Effects of antimony on the microstructure,thermal properties,mechanical performance,and interfacial behavior of Sn–0.7Cu–0.05Ni–xSb/Cu solder joints

Journal of Materials Science: Materials in Electronics - We investigated a new, lead-free solder alloy to replace traditional lead-based solder alloys. A Sn–0.7Cu–0.05Ni solder alloy...     

Tensile properties and wettability of SAC0307 and SAC105 low Ag lead-free solder alloys

In this article, the tensile properties of low Ag lead-free solder alloys, SAC0307 and SAC105, are examined under various strain rates and temperatures. The wettability of these solders on Cu pad is also characterized by using different fluxes. The SAC305 and Sn37Pb solder alloys are also studied for comparison. Our results show that the properties of all solder alloys are dependent on the strain rate and temperature. The ultimate tensile strength increases monotonously with the increment of strain rate. Both SAC0307 and SAC105 alloys possess lower strength and higher elongation ratio than SAC305 and Sn37Pb alloys. For all the fluxes used in this study, the SAC0307 and SAC105 alloys show the similar wettability to SAC305, whereas worse than that of Sn37Pb alloy. Increasing the activity of the flux does not improve the wettability of the SAC solder alloys on Cu pad effectively.     

Effects of indium addition on properties and wettability of Sn–0.7Cu–0.2Ni lead-free solders

This paper reports the investigation on indium addition into Sn–0.7Cu–0.2Ni lead-free solder to improve its various performances. The effects of indium addition on melting temperature, coefficient of thermal expansion (CTE), wettability, corrosion resistance and hardness of the solder alloys were studied. The results showed that when the addition of indium was ⩽0.3 wt.%, the change in melting temperature of Sn–0.7Cu–0.2Ni–xIn solders was negligible, but the melting range of the solder alloy increased. The CTE and spreading area of Sn–0.7Cu–0.2Ni–xIn solders on copper both increased with the addition of indium. An optimal CTE was 17.5 × 10⁻⁶/°C by adding 0.3 wt.% indium. At this concentration, the spreading area of solder on copper was about 15.6% larger than that of Sn–0.7Cu–0.2Ni indium-free solder. The corrosion resistance also increased with the addition of indium increasing, and the corrosion rate of Sn–0.7Cu–0.2Ni–0.3In solder was reduced by 32.8% compared with Sn–0.7Cu–0.2Ni alloy after 14 days in 5% hydrochloric acid solution at room temperature. However, a decrease of 11.7% in hardness of the solder was found when 0.3 wt.% indium was added.     

Thermal properties of Sn-based solder alloys

During last few decades, emerging environmental regulations worldwide, more notably in Europe and Japan, have targeted the elimination of Pb usage in electronic assemblies due to the inherent toxicity of this element. This situation drives to the replacement of the Sn–Pb solder alloy of eutectic composition commonly used as joining material to suitable lead-free solders for microelectronic assembly. Sn-based alloys containing Ag, Cu, Bi, and Zn are potential lead-free solders, usually close to the binary or ternary eutectic composition. For this reason a great effort was directed to establish reliable thermophysical data fundamental to interpret the solidification process and fluidity of alloys belonging to these systems. In this work, an analysis of the solidification process of pure Sn, binary Sn–Ag, Sn–Cu, Sn–Bi, Sn–Zn, Sn–Pb and ternary Sn–Ag–Cu eutectic alloys was carried out using computer aided-cooling curve analysis and differential scanning calorimetry.     

Properties and microstructure of Sn–0.7Cu–0.05Ni solder bearing rare earth element Pr

Effects of trace amount of rare earth element Pr on properties and microstructure of Sn–0.7Cu–0.05Ni solder were investigated in this paper. The solderability of Sn–Cu–Ni–xPr alloy and shear strengh of Sn–Cu–Ni–xPr soldered micro-joints were determined by means of the wetting balance method and shear test, respectively. Moreover, microstructure of solder alloys bearing Pr, as well as intermetallic compound (IMC) layer formed at solder/Cu interface after soldering were observed. It was concluded that the major benefits of rare earth element Pr on Sn–Cu–Ni lead-free solder are: improving solderability, refining microstructure, and depressing IMC (IMC) growth, which exhibited improved mechanical properties. It also revealed that (Cu,Ni)₆Sn₅ is the majority IMC phase at the interface of Sn–Cu–Ni–xPr/Cu solder joints. Ni added into the solder effectively suppressed the growth of Cu₃Sn and consequently also the total IMC layer thickness. Above all, the thickness and morphology of the interfacial (Cu,Ni)₆Sn₅ IMC were optimized due to alloying Pr. It can be inferred that Pr and Ni would play an important role in improving the reliability of Sn–Cu–Ni lead-free solder joints.     

Nanoparticles of Sn3.0Ag0.5Cu alloy synthesized at room temperature with large melting temperature depression

The Sn3.0Ag0.5Cu (wt%) lead-free 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 to the eutectic Sn–Pb solders. Nanoparticles of Sn3.0Ag0.5Cu lead-free solder alloy nanoparticles were prepared by chemical reduction with NaBH₄ as a reducing agent at room temperature. The melting temperature of the synthesized Sn3.0Ag0.5Cu alloy nanoparticles was determined by differential scanning calorimetry (DSC). The results showed that the calorimetric onset melting temperature of the Sn3.0Ag0.5Cu alloy nanoparticles could be as low as 200 °C, which was about 17 °C lower than that of the bulk alloy (217 °C). The field emission scanning electron microscopy (SEM) images of the as-prepared nanoparticles indicated that the major particle size of Sn3.0Ag0.5Cu nanoparticles is smaller than 50 nm. The structure and morphology of the nanoparticles were analyzed with high resolution transmission electron microscopy (HRTEM). The Ag3Sn and Sn phase were observed in the HRTEM images, which was in good agreement with the XRD results. These low melting temperature Sn3.0Ag0.5Cu alloy nanoparticles show a potential to manufacture high quality lead-free solders for electronic products.     

<Emphasis Type="Italic">In-situ</Emphasis> SEM observation on fracture behaviors of Sn-based solder alloys

The effects of displacement rate on fracture behaviors of 100Sn solder and 63Sn37Pb solder alloys have been investigated by SEM in-situ testing. It was found that for the 100Sn solder, grain boundary sliding was the dominant deformation mechanism at lower tensile rate regime, while a large area of slip lines crossing grains were detected at the surface of specimens at higher tensile rate regime. For the 63Sn37Pb eutectic alloy, however, because of existence of the second phase, fracture behavior depended on the growth and linkage of cavities ahead of crack tip, and the crack paths changed from intergranular to transgranular with the increasing of loading rate.     

Annealing effect to constitutive behavior of Sn–3.0Ag–0.5Cu solder

Sn–Ag–Cu based solder alloys are replacing Sn–Pb solders in electronic packaging structures of commercial electric devices. In order to evaluate the structural reliability, the mechanical property of solder material is critical to the numerical simulations. Annealing process has been found to stabilize material properties of Sn–37Pb solder material. In the current study, the annealing effect on tensile behaviour of Sn–3.0Ag–0.5Cu (SAC305) solder material is investigated and compared with Sn–37Pb solder. It is found that the tensile strength for both materials are more stabilized and consistent after the annealing process, nevertheless, the annealing process will improve the plasticity of SAC305 solder dominated by dislocation motion, and impede the occurrence of hardening deformation in Sn–37Pb solder dominated by grain-boundary sliding mechanism. Furthermore, the annealing effect is quantified in the proposed constitutive model based on unified creep–plasticity theory. The parameters are calibrated against the measured stress–strain relationships at the tensile strain rates ranging from 1?×?10^?4 to 1?×?10^?3 s^?1. The numerical regressions for dominant parameters in the proposed model reveal the intrinsic differences between SAC305 and Sn–37Pb solders under annealing treatment.     

Synthesis and DSC study on Sn3.5Ag alloy nanoparticles used for lower melting temperature solder

The traditional Sn–Pb eutectic solder alloys are being phased out from the electronics industry due to the toxicity of lead (Pb), leading to the development and implementation of lead-free solders. Sn3.5Ag lead-free solder alloy, considered to be one of the promising alternatives to replace the traditionally used Sn–Pb solder, however, still has some weaknesses, such as its higher melting temperature than that of the Sn–Pb solder alloy. A possible way to decrease the melting temperature of a solder alloy is to decrease the alloy particle size to the nanometer range. Sn3.5Ag nanoparticles with different size distribution were synthesized using chemical reduction method by applying NaBH₄ as reduction agent. The melting properties of these synthesized nanoparticles were studied by differential scanning calorimetry (DSC), and size-dependent melting temperature depression of these nanoparticles has been observed. Gibbs–Thomson equation was used to analyze the size-dependent melting temperature property, giving a good prediction of the melting temperature depression for the Sn-based lead-free solder alloy nanoparticles.     

温度对Cu颗粒增强复合钎料蠕变性能的影响

蠕变性能是影响钎焊接头可靠性的重要指标之一.采用搭接面积为1 mm2的单搭接钎焊接头,在恒定载荷下,测定了Cu颗粒增强锡铅基复合钎料钎焊接头的蠕变寿命,分析并讨论了温度对该复合钎料蠕变寿命的影响.结果表明:Cu颗粒增强的锡铅基复合钎料的蠕变抗力优于传统63Sn37Pb共晶钎料;钎焊接头蠕变寿命随温度的升高而降低,并且温度对复合钎料钎焊接头蠕变寿命的影响较传统63Sn37Pb钎料明显.     

Effect of ZnO nanoparticles addition on thermal, microstructure and tensile properties of Sn–3.5 Ag–0.5 Cu (SAC355) solder alloy

Regarding to the development of Sn–Ag–Cu (SAC) lead-free solders for advance electronic components, the effect of 0.5 wt% nano-sized ZnO particles on the thermal, microstructure and tensile properties of Sn–3.5 wt% Ag–0.5 wt% Cu (SAC355) lead-free solder alloy is investigated. The results showed that addition of 0.5 wt% nano-sized ZnO particles into the conventional lead-free SAC355 solder caused a slight increase of its liquidus temperature by about 1.1 K. Metallographic observations of SAC355–0.5 wt% ZnO (composite solder) revealed an obvious refinement in the microstructure compared with the SAC355 (non-composite) solder. Consequently, addition of nano sized-ZnO particles could improve the stress–strain characteristics proof stress (σ_y0.2) and ultimate strength (σ_UTS). This was rendered to suppressing effect of ZnO on the coarsening of the intemetallic compounds (IMCs) Ag₃Sn and Cu₆Sn₅ during the solidification process in the composite solder and subsequently dispersion strengthening is considered to be the dominating mechanism. This will allow the use of SAC355 composite lead-free solder alloy, to be consistent with the conditions of usage for conventional SAC solder alloys and to overcome the serious problem of the excessive growth of IMCs and the formation of microvoids in the SAC lead-free solder alloys.     

Melting and solidification properties of the nanoparticles of Sn3.0Ag0.5Cu lead-free solder alloy

The Sn3.0Ag0.5Cu (wt.%) lead-free solder alloy is considered to be one of the most promising candidates to replace the traditionally used Sn–Pb solder. However, this alloy composition has some weaknesses, mainly as a result of its higher melting temperature compared to the eutectic Sn–Pb solder. In this paper, lead-free solder alloy nanoparticles of Sn3.0Ag0.5Cu were synthesized by chemical reduction with NaBH₄ as reducing agent. The experimental results indicated that the major particle size of Sn3.0Ag0.5Cu nanoparticles was smaller than 100 nm. The melting and solidification properties of the Sn3.0Ag0.5Cu nanoparticles were studied by differential scanning calorimetry at different scanning rates. It was evidenced by the differential scanning calorimetry curves that the melting temperature of Sn3.0Ag0.5Cu nanoparticles was lower than that of the bulk alloy. In addition, the undercooling of the Sn3.0Ag0.5Cu nanoparticles was in the range of 82.0–88.5 °C at different cooling rates, which was much larger than that of the Sn3.0Ag0.5Cu micro-sized particles, showing stronger cooling rate dependence.     

Creep property of composite solders reinforced by nano-sized particles

In the present work the creep properties of Sn37Pb and Sn0.7Cu based composite solders with nano-sized metallic Cu, Ag and nano-sized oxide Al₂O₃, TiO₂ reinforcement particles have been studied. First, a series of volume percentages of reinforcements were selected for optimizing the content of particles. Then, the composite solder with optimum volume fraction of the reinforcement particles, corresponding to maximum creep rupture life, is selected for investigating the effect of applied stress level and test temperature on creep rupture life of the composite solder joints. In the creep rupture life test, small single-lap tensile-shear joints were adopted. The results indicate that all the composite solders have improved creep resistance, comparing to the eutectic Sn37Pb solder and the Sn0.7Cu lead-free solder. The creep rupture life of the composite solder joints is first increased with the increase in the volume fraction of reinforcement in the composite solders. Then, the creep rupture life is decreased, as the reinforcement content exceeds a certain value. The creep rupture life of the solder joints is decreased with the increase of applied stress and testing temperature. Moreover, the reinforced efficiency of nano-sized Ag particles is the best in all the tested nano-sized reinforcements for the Sn37Pb based and Sn0.7Cu based composite solders, when the particles contents are in their own optimum content.     

Effects of rare earths on properties and microstructures of lead-free solder alloys

In order to further enhance the properties of lead-free solder alloys such as SnAgCu, SnAg, SnCu and SnZn, trace amount of rare earths were selected by lots of researchers as alloys addition into these alloys. The enhancement include better wettability, physical properties, creep strength and tensile strength. For Sn3.8Ag0.7Cu bearing rare earths, when the rare earths were La and Ce, the creep-rupture life of solder joints can be remarkably improved, nine times more than that of the original Sn3.8Ag0.7Cu solder joints at room temperature. In addition, creep-rupture lifetime of RE-doped solders increases by over four times for SnAg and seven times for SnCu. This paper summarizes the effects of rare earths on the wettability, mechanical properties, physical behavior and microstructure of a series of lead-free solders.     

Creep behavior of near-peritectic Sn-5Sb solders containing small amount of Ag and Cu

Sn-5%Sb is one of the materials considered for replacing Pb-bearing alloys in electronic packaging. In the present study, the effects of minor additives of Ag and Cu on the as-cast microstructure and creep properties of the Sn-5Sb solder alloy are investigated by means of optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscope (EDS) and tensile tests. Results show that addition of Ag and Cu resulted not only in the formation of new Ag₃Sn and Cu₆Sn₅ intermetallic compounds (IMCs), but also in the refinement of the grain size of Sn-5Sb solder. Accordingly, the creep properties of the Ag or Cu-containing solder alloys are notably improved. Attention has been paid to the role of IMCs on creep behavior. The lead-free Sn-5Sb-0.7Cu solder shows superior creep performance over the other two solders in terms of much higher creep resistance and vastly elongated creep fracture lifetime. An analysis of the creep behavior at elevated temperatures suggested that the presence of hard Cu₆Sn₅ and fine SbSn IMCs in the Sn-5Sb-0.7Cu alloy increases the resistance to dislocation movement, which improves the creep properties.     

Characters of multicomponent lead-free solders

In the process of electronic packaging, such as flip chip technology, under bump metallization (UBM) can be consumed gradually by solder during soldering. Then dissolution of Ni, Au and Cu from UBM into the solder may change the original solder to a multicomponent one especially under the trend of miniaturization. It is quite necessary to evaluate the properties of the multicomponent solders that have new composition after soldering. In this study, the microstructure, thermal and mechanical properties of five types of multicomponent lead-free solders, i.e. Sn–2Cu–0.5Ni, Sn–2Cu–0.5Ni–0.5Au, Sn–3.5Ag–0.5Ni, Sn–3.5Ag–1Cu–0.5Ni and Sn–3.5Ag–2Cu–0.5Ni (all in wt% unless specified otherwise) were investigated. Comparison with eutectic Sn–0.7Cu, Sn–3.5Ag and Sn–3.5Ag–0.7Cu solders was made. There was no obvious difference of the melting point between the multicomponent lead-free solders and the eutectic ones. For Sn–2Cu–0.5Ni solder, Cu₆Sn₅ and (Cu,Ni)₆Sn₅ intermetallic compounds (IMCs) formed. In the case of Sn–2Cu–0.5Ni–0.5Au, besides (Cu,Ni)₆Sn₅, (Cu,Au)₆Sn₅ and (Cu,Ni,Au)₆Sn₅ were also observed. The IMCs formed in Sn–3.5Ag–0.5Ni solder were Ag₃Sn and Ni₃Sn₄. In both Sn–3.5Ag–1Cu–0.5Ni and Sn–3.5Ag–2Cu–0.5Ni solders, Ag₃Sn and (Cu,Ni)₆Sn₅ were detected. The mechanism for the formation of the IMCs was discussed. Tensile test was also conducted. The fractography indicated that all of the multicomponent lead-free solders exhibited a ductile rupture.     

Microstructural and mechanical behavior of SnCu–Ge solder alloy subjected to high temperature storage

This paper addresses the effect of high temperature storage on the microstructural and mechanical behavior of novel SnCu–Ge solder alloys. Eutectic Sn99.3Cu0.7 solder was micro-alloyed with the addition of minor Ge as an anti-oxidant and to improve the wetting performance of the alloy. The addition of Ge significantly reduced the aging degradation of the alloy. The ultimate tensile strength and yield stress dropped within first few days of aging and the fracture strain increased with aging. The corresponding microstructure changed after annealing at 125 °C for 3 months; the average grain size of the β-tin portions of the microstructure increased with aging and the imbedded IMC particles segregated along and/or within the grains. Based on growth kinetics and activation energy arguments, we suggest that the addition of Ge restricts the Cu diffusion into the alloy and inhibits the IMC growth.     

Analysis of tin whisker growth on lead-free alloys with Ni presence under thermal shock stress

This paper presents the results of whiskers formation after thermal shocks on various tin-rich materials used in electronics: Sn100, Sn99Cu1, Sn97Cu3, Sn99.3Cu0.7Ni, Sn99.3Cu0.7AgNiGe and Sn99Ag0.3Cu0.7NiGe. Alloys plated over an Ni/Au sublayer were compared with those plated directly over a Cu layer. Scanning electron microscope (SEM) imaging was applied to determine whisker densities, lengths and types. Different degrees of susceptibility to whisker formation were found for all the investigated alloys subjected to 1500 shocks in a cyclic temperature range of −45 °C to +85 °C. Although the whisker growth rates for the alloys plated over an Ni/Au sublayer were lower than for the alloys plated directly over a Cu layer, all the materials tested were more or less prone to whisker formation.     

Tensile creep behavior of Sn–Ag–Cu–Ni multicomponent lead-free solder alloy

In the process of electronic packaging, the dissolution of under bump metallizations, such as Cu and Ni, into liquid solder occurs during soldering, which can change the original solder to a multicomponent one. Under the trend of miniaturization, it is quite necessary to evaluate the properties of multicomponent solder with excessive Cu and Ni compositions. In this study, the tensile creep behavior of Sn–3.5Ag–2.0Cu–0.5Ni multicomponent lead-free solder alloy is investigated at three temperatures, i.e., 303, 348 and 393 K. The steady-rate creep rates are obtained in the range of 10^?4–10^?8 s^?1, when the normalized stress, σ/E, is in the range of 10^?4–10^?3. Based on the Dorn equation, the apparent stress exponent (n _a), threshold stress (σ _th), and activation energy of creep (Q _C) are calculated at the three temperatures. It is found that the Sn–3.5Ag–2.0Cu–0.5Ni solder alloy shows a better creep performance than pure tin and eutectic Sn–3.5Ag solder due to the strengthening effect of Ag₃Sn and (Cu,Ni)₆Sn₅ IMC precipitations. The true stress exponent for creep is identified to be 7, indicating that the creep behave is controlled by the dislocation-pipe diffusion in the tin matrix.     

Solder joint reliability of Sn–0·7Cu and Sn–0·3Ag–0·7Cu lead-free solder alloys solidified on copper substrates with different surface roughnesses

Abstract

The bond shear test was used to assess the integrity of Sn–0·7Cu and Sn–0·3Ag–0·7Cu lead-free solder alloy drops solidified on copper substrates with smooth and rough surface finishes. Solder alloys solidified on smooth substrates required higher shear force compared to that on rough substrates. Sn–0·3Ag–0·7Cu alloy required higher shear energy than Sn–0·7Cu alloy. Solder alloys solidified on smooth substrate surfaces exhibited complete ductile failure. On rough copper surfaces, solder alloys showed a transition ridge characterized by sheared intermetallic compounds (IMCs) and the presence of dimples. The peak shear strength decreased with increase in contact area of the solder bond on the substrate. Smooth surface and the presence of minor amount of Ag in the solder alloy enhance the integrity of the solder joint.