Comparative study of microstructures and properties of three valuable SnAgCuRE lead-free solder alloys

Lead-free solders with excellent material properties and low cost are essential for the electronics industry. It has been proved that mechanical properties of SnAgCu alloys can be remarkably improved with a minute addition of rare earth (RE) elements. For comparison and optimization, three valuable solder candidates, Sn3.8Ag0.7Cu0.05RE, Sn3Ag0.5Cu0.05RE, and Sn2.9Ag1.2Cu0.05RE, were chosen due to the excellent properties of their own SnAgCu basic alloys. Wetting properties, melting temperature, bulk tensile properties, and joint tensile and shear properties were investigated. In addition, the microstructures of solder joints were observed and the effects of microstructure on mechanical properties were analyzed. Experimental results indicated that the tensile and shear strengths of solder joints were decreased from Sn3.8Ag0.7Cu0.05RE, Sn2.9Ag1.2Cu0.05RE, to Sn3Ag0.5Cu0.05RE, in order. Such difference in mechanical properties could be attributed to the influence of slightly coarse or strong Cu₆Sn₅ scallops in the reaction layer as well as superior eutectic network and large volume percentage of large primary intermetallic compounds (IMCs) inside the solder joints. It is also suggested that the size and volume percentage of large primary IMCs inside the solder be controlled. In addition, serration morphology was observed at the edge of large primary and eutectic IMCs in the three solder joints, which could be related to the content of Ag, Cu, and RE. The serration morphology was proved to be beneficial to mechanical properties theoretically. Furthermore, the three alloys investigated possessed similar wetting properties, melting temperatures, and bulk tensile properties.     

Effects of Trace Amounts of Rare Earth Additions on Microstructure and Properties of Sn-Bi-Based Solder Alloy

The effect of trace amounts of rare earth additions on the microstructure and properties were studied for the Sn-58Bi and Sn-58Bi-Ag solder alloys. At the same time, the intermetallic compounds (IMCs) in the solder alloys and intermetallic layer (IML) thickness at the solder/Cu substrate interface were investigated, both as-reflowed and after high-temperature aging. The results indicate that adding trace amounts of rare earth (RE) elements has little influence on the melting temperature and microhardness of the solders investigated, but adding RE elements improves the wettability and shear strength of the Sn-58Bi and Sn-58Bi-Ag solder alloys. In addition, it was found that the addition of RE elements not only refines the microstructure and size of the IMC particles, but also decreases the IML thickness and shear strength of the Sn-58Bi solder joint after high-temperature aging. Adding trace amounts of RE elements is superior to adding trace amounts of Ag for improving the properties of the Sn-58Bi solder. The reason may be related to the modification of the microstructure of the solder alloys due to the addition of trace amounts of RE elements.     

Spreading Behavior and Evolution of IMCs During Reactive Wetting of SAC Solders on Smooth and Rough Copper Substrates

The effect of surface roughness of copper substrate on the reactive wetting of Sn-Ag-Cu solder alloys and morphology of intermetallic compounds (IMCs) was investigated. The spreading behavior of solder alloys on smooth and rough Cu substrates was categorized into capillary, diffusion/reaction, and contact angle stabilization zones. The increase in substrate surface roughness improved the wetting of solder alloys, being attributed to the presence of thick Cu₃Sn IMC at the interface. The morphology of IMCs transformed from long needle shaped to short protruded type with an increase in the substrate surface roughness for the Sn-0.3Ag-0.7Cu and Sn-3Ag-0.5Cu solder alloys. However, for the Sn-2.5Ag-0.5Cu solder alloy the needle-shaped IMCs transformed to the completely scallop type with increase in the substrate surface roughness. The effect of Ag content on wetting behavior was not significant.     

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.     

Microstructure characterization of SnAgCu solder bearing Ce for electronic packaging

The creep-rupture lives of Sn3.8Ag0.7Cu and Sn3.8Ag0.7Cu0.03Ce lead-free solder joints for electronic packaging were investigated, respectively. And the relationship between creep behavior and intermetallic compound (IMC: Ag₃Sn, Cu₆Sn₅, CeSn₃) particles in SnAgCu/SnAgCuCe solder joints has been obtained. Meanwhile, rare earth Ce concentration gradient and retardation effect of Ce on the IMC layer have been observed at the solder/Cu interface. Moreover, aging reaction of Sn and Cu, and the effect mechanism of rare earth Ce on two IMCs (Cu₆Sn₅ and Cu₃Sn) are reported.     

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.     

SnAgCuLa钎料合金表面Sn晶须的生长研究

在钎料中添加微量稀土可以显著改善钎料合金的综合性能。但添加过量的稀土时,将会出现Sn晶须的快速生长。研究发现,如果将Sn3.8Ag0.7Cu1.0La钎料内部的稀土相暴露于空气中,稀土相将发生氧化而产生体积膨胀,钎料基体对体积膨胀的抑制作用将使稀土相内部产生巨大的压应力从而加速Sn晶须的生长。晶须直径约1μm,长度可达300μm。     

Morphology and growth kinetics of intermetallic compounds in solid-state interfacial reaction of electroless Ni-P with Sn-based lead-free solders

A comparative study of solid/solid interfacial reactions of electroless Ni-P (15 at.% P) with lead-free solders, Sn-0.7Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn, was carried out by performing thermal aging at 150°C up to 1000 h. For pure Sn and Sn-3.5Ag solder, three distinctive layers, Ni₃Sn₄, SnNiP, and Ni₃P, were observed in between the solder and electroless Ni-P; while for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders, two distinctive layers, (CuNi)₆Sn₅ and Ni₃P, were observed. The differences in morphology and growth kinetics of the intermetallic compounds (IMCs) at the interfaces between electroless Ni-P and lead-free solders were investigated, as well as the growth kinetics of the P-enriched layers underneath the interfacial IMC layers. With increasing aging time, the coarsening of interfacial Ni₃Sn₄ IMC grains for pure Sn and Sn-3.5Ag solder was significantly greater than that of the interfacial (CuNi)₆Sn₅ IMC grains for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders. Furthermore, the Ni content in interfacial (CuNi)₆Sn₅ phase slightly increased during aging. A small addition of Cu (0.7 wt.%) resulted in differences in the type, morphology, and growth kinetics of interfacial IMCs. By comparing the metallurgical aspects and growth kinetics of the interfacial IMCs and the underneath P-enriched layers, the role of initial Cu and Ag in lead-free solders is better understood.     

La对Sn-Ag-Cu无铅钎料组织与性能的影响

研究了微量稀土La对Sn-3.0Ag-0.5Cu无铅钎料显微组织、力学性能、断口形貌、润湿性能和熔点的影响.结果表明:La的质量分数为0.1%可使钎料合金晶粒细化,并显著提高钎料合金力学性能和润湿性能;添加La的质量分数为0.4%将形成粗大LaSn3初生枝晶相,降低力学性能和润湿性能;微量La使钎料合金的熔点轻微增加.     

Constitutive and Aging Behavior of Sn3.0Ag0.5Cu Solder Alloy

We describe double-lap shear experiments on Sn3.0Ag0.5Cu solder alloy, from which fits to Anand's viscoplastic constitutive model, power-law creep model, and to time-hardening primary-secondary creep model are derived. Results of monotonic tests for strain rates ranging from 4.02E-6 to 2.40E-3 s^-1, and creep response at stress levels ranging from 19.5 to 45.6 MPa are reported. Both types of tests were conducted at temperatures of 25degC, 75degC , and 125degC. Following an earlier study where Anand model and time hardening creep parameters for Sn3.8Ag0.7Cu and Sn1.0Ag0.5Cu solder alloys were reported, here we report power law model parameters so as to enable a comparison between all three alloys. Primary creep in Sn3.0Ag0.5Cu solder alloy is shown to be significant and are considered in addition to secondary creep and monotonic behavior. Aging influence on behavior is also shown to be significant. On the basis of experimental data, the following four aspects are discussed: 1) difference between testing on bulk versus joint specimen; 2) consistency between the creep and monotonic behaviors; 3) comparison against behaviors of Sn1.0Ag0.5Cu and Sn3.8Ag0.7Cu alloys as well as aganist Sn40Pb, 62Sn36Pb2Ag and 96.5Sn3.5Ag alloys; and 4) comparison of Sn3.0Ag0.5Cu and Sn3.8Ag0.7Cu relative to their aging response.     

Drop impact reliability of Sn–1.0Ag–0.5Cu BGA interconnects with different mounting methods

The poor drop-shock resistance of near-eutectic Sn–Ag–Cu (SAC) solder interconnects drives the research and application low-Ag SAC solder alloys, especially for Sn–1.0Ag–0.5Cu (SAC105). In this work, by dynamic four-point bend testing, we investigate the drop impact reliability of SAC105 alloy ball grid array (BGA) interconnects with two different surface mounting methods: near-eutectic solder paste printing and flux dipping. The results indicate that the flux dipping method improves the interconnects failure strain by 44.7% over paste printing. Further mechanism studies show the fine interfacial intermetallic compounds (IMCs) at the printed circuit board side and a reduced Ag content inside solder bulk are the main beneficial factors overcoming other negative factors. The flux dipping SAC105 BGA solder joints possess fine Cu₆Sn₅ IMCs at the interface of solder/Cu pads, which increases the bonding strength between the solder/IMCs and the fracture resistance of the IMC grains themselves. Short soldering time of flux dipping joints above the solder alloy liquidus mitigates the growth of interfacial IMCs in size. In addition, a reduced Ag content in flux dipping joint bulk causes a low hardness and high compliance, thus increasing fracture resistance under higher-strain rate conditions.     

Intermetallic phase detection in lead-free solders using synchrotron x-ray diffraction

The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.     

Interfacial reactions and shear strengths between Sn-Ag-based Pb-free solder balls and Au/EN/Cu metallization

The morphological and compositional evolutions of intermetallic compounds (IMCs) formed at three Pb-free solder/electroless Ni-P interface were investigated with respect to the solder compositions and reflow times. The three Pb-free solder alloys were Sn3.5Ag, Sn3.5Ag0.75Cu, and Sn3Ag6Bi2In (in wt.%). After reflow reaction, three distinctive layers, Ni₃Sn₄ (or Ni-Cu-Sn for Sn3.5Ag0.75Cu solder), NiSnP, and Ni₃P, were formed on the electroless Ni-P layer in all the solder alloys. For the Sn3.5Ag0.75Cu solder, with increasing reflow time, the interfacial intermetallics switched from (Cu,Ni)₆Sn₅ to (Cu,Ni)₆Sn₅+(Ni,Cu)₃Sn₄, and then to (Ni,Cu)₃Sn₄ IMCs. The degree of IMC spalling for the Sn3.5Ag0.75Cu solder joint was more than that of other solders. In the cases of the Sn3.5Ag and Sn3Ag6Bi2In solder joints, the growth rate of the Ni₃P layer was similar because these two type solder joints had a similar interfacial reaction. On the other hand, for the Sn3.5Ag0.75Cu solder, the thickness of the Ni₃P and Ni-Sn-P layers depended on the degree of IMC spalling. Also, the shear strength showed various characteristics depending on the solder alloys and reflow times. The fractures mainly occurred at the interfaces of Ni₃Sn₄/Ni-Sn-P and solder/Ni₃Sn₄.     

Development of SnAg-based lead free solders in electronics packaging

Lead free solder alloys for electronic assembly is being driven by environmental and health concerns regarding toxicity of lead and, more importantly, by the perceived economic advantage of marketing “green” products. Of the currently available lead free solders, SnAg has the greatest potential. In this solder, the Ag₃Sn compound is distributed in a eutectic network throughout the β-Sn matrix and these results represent mechanical strength. In order to further improve the microstructures and properties of SnAg-based alloys, alloying elements such as rare earth, Zn, In, P, Cu, Ni and particles such as ZrO₂, POSS are selected to meet the requirement of high reliability of high-density electronics devices. For SnAg solder bearing rare earth (Ce and La), the creep-rupture life of solder joints can be remarkably increased up to four times more than that of the original SnAg solder joints at room temperature, meanwhile, rare earths can dramatically reduce the thickness of IMCs layer at solder/pad interfaces and also refine the microstructure of the alloy which results in the enhancement of mechanical properties of the SnAg solder. Moreover, the addition of ZrO₂ nanoparticles significantly refined the size of Ag₃Sn due to the adsorption effect of the ZrO₂ nanoparticles. This paper summarizes the effects of alloying elements and particles on the wettability, mechanical properties, creep behavior, microstructures, etc. of SnAg-based lead free solder alloys.     

Effect of rare earth element addition on the microstructure of Sn-Ag-Cu solder joint

The effects of minimal rare earth (RE) element additions on the microstructure of Sn-Ag-Cu solder joint, especially the intermetallic compounds (IMCs), were investigated. The range of RE content in Sn-Ag-Cu alloys varied from 0 wt.% to 0.25 wt.%. Experimental results showed that IMCs could be dramatically repressed with the appropriate addition of RE, resulting in a fine microstructure. However, there existed an effective range for the RE addition. The best RE content was found to be 0.1 wt.% in the current study. In addition to the typical morphology of Ag₃Sn and Cu₆Sn₅ IMCs, other types of IMCs that have irregular morphology and uncertain constituents were also observed. The IMCs with large plate shape mainly contained Ag and Sn, but the content of Ag was much lower than that of Ag₃Sn. The cross sections of Cu₆Sn₅ IMCs whiskers showed various morphologies. Furthermore, some eutectic-like structures, including lamellar-, rod-, and needle-like phases, were observed. The morphology of eutectic-like structure was related to the RE content in solder alloys. When the content of RE is 0.1 wt.%, the needle-like phase was dominant, while the lamellar structure prevailed when the RE content was 0.05 wt.% or 0.25 wt.%. It is suggested that the morphology change of the eutectic-like structure directly affects the creep properties of the solder joint.     

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.     

Ti对Sn0.7Cu无铅钎料润湿性和界面的影响

研究了Ti的加入对Sn0.7Cu无铅钎料润湿性能以及钎料/Cu界面微观组织的影响.结果表明:在Sn0.7Cu中添加微量Ti,提高了钎料的润湿性能,可使铺展面积提高5％左右,当钎焊时间为3s时,界面金属间化合物(IMC)形貌由原来的扇贝状变为锯齿状;随着钎焊时间延长,Sn0.7Cu/Cu和Sn0.7Cu0.008Ti/C...     

Effect of trace platinum additions on the interfacial morphology of Sn–3.8Ag–0.7Cu alloy aged for long hours

While the Sn–Ag–Cu (SAC) family of solders are considered good candidate as lead-free solder replacement materials, their relatively short processing history and application result in a host of materials as well as reliability problems. For good metallurgical bonding and electrical connection, a thin, even layer of intermetallic compound (IMC) is required but excessive growth of the IMC layer will cause various reliability problems. This is especially critical for miniaturized solder pitches in very large scale integration circuits. This work adopts the composite approach of adding 0.15 and 0.30 wt.% of Pt into Sn–3.8Ag–0.7Cu alloy to study the effect of these additions to the IMC layer thickness between the solder and substrate. Alloys were isothermally aged at 150 °C for up to 1000 h to observe contribution of Pt in suppressing excessive IMC growth. It was found that when more Pt was added to the alloy, the IMC layer became more even and continuous. Voids and IMC layer thickness were reduced. This is attributed to the role of Pt in replacing Cu in the solder and thus impeding excessive diffusion.     

Reaction of Liquid Sn-Ag-Cu-Ce Solders with Solid Copper

Small amounts of the rare-earth element Ce were added to the Sn-rich lead-free eutectic solders Sn-3.5Ag-0.7Cu, Sn-0.7Cu, and Sn-3.5Ag to improve their properties. The microstructures of the solders without Ce and with different amounts (0.1 wt.%, 0.2 wt.%, and 0.5 wt.%) of Ce were compared. The microstructure of the solders became finer with increasing Ce content. Deviation from this rule was observed for the Sn-Ag-Cu solder with 0.2 wt.% Ce, and for the Sn-0.7Cu eutectic alloy, which showed the finest microstructure without Ce. The melting temperatures of the solders were not affected. The morphology of intermetallic compounds (IMC) formed at the interface between the liquid solders and a Cu substrate at temperatures about 40°C above the melting point of the solder for dipping times from 2 s to 256 s was studied for the basic solder and for solder with 0.5 wt.% Ce addition. The morphology of the Cu₆Sn₅ IMC layer developed at the interface between the solders and the substrate exhibited the typical scallop-type shape without significant difference between solders with and without Ce for the shortest dipping time. Addition of Ce decreased the thickness of the Cu₆Sn₅ IMC layer only at the Cu/Sn-Ag-Cu solder interface for the 2-s dipping. A different morphology of the IMC layer was observed for the 256-s dipping time: The layers were less continuous and exhibited a broken relief. Massive scallops were not observed. For longer dipping times, Cu₃Sn IMC layers located near the Cu substrate were also observed.     

Intermetallic reactions in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes

The intermetallic compounds (IMCs) formed during the reflow and aging of Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes were investigated. After reflow, the thickness of (Cu, Ni, Au)₆Sn₅ interfacial IMCs in Sn3Ag0.5Cu0.06Ni0.01Ge was similar to that in the Sn3Ag0.5Cu specimen. The interiors of the solder balls in both packages contained Ag₃Sn precipitates and brick-shaped AuSn₄ IMCs. After aging at 150°C, the growth thickness of the interfacial (Ni, Cu, Au)₃Sn₄ intermetallic layers and the consumption of the Ni surface-finished layer on Cu the pads in Sn3Ag0.5Cu0.06Ni0.01Ge solder joints were both slightly less than those in Sn3Ag0.5Cu. In addition, a coarsening phenomenon for AuSn₄ IMCs could be observed in the solder matrix of Sn3Ag0.5Cu, yet this phenomenon did not occur in the case of Sn3Ag0.5Cu0.06Ni0.01Ge. Ball shear tests revealed that the reflowed Sn3Ag0.5Cu0.06Ni0.01Ge packages possessed bonding strengths similar to those of the Sn3Ag0.5Cu. However, aging treatment caused the ball shear strength in the Sn3Ag0.5Cu packages to degrade more than that in the Sn3Ag0.5Cu0.06Ni0.01Ge packages.