Rare-earth additions to lead-free electronic solders

The research in lead(Pb)-free solder alloy has been a popular topic in recent years, and has led to commercially available Pb-free alloys. Further research in certain properties to improve aspects such as manufacturability and long term reliability in many Pb-free alloys are currently undertaken. It was found by researchers that popular Pb-free solders such as Sn–Ag, Sn–Cu, Sn–Zn and Sn–Ag–Cu had improved their properties by doping with trace amounts of rare earth (RE) elements. The improvements include better wettability, creep strength and tensile strength. In particular, the increase in creep rupture time in Sn–Ag–Cu–RE was 7 times, when the RE elements were primarily Ce and La. Apart from these studies, other studies have also shown that the addition of RE elements to existing Pb-free could make it solderable to substrates such as semiconductors and optical materials. This paper summarizes the effect of RE elements on the microstructure, mechanical properties and wetting behavior of certain Pb-free solder alloys. It also demonstrates that the addition of RE elements would improve the reliability of the interconnections in electronic packaging. For example, when Pb-free-RE alloys were used as solder balls in a ball grid array (BGA) package, the intermetallic compound layer thickness and the amount of interfacial reaction were reduced.     

Materials behaviour and intermetallics characteristics in the reaction between SnAgCu and Sn–Pb solder alloys

The paper compares theoretical calculations with experimental data, to identify the metallurgical mechanisms with respect to the rework or repair that may be encountered in the transition period from Sn–Pb to Pb-free soldering. Thermodynamic calculations have been carried out to study material behaviour and possible formation of intermetallic precipitates during the reaction between Sn–Pb and Sn–Ag–Cu Pb-free alloys. Two Sn–Ag–Cu alloys that are relevant to current industrial interests, namely Sn–3.9Ag–0.6Cu* (known as ‘405 alloy’ in Europe and North America), and Sn–3.0Ag–0.5Cu (known as ‘305’ alloy in Asia), were reacted with different contamination levels of eutectic Sn–37Pb solder. The variables examined included those related to both the materials and processes, such as composition, temperature and cooling rate. Together these are the primary drivers with respect to the resultant solder microstructures, which were studied using scanning electron microscopy (SEM). Nanoindentation, which is suitable for the ultra-fine and complex microstructures, was also used to investigate the micromechanical properties, including hardness and elastic modulus, at both ambient and elevated temperatures. The results from this work provide guidance as to the consequence for microstructural evolution and hence mechanical integrity when small amounts of Pb exist in Pb-free alloys. The composition of alloys in this paper is in weight percentage (wt%)     

Mechanical behavior of NiTi shape memory alloy fiber reinforced Sn matrix “smart” composites

The detrimental effects of Pb on the environment and human health have provided the driving force for replacement of Pb–Sn solders with Pb-free alternatives. Sn-rich Pb-free solder alloys with silver and copper alloying additions have higher strength but lower elongation-to-failure than Pb–Sn solders. Thus, these alloys are more susceptible to failure under mechanical shock, drop, and thermal fatigue conditions. In this article, mechanical tensile testing of NiTi–Sn3.5Ag single fiber composites demonstrates superelastic behavior of the composite with 85% strain recovery. Fatigue experiments show an evolution in damage over cycles, and an S–N curve shows sharp transition between a nearly vertical low-cycle fatigue behavior and the high-cycle fatigue regime. The solder composite exhibits constant fatigue strength over the superelastic range of the NiTi fiber.     

Development of Sn–Ag–Cu and Sn–Ag–Cu–X alloys for Pb-free electronic solder applications

The global electronic assembly community is striving to accommodate the replacement of Pb-containing solders, primarily Sn–Pb alloys, with Pb-free solders due to environmental regulations and market pressures. Of the Pb-free choices, a family of solder alloys based on the Sn–Ag–Cu (SAC) ternary eutectic (T _eut. = 217°C) composition have emerged with the most potential for broad use across the industry, but the preferred (typically near-eutectic) composition is still in debate. This review will attempt to clarify the characteristic microstructures and mechanical properties of the current candidates and recommend alloy choices, a maximum operating temperature limit, and directions for future work. Also included in this review will be an exploration of several SAC + X candidates, i.e., 4th element modifications of SAC solder alloys, that are intended to control solder alloy undercooling and solidification product phases and to improve the resistance of SAC solder joints to high temperature thermal aging effects. Again, preliminary alloy recommendations will be offered, along with suggestions for future work.     

Multiple reflow study of ball grid array (BGA) solder joints on Au/Ni metallization

This paper evaluates the shearing behavior of ball grid array (BGA) solder joints on Au/Ni/Cu pads of FR4 substrates after multiple reflow soldering. A new Pb-free solder, Sn–3Ag–0.5Cu–8In (SACI), has been compared with Sn–3Ag–0.5Cu (SAC) and Sn–37Pb (SP) solders, in terms of fracture surfaces, shearing forces and microstructures. Three failure modes, ball cut, a combination of solder shear and solder/pad bond separation, and pad lift, are assessed for the different solders and reflow cycles. It is found that the shearing forces of the SP and SAC solder joints tend to increase slightly with an increase in the number of reflow cycles due to diffusion-induced solid solution strengthening of the bulk solder and augmentation of the shearing area. However, the shearing forces of the SACI solder joints decrease slightly after four cycles of reflow, which is ascribed to the thermal degradation of both the solder/intermetallic compound (IMC) and IMC/Ni interfaces. The SACI solder joints yield the highest strengths, whereas the SP solder joints give the smallest values, irrespective of the number of reflow cycles. Thickening of the interfacial IMC layer and coarsening of the dispersing IMC particles within the bulk solders were also observed. Nevertheless, the variation of shearing forces and IMC thickness with different numbers of reflow cycles was not so significant since the Ni under layer acted as an effective diffusion barrier. In addition, the initially-formed IMC layer retarded the further extensive dissolution of the pad material and its interaction with the solder.     

Creep and fatigue behaviors of the lead-free Sn–Ag–Cu–Bi and Sn60Pb40 solder interconnections at elevated temperatures

Creep and fatigue behaviors of the interconnections soldered by the lead-free Sn–Ag–Cu–Bi solder were investigated at different elevated temperatures (with the homologue temperature in the range of 0.71– 0.82), with a comparison to that of a traditional Sn60Pb40 solder. The results show that the lead-free Sn–Ag–Cu–Bi solder shows a superior anti-creep performance over the Sn60Pb40 solder, in terms of a much lower creep strain rate and a vastly elongated creep fracture lifetime; in the secondary creep regime, the calculated creep-activation energy for two solders is reasonably close to other published data. In addition, it has also been shown that the joints soldered by the lead-free Sn–Ag–Cu–Bi solder exhibits a superb fatigue property.     

Properties of SnAgCu/SnAgCuCe soldered joints for electronic packaging

For quad flat packages (QFP256), lead-free soldered joints reliability in service is a critical issue. In this paper, soldering experiments of quad flat package (QFP256) devices were carried out by means of infrared reflow soldering system with Sn–3.8Ag–0.7Cu and Sn–3.8Ag–0.7Cu–0.03Ce lead-free solders, respectively, and the mechanical properties of micro-joints of the QFP devices were tested and studied by STR micro-joints tester. The results indicate that the tensile strength of Sn–Ag–Cu–Ce soldered joints is better than that of Sn–Ag–Cu soldered joints. In particular, the addition of trace Ce to the Sn–Ag–Cu solder can refine the microstructures and decrease the thickness of the intermetallic compound layer of Sn–Ag–Cu solder alloys. In addition, the stress–strain response of Sn–Ag–Cu/Sn–Ag–Cu–Ce soldered joints in quad flat packaging was investigated using finite element method based on Garofalo–Arrhenius model. The simulated results indicate creep distribution of soldered joints is not uniform, the heel and toe of soldered joints, the area between soldered joints and leads are the creep concentrated sites. The creep strain of Sn–Ag–Cu–Ce soldered joints is lower than that of Sn–Ag–Cu soldered joints.     

Correlation between interfacial microstructure and shear behavior of Sn–Ag–Cu solder ball joined with Sn–Zn–Bi paste

Sn–8Zn–3Bi solder paste was applied as a medium to joint Sn–3.2Ag–0.5Cu solder balls and Cu/Ni/Au metallized ball grid array substrates at 210 °C. Sn–Ag–Cu joints without Sn–Zn–Bi addition were also conducted for comparison. The shear behavior of the specimens was investigated after multiple reflow and thermal aging. For each strength test, more than 40 solder balls were sheared. The shear strength of Sn–Ag–Cu specimens kept constant ranging from 15.5 ± 1.3 N (single reflow) to 16.2 ± 1.0 N (ten reflows) and the fractures occurred in the solder. Shear strength of Sn–Ag–Cu/Sn–Zn–Bi specimens fell from 15.9 ± 1.7 N (single reflow) to 13.4 ± 1.6 N (ten reflows). After single reflow, Sn–Ag–Cu/Sn–Zn–Bi specimens fractured in the solder along Ag–Au–Cu–Zn intermetallic compounds and at Ni metallization. After ten reflows, fractures occurred in the solder and at solder/Ni–Sn–Cu–Zn intermetallic compound interface. The shear strengths of the Sn–Ag–Cu and Sn–Ag–Cu/Sn–Zn–Bi packages changed little after aging at 150 °C. Sn–Ag–Cu/Sn–Zn–Bi joints kept higher strength than Sn–Ag–Cu joints. Sn–Ag–Cu joints fractured in the solder after aging. But the fractures of Sn–Ag–Cu/Sn–Zn–Bi specimens shifted to the solder with aging time.     

Phase Diagrams of Pb-Free Solders and their Related Materials Systems

Replacing Pb–Sn with Pb-free solders is one of the most important issues in the electronic industry. Melting, dissolution, solidification and interfacial reactions are encountered in the soldering processes. Phase diagrams contain equilibrium phase information and are important for the understanding and prediction of phase transformation and reactive phase formation at the solder joints. This study reviews the available phase diagrams of the promising Pb-free solders, and their related materials systems. The solders are Sn–Ag, Sn–Cu, Sn–Ag–Cu, Sn–Zn, Sn–Bi, Sn–In and Sn–Sb. The materials systems are the solders with the Ag, Au, Cu, Ni substrates, such as Sn–Ag–Au, Sn–Ag–Ni, Sn–Cu–Au, and Sn–Cu–Ni ternary systems. For the Pb-free solders and their related ternary and quaternary systems, preliminary phase equilibria information is available; however, complete and reliable phase diagrams over the entire compositional and temperature ranges of soldering interests are lacking.     

Lead-free Solders in Microelectronics

Practically all microelectronic assemblies in use today utilize Pb–Sn solders for interconnection. With the advent of chip scale packaging technologies, the usage of solder connections has increased. The most widely used Pb–Sn solder has the eutectic composition. Emerging environmental regulations worldwide, most notably in Europe and Japan, have targeted the elimination of Pb usage in electronic assemblies, due to the inherent toxicity of Pb. This has made the search for suitable “Pb-free” solders an important issue for microelectronics assembly. Approximately 70 Pb-free solder alloy compositions have been proposed thus far. There is a general lack of engineering information, and there is also significant disparity in the information available on these alloys. The issues involved can be divided into two broad categories: manufacturing and reliability/performance. A major factor affecting alloy selection is the melting point of the alloy, since this will have a major impact on the other polymeric materials used in microelectronic assembly and encapsulation. Other important manufacturing issues are cost, availability, and wetting characteristics. Reliability related properties include mechanical strength, fatigue resistance, coefficient of thermal expansion and intermetallic compound formation. The data available in the open literature have been reviewed and are summarized in this paper. Where data were not available, such as for corrosion and oxidation resistance, chemical thermodynamics was used to develop this information. While a formal alloy selection decision analysis methodology has not been developed, less formal approaches indicate that Sn-rich alloys will be the Pb-free solder alloys of choice, with three to four alloys being identified for each of the different applications. Research on this topic continues at the present time at a vigorous pace, in view of the imminence of the issue.     

Magnetic nanoparticle-based solder composites for electronic packaging applications

Sn–Ag–Cu (SAC) alloys are regarded as the most promising alternative for traditional Pb–Sn solders used in electronic packaging applications. However, the higher reflow temperature requirement, possible intermetallic formation, and reliability issues of SAC alloys generate several key challenges for successful adoption of Pb-free solder for next generation electronic packaging needs. Localized heating in interconnects can alleviate thermal stresses by preventing subjection of entire package to the higher reflow temperatures associated with the SAC solders. It had been demonstrated that SAC solder–FeCo magnetic nanoparticles (MNPs) composite paste can be reflowed locally with AC magnetic fields, enabling interconnect formation in area array packages while minimizing eddy current heating in the printed circuit board.Solder/magnetic nanocomposite pastes with varying MNP concentration were reflowed using AC magnetic fields. Differential scanning calorimetry results show a reduced undercooling of the composite pastes with the addition of MNPs. TEM results show that the FeCo MNPs are distributed in Sn matrix of the reflowed solder composites. Optical and SEM micrographs show a decrease in Sn dendrite regions as well as smaller and more homogeneous dispersed Ag₃Sn with the addition of MNPs. The MNPs promote Sn solidification by providing more heterogeneous nucleation sites at relatively low undercoolings. The mechanical properties were measured by nanoindentation. The modulus, hardness, and creep resistance, increase with the MNP concentration. The enhanced mechanical properties are attributed to grain boundary and dispersion strengthening.The reflow of solder composites have been modeled based on eddy current power loss in the substrate and magnetic power losses in the solder bumps. Induction reflow of pure solder bumps (<300 μm) in an area array package using 500 Oe magnetic field at 300 kHz requires excessive eddy current power loss in the substrate, resulting in extreme temperatures that lead to blistering and delamination of the substrate. Solder–MNP composites with modest MNP loading showed temperature increases sufficient to achieve solder reflow when subjected to the same AC magnetic fields. Thermomechanical behavior of a solder joint was also modeled under cyclic temperature variations. The stress and strain are highly localized at the interface between solder and substrate. Plastic work accumulated per cycle can be used for lifetime prediction.In this article we review lead-containing and lead-free solder systems, and the electronic packaging technologies pertinent to soldering process. Recent research on the effects of MNPs on localized heating, microstructure evolution, mechanical properties, and thermomechanical reliability are summarized.     

Development of Sn–Zn lead-free solders bearing alloying elements

Sn–Zn solder alloys have been considered as one of the more attractive lead-free solders since it can easily replace Sn–Pb eutectic alloy without increasing the soldering temperature. However, there are still some problems to be resolved, such as the argument about the poor oxidation resistance and embrittlement behavior. In order to overcome these drawbacks, and further enhance the properties of Sn–Zn lead-free solder alloys, a small amount of alloying elements (rare earths, Bi, Ag, Al, Ga, In, Cr, Cu, Sb, Ni, Ge) added into Sn–Zn alloys were selected by many researchers. For example, a small amount of Al, P, Bi, Ga can improve the high-temperature oxidation resistance of Sn–Zn solders remarkably as well as Cr. This paper summarizes the effects of alloying elements on the wettability, oxidation resistance, melting behavior, mechanical properties, creep properties, microstructures and intermetallic compounds layer of Sn–Zn lead-free solders.     

A review on the interfacial intermetallic compounds between Sn–Ag–Cu based solders and substrates

The objective of this review is to study the interfacial intermatallic compounds (IMCs) between Sn–Ag–Cu based solders and common substrates, which play a crucial role in solder joints typically present in Pb-free electronics manufacturing. The microstructural evolution of IMCs at the solder/substrate interfaces is analyzed, while the models and theories describing the formation/growth mechanism of interfacial IMCs are also introduced. We focus on the influence of a variety of factors that have been reported recently, including substrates, minor alloying, mechanical stress, electromigration and thermomigration etc., as full understanding of the mechanisms that determine the formation and growth of interfacial IMCs is important to reach for developing high reliability solder joints. In the end of this review, the characteristics of the IMCs are compared and illustrated, which have marked effect on the mechanical properties and fracture behavior as well as reliability of solder joints.     

Influence of minor Bi additions on the interfacial morphology between Sn–Zn–xBi solders and a Cu layer

The influence of minor Bi additions on the interfacial morphology between Sn–Zn–xBi (x = 0, 1, 3) solders and a Cu layer after reflowing were investigated by microstructural observations. The addition of minor amount of Bi into Sn–Zn solder reduced the tendency to form cracks at the solder/Cu interface. This is because alloying with Bi reduced the mismatch of the coefficient of thermal expansion (CTE) between the solder alloys and the Cu plate. Moreover, the Sn–Zn solder with Bi reduced the melting temperature of the solder alloy, and, this resulted in the coarsening of the gains and thickening of the intermetallic compound (IMC) layers because solder alloys with a lower melting temperature experienced a longer molten period during reflow. Because the Bi atoms accumulated at the surface of the IMC layers in homogeneously, partially impeding the IMC dissolving into the molten solder, a serrated-like Cu–Zn–Sn IMC layer was formed at the Sn–8Zn–3Bi/Cu interface.     

Wettability Studies of Pb-Free Soldering Materials

For Pb-free soldering materials, two main substitutes are currently being considered, consisting of Sn–Ag and Sn–Ag–Cu eutectics, both with melting points higher than that of the Sn–Pb eutectic. Therefore, both will require higher soldering temperatures for industrial applications. Also, both eutectics have a higher surface tension than the Sn–Pb eutectic, requiring wettability studies on adding Bi, Sb, and In to the eutectics to decrease the melting points and surface tension. The experimental results for the surface tension were compared with thermodynamic modeling by Butler’s method and were used to create the SURDAT database, which also includes densities for pure metals, binary, ternary, quaternary, and quinary alloys. To model the surface tension, excess Gibbs energies of the molten components were taken from the ADAMIS database. For the case of the Ag–Sn system, enthalpies of formation of Ag₃Sn from solution calorimetry were used for checking optimized thermodynamic parameters. In the study of Sn–Ag–Cu–Bi–Sb liquid alloys, the range of possible Bi compositions for practical applications has been used to formulate a generalized metric of wettability, which was checked by measurements of the influence of In on the Sn–Ag–Cu system.     

Thermal creep and fracture behaviors of the lead-free Sn–Ag–Cu–Bi solder interconnections under different stress levels

In our previous study, the creep behavior of the lead-free Sn–Ag–Cu–Bi solder joints has been proven to follow the Arrhenius power-law relationship, and the thermal fatigue behavior of the solder joints exhibits the typical creep deformation characteristics with a superposition of the pulsating features. In this study, the thermal creep and fracture behaviors of the lead-free Sn–Ag–Cu–Bi solder interconnections were characterized under different stress levels, with a systematical comparison to that of a traditional Sn60Pb40 near-eutectic solder. The results show that the creep strain rate of both solder connections follows Weertman-Dorn equation, and the calculated creep stress exponent for two solders is reasonably close to other published data. The SEM inspection and analysis of fractographies of creep fractured solder joints manifest that the creep failure of the lead-free Sn–Ag–Cu–Bi solder joint shows obviously intergranular fracture mechanism, while the Sn60Pb40 joint ruptures dominantly by a transgranular sliding mechanism.     

Recent advances on Sn–Cu solders with alloying elements: review

Nowadays, a major concern of Sn–Cu based solder alloy today is focused on continuously improving the comprehensive properties of the solder joints formed between the solders and substrates. The key issues and improvements about Sn–Cu–X (X = Ni, rare earths, Zn, Co, Ga, In, Bi, secondary particles etc.) solder are outlined and evaluated in this paper which compared to Sn–Cu solder. It can be summarized that by adding appropriate amounts of certain alloying elements X to Sn–Cu solder, and it is possible to tailor the properties of the solder, such as the melting and solidification behaviors, wettability, microstructure, interfacial reactions and mechanical properties of the solder. The reliability issues related to the implementation of Sn–Cu–X solder in advanced electronics system are also introduced, which indicates that further development on the Sn–Cu–X solders are to be underway.     

Synthesis and DSC study on Sn3.5Ag alloy nanoparticles used for lower melting temperature solder

The traditional Sn–Pb eutectic solder alloys are being phased out from the electronics industry due to the toxicity of lead (Pb), leading to the development and implementation of lead-free solders. Sn3.5Ag lead-free solder alloy, considered to be one of the promising alternatives to replace the traditionally used Sn–Pb solder, however, still has some weaknesses, such as its higher melting temperature than that of the Sn–Pb solder alloy. A possible way to decrease the melting temperature of a solder alloy is to decrease the alloy particle size to the nanometer range. Sn3.5Ag nanoparticles with different size distribution were synthesized using chemical reduction method by applying NaBH₄ as reduction agent. The melting properties of these synthesized nanoparticles were studied by differential scanning calorimetry (DSC), and size-dependent melting temperature depression of these nanoparticles has been observed. Gibbs–Thomson equation was used to analyze the size-dependent melting temperature property, giving a good prediction of the melting temperature depression for the Sn-based lead-free solder alloy nanoparticles.     

Standardization of a shear test method for lead-free solder paste chip joints

The electronics industry is moving to replace Pb-based solder with Pb-free solder because of the growing environmental regulations governing the use of lead. Solder joints made from Pb-free solder paste do not yet have an evaluation method to classify its mechanical properties such as shear strength. In this study, we reflowed solder joints from Sn–3.0Ag–0.5Cu solder paste. To standardize the shear test method, we measured the shear strength of the solder joint of a 2012 ceramic chip at a shear rate of 3–60 mm/min and a shear height of 10–380 μm using different shaped shear jigs. We statistically analyzed the optimum number of shear tests by calculating the accumulative average value, standard deviation, and width of the confidence interval. The fracture surface was examined by scanning electron microscope and discussed in terms of the shear conditions.     

Recrystallized grain rotation behavior in a Pb-free BGA solder joint under electron current stress

The grain orientations of a Pb-free ball grid arrays solder joint after thermomechanical fatigue (TMF) were characterized quantitatively using electron backscattered diffraction. Due to subgrain rotation, the small recrystallized grains evolved from the reflowed orientations appeared in a Pb-free solder joint subjected to thermomechanical stress. Also, these recrystallized grains rotated under electron current stress, indicating that the tin orientations of the Pb-free solder joints can significantly affect the response of the solder joints to service conditions such as TMF and electromigration. Meanwhile, two types of double twinning of tin in solder joints were observed in Pb-free solder joints. The change in orientation between the two groups of double twined orientations was in the range of 80°–90° (79.1°, 82.9° and 86.5° corresponding with 57.2° and 62.8°). Four orientations of tin grains, having the same twin grain with a [100] or [010] direction were observed in one of the systems, while the other one presented with two groups of tricrystals perpendicular to each other.