Creep Properties of Sn-1.0Ag-0.5Cu Lead-Free Solder with Ni Addition

In this work, tensile creep tests for Sn-1.0Ag-0.5Cu-0.02Ni solder have been conducted at various temperatures and stress levels to determine its creep properties. The effects of stress level and temperature on creep strain rate were investigated. Creep constitutive models (such as the simple power-law model, hyperbolic sine model, double power-law model, and exponential model) have been reviewed, and the material constants of each model have been determined based on experimental results. The stress exponent and creep activation energy have been studied and compared with other researchers’ results. These four creep constitutive models established in this paper were then implemented into a user-defined subroutine in the ANSYS™ finite-element analysis software to investigate the creep behavior of Sn-1.0Ag-0.5Cu-0.02Ni solder joints of thin fine-pitch ball grid array (TFBGA) packages for the purpose of model comparison and application. Similar simulation results of creep strain and creep strain energy density were achieved when using the different creep constitutive models, indicating that the creep models are consistent and accurate.     

Further Observations on Tin Pest Formation in Solder Alloys

The most recent observations of the response of bulk samples of several commercial solder alloys, exposed to temperatures below the allotropic transition for tin (13°C) for extended periods, are reported. Damage associated with tin pest development has been arbitrarily graded into six levels, and the formation of visible α-phase warts used for comparative purposes. Since the previous examination, some 2 years ago, tin pest has been observed for the first time in the traditional Sn-37Pb solder alloy after exposure at −18°C and −40°C, and actual warts were apparent in as-cast Sn-0.5Cu stored at −40°C and in as-cast Sn-3.5Ag after exposure at −18°C. No tin pest was detected in Sn-Zn-3Bi after exposure for periods up to 6 years. Tin pest continued to develop in those lead-free alloys in which it had previously been observed, indicating the probability that all would eventually disintegrate in time. In general, prior thermal or mechanical treatment accentuated tin pest formation. The influence of exposure temperature was unclear, since some alloys (Sn-0.5Cu and Sn-3.8Ag-0.7Cu) experienced more damage at −18°C, but others (Sn-37Pb and Sn-3.5Ag) were more susceptible at −40°C. From a consideration of the findings and other published information, it is contended that impurity levels below 0.1 mass% (1000 ppm) play a vital role in determining whether tin pest develops in realistic timescales. A major factor in the absence of tin pest, to date, on actual joints may be simply the mismatch between the timescales experienced in service and those in long-duration laboratory tests.     

Recent Observations on Tin Pest Formation in Solder Alloys

The most recent observations of the response of bulk samples of several lead-free solder alloys, exposed to temperatures below the allotropic transition for tin for extended periods, are reported. Tin pest has been observed in Sn-0.5Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and Sn-3.0Ag-0.5Cu alloys at both −18°C and −40°C. The process is slow and inconsistent, usually requiring several years, but may eventually result in complete disintegration of the sample. No tin pest was detected in Sn-Zn-3Bi or in the traditional Sn-37Pb solder alloy after exposure for up to 4 and 10 years, respectively. It is suggested that nucleation is affected by local composition and that extremely small amounts of either intentional solute or impurity are influential. Growth of tin pest is accompanied by a large volume change, and it is likely that stress relaxation ahead of the expanding grey tin front is a controlling factor. A stronger matrix would be more resistant in this case, and at the temperatures of exposure Sn-37Pb is stronger than either Sn-3.5Ag or Sn-0.5Cu. The absence of tin pest, to date, on actual joints is attributed to their restricted free surface area and the greater strength associated with very small samples.     

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。     

Tin Whisker Growth on the Surface of Sn-0.7Cu Lead-Free Solder with a Rare Earth (Nd) Addition

The phenomenon of rare earth (RE) additions inducing whisker growth in Sn-0.7Cu-Nd (0.1–5 wt.%Nd) solder is reported. The results showed that Nd exists as Sn₃Nd in the microstructure of the solder alloys. A snowflake-like Sn₃Nd was observed when Nd ≤ 0.5 wt.%. After exposure to ambient conditions, the Nd-bearing alloys have a strong tendency toward whisker growth, with a short incubation time for whisker nucleation (only several hours). All whiskers originated from the Sn-Nd compound, where whiskers grew relatively fast; the average growth rate of the five longest whiskers was approximately 4 ?/s, and a 190 μm whisker was observed within 480 h. Based on these results, it was predicted that whisker growth would be inevitable for all RE-bearing solders. The cause of this phenomenon is also discussed. Finally, the authors suggest that any solders doped with RE should be carefully considered again.     

Intermetallics Evolution in Sn-3.5Ag Based Lead-Free Solder Matrix on an OSP Cu Finish

The 0.2Co + 0.1Ni dual additives were used to dope a Sn-3.5Ag solder matrix to modify the alloy microstructure and the solder joint on an organic solderability preservative (OSP) Cu pad. The refined microstructure of the Sn-3.5Ag-0.2Co-0.1Ni solder alloy or the reduced β-Sn size was attributed to the depressed undercooling achieved by the Co-Ni addition. After soldering on the OSP Cu pad, a large Ag₃Sn plate was formed at the Sn-3.5Ag/OSP solder joint, whereas it was absent at the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joints. With isothermal aging at 150°C, large Ag₃Sn plates formed at the Sn-3.5Ag/OSP solder joint were still observed. A coarsened and dispersed Ag₃Sn phase was found in the solder joints with Co-Ni additions as well. Compared to Cu₆Sn₅, the (Co,Ni)Sn₂ intermetallic compound showed much lower microhardness values. However, (Co,Ni)Sn₂ hardness was comparable to that of the Ag₃Sn phase. Pull strength testing of Sn-3.5Ag-0.2Co-0.1Ni/OSP revealed slightly lower values than for Sn-3.5Ag/OSP during aging. Such results are thought be due to the phase transformation of (Co,Ni)Sn₂ to (Cu,Co,Ni)₆Sn₅.     

Sn-3.0Ag-0.5Cu真空再流焊工艺技术研究

为了获得低热阻和解决不同焊接材料之间的热应力匹配问题,大功率DC-DC模块电源产品广泛采用了载体组件作为功率元器件热沉的散热方法。载体组件由金属基板和陶瓷基板焊接而成,为了得到无空洞的焊接界面,载体组件采用了真空再流焊工艺技术。文中从焊料形态、焊接表面处理、真空度等几个方面介绍了载体组件的Sn-3.0Ag-0.5Cu真...     

Modeling Material Properties of Lead-Free Solder Alloys

A full set of physical and thermophysical properties for lead-free solder (LFS) alloys have been calculated, including liquidus/solidus temperatures, fraction solid, density, coefficient of thermal expansion, thermal conductivity, Young’s modulus, viscosity, and liquid surface tension, all as a function of composition and temperature (extending into the liquid state). The results have been extensively validated against data available in the literature. A detailed comparison of the properties of two LFS alloys Sn-20In-2.8Ag and Sn-5.5Zn-4.5In-3.5Bi with Sn-37Pb has been made to show the utility and need for calculations that cover a wide range of properties, including the need to consider the effect of nonequilibrium cooling. The modeling of many of these properties follows well-established procedures previously used in JMatPro software for a range of structural alloys. This paper describes an additional procedure for the calculation of the liquid surface tension for multicomponent systems, based on the Butler equation. Future software developments are reviewed, including the addition of mechanical properties, but the present calculations can already make a useful contribution to the selection of appropriate new LFS alloys.     

Creep Behavior of Bi-Containing Lead-Free Solder Alloys

The creep behavior of Sn-3.0Ag-0.5Cu (SAC305), Sn-3.4Ag-1.0Cu-3.3Bi (SAC-Bi), and Sn-3.4Ag-4.8Bi (SnAg-Bi, all wt.%) was studied in constant-stress creep tests from room temperature to 125°C. The alloys were tested in two microstructural conditions. As-cast alloys had a composite eutectic-primary Sn structure, while in aged alloys the eutectic regions were replaced by a continuous Sn matrix with coarsened intermetallic (Cu₆Sn₅ and Ag₃Sn) particles. After aging, Bi in SAC-Bi and SnAg-Bi was found as precipitates at grain boundaries and grain interiors. The creep resistance of of-cast SAC305 was higher than that of as-cast Bi-containing alloys, but after aging the SAC305 had the lowest creep resistance. The creep strain rates in SAC-Bi and SnAg-Bi were much less affected by aging. The apparent activation energy for creep was also changed more for SAC305 than for the other two alloys. The creep behavior of SAC-Bi and SnAg-Bi can be understood by considering the solubility of Bi in Sn. The difference in creep behavior between as-cast and aged SAC-Bi is greatly reduced when room-temperature test results are excluded from analysis. This suggests that the strongest influence on creep in these alloys is due to Bi solute interaction with moving dislocations during deformation.     

Sn-3.5Ag-0.5Cu无铅焊料力学性能与组织特征研究

研究了Sn-3.5Ag-0.5Cu无铅焊料的力学性能与组织特征,结果表明焊料的应力应变关系表现出明显的温度和应变速率相关性,当温度升高,应变速率降低时,焊料的强度极限均会减小,但强度极限与温度和应变速率之间呈非线性相关;焊料在拉断前后,内部晶粒会与排列方式发生变化,且变形大小与加载的应变速率相关.     

Corrosion Behavior of Pb-Free Sn-1Ag-0.5Cu-XNi Solder Alloys in 3.5% NaCl Solution

Potentiodynamic polarization techniques were employed in the present study to investigate the corrosion behavior of Pb-free Sn-1Ag-0.5Cu-XNi solder alloys in 3.5% NaCl solution. Polarization studies indicated that an increase in Ni content from 0.05 wt.% to 1 wt.% in the solder alloy shifted the corrosion potential (E _corr) towards more negative values and increased the linear polarization resistance. Increased addition of Ni to 1 wt.% resulted in significant increase in the concentration of both Sn and Ni oxides on the outer surface. Secondary-ion mass spectrometry and Auger depth profile analysis revealed that oxides of tin contributed primarily towards the formation of the passive film on the surface of the solder alloys containing 0.05 wt.% and 1 wt.% Ni. Scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDX) established the formation of a Sn whisker near the passive region of the solder alloy obtained from the polarization curves. The formation of Sn whiskers was due to the buildup of compressive stress generated by the increase in the volume of the oxides of Sn and Ni formed on the outer surface. The presence of Cl^? was responsible for the breakdown of the passive film, and significant pitting corrosion in the form of distinct pits was noticed in Sn-1Ag-0.5Cu-0.5Ni solder alloy after the polarization experiment.     

Interfacial Reactions of Sn-3.0Ag-0.5Cu Solder with Cu-Mn UBM During Aging

Cu under bump metallurgy (UBM) has been widely used in flip-chip technology. The major disadvantages of Cu UBM are fast consumption of copper, rapid growth of intermetallic compounds (IMCs), and easy formation of Kirkendall voids. In this study we added two different contents of Mn (2 at.% and 10 at.%) to Cu UBM by sputtering to modify the conventional Cu metallization. For the higher Mn concentration in the Cu-Mn UBM, a new Sn-rich phase formed between Cu₆Sn₅ and the Cu-Mn UBM, and cracks formed after aging. For the lower Mn concentration, growth of Cu₃Sn and Kirkendall voids was significantly suppressed after thermal aging. Kinetic analysis and x-ray elemental mapping provided evidence that Mn diffusion into Cu₃Sn slowed diffusion of Cu in the Cu₃Sn layer. The Mn-enriched Cu₃Sn layer may serve as a diffusion barrier to reduce the interfacial reaction rate and Kirkendall void formation. These results suggest that Cu-Mn UBM with low Mn concentration is beneficial in terms of retarding Cu pad consumption in solder joints.     

Electromigration Behavior in Sn-37Pb and Sn-3.0Ag-0.5Cu Flip-Chip Solder Joints under High Current Density

The electromigration of conventional Sn-37Pb and Pb-free Sn-3.0Ag-0.5Cu (in wt.%) solder bumps was investigated with a high current density of 2.5 × 10⁴ A/cm² at 423 K using flip-chip specimens comprised of an upper Si chip and a lower bismaleimide triazine (BT) substrate. Electromigration failure of the Sn-37Pb and Sn-3.0Ag-0.5Cu solder bumps occurred with complete consumption of electroless Ni immersion Au (ENIG) underbump metallization (UBM) and void formation at the cathode side of the solder bump. Finite element analysis and computational simulations indicated high current crowding of electrons in the patterned Cu on the Si chip side, whereas the solder bumps and Cu line of the BT substrate had a relatively low density of flowing electrons. These findings were confirmed by the experimental results. The electromigration reliability of the Sn-3.0Ag-0.5Cu solder joint was superior to that of Sn-37Pb.     

A Study on the Physical Properties and Interfacial Reactions with Cu Substrate of Rapidly Solidified Sn-3.5Ag Lead-Free Solder

A rapidly solidified Sn-3.5Ag eutectic alloy produced by the melt-spinning technique was used as a sample in this research to investigate the microstructure, thermal properties, solder wettability, and inhibitory effect of Ag₃Sn on Cu₆Sn₅ intermetallic compound (IMC). In addition, an as-cast Sn-3.5Ag solder was prepared as a reference. Rapidly solidified and as-cast Sn-3.5Ag alloys of the same size were soldered at 250°C for 1 s to observe their instant melting characteristics and for 3 s with different cooling methods to study the inhibitory effect of Ag₃Sn on Cu₆Sn₅ IMC. Experimental techniques such as scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectrometry were used to observe and analyze the results of the study. It was found that rapidly solidified Sn-3.5Ag solder has more uniform microstructure, better wettability, and higher melting rate as compared with the as-cast material; Ag₃Sn nanoparticles that formed in the rapidly solidified Sn-3.5Ag solder inhibited the growth of Cu₆Sn₅ IMC during aging significantly much strongly than in the as-cast material because their number in the rapidly solidified Sn-3.5Ag solder was greater than in the as-cast material with the same soldering process before aging. Among the various alternative lead-free solders, this study focused on comparison between rapidly solidified and as-cast solder alloys, with the former being observed to have better properties.     

Viscoplastic Creep Response and Microstructure of As-Fabricated Microscale Sn-3.0Ag-0.5Cu Solder Interconnects

The viscoplastic behavior of as-fabricated, undamaged, microscale Sn-3.0 Ag-0.5Cu (SAC305) Pb-free solder is investigated and compared with that of eutectic Sn-37Pb solder and near-eutectic Sn-3.8Ag-0.7Cu (SAC387) solder from prior studies. Creep measurements of microscale SAC305 solder shear specimens show significant piece-to-piece variability under identical loading. Orientation imaging microscopy reveals that these specimens contain only a few, highly anisotropic Sn grains across the entire joint. For the studied loads, the coarse-grained Sn microstructure has a more significant impact on the scatter in primary creep compared to that in the secondary creep. The observed lack of statistical homogeneity (microstructure) and joint-dependent mechanical behavior of microscale SAC305 joints are consistent with those observed for functional microelectronics interconnects. Compared with SAC305 joints, microscale Sn-37Pb shear specimens exhibit more homogenous behavior and microstructure with a large number of small Sn (and Pb) grains. Creep damage in the Pb-free joint is predominantly concentrated at highly misoriented Sn grain boundaries. The coarse-grained Sn microstructure recrystallizes into new grains with high misorientation angles under creep loading. In spite of the observed joint-dependent behavior, as-fabricated SAC305 is significantly more creep resistant than Sn-37Pb solder and slightly less creep resistant than near-eutectic SAC387 solder. Average model constants for primary and secondary creep of SAC305 are presented. Since the viscoplastic measurements are averaged over a wide range of grain configurations, the creep model constants represent the effective continuum behavior in an average sense. The average secondary creep behavior suggests that the dominant creep mechanism is dislocation climb assisted by dislocation pipe diffusion.