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.     

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.     

Reliability of Pb-free solders for harsh environment electronic assemblies

Abstract

Since 2006 and the implementation of environmental regulations, the electronic industry has moved to Pb-free solders. Harsh environment industries that were exempted from the regulations will soon have to follow suit. However, a suitable replacement solder for use in harsh environments still has to be validated and reliability models are yet to be established. In this review, research that led to the selection of currently used Pb-free alloys and the continuing search for high reliability alloys are described. Sn pest and Sn whiskers, potential major threats for electronics operating in harsh environments, are highlighted. This review also focuses on the microstructure, mechanical properties and deformation mechanisms of Pb-free alloys. Emphasis is placed on Sn–Ag–Cu alloys, now considered to be the alloys of choice for replacement of Sn–Pb solders. The reliability of Pb-free electronic assemblies is studied, focusing on thermal fatigue, believed to be the main source of failure through creep–fatigue mechanisms. The validity of models for Pb-free solder joints life time prediction is assessed and the lack of cohesiveness among the available reliability data is examined.     

Annealing effect to constitutive behavior of Sn–3.0Ag–0.5Cu solder

Sn–Ag–Cu based solder alloys are replacing Sn–Pb solders in electronic packaging structures of commercial electric devices. In order to evaluate the structural reliability, the mechanical property of solder material is critical to the numerical simulations. Annealing process has been found to stabilize material properties of Sn–37Pb solder material. In the current study, the annealing effect on tensile behaviour of Sn–3.0Ag–0.5Cu (SAC305) solder material is investigated and compared with Sn–37Pb solder. It is found that the tensile strength for both materials are more stabilized and consistent after the annealing process, nevertheless, the annealing process will improve the plasticity of SAC305 solder dominated by dislocation motion, and impede the occurrence of hardening deformation in Sn–37Pb solder dominated by grain-boundary sliding mechanism. Furthermore, the annealing effect is quantified in the proposed constitutive model based on unified creep–plasticity theory. The parameters are calibrated against the measured stress–strain relationships at the tensile strain rates ranging from 1?×?10^?4 to 1?×?10^?3 s^?1. The numerical regressions for dominant parameters in the proposed model reveal the intrinsic differences between SAC305 and Sn–37Pb solders under annealing treatment.     

Review on microstructure evolution in Sn–Ag–Cu solders and its effect on mechanical integrity of solder joints

The use of Pb-bearing solders in electronic assemblies is avoided in many countries due to the inherent toxicity and environmental risks associated with lead. Although a number of “Pb-free” alloys have been invented, none of them meet all the standards generally satisfied by a conventional Pb–Sn alloy. A large number of reliability problems still exist with lead free solder joints. Solder joint reliability depends on mechanical strength, fatigue resistance, hardness, coefficient of thermal expansion which are influenced by the microstructure, type and morphology of inter metallic compounds (IMC). In recent years, Sn rich solders have been considered as suitable replacement for Pb bearing solders. The objective of this review is to study the evolution of microstructural phases in commonly used lead free xSn–yAg–zCu solders and the various factors such as substrate, minor alloying, mechanical and thermo-mechanical strains which affect the microstructure. A complete understanding of the mechanisms that determine the formation and growth of interfacial IMCs is essential for developing solder joints with high reliability. The data available in the open literature have been reviewed and discussed.     

Microstructures formed from mixed solders on copper substrate

Abstract

With the development and use of a variety of Pb free solders, it is probable that some solder joints in electronic assemblies may be made with solders of two different compositions. To investigate possible microstructures resulting from such procedure, samples were prepared using small balls of four different Sn–Ag–Cu (SAC) Pb free solders, as well as Sn–Zn–Al solder, melted together with eutectic Pb–Sn solder paste and also various SAC solder pastes, on a copper substrate. It was observed that using eutectic Pb–Sn solder paste with an SAC solder ball introduced some Pb–Sn eutectic microstructure and changed the ternary eutectic present from Ag₃Sn–Cu₆Sn₅–Sn to Ag₃Sn–Pb–Sn. Use of an SAC solder paste with Sn–Zn–Al solder introduced an apparent Ag–Cu–Zn ternary compound, replacing Zn lamellae of the Sn–Zn eutectic. With eutectic Pb–Sn solder paste, the Pb–Sn–Zn ternary eutectic was formed. It was noted that use of a high Sn solder results in rapid dissolution of the copper substrate.     

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.     

Influence of Thermal Cycling on the Microstructure and Shear Strength of Sn3.5Ag0.75Cu and Sn63Pb37 Solder Joints on Au/Ni Metallization

The influence of thermal cycling on the microstructure and joint strength of Sn3.5Ag0.75Cu （SAC） and Sn63Pb37 （SnPb） solder joints was investigated. SAC and SnPb solder balls were soldered on 0.1 and 0.9 μm Au finished metallization, respectively. After 1000 thermal cycles between -40℃ and 125℃, a very thin intermetallic compound （IMC） layer containing Au, Sn, Ni, and Cu formed at the interface between SAC solder joints and underneath metallization with 0.1 μm Au finish, and （Au, Ni, Cu）Sn4 and a very thin AuSn-Ni-Cu IMC layer formed between SAC solder joints and underneath metallization with 0.9 μm Au finish. For SnPb solder joints with 0.1 μm Au finish, a thin （Ni, Cu, Au）3Sn4 IMC layer and a Pb-rich layer formed below and above the （Au, Ni）Sn4 IMC, respectively. Cu diffused through Ni layer and was involved into the IMC formation process. Similar interfacial microstructure was also found for SnPb solder joints with 0.9μm Au finish. The results of shear test show that the shear strength of SAC solder joints is consistently higher than that of SnPb eutectic solder joints during thermal cycling.     

Tensile properties and wettability of SAC0307 and SAC105 low Ag lead-free solder alloys

In this article, the tensile properties of low Ag lead-free solder alloys, SAC0307 and SAC105, are examined under various strain rates and temperatures. The wettability of these solders on Cu pad is also characterized by using different fluxes. The SAC305 and Sn37Pb solder alloys are also studied for comparison. Our results show that the properties of all solder alloys are dependent on the strain rate and temperature. The ultimate tensile strength increases monotonously with the increment of strain rate. Both SAC0307 and SAC105 alloys possess lower strength and higher elongation ratio than SAC305 and Sn37Pb alloys. For all the fluxes used in this study, the SAC0307 and SAC105 alloys show the similar wettability to SAC305, whereas worse than that of Sn37Pb alloy. Increasing the activity of the flux does not improve the wettability of the SAC solder alloys on Cu pad effectively.     

Constitutive models of creep for lead-free solders

The constitutive modeling of creep has been extensively studied due to the important of the creep failure mode in solder joints. However, there are very few studies that considered room temperature aging contributions in their creep modeling studies. This study investigated constitutive modeling of creep of solders by taking into account the possible contribution room temperature aging. Lead-free solder (Sn–4.0Ag–0.5Cu) was found to have a higher creep resistance than Sn–Pb solder at the same stress level and testing temperature. The higher creep resistance was contributed by the second phase intermetallic compounds, Ag₃Sn and Cu₆Sn₅. The precipitation of these intermetallic compounds can significantly block the movement of dislocations and increase the creep resistance of the material. Constitutive models of creep for both lead-free and Sn–Pb eutectic solders were constructed based on the experimental data. The activation energy for SAC405 is much higher than that of Sn–Pb, which also indicates that SAC405 possesses higher creep resistance. The constitutive models can be used in finite element analysis of actual electronic packages to predict solder joint failure. The creep mechanisms of both lead-free and Sn–Pb eutectic solders were also extensively discussed in this dissertation. Dislocation gliding and climb is believed to be the major failure mode at high stresses, while lattice diffusion and grain boundary diffusion is believed to be the major failure mode at low stress levels. Grain boundary sliding is believed to contribute to creep deformation at both high-stresses and low-stresses. For eutectic Sn–Pb, superplastic deformation is a major the creep mechanism at low-stresses and high-temperatures.     

A review of interconnect materials used in emerging memory device packaging: first- and second-level interconnect materials

The main motivation of this review is to study the evolution of first and second level of interconnect materials used in memory device semiconductor packaging. Evolutions of bonding wires from gold (Au) to silver (Ag) or copper (Cu) have been reported and studied in previous literatures for low-cost solution, but Au wire still gives highest rating in terms of the performance of temperature humidity test, high temperature storage, and bond-ability, etc. However, a new bonding wire material, Au-coated Ag, is recently developed to be an alternative solution which gives comparable performance, but lower cost compared to Au wire. In the first section of the article, the influence of a variety of factors were reviewed, which includes reliability performance and interfacial reaction that determines the performance of Au-coated Ag to reach for developing high reliability of bonded devices. With respect to second-level interconnects, SAC305 and SAC302 solder alloys give a balance performance between temperature cycling testing and drop testing, which are widely used in many field applications, such as mobile, consumer and computer. SAC405 and LF35 are developed for specific requirements such as SAC405 owns better temperature cycling performance, whereas LF35 gives excellent drop performance compared to SAC305 or SAC302. However, with market demands on automotive electronics get strong in recent years, solder joint reliability is being reviewed and discussed, especially in temperature cycling performance. Typical solder alloys on Ni/Au surface finish were not designed for automotive application to fulfill the requirement of board level reliability. Hence, newly developed solder alloys with Sn/Ag/Cu/Bi/Ni elements and Cu-OSP substrate surface finishes will be reviewed in the second section of the article.

     

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.     

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.     

The ‘IMC rings’ growth mechanism in Sn–Ag–Cu solder ball and NiAu-plated BGA ball pad

Due to environmental pollution concerns, the law says the lead (Pb) inside electronics devices must be eliminated. Lots of lead-free materials have been introduced and been used for electronic products and Sn–Ag–Cu (SAC) is one of most popular lead-free representatives and has been used in high-volume production. The most popular IC packages, BGA packages which have higher I/O counts, and better thermal and electrical performance than lead-frame type packages, use solder balls of SAC for lead-free applications to connect with printed circuit boards. A particular phenomenon, so-called ‘IMC rings’, is only observed on BGA solder ball pad surfaces after the SAC solder balls are mounted on BGA ball pads which are plated with NiAu. It has not been found in either eutectic solder or Sn–Ag solder welding on plated NiAu pads. No significant evidence exists to show that ‘IMC rings’ degrade the strength of solder joints or cause earlier failures in mechanical tests. ‘IMC rings’ appear to be an inevitable outcome after the SAC is soldered onto a plated NiAu ball pad. This study is to find the growth mechanism of ‘IMC rings’ on the ball pad which is created between SAC ball and plated NiAu pad during solder ball temperature reflow. The design of the experiment and data have been discussed.     

Effect of ZnO nanoparticles addition on thermal, microstructure and tensile properties of Sn–3.5 Ag–0.5 Cu (SAC355) solder alloy

Regarding to the development of Sn–Ag–Cu (SAC) lead-free solders for advance electronic components, the effect of 0.5 wt% nano-sized ZnO particles on the thermal, microstructure and tensile properties of Sn–3.5 wt% Ag–0.5 wt% Cu (SAC355) lead-free solder alloy is investigated. The results showed that addition of 0.5 wt% nano-sized ZnO particles into the conventional lead-free SAC355 solder caused a slight increase of its liquidus temperature by about 1.1 K. Metallographic observations of SAC355–0.5 wt% ZnO (composite solder) revealed an obvious refinement in the microstructure compared with the SAC355 (non-composite) solder. Consequently, addition of nano sized-ZnO particles could improve the stress–strain characteristics proof stress (σ_y0.2) and ultimate strength (σ_UTS). This was rendered to suppressing effect of ZnO on the coarsening of the intemetallic compounds (IMCs) Ag₃Sn and Cu₆Sn₅ during the solidification process in the composite solder and subsequently dispersion strengthening is considered to be the dominating mechanism. This will allow the use of SAC355 composite lead-free solder alloy, to be consistent with the conditions of usage for conventional SAC solder alloys and to overcome the serious problem of the excessive growth of IMCs and the formation of microvoids in the SAC lead-free solder alloys.     

温度对Cu颗粒增强复合钎料蠕变性能的影响

蠕变性能是影响钎焊接头可靠性的重要指标之一.采用搭接面积为1 mm2的单搭接钎焊接头,在恒定载荷下,测定了Cu颗粒增强锡铅基复合钎料钎焊接头的蠕变寿命,分析并讨论了温度对该复合钎料蠕变寿命的影响.结果表明:Cu颗粒增强的锡铅基复合钎料的蠕变抗力优于传统63Sn37Pb共晶钎料;钎焊接头蠕变寿命随温度的升高而降低,并且温度对复合钎料钎焊接头蠕变寿命的影响较传统63Sn37Pb钎料明显.     

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%)     

Effects of microstructure and temperature on corrosion behavior of Sn–3.0Ag–0.5Cu lead-free solder

The heterogeneous microstructure of solder could be obtained when cooling rate of the solder joint was not even, which would affect the corrosion behavior of solder during service. The ambient temperature would also affect the corrosion behavior of solder joint. In this paper, the effects of microstructure and temperature on the corrosion behavior of Sn–3.0Ag–0.5Cu (SAC305) lead-free solder were investigated. The various microstructures of SAC305 lead-free solder were obtained by cooling specimens in air and furnace. Compared to the fine-fibrous Ag₃Sn phase inside the commercial SAC305 solder, platelet-like Ag₃Sn formed as cooling speed decreasing. The polarization behavior of SAC305 solders in 3.5 wt.% NaCl solution was not significantly affected by various microstructures, but sensitive to temperature.     

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.     

Study on creep characterization of nano-sized Ag particle-reinforced Sn–Pb composte solder joints

In the present work, the creep strain of solder joints is measured using a stepped load creep test on a single specimen. Based on the experimental results, the constitutive model on the steady-state creep strain is established by applying a linear curve fitting for the nano-sized Ag particle-reinforced Sn37Pb based composite solder joint and the Sn37Pb solder joint, respectively. It is indicated that the activation energy of the Ag particle-reinforced Sn37Pb based composite solder joints is higher than that of Sn37Pb solder joints. It is expected that the creep resistance of the Ag particle-reinforced Sn37Pb based composite solder joints is superior to that of Sn37Pb solder.