Superplastic creep of low melting point solder joints

In prior work, we showed that eutectic Sn-Pb solder joints exhibit superplastic behavior after rapid solidification. Further examples of superplasticity in nominally air-cooled solder joints are reported in this study of three low-melting point alloys: 40In-40Sn-20Pb (wt. %), eutectic 52In-48Sn, and 43Sn-43Pb-14Bi, which were creep-tested in shear at 20°, 65°, and 90° C. The test results indicate that above 65° C, the indium-containing solders have stress exponents between 2.4 to 2.9, a possible overall shear strains of 500%, and an absence of primary creep; at 90° C, 43Sn-43Pb-14Bi solder has a stress exponent close to 2.3. Optical microstructures of the three solders are presented; they help to explain the superplastic behavior.     

Effects of cooling rate on mechanical properties of near-eutectic tin-lead solder joints

This paper reports the results of a study on the effect of the cooling rate during solidification on the shear creep and low cycle shear fatigue behavior of 60 Sn/40 Pb solder joints, and on bulk solder tensile properties. Solder joints were made with three different initial microstructures by quenching, air-cooling and furnace-cooling. They have similar steady-state strain rates under creep at relatively high shear stresses (i.e. in the matrix creep region) but creep at quite different strain rates at lower shear stresses (i.e. in the grain boundary creep region). These results are ascribed to the refined grain size and less lamellar phase morphology that results on increasing the cooling rate. Tensile tests on bulk solders that were cold-worked, quenched and furnace-cooled show that a faster cooling rate decreases the ultimate strength and increases the ductility at low strain rates. The fatigue life of quenched solder joints is shown to be longer than that of the furnace-cooled joints.     

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.     

Metallurgical reactions in composite 90Pb10Sn/lead-free solder joints and their effect on reliability of LTCC/PWB assembly

Use of 90Pb10Sn solder as a noncollapsible sphere material with 95.5Sn 4Ag0.5Cu and SnInAgCu lead-free solders is investigated. Practical reflow conditions led to strong Pb dissolution into liquid solder, resulting in >20 at.% Pb content in the original lead-free solders. The failure mechanism of the test joints is solder cracking due to thermal fatigue, but the characteristic lifetime of 90Pb10Sn/SnInAgCu joints is almost double that of 90Pb10Sn/95.5Sn4Ag0.5Cu in a thermal cycling test (TCT) over the temperature range from −40°C to 125°C. It is predicted that this is mainly a consequence of the better fatigue resistance of the SnPbInAgCu alloy compared with the SnPbAgCu alloy. Indium accelerates the growth of the intermetallic compound (IMC) layer at the low temperature co-fired ceramic (LTCC) metallization/solder interface and causes coarsening of IMC particles during the TCT, but these phenomena do not have a major effect on the creep/fatigue endurance of the test joints.     

Evaluation of the mechanical properties of a ternary Sn-20In-2.8Ag solder

The Sn-20In-2.8Ag solder alloy is a potential lead-free solder for replacing the traditional Sn-Pb solders. In this study, the mechanical properties of the bulk material are reported by tensile test at various strain rates and temperatures. The Sn-20In-2.8Ag solder possessed a solidus and liquidus between 170.8°C and 195.5°C. The ultimate tensile strength (UTS) and elongation were 59.3 MPa and 50.2% at a strain rate of 10⁻³ s⁻¹ at room temperature. Moreover, the UTS of this alloy decreased, but its elongation increased, with increasing testing temperature. Stress exponents of Sn-20In-2.8Ag alloy varied from 6.5 at room temperature to 4 at 100°C, and the activation energy for creep was 51.0 kJ/mol at the higher temperature range from 50°C to 100°C. The typical intergranular creep fracture mode was observed in Sn-20In-2.8Ag solder during tensile creep deformation.     

A microstructural study of the thermal fatigue failures of 60sn-40Pb solder joints

When an electronic package encounters thermal fluctuations, cyclical shear strain is imposed on the solder joint interconnections. The thermal cycling leads to a condition of thermal fatigue and eventual solder joint failure. This study was performed in order to understand the microstructural mechanisms that lead to solder joint failures in thermal fatigue. Thermal cycling tests were performed on 60Sn-40Pb joints using a -55° C to 125° C cycle and 19% imposed shear strain. A heterogeneously coarsened region of both Pb and Sn-rich phases develops within the 60Sn-40Pb solder joints. Cracks initiate in the heterogeneously coarsened Sn-rich phase at the Sn-Sn grain boundaries. Heterogeneous coarsening and failure occurs in both high (35 to 125° C) and low (-55 to 35° C) thermal cycles. The elevated temperature portion of the thermal cycle was found to be the most significant factor in the heterogeneous coarsening and failure of the solder joints.     

铜颗粒增强对锡铅钎料蠕变寿命的影响

颗粒增强是提高合金性能的重要手段之一.增强体的不同含量对基体的性能会产生不同的影响.主要分析和讨论了铜的不同含量对铜颗粒增强的锡铅基复合钎料蠕变性能的影响.测定6种铜颗粒增强的锡铅基复合钎料的蠕变寿命.试验结果表明:在相同的条件下,复合钎料的蠕变寿命与锡铅钎料相比,均有不同程度的提高.当铜的质量分数约为1%时,复合钎料的蠕变性能最好,约为锡铅钎料的17倍.     

Fatigue crack growth behavior in 63Sn-37Pb and 95Pb-5Sn solder materials

Fatigue crack growth behavior of two typical solders 63Sn-37Pb and 95Pb-5Sn has been investigated under room temperature (20°C) and frequency of 10 Hz. Fatigue crack growth behavior of the 63Sn-37Pb specimen tested at stress ratios up to 0.5 and the 95Pb-5Sn specimen tested at stress ratios up to 0.7 were dominantly cyclic dependent. Intergranular crack growth was observed for the 63Sn-37Pb specimen tested at stress ratio of 0.7, which indicates that a crack grows under influence of creep. The difference of effect of stress ratio on crack growth behavior between two solders may results from the difference of homologous temperature. Fatigue crack growth mechanisms for solder materials are summarized as follows: A crack propagates in a transgranular manner at low homologous temperature and low stress ratio, while it propagates along eutectic grain boundaries at high homologous temperature and high stress ratio under influence of creep. At the intermediate homologous temperatures, a crack propagates in a transgranular manner with some region of intergranular fracture.     

电子组装用高温无铅钎料的研制

Bi-Ag合金是一种替代高铅钎料的芯片封装无铅焊料。研制了Bi-2.5Ag、Bi-2.5Ag-0.1RE、Bi-5Ag-0.1RE、Bi-7.5Ag-0.1RE、Bi-10Ag、Bi-10Ag-0.1RE钎料。结果表明,该合金系钎料的熔化温度范围随Ag含量的增加而增大,而且其润湿性能良好,润湿角都处于30o～40o。不同Ag含量的Bi-Ag/Cu接头在界面处发生断裂,剪切强度差别不大,都略大于30MPa。Bi-Ag/Cu界面没有金属间化合物形成,结合强度较弱。     

Developing a lead-free solder alloy Sn-Bi-Ag-Cu by mechanical alloying

A new lead free alloy, Sn-6Bi-2Ag-0.5Cu, has been developed by mechanical alloying and has great potential as a lead-free solder system. Initial trials on the manufacture of solder joints with this alloy revealed that a high quality bond with copper could be formed. Its melting range of 193.87°C to 209.88°C is slightly higher than that of eutectic tin-lead solder. Examination of the microstructure of the as-soldered joints revealed that it mainly consists of small bismuth (1 μm to 2 μm) and Ag₃Sn (1 μm) particles finely dispersed in a nearly pure tin matrix with a small amount of η-Cu₆Sn₅ particles. The Cu-Sn intermetallic compound (IMC) layer formed at solder-copper interface is the η-Cu₆Sn₅ phase with grain size of 2 μm. The shear strength of the solder joint is higher than that of Sn-37Pb or Sn-3.5Ag. Under shear loading, fracture occurred at IMC layer-solder interface as well as in the bulk of solder.     

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.     

Microstructural evolution of a lead-free solder alloy Sn-Bi-Ag-Cu prepared by mechanical alloying during thermal shock and aging

In a previous study, a lead-free solder, Sn-6Bi-2Ag-0.5Cu, was developed by mechanical alloying. The alloy shows great potential as a lead-free solder system. In the present work, the microstructural evolution during thermal shock and aging was examined. In the as-soldered joints small bismuth (1 μm to 2 μm) and Ag₃Sn (1 μm) particles were finely dispersed in a nearly pure tin matrix with a small amount of η-Cu₆Sn₅ phase in the bulk of solder. During thermal shock and aging microstructural evolution occurred with Cu-Sn intermetallic compound (IMC) layer growth at interface, bismuth phase coarsening and Ag₃Sn phase coarsening. The microstructure of the solder appeared to be stable at high temperature. The shear strength of the present solder joint is higher than that of Sn-37Pb and Sn-3.5Ag solders. Shear failure occurred Cu-Sn IMC layer-solder interface and in the bulk of solder.     

Thermal and mechanical stability of soldering QFP with Sn-Bi-Ag lead-free alloy

Thermal stability of the circuit boards with a quad flat package (QFP) soldered with Sn-58wt%Bi-(0, 0.5 and 1.0) wt% Ag and their microstructural features were evaluated. The addition of 1.0 wt% Ag causes the formation of large primary Ag/sub 3/Sn precipitates in the solder while no primary Ag/sub 3/Sn is found in Sn-57Bi-0.5Ag. Thermo-Calc calculation indicates that the lowest limit content for the formation of primary Ag/sub 3/Sn is about 0.8 wt%. Heat-exposure below 100/spl deg/C has no serious degradation on the joint structure for all solders. Heat-exposure at 125/spl deg/C caused serious degradation in joint strength for all alloys. The contamination of Pb from Sn-Pb surface plating on the components reduces the interface tolerance by forming ternary Sn-Pb-Bi phase melting at low temperature. Thermal fatigue between -20 and 80/spl deg/C does not have any significant influence on joint structure.     

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.     

Viscoplastic Creep Response and Microstructure of As-Fabricated Microscale Sn-3.0Ag-0.5Cu Solder Interconnects

The viscoplastic behavior of as-fabricated, undamaged, microscale Sn-3.0 Ag-0.5Cu (SAC305) Pb-free solder is investigated and compared with that of eutectic Sn-37Pb solder and near-eutectic Sn-3.8Ag-0.7Cu (SAC387) solder from prior studies. Creep measurements of microscale SAC305 solder shear specimens show significant piece-to-piece variability under identical loading. Orientation imaging microscopy reveals that these specimens contain only a few, highly anisotropic Sn grains across the entire joint. For the studied loads, the coarse-grained Sn microstructure has a more significant impact on the scatter in primary creep compared to that in the secondary creep. The observed lack of statistical homogeneity (microstructure) and joint-dependent mechanical behavior of microscale SAC305 joints are consistent with those observed for functional microelectronics interconnects. Compared with SAC305 joints, microscale Sn-37Pb shear specimens exhibit more homogenous behavior and microstructure with a large number of small Sn (and Pb) grains. Creep damage in the Pb-free joint is predominantly concentrated at highly misoriented Sn grain boundaries. The coarse-grained Sn microstructure recrystallizes into new grains with high misorientation angles under creep loading. In spite of the observed joint-dependent behavior, as-fabricated SAC305 is significantly more creep resistant than Sn-37Pb solder and slightly less creep resistant than near-eutectic SAC387 solder. Average model constants for primary and secondary creep of SAC305 are presented. Since the viscoplastic measurements are averaged over a wide range of grain configurations, the creep model constants represent the effective continuum behavior in an average sense. The average secondary creep behavior suggests that the dominant creep mechanism is dislocation climb assisted by dislocation pipe diffusion.     

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.     

Effects of Ce Addition on the Microstructure and Mechanical Properties of Sn-58Bi Solder Joints

The effects of a rare-earth element on the microstructure, mechanical properties, and whisker growth of Sn-58Bi alloys and solder joints in ball grid array (BGA) packages with Ag/Cu pads have been investigated. Mechanical testing indicated that the elongation of Sn-58Bi alloys doped with Ce increased significantly, and the tensile strength decreased slightly, in compar- ison with undoped Sn-58Bi. In addition, the growth of both fiber- and hillock-shaped tin whiskers on the surface of Sn-58Bi-0.5Ce was retarded in the case of Sn-3Ag-0.5Cu-0.5Ce alloys. The growth of interfacial intermetallic compounds (IMC) in Sn-58Bi-0.5Ce solder joints was slower than that in Sn-58Bi because the activity of Ce atoms at the interface of the Cu₆Sn₅ IMC/solder was reduced. The reflowed Sn-58Bi and Sn-58Bi-0.5Ce BGA packages with Ag/Cu pads had a ball shear strength of 7.91 N and 7.64 N, which decreased to about 7.13 N and 6.87 N after aging at 100°C for 1000 h, respectively. The reflowed and aged solder joints fractured across the solder balls with ductile characteristics after ball shear tests.     

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.     

Intermetallic compound layer formation between copper and hot-dipped 100In, 50In-50Sn, 100Sn,and 63Sn-37Pb coatings

The growth kinetics of intermetallic compound layers formed between four hot-dipped solder coatings and copper by solid state, thermal aging were examined. The solders were l00Sn, 50In-50Sn, 100In, and 63Sn-37Pb (wt.%); the substrate material was oxygen-free, high conductivity Cu. The total intermetallic layer of the 100Sn/Cu system exhibited a combination of parabolic growth at lower aging temperatures and t^0.42 growth at the higher temperatures. The combined apparent activation energy was 66 kJ/mol. These results are compared to the total layer growth observed with the 63Sn-37Pb/Cu system which showed parabolic kinetics at similar temperatures and an apparent activation energy of 45 kJ/mol. Both 100Sn and 63Sn-37Pb diffusion couples showed a composite intermetallic layer comprised of Cu₃Sn and Cu₆Sn₅. The intermetallic compound layer formed between In and Cu changed from a CuIn₂ stoichiometry at short annealing times to a Cu₅₇In₄₃ composition at longer periods. The growth kinetics were parabolic with an apparent activation energy of 20 kJ/mol. The intermetallic layer growth of the 50In-50Sn/Cu system exhibited extreme variations in the layer thicknesses which prohibited a quantitative assessment of the growth kinetics. The layer was comprised of two compounds: Cu₂₆Sn₁₃In₈ which was the dominant phase and a thin layer of Cu₁₇Sn₉In24 adjacent to the solder.