Solderability testing of 95.5Sn-3.9Ag-0.6Cu solder on oxygen-free high-conductivity copper and Au-Ni-Plated kovar

The solderability of 95.5Sn-3.9Ag-0.6Cu solder on oxygen-free high-conductivity (OFHC) copper and Au-Ni-plated Kovar was examined as a function of flux and process temperature. The three solder fluxes included a rosin-based (R) material, a rosin mildly activated (RMA) flux, and a low-solids (LS) flux. The solderability metric was the contact angle, θ_C, measured by a meniscometer and wetting-balance techniques. The wetting rate and time to maximum force parameters were also documented. In most cases, the contact angles for the 95.5Sn-3.9Ag-0.6Cu solder alloy, regardless of the type of flux or temperature, were higher then those for the 63Sn-37Pb eutectic-solder alloy, indicating a less “solderable” surface.     

Effect of flux on the wetting characteristics of SnAg, SnCu, SnAgBi, and SnAgCu lead-free solders on copper substrates

The effect of flux on the wetting characteristics of four lead-free solders, Sn-3.5Ag, Sn-0.7Cu, Sn-3.5Ag-4.8Bi, and Sn-3.8Ag-0.7Cu (wt.%), on copper substrates have been studied at 240, 260, and 280°C. The fluxes investigated were rosin (R), mildly activated rosin (RMA), and activated rosin (RA). The wetting tests were conducted using the sessile-drop method. Results showed that fluxes significantly affect the wetting properties of the solders. Contact angles ranging from 10° to 30° for RMA, 20° to 30° for RA, and 35° to 60° for R were obtained. The effect of temperature on contact angle depended on the type of flux used. The contact angle decreased with increasing temperature; however, in some cases the contact angle was independent of temperature. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles indicating improved wettability with addition of bismuth. The microstructure of the solder/copper interface was analyzed by scanning electron microscopy.     

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.     

Sn-Cu、Sn-Ag-Cu系无铅钎料的钎焊特性研究

制备了Sn-0.7Cu、Sn-3.5Ag-0.6Cu钎料,用润湿平衡法测量了钎料对铜的润湿曲线,研究了温度、钎剂活性、钎焊时间对润湿行为的影响,并与Sn-37Pb钎料进行了比较。结果表明:升高温度能显著改善无铅钎料对铜的钎焊性。当温度<270℃时,Sn-0.7Cu的钎焊性明显低于Sn-3.5Ag-0.6Cu钎料;而当温度≥270℃时,两种钎料对铜都会显示较好的润湿性,而Sn-0.7Cu略优于Sn-3.5Ag-0.6Cu钎料。提高钎剂活性能显著增强钎料对铜的润湿性,其卤素离子的最佳质量分数均为0.4%左右。随着浸渍时间的延长,熔融钎料与铜的界面间产生失润现象。无铅钎料的熔点和表面张力较高,是钎焊性较差的根本原因。     

Microstructure, solderability, and growth of intermetallic compounds of Sn-Ag-Cu-RE lead-free solder alloys

The near-eutectic Sn-3.5 wt.% Ag-0.7 wt.% Cu (Sn-3.5Ag-0.7Cu) alloy was doped with rare earth (RE) elements of primarily Ce and La of 0.05–0.25 wt.% to form Sn-3.5Ag-0.7Cu-xRE solder alloys. The aim of this research was to investigate the effect of the addition of RE elements on the microstructure and solderability of this alloy. Sn-3.5Ag-0.7Cu-xRE solders were soldered on copper coupons. The thickness of the intermetallic layer (IML) formed between the solder and Cu substrate just after soldering, as well as after thermal aging at 170°C up to 1000 h, was investigated. It was found that, due to the addition of the RE elements, the size of the Sn grains was reduced. In particular, the addition of 0.1wt.%RE to the Sn-3.5Ag-0.7Cu solder improved the wetting behavior. Besides, the IML growth during thermal aging was inhibited.     

Wetting and reaction of Sn-2.8Ag-0.5Cu-1.0Bi solder with Cu and Ni substrates

The wettability of newly developed Sn-2.8Ag-0.5Cu-1.0Bi lead-free solder on Cu and Ni substrates was assessed through the wetting balance tests. The wettability assessment parameters such as contact angle (ϑ_c) and maximum wetting force (F_w) were documented for three solder bath temperatures with three commercial fluxes, namely, no-clean (NC), nonactivated (R), and water-soluble organic acid flux (WS). It was found that the lead-free Sn-2.8Ag-0.5Cu-1.0Bi solder exhibited less wetting force, i.e., poorer wettability, than the conventional Sn-37Pb solder for all flux types and solder bath temperatures. The wettability of Sn-2.8Ag-0.5Cu-1.0Bi lead-free solder on Cu substrate was much higher than that on Ni substrate. Nonwetting for Sn-2.8Ag-0.5Cu-1.0Bi and Sn-Pb solders on Ni substrate occurred when R-type flux was used. A model was built and simulations were performed for the wetting balance test. The simulation results were found very close to the experimental results. It was also observed that larger values of immersion depth resulted in a decrease of the wetting force and corresponding meniscus height, whereas the increase in substrate perimeter enhanced the wettability. The wetting reactions between the solder and Cu/Ni substrates were also investigated, and it was found that Cu atoms diffused into the solder through the intermetallic compounds (IMCs) much faster than did the Ni atoms. Rapid formation of IMCs inhibited the wettability of Sn-2.8Ag-0.5Cu-1.0Bi solder compared to the Sn-Pb solder.     

Intermetallic growth kinetics for Sn-Ag, Sn-Cu, and Sn-Ag-Cu lead-free solders on Cu, Ni, and Fe-42Ni substrates

Soldering with the lead-free tin-base alloys requires substantially higher temperatures (∼235–250°C) than those (213–223°C) required for the current tin-lead solders, and the rates for intermetallic compound (IMC) growth and substrate dissolution are known to be significantly greater for these alloys. In this study, the IMC growth kinetics for Sn-3.7Ag, Sn-0.7Cu, and Sn-3.8Ag-0.7Cu solders on Cu substrates and for Sn-3.8Ag-0.7Cu solder with three different substrates (Cu, Ni, and Fe-42Ni) are investigated. For all three solders on Cu, a thick scalloped layer of η phase (Cu₆Sn₅) and a thin layer of ε phase (Cu₃Sn) were observed to form, with the growth of the layers being fastest for the Sn-3.8Ag-0.7Cu alloy and slowest for the Sn-3.7Ag alloy. For the Sn-3.8Ag-0.7Cu solder on Ni, only a relatively uniform thick layer of η phase (Cu,Ni)₆Sn₅ growing faster than that on the Cu substrate was found to form. IMC growth in both cases appears to be controlled by grain-boundary diffusion through the IMC layer. For the Fe-42Ni substrate with the Sn-3.8Ag-0.7Cu, only a very thin layer of (Fe,Ni)Sn₂ was observed to develop.     

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.     

Interfacial behaviors of Sn-Pb,Sn-Ag-Cu Pb-free and mixed Sn-Ag-Cu/Sn-Pb solder joints during electromigration

SnPb-SnAgCu mixed solder joints with Sn-Pb soldering Sn-Ag-Cu Pb-free components are inevitably occurred in the high reliability applications. In this study, the interfacial behaviors in Sn-37Pb and Sn-3.0Ag-0.5Cu mixed solder joints was addressed and compared with Sn-37Pb solder joints and Sn-3.0Ag-0.5Cu solder joints with the influence from isothermal aging and electromigration. Considering the difference on the melting point between Sn-3.0Ag-0.5Cu and Sn-37Pb solder, two mixed solder joints: partial mixing and full mixing between Sn-Pb and Sn-Ag-Cu solders were reached with the peak reflowing temperature of 190 and 250 °C, respectively. During isothermal aging, the intermetallic compound (IMC) layer increased with aging time and its growth was diffusion controlled. There was also no obvious affect from the solder composition on IMC growth. After electromigration with the current density of 2.0 × 10³ A/cm², Sn-37Pb solder joints showed the shortest lifetime with the cracks observed at the cathode for the stressing time < 250 h. In Sn-3.0Ag-0.5Cu Pb-free solder joints, current stressing promoted the growth of IMC layer at the interfaces, but the growing rate of IMC at the anode interface was far faster than that at the cathode interface. Therefore, there existed an obvious polarity effect on IMC growth in Sn-Ag-Cu Pb-free solder joints. After Sn-37Pb was mixed with Sn-3.0Ag-0.5Cu Pb-free solder, whether the partial mixing or the full mixing between Sn-Pb and Sn-Ag-Cu can obviously depress both the crack formation at the cathode side and the IMC growth at the anode.     

elemental redistribution and interfacial reaction mechanism for the flip chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump with Al/Ni(V)/Cu under-Bump metallization during aging

In flip chip technology, Al/Ni(V)/Cu under-bump metallization (UBM) is currently applicable for Pb-free solder, and Sn−Ag−Cu solder is a promising candidate to replace the conventional Sn−Pb solder. In this study, Sn-3.0Ag-(0.5 or 1.5)Cu solder bumps with Al/Ni(V)/Cu UBM after assembly and aging at 150°C were employed to investigate the elemental redistribution, and reaction mechanism between solders and UBMs. During assembly, the Cu layer in the Sn-3.0Ag-0.5Cu joint was completely dissolved into solders, while Ni(V) layer was dissolved and reacted with solders to form (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). The (Cu_1−y,Ni_y)₆Sn₅ IMC gradually grew with the rate constant of 4.63 × 10⁻⁸ cm/sec^0.5 before 500 h aging had passed. After 500 h aging, the (Cu_1−y,Ni_y)₆Sn₅ IMC dissolved with aging time. In contrast, for the Sn-3.0Ag-1.5Cu joint, only fractions of Cu layer were dissolved during assembly, and the remaining Cu layer reacted with solders to form Cu₆Sn₅ IMC. It was revealed that Ni in the Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. During the period of 2,000 h aging, the growth rate constant of (Cu_1−y,Ni_y)₆Sn₅ IMC was down to 1.74 × 10⁻⁸ cm/sec^0.5 in, the Sn-3.0Ag-1.5Cu joints. On the basis of metallurgical interaction, IMC morphology evolution, growth behavior of IMC, and Sn−Ag−Cu ternary isotherm, the interfacial reaction mechanism between Sn-3.0Ag-(0.5 or 1.5)Cu solder bump and Al/Ni(V)/Cu UBM was discussed and proposed.     

Interfacial reaction and solder joint reliability of Pb-free solders in lead frame chip scale packages (LF-CSP)

Chip scale packages (CSP) have essential solder joint quality problems, and a board level reliability is a key issue in design and development of the CSP type packages. There has been an effort to eliminate Pb from solder due to its toxicology. To evaluate the various solder balls in CSP package applications, Pb-free Sn-Ag-X (X=In, Cu, Bi) and Sn-9Zn-1Bi-5In solder balls were characterized by melting behavior, phases, interfacial reaction, and solder joint reliability. For studying joint strength between solders and under bump metallurgy (UBM) systems, various UBMs were prepared by electroplating and electroless plating. After T/C (temperature cycle) test, Sn3.5Ag8.5In solder was partially corroded and its shape was distorted. This phenomenon was observed in a Sn3Ag10In 1Cu solder system, too. Their fractured surface, microstructure of solder joint interface, and of bulk solder ball were examined and analyzed by optical microscopy, SEM and EDX. To simulate the real surface mounting condition and evaluate the solder joint reliability on board level, Daisy chain test samples using LF-CSP packages were prepared with various Pb-free solders, then a temperature cycle test (−65∼ 150°C) was performed. All tested Pb-free solders showed better board level solder joint reliability than Sn-36Pb-2Ag. Sn-3.5Ag-0.7Cu and Sn-9Zn-1Bi-5In solders showed 35%, 100% superior solder joint reliability than Sn-36Pb-2Ag solder ball, respectively.     

Wetting interaction of Pb-free Sn-Zn-Al solders on metal plated substrate

A newly developed Pb-free Sn-9(Zn-5Al) solder was investigated for its wetting behavior on metal plated Cu substrate. The Cu substrate was plated with electroless nickel (EN) or with EN/Cu multilayer plating. The wetting behavior was investigated with a wetting balance which gave rise to a wetting curve. Fluxes including L-glutamic acid and dimethylammonium chloride were applied for enhancing the wetting behavior. The solder was unable to wet the EN plated Cu substrate without the assistance of flux until temperatures of 460°C and above. The material interaction between the solder and the substrate at this high temperature was investigated with scanning electron microscope elemental analysis. The wetting temperature between solder and EN plated copper was lowered to 310°C with the application of the above fluxes. The further incorporation of a layer of Cu plating with the EN layer further lowered the wetting temperature to 250°C.     

Fatigue crack-growth behavior of Sn-Ag-Cu and Sn-Ag-Cu-Bi lead-free solders

Fatigue crack-growth behavior and mechanical properties of Sn-3Ag-0.5Cu, Sn-3Ag-0.5Cu-1Bi, and Sn-3Ag-0.5Cu-3Bi solders have been investigated at room temperature (20°C). The tensile strength and hardness of the solders increased with increasing Bi content. However, the yield strengths of Sn-3Ag-0.5Cu-1Bi and Sn-3Ag-0.5Cu-3Bi solders were nearly similar, but the 3Bi solder exhibited the lowest ductility. Fatigue crack-growth behavior of the solders was dominantly cycle dependent in the range of stress ratios from 0.1–0.7 at a frequency of 10 Hz, except for the Sn-3Ag-0.5Cu solder tested at a stress ratio of 0.7. Mixed intergranular/transgranular crack propagation was observed for the Sn-3Ag-0.5Cu solder tested at the stress ratio of 0.7, indicating the importance of creep in crack growth. The Sn-3Ag-0.5Cu-1Bi and Sn-3Ag-0.5Cu-3Bi solders had higher resistance to time-dependent crack growth, resulting from the strengthening effect of the Bi constituent. It appears that the addition of Bi above a certain concentration is harmful to the mechanical properties of Sn-3Ag-0.5Cu.     

Effects of mechanical deformation and annealing on the microstructure and hardness of Pb-free solders

The microstructure property relations of several Pb-free solders are investigated to understand the microstructural changes during thermal and mechanical processes of Pb-free solders. The Pb-free solder alloys investigated include pure Sn, Sn-0.7% Cu, Sn-3.5% Ag, and Sn-3.8% Ag-0.7% Cu (in weight percent). To reproduce a typical microstructure observed in solder joints, the cooling rate, ingot size, and reflow conditions of cast alloys were carefully controlled. The cast-alloy pellets are subjected to compressive deformation up to 50% and annealing at 150°C for 48 h. The microstructure of Pb-free solders is evaluated as a function of alloy composition, plastic deformation, and annealing. The changes in mechanical property are measured by a microhardness test. The work hardening in Sn-based alloys is found to increase as the amount of alloying elements and/or deformation increases. The changes in microhardness upon deformation and annealing are correlated with the microstructural changes, such as recrystallization or grain growth, in Pb-free solder alloys.     

Microstructure and Creep Deformation of Sn-Ag-Cu-Bi/Cu Solder Joints

Sn-Ag-Cu solder is one of the candidate alternatives to Sn-Pb-based solders. In order to improve its performance, different materials have been added to Sn-Ag-Cu-based solders. Several studies on Sn-Ag-Cu-based solders with Bi additions have shown Sn-Ag-Cu-Bi to be a class of solders with good wetting behavior and good performance that show great promise for use in the electronics assembly and packaging industry. To investigate the mechanical reliability of the Sn-Ag-Cu-Bi solders further, single-lap shear creep characteristics have been studied in this work. Dog-bone-type solder joint specimens were formed using five types of solder alloys, Sn-3.0Ag-0.5Cu and Sn-3.0 Ag-0.5Cu-xBi (x = 1 wt.% to 4 wt.%) with Cu substrates, and creep tests were performed at temperatures of 120°C and 150°C under stresses of 5 MPa to 10 MPa. Results indicate that the rupture times for Sn-3.0Ag-0.5Cu-xBi solder joints up to 4 wt.% of Bi are longer than the rupture time for Sn-3.0Ag-0.5Cu. Stress exponents ranged from 3 to 7 for temperatures of 150°C and 120°C with stresses under 10 MPa. Microstructural analyses using scanning electron microscopy (SEM) were performed and related to the creep behavior of the solder joints.     

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.     

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.     

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.     

三种高Sn无铅钎料的表面张力和润湿性能研究

采用悬滴法测量了3种无铅钎料合金(Sn-3.0Ag-0.5Cu、Sn-0.7Cu与Sn-9.0Zn)在260℃时的表面张力,分别为525.5,534.8和595.4 mN/m;同时采用座滴法测量了其在260℃熔融状态下与Cu基板的接触角,分别为24.5°、28.0°和102.5°,并且与传统Sn-37.0Pb钎料进行了比较研究。结果表明,无铅钎料合金的表面张力与接触角均大于Sn-37.0Pb钎料。结合Young-Dupre公式讨论了钎料合金表面张力与其润湿性能的相关性,认为Sn基钎料合金在Cu基板上的润湿性能主要取决于其表面张力。     

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.