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。     

三种典型Sn-Ag-Cu无铅钎料的组织和性能研究

对比研究了三种典型标称成分的Sn-Ag-Cu钎料(即日本JEIDA推荐的Sn-3.0Ag-0.5Cu、欧盟IDEALS推荐的Sn-3.8Ag-0.7Cu和美国NEMI推荐的Sn-3.9Ag-0.6Cu)的显微组织特征、熔化特性、润湿性以及钎焊接头微焊点的力学性能等。结果表明,三种钎料的组织和性能非常接近。然而从性价比等方面综合考虑,Sn-3.0Ag-0.5Cu为三种钎料中最具优势的替代传统Sn-Pb钎料(共晶和近共晶钎料)的无铅合金。     

Sn-0.3Ag-0.7Cu-xBi低银无铅钎料的润湿性

以Bi为添加剂对低银型Sn-0.3Ag-0.7Cu无铅钎料进行改性,应用SAT—5100型润湿平衡仪对Sn-0.3Ag-0.7Cu-xBi(x=0,1,3和4.5)钎料的润湿性能作了对比分析。结果表明:适量Bi元素的加入可以改善Sn-0.3Ag-0.7Cu钎料合金的润湿性能,且在240℃下Sn-0.3Ag-0.7Cu-3.0Bi无铅钎料具有最佳的润湿性能,在250℃其润湿力达到最大值3.2×10–3N/cm。     

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.     

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。     

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.     

Microstructural Analysis of Reballed Tin-Lead,Lead-Free,and Mixed Ball Grid Array Assemblies Under Temperature Cycling Test

In this study, ball grid array (BGA) packages with Sn-3.0Ag-0.5Cu (SAC305) solder balls were reballed with Sn-37Pb solder balls. Three different reballing methods were used. The non-reballed lead-free BGAs were assembled with SAC305 and Sn-37Pb solder pastes to form the lead-free and mixed assemblies. The reballed Sn-Pb BGAs were assembled with Sn-37Pb solder paste to form the reballed Sn-Pb assemblies. All assemblies were subjected to a temperature cycling test with a temperature range of −55°C to 125°C. For the same component type, the reballed BGA assemblies showed similar temperature cycling reliability regardless of the reballing methods. However, the temperature cycling reliability of the reballed assemblies was worse than that of the mixed and the lead-free assemblies. The mean cycles-to-failure of the mixed assemblies was larger than or equal to that of the lead-free assemblies. Failure analysis revealed that the failure site in reballed Sn-Pb assemblies was located in the bulk solder at the component side regardless of the component type and the reballing method, indicating that the reballing method did not influence the crack propagation in reballed assemblies. The mixed assemblies had the same failure site as the lead-free assemblies, i.e., in the bulk solder at the component side. The microstructure differences between the tin-lead, lead-free, and mixed assemblies are also discussed in detail.     

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.     

Stress–Strain Characteristics of Tin-Based Solder Alloys for Drop-Impact Modeling

The stress–strain properties of eutectic Sn-Pb and lead-free solders at strain rates between 0.1 s⁻¹ and 300 s⁻¹ are required to support finite-element modeling of the solder joints during board-level mechanical shock and product-level drop-impact testing. However, there is very limited data in this range because this is beyond the limit of conventional mechanical testing and below the limit of the split Hopkinson pressure bar test method. In this paper, a specialized drop-weight test was developed and, together with a conventional mechanical tester, the true stress–strain properties of four solder alloys (63Sn-37Pb, Sn-1.0Ag-0.1Cu, Sn-3.5Ag, and Sn-3.0Ag-0.5Cu) were generated for strain rates in the range from 0.005 s⁻¹ to 300 s⁻¹. The sensitivity of the solders was found to be independent of strain level but to increase with increased strain rate. The Sn-3.5Ag and the Sn-3.0Ag-0.5Cu solders exhibited not only higher flow stress at relatively low strain rate but, compared to Sn-37Pb, both also exhibited higher rate sensitivity that contributes to the weakness of these two lead-free solder joints when subjected to drop impact loading.     

Effect of Strain Rate and Temperature on the Tensile Properties of Tin-Based Lead-Free Solder Alloys

The tensile properties of Sn-3Ag-0.5Cu, Sn-3.5Ag, and Sn-0.7Cu lead-free solders were investigated on small-scale specimens and compared with those of Sn-37Pb eutectic solder at various strain rates from 1 × 10⁻⁴ s⁻¹ to 1 × 10⁻² s⁻¹ and over a wide temperature range from 25°C to 150°C. The tests were under true strain-rate-controlled conditions. The ductility of each lead-free solder is relatively constant while that for Sn-Pb eutectic solder strongly depends on strain rate and temperature. The strain rate sensitivity index m for lead-free solders is relatively stable and showed little dependence on temperature, whereas the values of m for Sn-37Pb increased linearly with increasing temperature.     

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.     

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.     

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.     

The microstructures and mechanical properties of the Sn-Zn-Ag-Al-Ga solder alloys—The effect of Ga

The microstructures and mechanical properties of Sn-8.55Zn-0.5Ag-0.45Al-yGa (wt.%) lead-free solders were investigated. The y content of the solders investigated was 0.5–3.0 wt.%. The results indicate that Ga exhibits prominent influence in the microstructure as well as mechanical properties of the solders. By increasing Ga, the fraction of the Sn/Zn eutectic region decreases and the Sn-matrix region increases. An increase in the Ga content from 0.5 wt.% to 2.0 wt.% enhances the tensile strength while degrading the ductility. The mechanical properties and differential scanning calorimetry (DSC) behavior have been compared with that of the 63Sn-37Pb solder. Gallium lowers the melting point of the Sn-8.55Zn-0.5Ag-0.45Al-yGa solders. The Sn-8.55Zn-0.5Ag-0.45Al-0.5Ga solders exhibit greater tensile strength and better ductility than the 63Sn-37Pb solder.     

Impact Testing of Sn-3.0Ag-0.5Cu Solder with Ti/Ni(V)/Cu Under Bump Metallization After Aging at 150°C

Nonmagnetic Ni(V) metal and low consumption rate with solders are the advantages of sputtered Ti/Ni(V)/Cu under bump metallization (UBM). However, a Sn-rich phase (“Sn-patch” herein) can form in the Ni(V) layer after reflow and aging. In lead-free solder, Sn-patches form and grow more quickly than in Sn-Pb solder. Thus, the effect of Sn-patches on solder joint reliability becomes critical. In this study, Sn-3.0Ag-0.5Cu solder was reflowed with Ti/Ni(V)/Cu UBM at 250°C for 60 s, and then aged at 150°C for various durations. A high-speed impact test was introduced to evaluate solder joint reliability. After impact testing, it was found that, the larger the Sn-patch, the greater the propensity of the solder joint to suffer brittle fracture. The correlation between Sn-patch and solder joint reliability is discussed.     

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.     

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.     

Influence of Cu content on compound formation near the chip side for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump during aging

Sn-Ag-Cu solder is a promising candidate to replace conventional Sn-Pb solder. Interfacial reactions for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder joints were investigated after aging at 150°C. The under bump metallization (UBM) for the Sn-3.0Ag-(0.5 or 1.5)Cu solders on the chip side was an Al/Ni(V)/Cu thin film, while the bond pad for the Sn-3.0Ag-0.5Cu solder on the plastic substrate side was Cu/electroless Ni/immersion Au. In the Sn-3.0Ag-0.5Cu joint, the Cu layer at the chip side dissolved completely into the solder, and the Ni(V) layer dissolved and reacted with the solder to form a (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). For the Sn-3.0Ag-1.5Cu joint, only a portion of the Cu layer dissolved, and the remaining Cu layer reacted with solder to form Cu₆Sn₅ IMC. The Ni in Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. At the plastic substrate side, three interfacial products, (Cu_1−y,Ni_y)₆Sn₅, (Ni_1−x,Cu_x)₃Sn₄, and a P-rich layer, were observed between the solder and the EN layer in both Sn-Ag-Cu joints. The interfacial reaction near the chip side could be related to the Cu concentration in the solder joint. In addition, evolution of the diffusion path near the chip side in Sn-Ag-Cu joints during aging is also discussed herein.     

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.     

Intermetallic compounds and adhesion strength between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder and unfluxed Cu substrate

The intermetallic compounds (IMCs) formed at the interface between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder alloy and unfluxed Cu substrate have been investigated by x-ray diffraction, optical microscopy, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The melting point and melting range of the Sn-9Zn-1.5Ag-0.5Bi solder alloy are determined as 195.9°C and 10°C, respectively, by differential scanning calorimetry (DSC). Cu₆Sn₅ and Cu₅Zn₈ IMCs are formed between the Sn-9Zn-1.5Ag-0.5Bi/unfluxed Cu substrate wetted at 250°C for 10 sec. The interfacial adhesion strength changes from 10.27±0.68 MPa to 8.58±0.59 MPa when soldering time varies from 10 sec to 30 sec at 250°C.