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%)     

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.     

Impression creep of monolithic and composite lead free solders

Even though several EMS (Electronic manufacturing services) companies are currently producing “lead free” products, a general notion of apprehension still exists in the industry, primarily due to the lack of sufficient mechanical reliability data supporting the use of lead free alloys. The current study was an effort to generate an understanding of the mechanisms of creep deformation in monolithic and composite (Ag and Cu reinforced) Sn–3.5Ag and Sn–3.0Ag–0.5Cu lead free alloys in the high stress high temperature regime. Small volume solder samples were reflowed using a custom built computer controlled resistance furnace. Impression creep testing was employed to determine the activation energy and stress exponent. A careful analysis of the collected data revealed the underlying creep mechanisms and the following conclusions could be made. Both Sn–3.5Ag and Sn–3.0Ag–0.5Cu exhibited higher creep resistance as compared to the eutectic tin–lead solder under all tested conditions, with the ternary lead free alloy marginally outperforming the binary lead free alloy. Composite solders performed better as compared to monolithic solders. Furthermore, Cu reinforced solders demonstrated higher creep resistance as compared to Ag reinforced solders.     

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.     

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.     

Issues related to the implementation of Pb-free electronic solders in consumer electronics

Consumer electronic applications are the primary target of the Pb-free initiative and package assembly and performance is affected by the move from eutectic Sn–Pb to Pb-free solder alloys. This paper outlines the key issues and mitigation possibilities for package assembly using Pb-free solders: High temperature reflow, Interfacial reactions, and Reliability. At the high temperatures required to reflow Pb-free alloys, moisture absorbed into the package can result in delamination and failure. The reaction of the Pb-free solder with Ni and Cu metallizations results in interfacial intermetallics that are not significantly thicker than with Sn–Pb but provide a path for fracture under mechanical loading due to the increased strength of the Pb-free alloys. The reliability issues discussed include thermomechanical fatigue, mechanical shock, electromigration and whiskering. The Pb-free alloys tend to improve thermomechanical fatigue and electromigration performance but are detrimental to mechanical shock and whiskering. Design trade-offs must be made to successfully implement Pb-free alloys into consumer applications.     

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.     

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.     

The effects of third alloying elements on the bulk Ag<Subscript>3</Subscript>Sn formation in slowly cooled Sn–3.5Ag lead-free solder

The effects of third alloying elements (Cu, In, Zn) on the formation of bulk Ag₃Sn intermetallic compounds (IMCs) in slowly cooled Sn–3.5Ag lead-free solder were investigated by microstructural observation and thermal analysis technique. Microstructural observation shows that bulk Ag₃Sn IMCs existed in the microstructure of slowly cooled Sn–3.5Ag, Sn–3.5Ag–0.75Cu and Sn–3.5Ag–1.5In alloys, while no bulk Ag₃Sn IMCs formed in the slowly cooled Sn–3.5Ag–2.0Zn alloys. Thermal analysis results indicate that Ag preferably reacted with Zn to form Ag–Zn IMCs at high temperature rather than reacted with Sn to form Ag₃Sn plate.     

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.     

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.     

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.     

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.     

Effect of adding Ce on interfacial reactions between Sn–Ag solder and Cu

We investigated the effect of adding cerium (Ce) to low Ag content Sn–1.0wt.%Ag solder on the interfacial reactions between the Sn–1.0Ag solder and Cu substrate. The formation and growth of interfacial intermetallic compounds (IMCs) between the Sn–1.0Ag–0.3Ce solder and Cu substrate were studied and the results were compared to those obtained for the Ce-free Sn–1.0Ag/Cu and most promising Sn–3.0Ag–0.5Cu/Cu systems. The addition of Ce to the Sn–Ag solder significantly reduced the growth of the interfacial Cu–Sn IMCs, retarded the interfacial reactions between the solder and the substrate, and prevented the IMC from spalling from the interface. The Sn–1.0Ag–0.3Ce solder alloy had a good interfacial stability with the Cu substrate during solid-state isothermal aging in the viewpoint of IMC growth.     

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.     

Suppressing the growth of interfacial Cu–Sn intermetallic compounds in the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint during thermal aging

Evolution of interfacial phase formation in Sn–3.0Ag–0.5Cu/Cu (wt%), Sn–3.0Ag–0.5Cu–0.1Ni/Cu, Sn–3.0Ag–0.5Cu/Cu–15Zn, and Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joints are investigated. Doping Ni in the solder joint can suppress the growth of Cu₃Sn and alter the morphology of the interfacial intermetallic compounds (IMCs), however it shows rapid growth of (Cu,Ni)₆Sn₅ at the Sn–3.0Ag–0.5Cu–0.1Ni/Cu interface. In comparison with the Cu substrates, the Cu–Zn substrates effectively suppress the formation of Cu–Sn IMCs. Among these four solder joints, the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint exhibits the thinnest IMC, and only (Cu,Ni)₆(Sn,Zn)₅ formed at the interface after aging. It is revealed that the presence of Ni acts to enhance the effect of Zn on the suppression of Cu–Sn IMCs in the SAC305–0.1Ni/Cu–15Zn solder joint. The limited formation of IMCs is related to the elemental redistribution at the joint interfaces during aging. The Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn joint can act as a stabilized interconnection due to the effective suppression of interfacial reaction.     

Formation of interfacial structure of Sn–3.7Ag–0.9Zn eutectic solder with different Al additions

The structural evolution of interfaces between the Sn–3.5Ag–0.9Zn–xAl (x = 0.5 and 1.0) solders and Cu substrate has been investigated by microstructural observations. The results suggest that the addition of Al in the Sn–3.5Ag–0.9Zn restrains the formation of Cu₅Zn₈ intermetallic compounds (IMCs) at the soldered interface. Moreover, the formation of Al₂Cu and Cu₉Al₄ IMCs leads to a crack failure near the interface of the Sn–3.7Ag–0.9Zn–1Al and Cu pad. It is suggested that the increase of Al content (e.g. 1 wt%) in the Sn–Ag–Zn eutectic solder would do harm to the reliability of the solder joint.     

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.     

Liquid–solid interfacial reactions of Sn–Ag and Sn–Ag–In solders with Cu under bump metallization

Intermetallic compounds formed during the liquid–solid interfacial reaction of Sn–Ag and Sn–Ag–In solder bumps on Cu under bump metallization at temperatures ranging from 240 to 300 °C were investigated. Two types of intermetallic compounds layer, η Cu₆Sn₅ type and ε Cu₃Sn type, were formed between solder and Cu. It was found that indium addition was effective in suppressing the formation of large Ag₃Sn plate in Sn–Ag solder. During interfacial reaction, Cu consumption rate was mainly influenced by superheat of solder, contact area between solder and Cu and morphology of intermetallic compounds. The growth of η intermetallic compounds was governed by a kinetic relation: ΔX = tⁿ, where the exponent n values for Sn–Ag/Cu and Sn–Ag–In/Cu samples at 240 °C were 0.35 ± 0.01 and 0.34 ± 0.02, respectively. The n values increased with reaction temperature, and it was higher for Sn–Ag/Cu than that for Sn–Ag–In/Cu sample at the same temperature. After Cu was exhausted, ε intermetallic compound was converted to η intermetallic compound. The mechanisms for such growth of interfacial intermetallic compounds during the liquid–solid reaction were investigated.     

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.