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.     

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.     

Inhibition of Whisker Growth on the Surface of Sn-3Ag-0.5Cu-0.5Ce Solder Alloyed with Zn

Solder alloys doped with rare-earth elements have been reported to show many beneficial effects. However, tin whiskers have been observed to appear on the surface of Sn-3Ag-0.5Cu-0.5Ce solder joints after air exposure for short periods. Such a phenomenon of abnormal whisker growth may significantly degrade the reliability of electronic packaging. The present study shows that the tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder. The inhibition effect on the whisker growth is correlated to the refining of (Ce_0.9Zn_0.1)Sn₃ intermetallics in this Sn-3Ag-0.5Cu-0.5Ce-0.5Zn alloy.     

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.     

Demonstration and Characterization of Sn-3.0Ag-0.5Cu/ Sn-57Bi-1Ag Combination Solder for 3-D Multistack Packaging

A combination solder of Sn-3.0Ag-0.5Cu (numbers are all in weight percent unless specified otherwise) wrapped by Sn-57Bi-1Ag was tested for application to three-dimensional (3-D) multistack packaging. The experimental variables controlled were the reflow peak temperatures (170, 185, 200, and 230°C), the reflow cycles (up to four times), and the mask which controls the amount of Sn-57Bi-1Ag solder paste (two sizes). We demonstrate and evaluate the combination solder structure, focusing on microstructural changes and the shear strength. The degree of mixing in the combination solder, which is enhanced by an increase in the reflow peak temperature, is independent of the number of reflow cycles. The ball shear strength and the lab shear strength both increased with increases in the reflow peak temperatures. This behavior is explained by the amount of the brittle Bi phase that constitutes the eutectic Sn-Bi phase.     

Effects of strain ratio and tensile hold time on low-cycle fatigue of lead-free Sn-3.5Ag-0.5Cu solder

Low-cycle fatigue (LCF) behavior of a lead-free Sn-3.5Ag-0.5Cu solder alloy was investigated at various combinations of strain ratio (R = −1, 0, and 0.5) and tensile hold time (0, 10, and 100 sec). Results showed that the LCF life of the given solder, at each given combination of testing conditions, could be individually described by a Coffin-Manson relationship. An increase of strain ratio from R=−1 to 0 and to 0.5 would cause a significant reduction of LCF life due to a mean strain effect instead of mean stress effect. LCF life was also markedly reduced when the hold time at tensile peak strain was increased from 0 to 100 sec, as a result of additional creep damage generated during LCF loading. With consideration of the effects of strain ratio and tensile hold time, a unified LCF lifetime model was proposed and did an excellent job in describing the LCF lives for all given testing conditions.     

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。     

Creep properties of eutectic Sn-3.5Ag solder joints reinforced with mechanically incorporated Ni particles

The creep deformation behavior of eutectic Sn-3.5Ag based Ni particle rein forced composite solder joints was investigated. The Ni particle reinforced composite solder was prepared by mechanically dispersing 15 vol.% of Ni particles into eutectic Sn-3.5Ag solder paste. Static-loading creep tests were carried out on solder joint specimens at 25 C, 65 C, and 105 C, representing homologous temperatures ranging from 0.6 to 0.78. A novel-design, miniature creep-testing frame was utilized in this study. Various creep parameters such as the global and localized creep strain, steady-state creep rate, onset of tertiary creep and the activation energy for creep were quantified by mapping the distorted laser ablation pattern imprinted on the solder joint prior to testing. The Ni-reinforced composite solder joint showed improved creep resistance compared to the results previously reported for eutectic Sn-3.5Ag solder, Sn-4.0Ag-0.5Cu solder alloys, and for eutectic Sn-3.5Ag solder reinforced with Cu or Ag particle reinforcements. The activation energy for creep was ∼0.52 eV for Sn-3.5Ag and Sn-4Ag-0.5Cu solder alloys. The activation energies ranged from 0.55–0.64 eV for Cu, Ag, and Ni reinforced composite solder joints, respectively. Most often, creep fracture occurred closer to one side of the solder joint within the solder matrix.     

Effect of microelements addition on the interfacial reaction between Sn-Ag-Cu solders and the Cu substrate

Three kinds of Sn-Ag-based lead-free solders, Sn-3.5Ag-0.7Cu, Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge, and Sn-3.5Ag-0.07Ni (in wt.%), were selected to explore the effect of microelements (Ni and Ge) on the interfacial reaction between the solder and the Cu substrate. The thickness of the interfacial intermetallics formed with the Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge and Sn-3.5Ag-0.07Ni solders is several times that of the Sn-3.5Ag-0.7Cu solder. The added microelements converted the feature of interfacial intermetallics from pebble shape to worm shape. However, the results of x-ray diffraction (XRD) analysis suggest that the interfacial intermetallics formed with both solders have the same crystal structure. The results of energy dispersive spectroscopy (EDS) analysis show that the major interfacial intermetallic formed with the Sn-3.5Ag-0.7Cu solder is Cu₆Sn₅, while it is (Cu_x,Ni_1−x)₆Sn₅ with Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge. Ni influences the interfacial intermetallics and plays the influential role on the difference of interfacial reaction rate between liquid solder and solid Cu and the morphology of interfacial intermetallics. Additionally, the growth kinetics of the interfacial intermetallic compounds (IMCs) formed in the systems of Cu/Sn-3.5Ag-0.7Cu and Cu/Sn-3.5Ag-0.07Ni at high-temperature storage was also explored.     

Y2O3增强Sn-3Ag-0.5Cu复合无铅钎料

研究了稀土氧化物颗粒增强复合无铅钎料Sn-3Ag-0.5Cu-Y2O3的钎焊接头的显微组织形貌、性能特点及有关影响机制.结果表明:Y2O3增强颗粒均匀分布于Sn-3Ag-0.5Cu钎料基体中,不仅细化了钎焊接头中共晶相Ag3Sn和Cu6Sn5相颗粒尺寸,而且也显著提高了钎焊接头的剪切强度.另外适量Y2O3颗粒的添加对钎料润湿性影响不大.     

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.     

Evaluation of solder joint reliability in flip-chip packages during accelerated testing

The microstructural investigation and thermomechanical reliability evaluation of the Sn-3.0Ag-0.5Cu solder bumped flip-chip package were carried out during the thermal shock test of the package. In the initial reaction, the reaction product between the solder and Cu mini bump of chip side was Cu₆Sn₅ intermetallic compound (IMC) layer, while the two phases which were (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄ were formed between the solder and electroless Ni-P layer of the package side. The cracks occurred at the corner solder joints after the thermal shocks of 400 cycles. The primary failure mechanism of the solder joints in this type of package was confirmed to be thermally-activated solder fatigue failure. The premature brittle interfacial failure sometimes occurred in the package side, but nearly all of the failed packages showed the occurrence of the typical fatigue cracks. The finite-element analyses were conducted to interpret the failure mechanisms of the packages, and revealed that the cracks were induced by the accumulation of the plastic work and viscoplastic shear strains.     

Nanoparticles of the Lead-free Solder Alloy Sn-3.0Ag-0.5Cu with Large Melting Temperature Depression

Due to the toxicity of lead (Pb), Pb-containing solder alloys are being phased out from the electronics industry. This has lead to the development and implementation of lead-free solders. Being an environmentally compatible material, the lead-free Sn-3.0Ag-0.5Cu (wt.%) solder alloy is considered to be one of the most promising alternatives to replace the traditionally used Sn-Pb solders. This alloy composition possesses, however, some weaknesses, mainly as a result of its higher melting temperature compared with the Sn-Pb solders. A possible way to decrease the melting temperature of a solder alloy is to decrease the alloy particle size down to the nanometer range. The melting temperature of Sn-3.0Ag-0.5Cu lead-free solder alloy, both as bulk and nanoparticles, was investigated. The nanoparticles were manufactured using the self-developed consumable-electrode direct current arc (CDCA) technique. The melting temperature of the nanoparticles, with an average size of 30 nm, was found to be 213.9°C, which is approximately 10°C lower than that of the bulk alloy. The developed CDCA technique is therefore a promising method to manufacture nanometer-sized solder alloy particles with lower melting temperature compared with the bulk alloy.     

Evaluations of Whisker Growth and Fatigue Reliability of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.05Ce Solder Ball Grid Array Packages

Sn-Ag-Cu solders doped with rare-earth elements were reported to exhibit beneficial mechanical properties; however, rapid whisker growth could be induced. In order to retain the advantageous effects of rare-earth doping without causing the formation of tin whiskers, a Sn-3Ag-0.5Cu-0.05Ce alloy was suggested. In the present study, metallographic observations indicate that whisker growth is indeed prevented in this alloy. However, tensile tests with the bulk materials show that the ultimate tensile strength and Young’s modulus of this Sn-3Ag-0.5Cu-0.05Ce alloy are only slightly higher than those of undoped Sn-3Ag-0.5Cu. Further reliability tests with actual ball grid array packages indicate that the Sn-3Ag-0.5Cu-0.05Ce solder joints have fatigue lives similar to those of undoped Sn-3Ag-0.5Cu specimens regardless of the various surface finishes, such as electroless nickel/immersion gold (ENIG), immersion tin (ImSn), and organic solderability preservatives (OSP). The results suggest that, although lowering the content of rare-earth elements in solders can inhibit the occurrence of rapid whisker growth, it cannot ensure the improvement of the tensile properties of bulk solders and the fatigue reliability of solder joints in actual packages.     

Interfacial reaction between multicomponent lead-free solders and Ag,Cu, Ni,and Pd substrates

The interfacial reaction between two prototype multicomponent lead-free solders, Sn-3.4Ag-1Bi-0.7Cu-4In and Sn-3.4Ag-3Bi-0.7Cu-4In (mass%), and Ag, Cu, Ni, and Pd substrates are studied at 250°C and 150°C. The microstructural characterization of the solder bumps is carried out by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis. Ambient temperature, isotropic elastic properties (bulk, shear, and Young’s moduli and Poisson’s ratio) of these solders along with eutectic Sn-Ag, Sn-Bi, and Sn-Zn solders are measured. The isotropic elastic moduli of multicomponent solders are very similar to the eutectic Sn-Ag solder. The measured solubility of the base metal in liquid solders at 250°C agrees very well with the solubility limits reported in assessed Sn-X (X=Ag, Cu, Ni, Pd) phase diagrams. The measured contact angles were generally less than 15° on Cu and Pd substrates, while they were between 25° and 30° on Ag and Ni substrates. The observed intermediate phases in Ag/solder couples were Ag₃Sn after reflow at 250°C and Ag₃Sn and ζ (Ag-Sn) after solid-state aging at 150°C. In Cu/solder and Ni/solder couples, the interfacial phases were Cu₆Sn₅ and (Cu,Ni)₆Sn₅, respectively. In Pd/solder couples, only PdSn₄ after 60-sec reflow, while both PdSn₄ and PdSn₃ after 300-sec reflow, were observed.     

Investigation of Dissolution Behavior of Metallic Substrates and Intermetallic Compound in Molten Lead-free Solders

This study investigates the dissolution behavior of the metallic substrates Cu and Ag and the intermetallic compound (IMC)-Ag₃Sn in molten Sn, Sn-3.0Ag-0.5Cu, Sn-58Bi and Sn-9Zn (in wt.%) at 300, 270 and 240°C. The dissolution rates of both Cu and Ag in molten solder follow the order Sn > Sn-3.0Ag-0.5Cu >Sn-58Bi > Sn-9Zn. Planar Cu₃Sn and scalloped Cu₆Sn₅ phases in Cu/solders and the scalloped Ag₃Sn phase in Ag/solders are observed at the metallic substrate/solder interface. The dissolution mechanism is controlled by grain boundary diffusion. The planar Cu₅Zn₈ layer formed in the Sn-9Zn/Cu systems. AgZn₃, Ag5Zn₈ and AgZn phases are found in the Sn-9Zn/Ag system and the dissolution mechanism is controlled by lattice diffusion. Massive Ag₃Sn phases dissolved into the solders and formed during solidification processes in the Ag₃Sn/Sn or Sn-3.0Ag-0.5Cu systems. AgZn₃ and Ag₅Zn₈ phases are formed at the Sn-9Zn/Ag₃Sn interface. Zn atoms diffuse through Ag-Zn IMCs to form (Ag, Zn)Sn₄ and Sn-rich regions between Ag₅Zn₈ and Ag₃Sn.     

Improvement of Thermal Fatigue Properties of Sn-Ag-Cu Lead-Free Solder Interconnects on Casio’s Wafer-Level Packages Based on Morphology and Grain Boundary Character

Thermal fatigue properties of commercial LF35 (Sn-1.2Ag-0.5Cu-0.05Ni), SAC105 (Sn-1Ag-0.5Cu), and SAC305 (Sn-3Ag-0.5Cu) solders on Casio’s wafer-level packages are discussed from the viewpoints of both morphology and grain boundary character. Orientation imaging microscopy revealed that both LF35 and SAC305 resisted the coarsening of tin grains during thermal fatigue as compared with SAC105, correlating with their greater fraction of coincidence site lattice boundaries. This seems to explain why LF35 has superior thermal fatigue life in spite of its lower silver content.     

Interfacial microstructure and bonding strength of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder BGA packages with immersion Ag surface finish

Although it has been verified that tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder, no detailed studies have been conducted on interfacial reactions and mechanical properties of Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with an immersion Ag surface finish. The intermetallic compounds formed during the reflow and aging of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder ball grid array (BGA) packages were investigated. Because more heterogeneous nucleation sites, provided by CeSn₃ intermetallics and Zn atoms, formed in the Sn-3Ag-0.5Cu-0.5Ce-xZn solder matrix, and Cu and Zn have a stronger affinity than Cu and Sn, the Cu-Sn intermetallics growth in Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with Ag/Cu pads was suppressed. The 0.2% Zn addition for inhibiting rapid whisker growth in RE-doped Sn-Ag-Cu solder joints is more appropriate than 0.5 wt.% additions, as excess Zn addition causes poor oxidation resistance and inferior bonding strength.     

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.     

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.