Wetting interaction between Sn-Zn-Ag solders and Cu

The wetting interaction of Sn-(7.1–9)Zn-(0–3)Ag solders with Cu was investigated from 230°C to 300°C. The wetting time, wetting forces, and activation energy of the wetting reaction were studied. The wetting time decreases with increasing temperature and increases with Ag content. The wetting force exhibits a disproportional correlation to temperature rise, while no trend was observed with respect to Ag content. The wetting behavior was ascribed to the interaction between Cu and Zn. The AgZn₃ compound was formed at the interface when the solder contains 0.3% Ag and above, while it was formed within the bulk solder at 2% Ag and above.     

Effect of adding Sb on microstructure and adhesive strength of Sn-Ag solder joints

This study investigates the influence of adding Sb on the microstructure and adhesive strength of the Sn3.5Ag solder. Both solidus and liquidus temperatures increase as Sb additions increase. Adding 1.5wt.%Sb leads to the narrowest range (6.6°C) between the solidus and liquidus temperature of the solder. Adding Sb decomposes the as-soldered ringlike microstructure of Sn3.5Ag and causes solid-solution hardening. The as-soldered hardness increases with increasing Sb addition. For long-term storage, adding Sb reduces the size of the rodlike Ag₃Sn compounds. The hardness also increases with increasing Sb addition. Adding Sb depresses the growth rate of interfacial intermetallic compounds (IMCs) layers, but the difference between 1% and 2% Sb is not distinct. For mechanical concern, adding Sb improves both adhesive strength and thermal resistance of Sn3.5Ag, where 1.5% Sb has the best result. However, adding Sb causes a variation in adhesive strength during thermal storage. The more Sb is added, the higher the variation reveals, and the shorter the storage time requires. This strength variation helps the solder joints to resist thermal storage.     

Microstructure and mechanical behavior of novel rare earth-containing Pb-Free solders

Sn-rich solders have been shown to have superior mechanical properties when compared to the Pb-Sn system. Much work remains to be done in developing these materials for electronic packaging. In this paper, we report on the microstructure and mechanical properties of La-containing Sn-3.9Ag-0.7Cu alloys. The addition of small amounts of La (up to 0.5 wt.%) to Sn-Ag-Cu refined the microstructure by decreasing the length and spacing of the Sn dendrites and decreased the thickness of the Cu₆Sn₅ intermetallic layer at the Cu/solder interface. As a result of the change in the microstructure, Sn-Ag-Cu alloys with La additions exhibited a small decrease in ultimate shear strength but significantly higher elongations compared with Sn-Ag-Cu. The influence of LaSn₃ intermetallics on microstructural refinement and damage evolution in these novel solders is discussed. Our results have profound implications for improving the mechanical shock resistance of Pb-free solders.     

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.     

Effect of SiC Nanoparticle Additions on Microstructure and Microhardness of Sn-Ag-Cu Solder Alloy

In this work, lead-free composite solders were produced by mechanically mixing nominal 20 nm moissanite SiC particles with Sn-3.8Ag-0.7Cu solder paste. The effects of the amount of SiC addition on the melting behavior, microstructure, and microhardness of as-solidified composite solders were systematically investigated. In comparison with solder without the addition of SiC nanoparticles, the subgrain of β-Sn, the intermetallic compounds (IMCs) average grain size and distance decreased significantly in the composite solder matrix. This was possibly ascribed to the strong adsorption effect and high surface free energy of the SiC nanoparticles. Our results showed that 0.05 wt.% addition of SiC nanoparticles could improve the microhardness by 44% compared with the noncomposite and that the average grain size and distance changed from 0.5 μm to 0.2 μm and from 0.6 μm to 0.32 μm, respectively. The refined IMCs, acting as a strengthening phase in the solder matrix, enhanced the microhardness of the composite solders, in good agreement with the prediction of the classic theory of dispersion strengthening.     

Solid state intermetallic compound growth between copper and high temperature,tin-rich solders—part I: Experimental analysis

An experimental study was performed which examined the solid state growth kinetics of the interfacial intermetallic compound layers formed between copper and the high temperature, tin-rich solders 96.5Sn-3.5Ag (wt.%) and 95Sn-5Sb. These results were compared with baseline data from the 100Sn/copper system. Both the 96.5Sn-3.5Ag and 95Sn-5Sb solders exhibited the individual Cu₃Sn and Cu₆Sn₅ layers at the interface; the thickness of the Cu₃Sn layer being a function of the aging time and temperature. The total thickness of the intermetallic compound layer formed in the 96.5Sn-3.5Ag solder/copper couple showed a mixture of linear and √t dependencies at the lower temperatures of 70,100, and 135°C, and a t^0.42 dependence at 170 and 205°C. The combined apparent activation energy was 59 kJ/mol, the Arrhenius plot showed a knee between the low and high temperature data. The total layer thickness of the 95Sn-5Sb/copper system exhibited √t dependence at the three lower temperatures and t^0.42 growth kinetics at 170 and 205°C. The combined apparent activation energy was 61 kJ/mol.     

Solid-state intermetallic compound layer growth between copper and 95.5Sn-3.9Ag-0.6Cu solder

Long-term, solid-state intermetallic compound (IMC) layer growth was examined in 95.5Sn-3.9Ag-0.6Cu (wt.%)/copper (Cu) couples. Aging temperatures and times ranged from 70°C to 205°C and from 1 day to 400 days, respectively. The IMC layer thicknesses and compositions were compared to those investigated in 96.5Sn-3.5Ag/Cu, 95.5Sn-0.5Ag-4.0Cu/Cu, and 100Sn/Cu couples. The nominal Cu₃Sn and Cu₆Sn₅ stoichiometries were observed. The Cu₃Sn layer accounted for 0.4–0.6 of the total IMC layer thickness. The 95.5Sn-3.9Ag-0.6Cu/Cu couples exhibited porosity development at the Cu₃Sn/Cu interface and in the Cu₃Sn layer as well as localized “plumes” of accelerated Cu₃Sn growth into the Cu substrate when aged at 205°C and t>150 days. An excess of 3–5at.%Cu in the near-interface solder field likely contributed to IMC layer growth. The growth kinetics of the IMC layer in 95.5Sn-3.9Ag-0.6Cu/Cu couples were described by the equation x=x_o+Atⁿexp [−ΔH/RT]. The time exponents, n, were 0.56±0.06, 0.54±0.07, and 0.58±0.07 for the Cu₃Sn layer, the Cu₆Sn₅, and the total layer, respectively, indicating a diffusion-based mechanism. The apparent-activation energies (ΔH) were Cu₃Sn layer: 50±6 kJ/mol; Cu₆Sn₅ layer: 44±4 kJ/mol; and total layer: 50±4 kJ/mol, which suggested a fast-diffusion path along grain boundaries. The kinetics of Cu₃Sn growth were sensitive to the Pb-free solder composition while those of Cu₆Sn₅ layer growth were not so.     

The thermal property of lead-free Sn-8.55Zn-1Ag-XAl solder alloys and their wetting interaction with Cu

The wetting behaviors between the quaternary Sn-8.55Zn-1Ag-XAl solder alloys and Cu have been investigated with the wetting balance method. The Al contents, x, of the quaternary solder alloys investigated were 0.01–0.45 wt.%. The results of differential scanning calorimeter (DSC) analysis indicate that the solders exhibit a solid-liquid coexisting range of about 7–10°C. The solidus temperature of the quaternary Sn-8.55Zn-1Ag-XAl solder alloys is about 198.2°C, while the liquidus temperatures are 205–207°C. The experimental results showed that the wettability of the Sn-8.55Zn-1Ag-XAl solder alloys is improved by the addition of Al. The mean maximum wetting force of the solders with Cu is within 0.75–1.18 mN and the mean wetting time is around 1.0–1.1 sec, better than the ∼1.3 sec of eutectic Sn-9Zn and Sn-8.55Zn-1Ag solder alloys. The addition of Al also depresses the formation of ε-Ag-Zn compounds at the interface between Sn-8.55Zn-1Ag-XAl solders and copper.     

Morphology of intermetallic compounds formed between lead-free Sn-Zn based solders and Cu substrates

The morphologies of intermetallic compounds formed between Sn-Zn based solders and Cu substrates were investigated in this study. The investigated solders were Sn-9Zn, Sn-8.55Zn-0.45Al, and Sn-8.55Zn-0.45Al-0.5Ag. The experimental results indicated that the Sn-9Zn solder formed Cu₅Zn₈ and CuZn₅ compounds on the Cu substrate, while the Al-containing solders formed the Al_4.2Cu_3.2Zn_0.7 compound. The addition of Ag to the Sn-8.55Zn-0.45Al solder resulted in the formation of the AgZn₃ compound at the interface between the Al_4.2Cu_3.2Zn_0.7 compound and the solder. Furthermore, it was found that the cooling rate of the specimen after soldering had an effect on the quantity of AgZn₃ compound formed at the interface. The AgZn₃ compound formed with an air-cooling condition exhibited a rougher surface and larger size than with a water-quenched condition. It was believed that the formation of the AgZn₃ compound at the interface occurs through heterogenous nucleation during solidification.     

Interfacial reactions between In 10Ag solders and Ag substrates

The morphology and growth kinetics of intermetallic compounds formed during the reaction of liquid In 10Ag on Ag substrates in the temperature range between 250°C and 375°C are studied. The results indicate that the Ag₂In intermetallic compounds that appear at the interface are in the columnar shape, enveloped by thin AgIn₂ shells. The growth kinetics of intermetallic compounds are parabolic, indicating that the reaction is diffusion-controlled. The Arrhenius reaction activation energy was found to be 44.9 kJ/mol. Also, the wetting behavior of the In10Ag on Ag substrates was studied. The results show that there exists a transient plateau of the contact angle variation. Such a phenomenon can be explained by the intermetallic compound precursor halo formation preceding the edge of the solder drop.     

Impact of Thermal Cycling on Sn-Ag-Cu Solder Joints and Board-Level Drop Reliability

The electronic packaging industry uses electroless nickel immersion gold (ENIG) or Cu-organic solderability preservative (Cu-OSP) as a bonding pad surface finish for solder joints. In portable electronic products, drop impact tests induce solder joint failures via the interfacial intermetallic, which is a serious reliability concern. The intermetallic compound (IMC) is subjected to thermal cycling, which negatively affects the drop impact reliability. In this work, the reliability of lead-free Sn-3.0Ag-0.5Cu (SAC) soldered fine-pitch ball grid array assemblies were investigated after being subjected to a combination of thermal cycling followed by board level drop tests. Drop impact tests conducted before and after thermal aging cycles (500, 1000, and 1500 thermal cycles) show a transition of failure modes and a significant reduction in drop durability for both SAC/ENIG and SAC/Cu-OSP soldered assemblies. Without thermal cycling aging, the boards with the Cu-OSP surface finish exhibit better drop impact reliability than those with ENIG. However, the reverse is true if thermal cycle (TC) aging is performed. For SAC/Cu-OSP soldered assemblies, a large number of Kirkendall voids were observed at the interface between the intermetallic and Cu pad after thermal cycling aging. The void formation resulted in weak bonding between the solder and Cu, leading to brittle interface fracture in the drop impact test, which resulted in significantly lower drop test lifetimes. For SAC/ENIG soldered assemblies, the consumption of Ni in the formation of NiCuSn intermetallics induced vertical voids in the Ni(P) layer.     

The interfacial reaction between Sn-Zn-Ag-Ga-Al solders and metallized Cu substrates

The interfacial interaction between the Sn-8.55Zn-0.5Ag-0.5Ga-0.1Al solder and three kinds of metallized substrates (Cu, Cu/Au, and Cu/Ni-P/Au) does not form the Cu-Sn intermetallic compound (IMC). Continuous Cu-Zn and discontinuous Ag-Zn interfacial IMC layers formed between the Cu and Sn-Zn-Ag-Ga-Al solder, while Cu-Zn and Au-Al-Zn IMCs formed on the Cu/Au substrate. Only the Au-Al-Zn IMC formed at the interface when the electroless Ni-P deposit was the diffusion barrier between Cu and the Au surface layer.     

Interfacial reactions between Bi-Ag high-temperature solders and metallic substrates

This study investigated the interfacial morphology and tensile properties of the joints between Bi-Ag solders and two metallic substrates, Cu and Ni. Instead of forming intermetallic compounds, grooving occurred at the intersections of Cu grain boundaries with the Bi-Ag/Cu interface and thus provided mechanical bonding. As for the Ni substrate, cellular NiBi₃ was observed at the interface and also, massive NiBi₃ in the form of long blades emanating from the interface was located within the solder region. A thin NiBi layer formed through a solid-state reaction between NiBi₃ and the solder. The formation of those Ni-Bi intermetallics had a strong influence on the tensile strength and fracture morphology of the Bi-Ag/Ni joints.     

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.     

无铅焊点在热疲劳和电迁移作用下的组织演变

研究了Cu/Sn-58Bi/Cu焊点接头在室温和55℃下通电过程中阴极和阳极界面处微观组织的演变,电流密度均采用104 A/cm2.结果表明,室温条件下通电达到25 d,Bi原子由阴极向阳极发生了扩散迁移,在阳极界面处形成了厚度约22.4μm的均匀Bi层,而阴极出现了Sn的聚集,加载55℃通电2d后,焊点发生了熔融,阴极界面处形成了厚度为34.3 μm的扇贝状IMC,而阳极界面IMC的厚度仅为9.7 μm.在IMC层和钎料基体之间形成了厚度约7.5μm的Bi层,它的形成阻碍了Sn原子向阳极界面的扩散迁移,进而阻碍了阳极界面IMC的生长,导致了异常极化效应的出现.     

Contact angle measurements of Sn-Ag and Sn-Cu lead-free solders on copper substrates

In this study, the contact angles of four lead-free solders, namely, Sn-3.5Ag, Sn-3.5Ag-4.8Bi, Sn-3.8Ag-0.7Cu, and Sn-0.7Cu (wt.%), were measured on copper substrates at different temperatures. Measurements were performed using the sessile-drop method. Contact angles ranging from 30° to 40° after wetting under vacuum with no fluxes and between 10° and 30° with rosin mildly activated (RMA) and rosin activated (RA) fluxes were obtained. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles, indicating improved wettability with the addition of bismuth. For all soldering alloys, lower contact angles were observed using RMA flux. Intermetallics formed at the solder/Cu interface were identified as Cu₆Sn₅ adjacent to the solder and Cu₃Sn adjacent to the copper substrate. The Cu₃Sn intermetallic phase was generally not observed when RMA flux was used. The effect of temperature on contact angle was dependent on the type of flux used.     

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.     

Microstructure and mechanical properties predicted by indentation testing of lead-free solders

Microstructure and mechanical properties were investigated for ten systems of lead-free solders compared with the eutectic Sn-Pb solder. Mechanical properties including elastic, plastic, and creep deformations were predicted by indentation testing. This method was established based on the elastic-plastic-creep finite-element method (FEM). The predicted mechanical properties were obtained for the temperatures ranging between −20°C and 160°C.