain dimensions and formation of new inter-metallic compounds (IMCs) in the ternary and quaternary alloys.     

Combined effects of Bi and Sb elements on microstructure,thermal and mechanical properties of Sn-0.7Ag-0.5Cu solder alloys

This research investigated the combined effects of addition of Bi and Sb elements on the microstructure, thermal properties, ultimate tensile strength, ductility, and hardness of Sn-0.7Ag-0.5Cu (SAC0705) solder alloys. The results indicated that the addition of Bi and Sb significantly reduced the undercooling of solders, refined the β-Sn phase and extended the eutectic areas of the solders. Moreover, the formation of SbSn and Bi phases in the solder matrix affected the mechanical properties of the solder. With the addition of 3 wt.% Bi and 3 wt.% Sb, the ultimate tensile strength and hardness of the SAC0705 base alloy increased from 31.26 MPa and 15.07 HV to 63.15 MPa and 23.68 HV, respectively. Ductility decreased due to grain boundary strengthening, solid solution strengthening, and precipitation strengthening effects, and the change in the fracture mechanism of the solder alloys.     

Ag和Ni元素对Sn-Sb-Cu无铅钎料熔化温度和铺展性能的影响

在Sn-Sb-Cu三元钎料合金中添加微量元素Ag和Ni,通过合金化形成Sn-Sb-Cu-Ag和Sn-Sb-Cu-Ni两种新型四元无铅钎料合金,以改善基体钎料性能.结果表明,在Sn-Sb-Cu钎料合金中添加微量元素Ag,合金熔化温度较基体钎料下降,铺展面积增大,这与钎料过热度增大,形成弥散低熔点相SnAg和液态钎料表面张力减小有关;添加微量元素Ni,合金熔化温度较基体钎料下降,铺展性能稍稍变差,这是因为添加微量元素Ni后,Sn-Sb-Cu-Ni液态钎料粘度提高,表面张力增大.且在钎料与铜基板处形成了多面体形状(Cu,Ni)6Sn5,且该相覆盖在Cu6Sn5表面,不利于液态钎料的润湿铺展.     

Sn-6Bi-2Ag(Cu, Sb)无铅钎料合金微观组织分析

利用差示扫描量热计 (DSC)测定了Sn 6Bi 2Ag ,Sn 6Bi 2Ag 0 .5Cu ,Sn 6Bi 2Ag 2 .5Sb三种新无铅钎料合金的熔化温度。结果表明 ,少量Cu的加入能降低Sn Bi Ag系无铅钎料合金的熔化温度 ,而Sb的加入使合金的熔化温度升高。利用光学显微镜 (OM )、扫描电子显微镜 (SEM )、能谱分析 (EDX)对合金的微观组织进行了分析与比较 ,钎料合金的微观组织与冷却条件和合金元素的含量有关 ,Sb的加入使析出相的尺寸细化。硬度测定表明Sn Bi Ag(Cu ,Sb)无铅钎料合金的硬度远大于纯Sn的硬度 ,加入少量的Cu(0 .5 % ) ,Sb(2 .5 % )对Sn Bi Ag系钎料合金的硬度影响较小     

添加Ag对Sn-9Zn无铅钎料合金性能的影响

通过试验研究了添加Ag对Sn-9Zn无铅钎料合金在Cu表面的润湿性、焊点剪切强度、抗蠕变性能与组织的影响。结果表明，当添加量较低时，Ag能够改善Sn-9Zn合金熔体对Cu的润湿性和焊点剪切强度，而添加量较高时Ag则会使它们降低；就焊点润湿性和剪切强度而言，最佳Ag含量（质量分数）为0．30％～0．60％。Ag的添加能显著提高Sn-9Zn合金体材的抗蠕变性能。显微分析表明，在含Ag合金中形成了弥散分布、尺度为微米级的Ag—Zn化合物颗粒，这可能是合金得到强化的原因。     

Ni含量对304/Sn-8Sb-4Cu-xNi/304钎焊接头组织与剪切性能的影响

研究了Ni含量对Sn-8Sb-4Cu-xNi(x=0, 0.5, 1和2,质量分数)钎料熔点和微观组织的影响,用Sn-8Sb-4CuxNi钎料对304不锈钢进行钎焊连接,分析了接头的界面组织与剪切性能.结果表明,添加不同含量的Ni后,Sn-8Sb-4Cu-xNi均为近共晶钎料,其熔点约为245℃;Sn-8Sb-4Cu钎料组织由α相基体、Sb₂Sn₃+Cu₆Sn₅+Sn复合相和Cu₆(Sn,Sb)₅相组成.添加Ni元素后,钎料中块状Cu₆(Sn,Sb)₅转变为细小、均匀分布的(Cu,Ni)₆(Sn,Sb)₅.当Ni含量小于1%时,随Ni含量的增加,钎料中的复合相和(Cu,Ni)₆(Sn,Sb)₅相均增加;当Ni含量为2%时,钎料中的复合相和(Cu,Ni)₆(Sn,Sb)₅相均减少,但(...     

Property alterations of Sn-0.6Cu-0.05Ni-Ge lead-free solder by Ag,Bi, In and Sb addition

The Sn-Cu-Ni-Ge solder is a strong challenger to the Sn-Ag-Cu (SAC) solders as a replacement for the Sn-Pb eutectic solder. This research investigated the effects of addition of Ag, Bi, In, and Sb on the physical properties of the Sn-0.6Cu-0.05Ni-Ge (SCNG) lead-free solder and the interfacial reaction with the Cu substrate. The melting behavior, microstructure, tensile strength, and wettability of the SCNG–x (x=Ag, Bi, In, Sb) solders were examined. The findings revealed that the introduction of Ag, Bi, In, and Sb minimally altered the solidus temperature, liquidus temperature, and tensile strength of the solder. However, the cooling behavior and solidified microstructure of the solder were affected by the concentration of the alloying elements. The wettability of the SCNG solder was improved with the doping of the alloying elements except Sb. The thickness of intermetallic layer was increased by the addition of the alloying elements and was related to the cooling behavior of the solder. The morphology of intermetallic layer between the SCNG–x solders and the Cu substrate was different from that of the typical SAC solders. In conclusion, alloying the SCNG solder with Ag, Bi, In or Sb is able to improve particular properties of the solder.     

Pb-free solders for flip-chip interconnects

A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag₃Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni₃Sn₄ formed and on copper, Cu₆Sn₅Cu₃Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu. Editor’s Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/Frear-0106.html For more information, contact D.R. Frear, Interconnect Systems Laboratories, Motorola, Tempe, AZ 85284; (480) 413-6655; fax (480) 413-4511; e-mail darrel.frear@motorola.com.     

Sn-0.7Cu-xNb复合钎料微观组织和力学性能

文中主要研究了纳米Nb颗粒对Sn-0.7Cu基复合钎料显微组织和力学性能的影响。结果表明,添加纳米Nb颗粒细化了Sn-0.7Cu复合钎料微观组织,提高了Sn-0.7Cu复合钎料的抗拉强度。当Nb含量为0.12%时抗拉强度达最大值25.36 MPa,但此时钎料的断后伸长率有所降低。Sn-0.7Cu-x Nb复合钎料的断裂模式均为塑性断裂,随Nb含量的增加,Sn-0.7Cu基复合钎料断口表面的韧窝尺寸逐渐变小,表明微量的纳米Nb可以抑制合金内Cu 6 Sn 5金属间化合物的长大。     

Structural and elastic properties of eutectic Sn-Cu lead-free solder alloy containing small amount of Ag and In

Sn-Cu alloys have been considered as a candidate for high temperature lead-free microelectronic solders. In the present study, the change in microstructure, attenuation and elastic behavior associated with alloying of Ag and/or In into the eutectic Sn-Cu solder alloy system have been evaluated. The study involved measurements of longitudinal and shear wave velocities, attenuation, hardness, bulk and shear moduli, Young's and Poisson's ratio. The results of attenuation show that a clear attenuating effect in the ternary Sn-Cu-Ag and Sn-Cu-In alloys is realized, whereas the quaternary Sn-Cu-Ag-In solder displays an obscure attenuating effect. The obscure effect is mainly attributed to the competition for In between Sn and Ag, which results in weak interface formed between intermetallic compounds (IMCs) and β-Sn matrix. Likewise, Poisson's ratio results indicate that its value decreases with increasing the elastic moduli and ultrasonic velocities of Ag and In-containing alloys. The analyzed enhanced ductility of Sn-0.7Cu and Sn-0.7Cu-2In alloys and brittleness of Sn-0.7Cu-2Ag and Sn-0.7Cu-2Ag-2In alloys were rationalized on the basis of Poisson's ratio and the quotient of shear modulus to bulk modulus (Pugh's ratio). Microstructural analysis revealed that the origin of change in the elastic properties of the ternary and quaternary alloys is ascribed to smaller β-Sn dendrite grain dimensions and formation of new IMCs in the ternary and quaternary alloys.     

无铅焊料在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为

研究了Sn-3.5Ag-0.75Cu和Sn-0.75Cu焊料合金在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为,并与Sn-37Pb焊料合金的腐蚀浸出行为对比分析。研究表明,这3种焊料合金中Sn的浸出量随时间的延长趋于平缓,且Sn-0.75Cu焊料合金中Sn的浸出量最高,添加Ag元素后明显抑制了Sn-3·5Ag-0·75Cu焊料合金中Sn的浸出;Ag,Cu,Pb的浸出量随时间的延长呈线性增加,且Ag,Cu的浸出量较少。3种焊料合金浸出后表面产物层较厚,主要由Sn_4(OH)_6Cl_2和SnO组成,其中Sn-0.75Cu焊料合金的表面产物层有裂纹和孔洞,Sn-3.5Ag-0.75Cu焊料合金的表面产物相对致密,而Sn-37Pb焊料合金的表面产物局部出现剥落现象。这3种焊料合金浸出动力学行为存在差异,主要与表面产物的相组成和形貌有关。     

Ag元素含量对Sn-Ag-Cu钎料焊接性的影响

以Sn-xAg-0.5Cu为基体制备了低银无铅钎料,其中Ag元素的质量分数分别为0.3%,0.5%,0.7%,0.9%.借助钎料合金的DSC熔化曲线,分析了Ag元素含量对合金熔点的影响规律.通过比较各组钎料合金在Cu基板上的铺展面积和铺展率,分析了Ag元素含量的变化对各组钎料润湿性的影响规律.结果表明,随着Ag元素含量...     

Sn-0.3Ag-0.7Cu-xNd钎料显微组织及性能

研究了稀土元素Nd的添加量对超低银无铅钎料Sn-0.3Ag-0.7Cu的润湿性能、显微组织和力学性能的影响.结果表明,微量Nd元素的加入可以显著改善Sn-0.3Ag-0.7Cu超低银无铅钎料的润湿性能和焊点的力学性能,并且能够起到细化基体组织的作用.当钎料中Nd元素的质量分数达到0.1%时,钎料的综合性能最佳,基体组织最为均匀细化.虽然Ag元素含量的降低使钎料的性能有所下降,但是加入适量Nd元素后钎料的润湿性能已接近传统Sn-3.8Ag-0.7Cu钎料.     

纳米Ag颗粒增强复合钎料蠕变性能的研究

制备纳米Ag颗粒增强的Sn-Cu基复合钎料.研究不同温度载荷下复合钎料钎焊接头的蠕变断裂寿命,并与Sn-0.7Cu基体钎料钎焊接头进行对比.此外,确定纳米Ag颗粒增强的Sn-Cu基复合钎料钎焊接头在不同温度和应力水平下的应力指数和蠕变激活能,建立复合钎料钎焊接头的稳态蠕变本构方程.结果表明,在不同的温度和应力下,与Sn-0.7Cu钎料钎焊接头相比,纳米Ag颗粒增强的Sn-Cu基复合钎料钎焊接头的蠕变断裂寿命均有所提高,且具有更高的蠕变激活能,说明复合钎料钎焊接头具有更优的抗蠕变性能.     

Cu和Sb元素添加对Sn-Bi共晶合金性能的影响

向Sn-Bi共晶合金中同时添加Cu和Sb元素设计额定温度为142℃的易熔合金,并对合金的熔点、相组成、准静态拉伸性能、焊接接头力学性能进行了研究.结果表明,Cu与Sb元素的添加使合金的熔点上升,但是合金的过冷度和熔化潜热下降.添加Cu和Sb元素后,在合金基体内形成了块状的SnSb相和长条状的Cu6Sn5、Cu3Sn相,...     

Ni对SnAgCuRE钎料及其钎焊接头性能的影响

以商用Sn3.8Ag0.7Cu为参照系,研究了Ni对Sn2.5Ag0.7Cu0.1 RE钎料合金及其钎焊接头性能的影响。研究结果表明,添加0.05%(质量分数)Ni能在不降低Sn2.5Ag0.7Cu0.1RE钎料合金抗拉强度的同时显著提高其伸长率,是商用Sn3.8Ag0.7Cu的1.4倍;相应地钎焊接头的蠕变断裂寿命最长,为未添加Ni时的13.3倍,远高于现行商用Sn3.8Ag0.7Cu的,满足微电子连接高强韧高可靠性无铅钎料合金系的需求。     

RE对SnAgCu钎料合金及焊点性能的影响

利用JSM-5610LV扫描电镜（SEM）及能谱分析（EDS）等测量方法,研究了微量RE对Sn-2.5Ag-0.7Cu无铅钎料的显微组织、润湿特性、拉伸强度及焊点剪切强度和蠕变断裂寿命的影响。结果表明,向Sn-2.5Ag-0.7Cu中添加0.1%RE可明显细化钎料合金的显微组织,改善钎料合金的润湿特性,提高钎料合金的抗拉强度、伸长率及焊点剪切强度,增加焊点的蠕变断裂寿命。当RE添加量为0.5%时,由于形成了RE化合物而明显恶化钎料合金的性能。     

Evaluation of Bulk Mechanical Properties of Selected Lead-Free Solders in Tension and in Shear

Lead-free solders are fast emerging as better alternatives to Sn-Pb solders. The reliability of a soldered joint to withstand imposed stresses in an assembly is decided by its mechanical properties. The present work is about the investigation of tensile and shear properties of four binary eutectic alloys Sn-3.5Ag, Sn-58Bi, Sn-0.7Cu, Sn-9Zn and a ternary alloy Sn-57Bi-1.3Zn in comparison with conventional Sn-38Pb alloy. It is observed that the lead-free solders have better mechanical properties than the latter. SEM studies of tensile and shear fracture show ductile dimples circular in tension and parabolic in shear modes supporting the mechanical behavior of the alloys investigated. Eutectic alloys Sn-Ag, Sn-Zn, and Sn-Cu form potential substitutes for Sn-Pb for electronic interconnects exposed to high temperatures, while Sn-Bi and Sn-Bi-Zn are attractive alternatives in addressing the need of lower processing temperatures in printed circuit boards and other applications.     

Microstructure and Mechanical Properties of a Ag Micro-Alloyed Mg-5Sn Alloy

Effects of 1.5 wt.% Ag addition and solid solution?+?artificial ageing at 160 °C on the microstructure and mechanical properties of a Mg-5Sn alloy have been studied. The results show that Ag addition has significantly hardened the solution-treated Mg-5Sn alloy. During the ageing process, the hardness increase rate and the strength and ductility of the Mg-5Sn alloy at each state are also improved by Ag addition. The improved strengthening behavior is primarily attributed to the refinement distribution of the Mg₂Sn precipitates, the enhanced precipitation process, and the synergistic strengthening effect of Mg₂Sn and a metastable plate DO₁₉ phase formed at lower ageing temperature. For each solution-treated alloy, the strength and ductility are higher than the corresponding cast ones. Ageing further enhances the yield strength, and the ductility of the Mg-5Sn-1.5Ag alloy is also increased after ageing. The fracture surfaces of the both peak-aged alloys exhibit the characteristic of a mixture of quasi-cleavage and ductile fracture.     

Using Microwave-Assisted Powder Metallurgy Route and Nano-size Reinforcements to Develop High-Strength Solder Composites

In the present study, Sn-0.7Cu and Sn-3.5Ag lead-free solders used in the electronics packaging industry were reinforced with different volume percentages of nano-size alumina and tin oxide particulates, respectively, to synthesize two new sets of nanocomposites. These composites were developed using microwave-assisted powder metallurgy route followed by extrusion. The effects of addition of particulates on the physical, microstructural, and mechanical properties of the nanocomposites were investigated. Mechanical properties (microhardness, 0.2% YS, and UTS) for both composite systems increase with the presence of particulates. The best tensile strength was realized for composite solders reinforced with 1.5 vol.% alumina and 0.7 vol.% tin oxide particulates, which far exceeds the strength of eutectic Sn-Pb solder. The morphology of pores was observed to be one of the most dominating factors affecting the strength of materials.