The properties of Sn-9Zn lead-free solder alloys doped with trace rare earth elements

The Sn-Zn alloys have been considered as lead-free solders. It is well known that their poor properties of wetting and oxidation resistance are the main problems to prevent them from becoming commercially viable solders. In this paper, trace rare earth (RE) elements of mainly Ce and La have been used as alloying elements into the Sn-9Zn alloy. The results indicated that with the RE addition the originally coarse β-Sn grains in the microstructure of the alloy were refined. The tensile strength significantly increased with only a slight decrease in ductility. The surface tension was decreased, resulting in great improvement in wetting properties with rosin-based active flux.     

Study on the microstructure of a novel lead-free solder alloy SnAgCu-RE and its soldered joints

This paper focused on the microstructure of SnAgCu-rare earth (RE) solder alloy and its small single-lap joints, focusing on phases present and the distribution of RE in the SnAgCu solder. Energy dispersive x-ray (EDX) analysis was used to observed the RE-rich phase. The RE atoms also tended to aggregate at boundaries of primary dendrites in the joints and form as a weblike structure, which surrounded the dendrites and restrained the dendrites from sliding or moving. It is assumed that this would strengthen the boundaries and increase the resistance to creep deformation of the solder matrix. The creep-rupture life of joints can be remarkably increased, at least seven times more than that of SnAgCu at room temperature. The aggregation mechanism of RE at dendrite boundaries in SnAgCu solder joints was presented. The drive for RE atoms to aggregate at the boundary is the difference of the lattice-aberration energy between the interior and the boundaries of the dendrites, which is caused by a solution of RE atoms.     

Microstructure, solderability, and growth of intermetallic compounds of Sn-Ag-Cu-RE lead-free solder alloys

The near-eutectic Sn-3.5 wt.% Ag-0.7 wt.% Cu (Sn-3.5Ag-0.7Cu) alloy was doped with rare earth (RE) elements of primarily Ce and La of 0.05–0.25 wt.% to form Sn-3.5Ag-0.7Cu-xRE solder alloys. The aim of this research was to investigate the effect of the addition of RE elements on the microstructure and solderability of this alloy. Sn-3.5Ag-0.7Cu-xRE solders were soldered on copper coupons. The thickness of the intermetallic layer (IML) formed between the solder and Cu substrate just after soldering, as well as after thermal aging at 170°C up to 1000 h, was investigated. It was found that, due to the addition of the RE elements, the size of the Sn grains was reduced. In particular, the addition of 0.1wt.%RE to the Sn-3.5Ag-0.7Cu solder improved the wetting behavior. Besides, the IML growth during thermal aging was inhibited.     

Constitutive relations on creep for SnAgCuRE lead-free solder joints

Taking the most promising substitute of the Sn-3.8Ag-0.7Cu solder as the research base, investigations were made to explore the effect of rare earths (REs) on the creep performance of the Sn-3.8Ag-0.7Cu solder joints. The SnAgCu-0.1RE solder with the longest creep-rupture life was selected for subsequent research. Creep strain tests were conducted on Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints in the intermediate temperature range from 298 K to 398 K, corresponding to the homologous temperatures η=0.606, 0.687, 0.748, and 0.809 and η = 0.602, 0.683, 0.743, and 0.804, respectively, to acquire the relevant creep parameters, such as stress exponent and activation energy, which characterize the creep mechanisms. The final creep constitutive equations for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints were established, demonstrating the dependence of steady-state creep rate on stress and temperature. By correcting the apparent creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints from the experiments, the true creep-activation energy is obtained. Results indicated that at low stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the lattice self-diffusion activation energy, so the steady-state creep rates of these two solder joints are both dominated by the rate of lattice self-diffusion. While at high stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the dislocation-pipe diffusion activation energy, so the steady-state creep rates are dominated by the rate of dislocation-pipe diffusion. At low stress, the best-fit stress exponents n of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are 6.9 and 8.2, respectively, and the true creep-activation energy of them both is close to that of lattice self-diffusion. At high stress, it equals 11.6 and 14.6 for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints, respectively, and the true creep-activation energy for both is close to that of the dislocation-pipe diffusion. Thus, under the condition of the experimental temperatures and stresses, the dislocation climbing mechanism serves as the controlling mechanism for creep deformation of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints. The creep values of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are both controlled by dislocation climbing. Dislocation glide and climb both contribute to creep deformation, but the controlling mechanism is dislocation climb. At low stress, dislocation climbing is dominated by the lattice self-diffusion process in the Sn matrix and dominated by the dislocation-pipe diffusion process at high stress.     

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.     

Properties of lead-free solder SnAgCu containing minute amounts of rare earth

Because of excellent wetting and mechanical properties, SnAgCu solder alloys have been regarded as the most promising Pb-free substitutes for the SnPb solder. The Sn-3.8Ag-0.7Cu solder has garnered attention because of its creep resistance. However, under the drives of increasingly finer pitch design and severe service conditions, novel lead-free solders with higher creep performance may be needed. Adding a surface-active element to an alloy is an effective way to improve the high-temperature performance of the solder. The present work focuses on the effect of rare earth (RE) on the physical properties, spreading property, and mechanical properties of SnAgCu solder. Results show that the creep-rupture life of SnAgCu solder joints at room temperature could be notably increased by adding a minute amount of RE, up to 7 times more than that of SnAgCu solder joints when containing 1.0wt.%RE. The differential scanning calorimetry (DSC) curves indicated that the melting temperature of SnAgCu solder with RE increased a little, and no lower melting-temperature, eutectic endothermal peak appears on the DSC curve. The electrical conductivity of the solder decreased slightly, but it is still superior to the SnPb eutectic solder. Compared to that of SnPb solder, the coefficient of thermal expansion (CTE) of SnAgCu (RE) is closer to copper, which usually serves as the substrate of printed circuit boards (PCBs). It is assumed that this will comparably reduce the thermal stress derived from thermal mismatch between the solder and the PCBs. The RE had no apparent effect on the spreading property, but when RE added up to 1.0 wt.%, the spreading area of the solder on the copper substrate decreased, obviously, because of mass oxide. The RE improved the ultimate tensile strength little, but it increased the elongation up to 30%. However, as the content of the RE increases, the elongation of the solder gradually decreased to the level of SnAgCu when the RE exceeds 0.25 wt.%. Additionally, RE made the elastic modulus of SnAgCu solder increase, so the resistance to elastic deformation of the solder is enhanced. The microstructure of SnAgCuRE led to a refining trend as the RE content increased. The RE compounds appeared in the solder when RE was 0.1 wt.%. This deteriorates the mechanical properties of the solder. The fractography of the tensile specimen containing 0.1 wt.% indicated a superior ductility to Sn-3.8Ag-0.7Cu bulk solder. However, as RE is increased to 1.0 wt.%, the fractography shows less ductile characteristics, which is believed to serve as the reason that the elongation of solder degrades as RE increases. Summarily, the most suitable content of RE is within 0.05–0.5 wt.% and is inadvisable beyond 1.0 wt.%.     

锡基无铅钎料的性能研究与新进展

介绍了现阶段锡基无铅钎料的使用和生产情况,归纳了钎料合金的特点,综述了不同系列无铅钎料的熔化特性、焊后的剪切强度及可焊性等,总结了目前无铅钎料研究所取得的新成果、新进展以及存在的问题。从锡晶须,虚焊等方面指出了无铅钎料可靠性的不足,并提出部分解决方案,指出了无铅钎料的发展趋势和应用前景。     

Microstructure and mechanical properties of Pb-free solder alloys for low-cost electronic assembly: A review

Lead-free solders, including Sn-58Bi, Sn-52In, and Sn-3.5Ag, are potential replacements for Sn-37Pb solder in low-cost electronic assembly. This paper reviews the literature on the microstructure and mechanical properties of these alloys. Because of the processing and testing conditions, many of the data are not predictive for electronic assembly applications. However, eutectic Sn-Bi seems to have properties approaching those of eutectic Sn-Pb under most conditions, while eutectic Sn-In seems far inferior in most respects. Eutectic Sn-Ag has many promising characteristics, but its relatively high melting temperature may preclude its use for this type of application.     

Ag和RE对SnAgCuRE无铅钎料拉伸性能的影响

利用正交试验法,对SnAgCuRE系钎料合金的拉伸性能进行了检验。结果表明:SnAgCuRE系钎料合金的拉伸性能与Ag和RE的添加量密切相关,即拉伸强度会随Ag含量增大而提高;延伸率受RE影响最大,并在w(RE)为0.1%时延伸率和拉伸强度都达到最佳。当w(RE)达到0.5%时,会导致延伸率的下降。     

稀土相表面Sn晶须生长的研究

研究了Sn-3.8Ag-0.7Cu-RE(RE为Ce、Er或Y)焊料在空气中室温与高温时效过程中稀土相CeSn3、ErSn3与YSn3表面Sn晶须的生长情况。结果表明,Sn晶须的开始生长时间、形态及数量与稀土相的种类及时效条件有密切关系。稀土相因氧化产生的体积膨胀提供了Sn晶须生长的驱动力。稀土与氧的化学亲和力参数及时效温度共同影响稀土相表面Sn晶须的生长。室温实效条件下,三种稀土相表面Sn晶须的直径为0.1~2.0μm,长度可达几百微米;150℃时效条件下,Sn晶须的直径为0.1~0.2μm,长度也可达上百微米。     

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.     

The anomalous microstructural,tensile, and aging response of thin-cast Sn3.9Ag0.6Cu lead-free solder

In this study, bulk and thin-cast samples were produced with an identical Sn3.9Ag0.6Cu composition. The thin-cast material exhibited a much finer as-quenched microstructure than the bulk material with the intermetallic compound (IMC) phase restricted to a thin network. Both the bulk and thincast materials continually softened during room-temperature aging, while both materials initially softened and then subsequently hardened when aged at 120°C and 180°C. The thin-cast material was in all cases significantly softer than the bulk material, and responded to aging as if it were bulk material aged at a higher temperature. These results have significant implications for the elevated temperature application of Sn3.9Ag0.6Cu.     

SnAgCuRE系钎料的钎焊接头组织与力学性能

以Sn2.5Ag0.7Cu为基础,添加微量的稀土(RE)r(Ce︰La)为4︰1,研究了钎焊接头的显微组织与力学性能。结果表明:添加微量的RE后,钎料与Cu试样间的界面层厚度明显减小,且界面处的组织更加平滑,相应地其剪切强度随微量RE的添加而增大,并在RE含量(质量分数)为0.1%时达到最大值36MPa。     

Creep resistance of tin-based lead-free solder alloys

This paper reports on the microstructure-creep property relationship of three precipitation-strengthened tin (Sn)-based lead (Pb)-free solder alloys (Sn-0.7Cu, Sn-3.5Ag, and Sn-3.8Ag-0.7Cu) in bulk samples, together with Sn-37Pb as the alloy for comparison at temperatures of 303 K, 348 K, and 393 K. The creep resistance of these three Sn-based Pb-free solders increases, i.e., the steady-state creep rates decrease, with increasing volume fraction of precipitate phases for the Pb-free solder alloys. Their apparent stress exponents (n_a ∼ 7.3-17), which are all higher than that of pure Sn, attain higher values with increasing volume fraction of precipitate phases at constant temperature, and with decreasing temperature for the same solder alloy.     

SnAgCuY钎料高温时效过程的显微组织演化

研究了无铅钎料合金Sn3.8Ag0.7Cu高温时效过程中显微组织,特别是金属间化合物(IMC)的演化规律,以及稀土Y的添加对其产生的影响。结果表明:在高温时效过程中合金内部组元发生扩散与重组,伴随着共晶组织的逐渐溶解,新的IMC在组织内部呈球形弥散析出。结晶初期形成的具有规则形状的较粗大的IMC逐渐发生解体,树枝状富Sn相逐渐取代共晶组织成为受腐蚀的对象。随着时效时间的延长,合金内部各组元的成分也在不断发生变化。     

纳米压痕法分析无铅焊点内界面金属化合物的力学性能

根据实际工艺流程和服役工况制备了微电子封装中3种无铅焊点(Sn3.0Ag0.5Cu、Sn0.7Cu和Sn3.5Ag)内界面金属化合物(IMC)的试样;利用扫描电镜(SEM)和能量色散X射线荧光光谱仪(EDX)对所制IMC的形貌和化学成分进行了分析;另外,借助纳米压痕仪,采用连续刚度测量(CSM)技术在不同的加载速率下对所制IMC的弹性模量和硬度进行了测量。结果表明,3种无铅焊点内的IMC均为Cu6Sn5,其弹性模量分别为98.93±3.37,113.55±4.58和(102.16±3.11)GPa,硬度分别为5.18±0.14,5.78±0.11和(5.55±0.19)GPa。     

热时效和焊点尺寸对SnAgCu微焊点强度的影响

针对高度为100～300μm的无铅钎料Sn-3.0Ag-0.5Cu微焊点,研究了等温热时效和焊点尺寸对其在100℃下拉伸强度的影响。结果表明,保持焊点直径不变时,高度为100,200和300μm微焊点未经热时效的平均拉伸强度分别为53.75,46.59和44.38MPa;热时效时间延长使微焊点内钎料合金显微组织明显粗化,导致焊点拉伸强度降低,前述三种高度的微焊点96h热时效后平均拉伸强度分别为44.13,38.38和33.48MPa,但96h热时效对IMC厚度无明显影响。     

Ce对Sn-Ag-Cu系焊料合金的组织与性能影响

通过添加稀土Ce研究了Sn-3.0Ag-2.8Cu系焊料合金的显微组织和性能。用光学显微镜、SEM、EDX对其显微组织进行分析,并且对其导电性,润湿性,硬度等重要性能进行测试。结果表明,添加稀土w(Ce)为1%焊料合金的导电性明显提高;而润湿角明显减小,润湿性增强;同时焊料合金的硬度也有所增加。     

A quantitative evaluation of time-independent and time-dependent deformations of lead-free and lead-containing solder alloys

A method to separate plasticity and creep is discussed for a quantitative evaluation of the plastic, transient creep, and steady-state creep deformations of solder alloys. The method of separation employs an elasto-plastic-creep constitutive model comprised of the sum of the plastic, transient creep, and steady-state creep deformations. The plastic deformation is expressed by the Ramberg-Osgood law, the steady-state creep deformation by Garofalo’s creep law, and the transient creep deformation by a model proposed here. A method to estimate the material constants in the elasto-plastic-creep constitutive model is also proposed. The method of separation of the various deformations is applied to the deformation of the lead-free solder alloy Sn/3Ag/0.5Cu and the lead-containing solder alloy Sn/37Pb to compare the differences in the plastic, transient creep, and steady-state creep deformations. The method of separation provides a powerful tool to select the optimum lead-free solder alloys for solder joints of electronic devices.     

Sn-Ag-Cu系无铅焊锡的力学性能和实用性能

研究添加稀土Ce对Sn-Ag-Cu合金的力学性能和实用性能的影响,利用光学显微镜、SEM、EDX对合金的组织、形貌、成分进行分析。结果表明,在Sn-Ag-Cu系无铅焊锡中添加稀土Ce可以细化合金组织,使合金成分分布更加均匀;稀土Ce的添加可以明显提高合金的延伸率;添加Ce后延伸率提高了6.1%,从而使力学性能大大提高;适量稀土的加入使焊料与基体结合更加紧密,外观平整,对合金的实用性能有很大提高。