High temperature lead-free solder for microelectronics

This paper reports results of a four-year industrial consortium effort to develop lead-free solders for high-temperature applications (up to 160°C). Work included preliminary evaluations of 32 tin-based alloys, a screening of the thermomechanical fatigue performance of 13 promising alloys, and a full manufacturability and fatigue testing of the seven most promising of those alloys, namely Sn-3.5Ag, Sn-4Ag-1Cu, Sn-4Ag-0.5Cu, Sn-2.5Ag-0.8Cu-0.5Sb, Sn-4.6Ag-1.6Cu-1Sb-1Bi, Sn-3.3Ag-1Cu-3.3Bi, and Sn-3.5Ag-1.5In (compositions in weight percent). Eight different components were used on the reliability test vehicle, and the alloys were compared through Weibull analysis. In addition, the same seven experimental alloys were tested with ball grid array packages cycled up to 100°C or 125°C. All the lead-free alloys performed well, but those containing bismuth showed especially outstanding performance. In general, the ternary and higher alloys performed as well or better than the industry standard tin-silver eutectic, suggesting that solders other than the tin-silver eutectic should be considered for high-reliability, high-temperature applications. Frank W. Gayle is with NIST, Stop 8555, 100 Bureau Drive, Gaithersburg, MD 20899, frank.gayle@nist.gov.     

Improving the shear strength of Sn–Ag–Cu–Ni/Cu–Zn solder joints via modifying the microstructure and phase stability of Cu–Sn intermetallic compounds

This study focuses on the correlation between high-speed impact tests and the interfacial reaction in Sn-3.0Ag-0.5Cu-0.1Ni/Cu (wt%) and Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints. Adding Ni into the Sn–Ag–Cu solder alters the interfacial morphology from scallop type to layer type and exhibits high shear strength after reflow in both solder joints. However, the shear strength of Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints degrades significantly after thermal aging at 150 °C for 500 h. It is notable that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints still present higher shear strength after aging at 150 °C. The weakened shear strength in Sn-3.0Ag-0.5Cu-0.1Ni/Cu solder joints is due to stress accumulation in the interfacial (Cu,Ni)₆Sn₅ compound induced by the phase transformation from a high-temperature hexagonal structure (η-Cu₆Sn₅) to a low-temperature monoclinic structure (η'-Cu₆Sn₅). However, doping small amounts of Zn into (Cu,Ni)₆(Sn,Zn)₅ can inhibit the phase transformation during thermal aging and maintain strong shear strength. These experiments demonstrate that Sn-3.0Ag-0.5Cu-0.1Ni/Cu-15Zn solder joints can act as a stable connection in the micro-electronic packaging of most electronic products at their average working temperatures.     

Ni-Ti 钎料高温钎焊TZM晶间渗入行为研究

采用SEM,EDS,XRD和力学试验机等分析测试方法,研究了Ni-Ti钎料对TZM合金钎缝组织和性能的影响。结果表明：Ni-Ti钎料可实现TZM的高温真空钎焊连接。Ni-13.7Ti/TZM界面区,母材中的Mo与钎料中的Ni形成MoNi相,是钎料与TZM形成冶金结合的主要原因。TZM/Ni-44Ti/TZM界面区Ni-44Ti钎料中的Ti与Mo反应,Mo-Ti固溶体,使钎料和TZM形成冶金结合。Ni-44Ti钎料钎焊TZM合金产生严重晶间渗入现象。降低钎料中Ti的含量,晶间渗入和母材溶蚀现象大幅减弱;TZM/Ni-13.7Ti/TZM钎焊接头剪切强度193MPa,TZM/Ni-44Ti/TZM钎焊接头剪切强度167MPa,晶间渗入使钎缝强度降低,降低钎料中的Ti含量,钎焊接头强度提高。     

Age-hardening behavior and microstructure of Cu-15Ni-8Sn-0.3Nb alloy prepared by powder metallurgy and hot extrusion

Cu-15Ni-8Sn-0.3Nb alloy rods were prepared by means of powder metallurgy followed by hot extrusion. Element maps obtained by electron probe micro analyzer (EPMA) showed that Nb-rich phases were formed and distributed within grains and at grain boundaries of the Cu-15Ni-8Sn-0.3Nb alloy. Transmission electron microscope (TEM) results indicated that there was no obvious orientation relationship between these phases and the matrix. Spinodal decomposition and ordering transformation appeared at early stages of aging at 400 °C and caused significant strengthening. Cu-15Ni-8Sn-0.3Nb alloy exhibited both higher strength (ultimate tensile strength >1030 MPa) and higher tensile ductility (elongation>9.1%) than Cu-15Ni-8Sn alloy after aging treatment. The improvement was caused by Nb-rich phases at grain boundaries which led o the refinement of grain size and postponed the growth of discontinuous precipitates during aging.     

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.     

Effects of Ti addition and heat treatments on mechanical and electrical properties of Cu-Ni-Si alloys

The mechanical and electrical properties of Cu-5.98Ni-1.43Si and Cu-5.98Ni-1.29Si-0.24Ti alloys under heat treatment at 400 and 500 °C after hot- and cold-rolling were investigated, and a microstructural analysis using transmission electron microscopy was performed. Cu-5.98Ni-1.29Si-0.24Ti alloy displayed the combined Vickers hardness/electrical conductivity value of 315.9 Hv/57.1%IACS. This was attributed to a decrease of the solution solubility of Ni and Si in the Cu matrix by the formation of smaller and denser δ-Ni₂Si precipitates. Meanwhile, the alloyed Ti was detected in the coarse Ni-Si-Ti phase particles, along with other large Ni-Si phase particles, in Cu-5.98Ni-1.29Si-0.24Ti.     

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.     

Electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys in chloride containing aqueous solution

The electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys was investigated in 3.5% NaCl solution by using potentiodynamic polarization techniques. The results obtained from polarization studies revealed that there was a negative shift in the corrosion potential with increase in Ga content from 0.02 to 0.2 wt% in the Sn-8.5Zn-0.05Al-XGa alloy. These changes were also reflected in the corrosion current density (I_corr) value, corrosion rate and linear polarization resistance (LPR) of the four element alloy. However, for Sn-3Ag-0.5Cu alloy a significant increase in the corrosion rate and corrosion current density was observed as compared to the four element alloys. SIMS depth profile results established that ZnO present on the outer surface of Sn-8.5Zn-0.05Al-0.05Ga alloy played a major role in the formation of the oxide film. Oxides of Sn, Al and Ga contributed a little towards the formation of film on the outer surface of the alloy. On the other hand, Ag₂O was primarily responsible for the formation of the oxide film on the outer surface of Sn-3Ag-0.5Cu alloy.     

Low-melting-point titanium-base brazing alloys—part 1: Characteristics of two-, three-, and four-component filler metals

The melting point, microstructure, phase, and electrochemical behavior of Ti-21Ni-15Cu alloy, together with two-, three-, and four-component low-melting-point titanium-base brazing alloys, are presented in this paper. Five filler metals were selected for the study, in which melting points were measured by differential thermal analysis, phases identified by x-ray diffractometry, and corrosion behaviors tested by potentiodynamic polarization. The experimental results show that the three-component Ti-15Cu-15Ni and the newly developed Ti-21Ni-14Cu alloys exhibit the combination of lower melting point and superior corrosion resistance compared to the two-and four-component titanium alloys, 316L stainless steel, and a Co-Cr-Mo alloy in Hank’s solution at 37 °C. On a short time basis, the presence of Ti₂Ni and Ti₂Cu intermetallics in the Ti-15Cu-15Ni and Ti-21Ni-14Cu alloys should not be preferentially dissolved in galvanic corrosion with respect to the dissimilar Ti-6Al-4V alloy.     

Microstructural characterization of diamond/CBN grains steel braze joint interface using Cu–Sn–Ti active filler alloy

In order to develop the new generation superhard abrasive tools of diamond and cubic boron nitride (CBN), the brazing joint experiments of diamond/CBN crystals and AISI 1045 steel matrix using Cu–Sn–Ti active filler powder alloy were investigated in vacuum furnace. The brazing temperature was 930 °C and the dwelling time was 20 min. Interfacial characteristics of the brazing joint among the diamond/CBN grains, the active filler layer and the steel substrate were analyzed using scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction techniques. The results indicated that Ti element in the Cu–Sn–Ti alloys diffused preferentially to the surface of diamond/CBN grits to form a Ti-rich reaction layer in the brazed joints by microanalyses. Moreover, the TiC, TiN and TiB₂ phases in diamond/CBN interface and Cu–Ti phase in steel interface were confirmed by X-ray diffraction phase analysis. The wetting and bonding reactions on diamond/CBN by melting Cu–Sn–Ti alloy were realized through the interfacial reaction products like TiC, TiN and TiB₂ compounds during the brazing process. The adhesive strength experiments of the joint interfaces revealed that the grains were not pulled out from the bond interface. The reliable bonding strength of brazed diamond/CBN grains to the steel substrate can meet the application requirements of high efficiency machining in the industrial field.     

金刚石工具真空钎焊钎料的适应性

应用真空钎焊技术，分别采用含有强碳化物形成元素Cr、Ti的BNi2、BNi7及自制的CuSnNiTi钎料试制了单层金剐石圆锯片，在一定的钎焊温度、时间及真空度下，金刚石与钎料及基体之间均可形成化学冶金结合，但结合的状况及锯切性能随钎料的不同而改变。试验证实自制的CuSnNiTi钎料钎焊温度低，焊接时金刚石的热损伤小，钎料与金剐石有很好的润湿性。不仅基体对金刚石有较高的把持力而且钎料与所切割的石材有很好的适应性。     

SiO2-BN复相陶瓷润湿性及其接头微观组织

采用座滴法开展Ag-21Cu-4.5Ti合金钎料对SiO₂-BN复相陶瓷润湿与铺展行为研究. 利用SEM、XRD分析润湿界面微观组织以及形成机理. 通过调控SiO₂-BN复相陶瓷中BN含量,研究Ag-21Cu-4.5Ti/SiO₂-BN复相陶瓷润湿体系的润湿模型. 结果表明,Ag-21Cu-4.5Ti/SiO₂-BN复相陶瓷润湿体系的典型界面反应产物为TiN和TiB₂,随着体系BN含量的增加,润湿性逐渐变好. 对SiO₂-BN复相陶瓷与Nb进行钎焊试验,典型界面组织为SiO₂-BN复相陶瓷/TiN + TiB₂/Ti₂Cu + (Ag,Cu)/(βTi,Nb)/Nb. 接头抗剪强度随着钎焊时间升高先增大后减小,当钎焊温度为880 ℃,保温时间10 min时,钎焊接头抗剪强度最高,到达39 MPa.     

金刚石/铜复合材料与氧化铝陶瓷的Ag-Cu-Ti活性钎焊(英文)

金刚石/铜复合材料具有低膨胀系数和高热导率等优异性能,使其成为一种理想的电子封装材料。采用97%(72Ag-28Cu)-3%Ti活性钎料对金刚石/铜复合材料和氧化铝陶瓷进行钎焊。发现活性钎料在氧化铝陶瓷和金刚石薄膜表面均具有良好的润湿性,在两者表面的平衡润湿角均小于5°。讨论了主要钎焊条件(如钎焊温度和保温时间等)对接头性能的影响。发现钎焊过程中Ti元素聚集在金刚石颗粒的表面形成TiC化合物,且TiC化合物的形貌与钎焊接头的剪切强度具有紧密联系。推测合适的TiC化合物层厚度可改善钎焊接头的剪切强度,而颗粒状的TiC化合物及过厚的TiC化合物层却会损害钎焊接头的性能。获得的最大剪切强度为117MPa。     

The Effect of Wetting Gravity Regime on Shear Strength of SAC and Sn-Pb Solder Lap Joints

The failure of solder joints due to imposed stresses in an electronic assembly is governed by shear bond strength. In the present study, the effect of wetting gravity regime on single-lap shear strength of Sn-0.3Ag-0.7Cu and Sn-2.5Ag-0.5Cu solder alloys reflowed between bare copper substrates as well as Ni-coated Cu substrates was investigated. Samples were reflowed for 10 s, T _gz (time corresponding to the end of gravity regime) and 100 s individually and tested for single-lap shear strength. The single-lap shear test was also carried out on eutectic Sn-Pb/Cu- and Sn-Pb/Ni-coated Cu specimens to compare the shear strength values obtained with those of lead-free alloys. The eutectic Sn-Pb showed significantly higher ultimate shear strength on bare Cu substrates when compared to Sn-Ag-Cu alloys. However, SAC alloys reflowed on nickel-coated copper substrate exhibited higher shear strength when compared to eutectic Sn-Pb/Ni-coated Cu specimens. All the substrate/solder/substrate lap joint specimens that were reflowed for the time corresponding to the end of gravity regime exhibited maximum ultimate shear strength.     

大粒度镍基合金焊料真空钎焊金刚石工艺

为解决金刚石钎焊工艺所用粉末状合金焊料用量难以控制、焊料层均匀性较差的问题,提出大粒度合金焊料真空钎焊金刚石的工艺构想并建立了几何模型,得出金刚石最优钎焊效果的大粒度合金焊料与金刚石粒度关系方程组,并求得基于合金焊料润湿角的实际解. 根据测定的镍基合金焊料润湿角得出50目大粒度合金焊料匹配的金刚石粒度为60目. 进行了金刚石真空钎焊试验与重负载磨削试验,试验表明,大粒度镍基合金焊料熔化完全,流淌性好,对金刚石具有良好的包埋、爬升效果;金刚石出露60%~70%,表面清洁无杂质. 重负载磨削后金刚石出现刃口磨损、局部破碎、磨平三个正常磨损状态,证明了新工艺的可行性.     

Bi对Sn-0.3Ag-0.7Cu无铅钎料熔点及润湿性能的影响

研究了添加适量的Bi元素对低银型Sn-0．3Ag-0．7Cu无铅钎料合金性能的影响,应用差示扫描量热仪和SAT-5100型润湿平衡仪对Sn-0．3Ag-0．7Cu·xBi（x=0.1,3,4．5）钎料的熔点、润湿性能作了对比试验分析。结果表明,一定量Bi元素的加入可以降低Sn-0．3Ag-0．7Cu钎料合金的熔点,并改善其润湿性能。但过多的Bi元素会导致钎料的液固相线温度差增大,塑性下降,造成焊点剥离缺陷。综合考虑得到Sn-0．3Ag-0．7Cu-3．0Bi无铅钎料具有最佳的综合性能。     

BGA单板结构与板级结构焊点剪切力学行为分析

采用试验方法研究BGA封装结构中焊点的剪切力学行为. 分析并比较了Sn-3Ag-0.5Cu,Sn-0.3Ag-0.7Cu,Sn-0.3Ag-0.7Cu-0.07La和Sn-0.3Ag-0.7Cu-0.07La-0.05Ce四种钎料焊点在单板结构与板级结构中的力学性能. 结果表明, 单板结构中焊点的抗剪强度高于板级结构中焊点的抗剪强度. 在单板结构中,高银焊点的抗剪强度最大,加入稀土元素的低银焊点只是得到了一定程度上的改善,然而对于板级结构,加入稀土元素的低银焊点剪切力学性能基本与高银焊点相当. 在同等拘束条件下,低银焊点的延展性优于高银焊点. 此外,对于同一种钎料而言,单板结构中的焊点断裂在体钎料上,而板级结构则断裂在IMC/体钎料界面处.     

AgCuTi活性钎料的轧制加工和性能研究

采用粉末冶金的方法,制备了两种成分的AgCuTi活性钎料。用金相显微镜、扫描电子显微镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)等研究了合金片材的组织形貌与结构。探讨了在不同的轧制变形量下,两种合金的变形量与组织结构、硬度、密度、电导率等物理、力学、电学性能的关系,分析了轧制撕裂断口的形貌和类型。结果表明,Ag-27.5Cu-2.5Ti和Ag-28Cu-4Ti两种成分活性钎料的组织结构、性能、断裂机理不一样,Ag-28Cu-4Ti的铜钛相分布较多、硬度较高、密度较低、电导率较小,同时塑性较差,轧制撕裂过程脆性断裂占主要部分;Ag-27.5Cu-2.5Ti塑性较好,轧制撕裂过程塑性断裂占主要部分。     

Ti含量对Ni-14Cr-10P-xTi焊膏连接C/C复合材料组织及性能的影响

将不同质量分数的钛粉加入Ni-14Cr-10P合金粉末中,再配合高分子聚合物制得膏状Ni-14Cr-10P-x Ti活性钎料,用制得的焊膏钎焊C/C复合材料,然后测试了钎焊接头的剪切强度,通过扫描电子显微镜、能谱分析仪、电子探针显微分析仪等对钎焊接头界面组织特征进行分析。结果表明:活性元素Cr、Ti与C/C复合材料表面的C反应而起到表面改性的作用,使得钎料能在C/C复合材料表面润湿、填缝。随着Ti元素加入量的增加,钎焊接头剪切强度先增加再降低。Ti质量分数为1%时,TiC呈颗粒状弥散分布,使得钎料层强化,接头剪切强度增加;当Ti增加到3%时,在界面处形成了连续的Cr_3C_2/TiC脆性材料层,接头剪切强度下降;Ti质量分数达到5%时,Ti与Cr_3C_2反应使得梯度界面层消失,界面物质热膨胀系数差异增大,残余热应力增加,同时Ti与Ni、Cr形成的金属间化合物增加并集中分布在钎料层中,导致接头剪切强度急剧下降。     

Kinetics of internal oxidation in Ag-6Sn-2In-1Te-0.2Ni and Ag-6Sn-0.6Cu-1Bi-0.2Ni type alloys

Internal oxidation process was followed in Ag-6Sn-2In-1Te-0.2Ni and Ag-6Sn-0.6Cu-1Bi-0.2Ni alloy types in free air and oxygen at 650 °C and 680 °C. It was found that the Cu and Bi bearing alloy had a higher rates of internal oxidation in all of the tested conditions, whish was due to Bi effect accelerating the internal oxidation. In the early stage of internal oxidation of the Ag-6Sn-2In-1Te-0.2Ni alloy, an inhomogeneous structure revealed, which changed to a homogenous pattern after longer oxidation times. Such a structure was suppressed in the Bi bearing alloy. The applied 6 bar oxygen atmosphere brought on a 5–6 times higher rate of internal oxidation, with a homogenous structure compared to the free air oxidation. In free air after long time oxidation (200 h–250 h), the rate of internal oxidation was found to have almost doubled in both alloys.