Processing and aging characteristics of eutectic Sn-3.5Ag solder reinforced with mechanically incorporated Ni particles

Composite solders offer improved properties compared to non-composite solders. Ni reinforced composite solder was prepared by mechanically dispersing 15 vol.% of Ni particles into eutectic Sn-3.5Ag solder paste. The average size of the Ni particle reinforcements was approximately 5 microns. The morphology, size and distribution of the reinforcing phase were characterized metallographically. Solid-state isothermal aging study was performed on small realistic size solder joints to study the formation and growth of the intermetallic (IM) layers at Ni reinforcement/solder and Cu substrate/solder interfaces. Effects of reflow on microstructure and solderability, were studied using Cu substrates. Regarding solderability, the wetting angle of multiple reflowed Ni reinforced composite solder was compared to the solder matrix alloy, eutectic Sn-3.5Ag. General findings of this study revealed that Ni particle reinforced composite solder has comparable wetting characteristics to eutectic Sn-3.5Ag solder. Significant IM layers growth was observed in the Ni composite solder joint under isothermal aging at 150 C. Microstructural evolution was insignificant when aging temperature was lower than 100 C. Multiple reflow did not significantly change the microstructure in Ni composite solder joint.     

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.     

Mechanical strength of Sn-3.5Ag-based solders and related bondings

The tensile strengths of bulk solders and joint couples of Sn-3.5Ag-0.5Cu, Sn-3.5Ag-0.07Ni, and Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge solders and the shear strengths of ball grid array (BGA) specimens, solder-ball-attached Cu/Ni/Au metallized substrates were investigated. The tensile strength of the bulk is degraded by thermal aging. The Ni-containing solder exhibits lower tensile strength than Sn-3.5Ag-0.5Cu after thermal aging. However, the Ni-containing solder joints show greater tensile strength than the Cu/Sn-3.5Ag-0.5Cu/Cu joint. Fracture of the solder joint occurs between the intermetallic compound (IMC) and the solder. The shear strength and fracture mechanism of BGA specimens are the same regardless of solder composition.     

Creep Behavior of Lead-Free Sn-Ag-Cu + Ni-Ge Solder Alloys

We developed a new lead-free solder alloy, an Sn-Ag-Cu base to which a small amount of Ni and Ge is added, to improve the mechanical properties of solder alloys. We examined creep deformation in bulk and through-hole (TH)␣form for two lead-free solder alloys, Sn-3.5Ag-0.5Cu-Ni-Ge and Sn-3.0Ag-0.5Cu, at elevated temperatures, finding that the creep rupture life of the Sn-3.5Ag-0.5Cu-Ni-Ge solder alloy was over three times better than that of the Sn-3.0Ag-0.5Cu solder at 398 K. Adding Ni to the solder appears to make microstructural development finer and more uniform. The Ni added to the solder readily combined with Cu to form stable intermetallic compounds of (Cu, Ni)₆Sn₅ capable of improving the creep behavior of solder alloys. Moreover, microstructural characterization based on transmission electron microscopy analyses observing creep behavior in detail showed that such particles in the Sn-3.5Ag-0.5Cu-Ni-Ge solder alloy prevent dislocation and movement.     

Reactions of lead-free solders with CuNi metallizations

We have done experimental research on the dissolution rate and intermetallic growth on Cu, Ni, and CuNi-alloy substrates as a function of time and Cu/Ni ratio of the substrate. Reactions that occur when CuNi metallizations are soldered with lead-free solders were investigated. The experiments were performed using Sn-3.5Ag and Sn-3.8Ag-0.7Cu solders and different CuNi alloys. To determine the rate of dissolution of the substrate material into the solder, CuNi foils of different concentrations were immersed in Sn-3.5Ag and Sn-3.8Ag-0.7Cu solder baths for soldering times ranging from 15 sec to 5 min at 250°C. In addition, reflows of solder balls were made on top of bulk substrates to study the reaction when there is a practically infinite amount of CuNi available compared to the amount of solder. Thin film experiments were also done, where Ni containing under bump metallizations (UBMs) were fabricated and reflowed with eutectic SnAg solder balls. The nickel slows down the dissolution of the UBM into the solder and the formation of intermetallics during reflow compared to Cu metallizations. The solder/UBM interfaces were analyzed with SEM to find out how Ni concentration affects the reaction, and how much Ni is needed to obtain a sufficiently slow reaction rate.     

Ball Impact Responses of Ni- or Ge-Doped Sn-Ag-Cu Solder Joints

In this work, we present ball impact test (BIT) responses and fractographies obtained at an impact velocity of 500 mm/s on Sn-4Ag-0.5Cu, Sn-1Ag-0.5Cu, Sn-1Ag-0.5Cu-0.05Ni, Sn-1.2Ag-0.5Cu-0.05Ni, and Sn-1Ag-0.5Cu-0.05Ge package-level solder joints. The solder joints are bonded on substrate pads of either immersion tin (IT) or direct solder on pad (DSOP) surface finishes. Differences of BIT results with respect to multi-reflow are also reported. Taking the impact energy as an indication of board-level drop reliability of the solder joints, the BIT results indicate that better reliability can be achieved by adopting Sn-Ag-Cu solder alloys with low Ag weight contents as well as IT substrate pad finish rather than DSOP. Moreover, the addition of Ni or Ge to the solder alloy provides a large improvement; Ni alters the interfacial intermetallic compound (IMC) structure while Ge enhances the mechanical behavior of the bulk solder.     

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.     

Interfacial reactions in the pb-free composite solders with indium layers

A Pb-free composite solder is prepared with a Pb-free solder substrate and a plated-indium layer. The indium layer melts during the soldering process, wets the substrates, and forms a sound solder joint. Since the melting temperature of indium is 156.6°C, lower than that of the eutectic Sn-Pb, which is at 183°C, the soldering process can be carried out at a temperature lower than that of the conventional soldering process. Composite solder joints with three different Pb-free solders, Sn, Sn-3.5 wt.% Ag, and Sn-3.5 wt.% Ag-0.5 wt.% Cu, and two substrates, Ni and Cu, are prepared. The interfaces between the indium layer, Pb-free solder, and Ni and Cu substrate are examined. A good solder joint is formed after a 2-min reflow at 170°C. A very thick reaction zone at the indium/Pb-free solder interface and a thin reaction layer at the indium/substrate interface are observed.     

Thermal Fatigue Endurance of Lead-Free Composite Solder Joints over a Temperature Range of −55°C to 150°C

The thermal fatigue endurance of two lead-free solder/plastic-core solder ball (PCSB) composite joint structures in low-temperature co-fired ceramic (LTCC) modules was investigated using a thermal cycling test over a temperature range of −55°C to 150°C. The investigated solder alloys were Sn-7In-4.1Ag-0.5Cu (SAC-In) and 95.5Sn-4Ag-0.5Cu (SAC). Three failure mechanisms were observed in the test joints. Transgranular (fatigue) cracking mixed with minor intergranular cracking was the dominant failure mechanism at the outer edge of the joints in both test assemblies, whereas separation of the solder/intermetallic compound (IMC) interface and creep cracking occurred in the other parts of the test joints. The propagation rate of the transgranular crack was lower in the SAC-In joints compared with in the SAC joints. Furthermore, the SAC solder seemed to be more prone to separation of the solder/IMC interface, and more severe intergranular (creep) cracking occurred in it compared with in the SAC-In solder. In the thermal cycling test conditions, the better thermal fatigue endurance of the SAC-In solder composite joints resulted in a 75% higher characteristic lifetime compared with the SAC composite joints.     

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

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

颗粒增强Sn-Ag基无铅复合钎料显微组织与性能

通过外加法向Sn-3.5Ag焊料中加入体积分数为10%的微米级Cu、Ni颗粒制备了无铅复合钎料,对钎料的显微组织、拉剪及润湿性能进行了研究。结果表明,颗粒周围以及基板界面处的显微组织中生成了金属间化合物,其形态及大小因加入颗粒而不同。颗粒的加入提高了钎料钎焊接头的剪切强度,其中Cu颗粒增强的接头的剪切强度提高了33%,Ni颗粒的提高了20%。两种复合钎料的铺展面积均下降了约15%,其中Cu颗粒增强复合钎料润湿角由11°增加到18°。     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Recent Observations on Tin Pest Formation in Solder Alloys

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

Application of an asymmetrical four point bend shear test to solder joints

The asymmetrical four-point bend shear (AFPB) test method was used to measure the shear strength and creep properties through the stress relaxation experiments using three different Pb-free solder joint compositions in an assolidified condition. Since it was difficult to shear the uniform specimens and the local bending usually occurs at the inner loading points, the notches were introduced at the joint line to preferentially weaken this region. The stress analysis by finite element modeling showed that the straight notches transform the parabolic shear stress distribution in the uniform specimen into a relatively uniform shear distribution along the bond line in the notched specimens. Therefore, the shear strength results from the notched specimens are expected to be much more accurate. Experiments showed that both the Sn-3.6Ag-1Cu (wt.%) and Sn-3.6Ag-1Cu-0.45Co joints have superior strength and creep properties as compared to the Sn-3.5Ag joint. However, there was no statistical difference between the shear strength of the Sn-3.6Ag-1Cu and Sn-3.6Ag-1Cu-0.45 Co joints. Moreover, the difference between the creep resistance of these two types of joints was small.     

Dissolution behavior of Cu and Ag substrates in molten solders

This study investigated the dissolution behavior of Cu and Ag substrates in molten Sn, Sn-3.5Ag, Sn-4.0Ag-0.5Cu, Sn-8.6Zn and Sn-8.55Zn-0.5Ag-0.1Al-0.5Ga lead-free solders as well as in Sn-37Pb solder for comparison at 300, 350, and 400°C. Results show that Sn-Zn alloys have a substantially lower dissolution rate of both Cu and Ag substrates than the other solders. Differences in interfacial intermetallic compounds formed during reaction and the morphology of these compounds strongly affected the substrate dissolution behavior. Soldering temperature and the corresponding solubility limit of the substrate elements in the liquid solder also played important roles in the interfacial morphology and dissolution rate of substrate.     

Low-cycle fatigue behavior of Sn-Ag, Sn-Ag-Cu, and Sn-Ag-Cu-Bi lead-free solders

Low-cycle fatigue (LCF) tests on as-cast Sn-3.5Ag, Sn-3Ag-0.5Cu, Sn-3Ag-0.5Cu-1Bi, and Sn-3Ag-0.5Cu-3Bi solders was carried out using a noncontact strain-controlled system at 20°C with a constant frequency of 0.1 Hz. The addition of Cu does not significantly affect the fatigue life of eutectic Sn-Ag solder. However, the fatigue life was significantly reduced with the addition of Bi. The LCF behavior of all solders followed the Coffin-Manson relationship. The fatigue life of the present solders is dominated by the fracture ductility and can be described by the ductility-modified Coffin-Manson’s relationship. Steps at the boundaries of dendrite phases were the initiation sites for microcracks for Sn-3.5Ag, Sn-3Ag-0.5Cu, and Sn-3Ag-0.5Cu-1Bi solders, while for Sn-3Ag-0.5Cu-3Bi solder, cracks initiated along both the dendrite boundaries and subgrain boundaries in the dendrite phases. The linking of these cracks and the propagation of cracks inside the specimen occurred both transgranularly through eutectic phases and intergranularly along dendrite boundaries or subgrain boundaries.     

Joint Strength and Microstructure for Sn-Ag-(Cu) Soldering on an Electroless Ni-Au Surface Finish by Using a Flux Containing a Cu Compound

The effect of a flux containing Cu(II) stearate (barrier flux) on the strength of soldered joints between an electroless Ni-Au surface finish and two Pb-free soldering systems, Sn-3Ag-0.5Cu and Sn-3.5Ag (wt.%), was examined. Pull and shock tests showed that barrier flux gave a higher joint strength for both solder compositions than did a flux containing no Cu compounds. Interface analysis revealed that a thin P-rich layer and refined Cu-Ni-Sn intermetallic compounds were formed at the joint interface when barrier flux was used. It is assumed that the supply of Cu from barrier flux suppresses diffusion of Ni into the solder.     

Constitutive relations on creep for SnAgCuRE lead-free solder joints

Taking the most promising substitute of the Sn-3.8Ag-0.7Cu solder as the research base, investigations were made to explore the effect of rare earths (REs) on the creep performance of the Sn-3.8Ag-0.7Cu solder joints. The SnAgCu-0.1RE solder with the longest creep-rupture life was selected for subsequent research. Creep strain tests were conducted on Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints in the intermediate temperature range from 298 K to 398 K, corresponding to the homologous temperatures η=0.606, 0.687, 0.748, and 0.809 and η = 0.602, 0.683, 0.743, and 0.804, respectively, to acquire the relevant creep parameters, such as stress exponent and activation energy, which characterize the creep mechanisms. The final creep constitutive equations for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints were established, demonstrating the dependence of steady-state creep rate on stress and temperature. By correcting the apparent creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints from the experiments, the true creep-activation energy is obtained. Results indicated that at low stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the lattice self-diffusion activation energy, so the steady-state creep rates of these two solder joints are both dominated by the rate of lattice self-diffusion. While at high stress, the true creep-activation energy of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints is close to the dislocation-pipe diffusion activation energy, so the steady-state creep rates are dominated by the rate of dislocation-pipe diffusion. At low stress, the best-fit stress exponents n of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are 6.9 and 8.2, respectively, and the true creep-activation energy of them both is close to that of lattice self-diffusion. At high stress, it equals 11.6 and 14.6 for Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints, respectively, and the true creep-activation energy for both is close to that of the dislocation-pipe diffusion. Thus, under the condition of the experimental temperatures and stresses, the dislocation climbing mechanism serves as the controlling mechanism for creep deformation of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints. The creep values of Sn-3.8Ag-0.7Cu and SnAgCu-0.1RE solder joints are both controlled by dislocation climbing. Dislocation glide and climb both contribute to creep deformation, but the controlling mechanism is dislocation climb. At low stress, dislocation climbing is dominated by the lattice self-diffusion process in the Sn matrix and dominated by the dislocation-pipe diffusion process at high stress.     

Effect of Ag and Cu Concentrations on the Creep Behavior of Sn-Based Solders

The creep behavior of Sn-1Ag-0.5Cu, Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu ball grid array (BGA) solder balls and 99.99% pure polycrystalline bulk Sn was studied using impression creep and related to the microstructure. Sn-Ag-Cu solders generally consist of primary dendrites/grains of β-Sn, and a eutectic microconstituent comprising fine Ag₃Sn and Cu₆Sn₅ particles in β phase. With increasing concentrations of Ag and Cu in the alloy, the proportion of the eutectic microconstituent in relation to the primary β phase increases. In pure Sn and Sn-1Ag-0.5Cu, the β grains form the continuous matrix, whereas in Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu, the eutectic microconstituent forms a continuous network around the β grains, which form isolated islands within the eutectic. The steady-state creep behavior of the alloys was dominated by the response of the continuous microstructural constituent (β-Sn or solid solution β for pure Sn and Sn-1Ag-0.5Cu, and the eutectic microconstituent for Sn-2.5Ag-0.5Cu and Sn-4Ag-0.5Cu). In general, the steady-state creep rate decreased with increasing alloy content, and in particular, the volume fraction of Ag₃Sn and Cu₆Sn₅ precipitates. The rate-limiting creep mechanism in all the materials investigated here was core diffusion controlled dislocation climb. However, subtle changes in the stress exponent n and activation energy Q were observed. Pure Sn shows n = 5, Q = 42 kJ/mol, Sn-1Ag-0.5Cu shows n = 5, Q = 61 kJ/mol, whereas both Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu show n = 6 and Q = 61 kJ/mol. Rationalizations for the observed changes of n and Q are provided, based on the influence of the microstructure and the solute concentrations.     

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.