Isothermal aging of near-eutectic Sn-Ag-Cu solder alloys and its effect on electrical resistivity

Solder joints were prepared from seven eutectic and near-eutectic Sn-based compositions and characterized for electrical resistivity after 100 h and 1,000 h of isothermal aging at 423 K. The solder joint samples were prepared by hand soldering to copper substrates, and the post-heat treatment resistivity was measured at room temperature in a specially designed, four-point probe fixture. Compositions tested included Sn-3.5Ag, Sn-3.7Ag-0.9Cu, Sn-3.0Ag-0.5Cu, Sn-3.6Ag-1.0Cu, and Sn-3.9Ag-0.6Cu. In addition, the effect of a minor addition of a fourth element, designed to improve high-temperature shear strength, was also evaluated in the compositions Sn-3.7Ag-0.6Cu-0.3Co and Sn-3.7Ag-0.7Cu-0.2Fe. The observed changes in electrical resistivity are discussed in terms of microstructural coarsening, diffusional transport from the substrate, and nucleation of precipitate phases.     

The solid solubility of Ag and Cu in the Sn phase of eutectic and near-eutectic Sn-Ag-Cu solder alloys

Early studies of Ag-Sn and Cu-Sn binary alloys showed very low values, 0.04 wt.% for Ag and 0.0063 wt.% for Cu, for the solid solubility of these elements in Sn at the eutectic temperature. In recent work on “as-cast” Sn-Ag-Cu solder alloys, much higher values have been reported for the Ag and Cu content of the Sn phase. In the present study, wavelength dispersive x-ray microprobe measurements made on a near-equilibrium sample confirmed the earlier solubility values. It was concluded that higher values, some of which are reported in the current paper, represent nonequilibrium, supersaturated solid solutions.     

Alloying effects in near-eutectic Sn-Ag-Cu solder alloys for improved microstructural stability

This study included a comparison of the baseline Sn-3.5Ag eutectic to one near-eutectic ternary alloy, Sn-3.6 Ag-1.0Cu and two quaternary alloys, Sn-3.6Ag-1.0Cu-0.15Co and Sn-3.6Ag-1.0 Cu-0.45 Co, to increase understanding of the beneficial effects of Co on Sn-Ag-Cu solder joints cooled at 1–3 C/sec, typical of reflow practice. The results indicated that joint microstructure refinement is due to Co-enhanced nucleation of the Cu₆Sn₅ phase in the solder matrix, as suggested by Auger elemental mapping and calorimetric measurements. The Co also reduced intermetallic interface faceting and improved the ability of the solder joint samples to maintain their shear strength after aging for 72 hr at 150 C. The baseline Sn-3.5Ag joints exhibited significantly reduced strength and coarser microstructures.     

Effect of stress on the electrical resistivity of solder

The electrical resistivity of tin-lead eutectic solder was found to increase upon tension. The effect was partially reversible. The fractional change in resistance per unit strain was 60. The irreversible part of the effect was due to plastic deformation.     

The growth of intermetallic compounds at Sn-Ag-Cu solder/Cu and Sn-Ag-Cu solder/Ni interfaces and the associated evolution of the solder microstructure

The evolution of intermetallics at and near SnAgCu/Cu and SnAgCu/Ni interfaces was examined, and compared to the behavior, near PbSn/metal and Sn/metal interfaces. Two different solder compositions were considered, Sn_93.6Ag_4.7Cu_1.7 and Sn_95.5Ag_3.5Cu_1.0 (Sn_91.8Ag_5.1 Cu_3.1 and Sn_94.35Ag_3.8Cu_1.85 in atomic percent). In both cases, phase formation and growth at interfaces with Cu were very similar to those commonly observed for eutectic SnPb solder. However, the evolution of intermetallics at SnAgCu/Ni interfaces proved much more complex. The presence of the Cu in the solder dramatically altered the phase selectivity at the solder/Ni interface and affected the growth kinetics of intermetallics. As long as sufficient Cu was available, it would combine with Ni and Sn to form (Cu,Ni)₆)Sn₅ which grew instead of the Ni₃Sn₄ usually observed in PbSn/Ni and Sn/Ni diffusion couples. This growing phase would, however, eventually consume essentially all of the available Cu in the solder. Because the mechanical properties of Sn-Ag-Cu alloys, depend upon the Cu content, this consumption can be expected to alter the mechanical properties of these Pb-free solderjoints. After depletion of the Cu from the solder, further annealing then gradually transformed the (Cu,Ni)₆Sn₅ phase into a (Ni,Cu)₃Sn₄ phase.     

Effect of heating on the electrical resistivity of conductive adhesive and soldered joints

Thermal cycling from room temperature to 60°C was found to cause the contact resistivity of a silver-epoxy conductive adhesive joint to decrease irreversibly, due to an irreversible decrease of the thickness of the joint. This effect was much smaller for a soldered joint cycled to 40°C. An extended period of current on-off cycling caused a slight irreversible increase in the contact resistivity of the adhesive and soldered joints, but thermal cycling using a heater did not. Within each thermal cycle, the contact resistivity increased reversibly with increasing temperature, due to the increase in volume resistivity of the solder or adhesive. Temperature variation caused fractional changes in contact resistivity up to 48% and 6% for adhesive and soldered joints, respectively.     

Effect of rare earth element addition on the microstructure of Sn-Ag-Cu solder joint

The effects of minimal rare earth (RE) element additions on the microstructure of Sn-Ag-Cu solder joint, especially the intermetallic compounds (IMCs), were investigated. The range of RE content in Sn-Ag-Cu alloys varied from 0 wt.% to 0.25 wt.%. Experimental results showed that IMCs could be dramatically repressed with the appropriate addition of RE, resulting in a fine microstructure. However, there existed an effective range for the RE addition. The best RE content was found to be 0.1 wt.% in the current study. In addition to the typical morphology of Ag₃Sn and Cu₆Sn₅ IMCs, other types of IMCs that have irregular morphology and uncertain constituents were also observed. The IMCs with large plate shape mainly contained Ag and Sn, but the content of Ag was much lower than that of Ag₃Sn. The cross sections of Cu₆Sn₅ IMCs whiskers showed various morphologies. Furthermore, some eutectic-like structures, including lamellar-, rod-, and needle-like phases, were observed. The morphology of eutectic-like structure was related to the RE content in solder alloys. When the content of RE is 0.1 wt.%, the needle-like phase was dominant, while the lamellar structure prevailed when the RE content was 0.05 wt.% or 0.25 wt.%. It is suggested that the morphology change of the eutectic-like structure directly affects the creep properties of the solder joint.     

Sn-Ag-Cu焊料中金属间化合物对焊接性能的影响

讨论了Sn-Ag-Cu焊料与Cu焊盘间在回流焊过程中形成的金属间化合物(IMC)的种类、形态,Ag含量和Cu含量对IMC的影响,IMC在老化过程中的生长演变及其对焊接性能的影响。结果表明:Sn-Ag-Cu焊料与Cu焊盘之间的金属间化合物主要是Cu6Sn5和长针状的Ag3Sn,Ag和Cu的添加对组织有明显细化作用,但过量添加会影响IMC的性能。IMC的演变主要是与老化温度、老化时间有关,较厚的IMC不利于焊接性能的提高。     

Influence of Au addition on the phase equilibria of near-eutectic Sn-3.8Ag-0.7Cu Pb-free solder alloy

This paper illustrates the influence of Au addition on the phase equilibria of Sn-Ag-Cu (SAC) near-eutectic alloys and on the interface reaction with the Cu substrate. From the thermal and microstructural characterization of Sn-3.8Ag-0.7Cu alloys containing various amounts of Au, it is found that the Au promotes the formation of a quaternary-eutectic reaction at 204.5°C ± 0.3°C. The equilibrium phases in the quaternary-eutectic microstructure are found to be AuSn₄, Ag₃Sn, βSn, and Cu₆Sn₅. While the addition of Au to Sn-3.8Ag-0.7Cu alloys is also found to increase liquidus temperature and the temperature ranges of the phase equilibria field for primary phases, such influences from Au are found to be less pronounced when the alloys were reacted with the Cu substrate. Because of the formation of the Au-Cu-Sn-ternary interface intermetallic, it is found that a majority of Au added to the solder is drained from the melt. The drainage of Au reduces the impact of Au on the phase equilibria of the solder alloys in the joint. It is further found that the involvement of Au in the interface reaction results in a change of the interface phase morphology from the conventional scallop structure to a compositelike structure consisting of (AuCu)₆Sn₅ grains and finely dispersed, βSn islands.     

Phase equilibria and the related properties of Sn-Ag-Cu based Pb-free solder alloys

We have recently developed a thermodynamic database for micro-soldering alloys which consists of the elements Pb, Bi, Sn, Sb, Cu, Ag, Zn, and In. In this paper, the phase equilibria and the related thermodynamic properties of the Sn-Ag-Cu base alloys are presented using this database, alloy systems being one of the promising candidates for Pb-free solders. The isothermal section diagrams of the Sn-Ag-Cu ternary system were experimentally determined by SEM-EDS, x-ray diffraction and metallographic techniques. Based on the present results as well as the previous data on phase boundaries and thermochemical properties, thermodynamic assessment of this system was carried out. The isothermal and vertical section diagrams, liquidus surface, mass fractions of the phase constitution, etc., were calculated. The predictions of surface energy and viscosity were also investigated. Moreover, a non-equilibrium solidification process using the Scheil model was simulated and compared with the equilibrium solidification behavior in some Sn-Ag-Cu base alloys. Calculated results based on the Scheil model were incorporated into a three-dimensional solidification simulation and the prediction of practical solidification procedures was performed.     

Studies of the mechanical and electrical properties of lead-free solder joints

The mechanical and electrical properties of several Pb-free solder joints have been investigated including the interfacial reactions, namely, the thickness and morphology of the intermetallic layers, which are correlated with the shear strength of the solder joint as well as its electrical resistance. A model joint was made by joining two “L-shaped” copper coupons with three Pb-free solders, Sn-3.5Ag (SA), Sn-3.8Ag-0.7Cu (SAC), and Sn-3.5Ag-3Bi (SAB) (all in wt.%), and combined with two surface finishes, Cu and Ni(P)/Au. The thickness and morphology of the intermetallic compounds (IMCs) formed at the interface were affected by solder composition, solder volume, and surface finish. The mechanical and electrical properties of Pb-free solder joints were evaluated and correlated with their interfacial reactions. The microstructure of the solder joints was also investigated to understand the electrical and mechanical characteristics of the Pb-free solder joints.     

Effect of rare earth element additions on the microstructure and mechanical properties of tin-silver-bismuth solder

There are numerous intermetallic compounds (IMCs) with various shapes in a tin-silver-bismuth solder alloy. These IMCs can affect the mechanical properties of the solder and, therefore, the reliability of the joints. In this study, minimal rare earth elements added into the solder were adsorbed at the grain boundary of IMCs. This adsorption behavior changed the relationship between growth velocities of the various crystalline directions of the IMC polycrystalline, which resulted in finer particles and more uniform distribution of the IMC phase. The average size of IMC particles decreased from 0.20 μm to 0.12 μm, while their average distance decreased from 1.25 μm to 0.65 μm. These fine IMC particles made the alloy stronger and more ductile through dispersion strengthening.     

Microstructure,Defects, and Reliability of Mixed Pb-Free/Sn-Pb Assemblies

The results of an intensive reliability study on Pb-free ball grid array (BGA)/Sn-Pb solder assemblies as well as some lessons learnt dealing with mixed assembly production at Celestica are described in this paper. In the reliability study, four types of Pb-free ball grid array components were assembled on test vehicles using the Sn-Pb eutectic solder and typical Sn-Pb reflow profiles with 205°C to 220°C peak temperatures. Accelerated thermal cycling (ATC) was conducted at 0°C to 100°C. The influence of the microstructure on Weibull plot parameters and the failure mode will be shown. Interconnect defects such as nonuniform phase distribution, low-melting structure accumulation, and void formation are discussed. Recommendations on mixed assembly and rework parameters are given.     

Microstructural modifications and properties of Sn-Ag-Cu solder joints induced by alloying

Slow cooling (1–3°C/sec) of Sn-Ag-Cu and Sn-Ag-Cu-X (X = Fe, Co) solder-joint specimens, made by hand soldering, simulated reflow in a surface-mount assembly to achieve similar as-solidified joint microstructures for realistic shear-strength testing, using Sn-3.5Ag (wt.%) as a baseline. Consistent with predictions from a recent Sn-Ag-Cu ternary phase-diagram study, either Sn dendrites, Ag₃Sn primary phase, or Cu₆Sn₅ primary phase were formed during solidification of joint samples made from the selected near-eutectic Sn-Ag-Cu alloys. Minor substitution of Co for Cu in Sn-3.7Ag-0.9Cu refined the joint-matrix microstructure by an apparent catalysis effect on the Cu₆Sn₅ phase, whereas Fe substitution promoted extreme refinement of the Sn-dendritic phase. Ambient-temperature shear strength was reduced by Sn dendrites in the joint microstructure, especially coarse dendrites in solute poor Sn-Ag-Cu, e.g., Sn-3.0Ag-0.5Cu, while Sn-3.7Ag-0.9Cu with Co and Fe additions have increased shear strength. At elevated (150°C) temperature, no significant difference exists between the maximum shear-strength values of all of the alloys studied.     

The microstructures of the Sn-Zn-Al solder alloys

The microstructures of the Sn-Zn-Al lead-free solders have been investigated using scanning electron microscopy. The Al and Zn contents of the solders investigated were 0.45%∼4.5% and 8.55%∼85.5%, respectively. The solders were prepared from the Zn-5Al master alloy and Sn. The precipitates formed in these solders were analyzed for their compositions with energy dispersive spectroscopy. The eutectic temperature and the transition temperatures of these solders upon cooling were identified with cooling curves as well as with differential scanning calorimetry.     

Wetting reaction of Sn-Ag based solder systems on Cu substrates plated with Au and/or Pd layer

The wetting behavior of SnAg based Pb-free solders on Cu and Cu substrates plated with Au, Pd, and Au/Pd thin films have been studied. The wetting angle and kinetics of interfacial reaction were measured. The Au-plated substrates exhibit better wetting than the Pd-plated substrates. In the case of SnAg on Pd-plated Cu, SEM observation revealed that the solder cap was surrounded by an innerring of Cu−Sn compound and an outer ring of Pd−Sn compound. This implies that the molten SnAg solder had removed the Pd and wetted the Cu directly in the equilibrium state. The effects of pre-doping Cu in the SnAg solder on wetting behavior were also investigated. We found that wettability decreases with increasing Cu content in the solder. We also observed that the SnAgCu solders have a lower Cu consumption rate than the SnAg solder.     

Elevated temperature aging of solder joints based on Sn-Ag-Cu: Effects on joint microstructure and shear strength

The shear strength behavior and microstructural effects after aging for 100 h and 1,000 h at 150°C are reported for near-eutectic Sn-Ag-Cu (SAC) solder joints (joining to Cu) made from Sn-3.5Ag (wt.%) and a set of SAC alloys (including Co- and Fe-modified SAC alloys). All joints in the as-soldered and 100-h aged condition experienced shear failure in a ductile manner by either uniform shear of the solder matrix (in the strongest solders) or by a more localized shear of the solder matrix adjacent to the Cu₆Sn₅ interfacial layer, consistent with other observations. After 1,000 h of aging, a level of embrittlement of the Cu₃Sn/Cu interface can be detected in some solder joints made with all of the SAC alloys and with Sn-3.5Ag, which can lead to partial debonding during shear testing. However, only ductile failure was observed in all solder joints made from the Co- and Fe-modified SAC alloys after aging for 1,000 h. Thus, the strategy of modifying a strong (high Cu content) SAC solder alloy with a substitutional alloy addition for Cu seems to be effective for producing a solder joint that retains both strength and ductility for extended isothermal aging at high temperatures.     

Creep resistance of tin-based lead-free solder alloys

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