Additive Effect of Kirkendall Void Formation in Sn-3.5Ag Solder Joints on Common Substrates

The Sn-3.5Ag and Sn-3.5Ag-0.2Co-0.1Ni lead-free solders were investigated on common electronics substrates, namely, organic solderability preservative (OSP) and electroless Ni/immersion Au (ENIG) surface finishes. The formation of Kirkendall voids at the interfacial region during isothermal solid aging was explored. For the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joint, the Kirkendall voids were present after isothermal solid-state aging at higher temperature (e.g., 150°C); however, the size of voids did not change remarkably with prolonged aging time due to the depressed Cu₃Sn layer growth. For ENIG surface finishes, the 0.2Co-0.1Ni additions seemed to enhance the longitudinal groove-shaped voids at the Ni₃P layer; however, void formation at the solder/Ni₃Sn₄ interface was effectively reduced. This might be attributed to the reduced Sn activity in the solder matrix and the suppressed Ni-P-Sn layer formation.     

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.     

On the Nature of the Interface between Ag<Subscript>3</Subscript>Sn Intermetallics and Sn in Sn-3.5Ag Solder Alloys

We report on the nature of the orientation of Ag₃Sn and the Ag₃Sn/Sn interface in Sn-3.5Ag solder. Orientation imaging microscopy (OIM) and transmission electron microscopy (TEM) were used to characterize the orientation and nature of the interface, respectively. OIM and TEM showed that Sn-3.5Ag containing spherical Ag₃Sn particles does not have a preferred orientation with respect to the Sn matrix. However, needle-like Ag₃Sn formed during slower cooling appeared to have a preferred orientation within individual Sn colonies. The interface between Sn and Ag₃Sn appeared to be incoherent, as confirmed by high-resolution TEM analysis.     

Effects of Co addition in eutectic Sn-3.5Ag solder on shear strength and microstructural development

In this study, the approach of composite solder using eutectic Sn-3.5Ag solder and Co was tried. Co particles and Sn-3.5Ag solder paste were mechanically mixed at Co weight fractions from 0.1% to 2.0%. For the Co-mixed Sn-3.5Ag solder pastes, their melting temperatures and spreading areas were measured. The solder pastes were stencil printed on test substrates and reflowed to form solder bumps. Ball shear test was performed to examine shear strength of Co-reinforced Sn-3.5Ag solder bumps. As a result, Co addition up to 2 wt.% did not alter the melting temperature under heating but reduced undercooling. The maximum shear strength of Co-reinforced Sn-3.5Ag solder bumps increased by 28% compared to normal ones. The increase in shear strength can be attributed to the (Cu,Co)₃Sn₂ intermetallic compounds.     

Microstructural effect on the creep strength of a Sn-3.5%Ag solder alloy

The effect of microstructure obtained by rapid or slow solidification and cooling of a Sn-3.5%Ag lead-free solder alloy on the creep strength has been investigated. The rapidly cooled alloy showed that the microstructure consisted of the primarily crystallized Sn phase and the quasi-eutectic phase, where fine Ag₃Sn particles dispersed in the Sn matrix. In the slowly cooled alloy, large platelets of Ag₃Sn were formed sparsely in the Sn matrix. A difference of about 2.5 orders of magnitude in the cooling rate translates to about 1.5 orders of magnitude in the creep-rupture time. Accordingly, fine particle dispersion of Ag₃Sn is considered to be very beneficial for the restraining of creep deformation, that is, for the decreasing of creep rate of the Sn-3.5%Ag alloy, compared with the effect of large platelets of Ag₃Sn sparsely formed in the Sn matrix.     

热处理对96.5Sn3.5Ag焊点中Cu-Sn合金层的影响

在焊点与铜基之间形成的Ｃｕ－Ｓｎ合金成分对表面安装器件的疲劳寿命起着关键性的作用。本文着重研究了９３．５Ｓｎ３．５Ａｇ（简写为Ｓｎ－Ａｇ）焊料与Ｃｕ基界面间形成的合金层,通过电子扫描显微镜（ＳＥＭ）,Ｘ衍射（ＸＤＡ）及能谱Ｘ射线（ＥＤＸ）等分析发现,在Ｓｎ－Ａｇ与Ｃｕ基界面上存在Ｃｕ６Ｓｎ５及Ｃｕ３Ｓｎ两种合金成分,且随着热处理时间增加,Ｃｕ６Ｓｎ５合金层增厚,并在该处容易出现裂纹而导致焊点强度减弱,从而使焊点产生疲劳失效。     

The effect of Ag content on the formation of Ag3Sn plates in Sn-Ag-Cu lead-free solder

The formation of Ag₃Sn plates in the Sn-Ag-Cu lead-free solder joints for two different Ag content solder balls was investigated in wafer level chip scale packages (WLCSPs). After an appropriate surface mount technology reflow process on a printed circuit board, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging, or 1,000 cycles thermal cycling test (TCT). Sequentially, the cross-sectional analysis was scrutinized using a scanning electron microscope/energy dispersive spectrometer (SEM/EDX) to observe the metallurgical evolution of the amount of the Ag₃Sn plates at the interface and the solder bulk itself. Pull and shear tests were also performed on samples. It was found that the interfacial intermetallic compound (IMC) thickness, the overall IMC area, and the numbers of Ag₃Sn plates increase with increasing HTS and TCT cycles. The amount of large Ag₃Sn plates found in the Sn-4.0Ag-0.5 Cu solder balls is much greater than that found in the Sn-2.6Ag-0.5Cu solder balls; however, no significant difference was found in the joint strength between two different Ag content solder joints.     

Sn0．45Ag0．68Cu无铅焊点热冲击性能的研究

采用Sn0．45A g0．68Cu亚共晶无铅钎料通过热浸焊获得铜接头,在－45～125℃的温度循环区间内对焊接接头进行200、400、600、800、1000周期高低温热冲击循环实验,分析了焊点的剪切强度变化,组织演变及界面IM C的生长规律。结果表明：焊点组织中弥散分布的Cu6Sn5相内部晶粒逐渐粗化长大,最后转变为圆形或者椭圆形;焊点界面IM C层厚度明显增厚,且由最初的细小扇贝状转变为大的波浪状,最终趋于平缓;焊点的剪切强度随热冲击循环周期的增加而急剧下降,经400周期的热冲击循环之后,焊点的剪切强度已下降了约22．5％,在400周期的热冲击循环后开始变得平缓,最后趋于稳定。     

Microstructure and mechanical properties evolution of intermetallics between Cu and Sn-3.5Ag solder doped by Ni-Co additives

The evolution of intermetallic compounds (IMCs) generated between Sn-3.5Ag solder doped by additive couples (namely, 0.2mass%Co and 0.1mass%Ni) and Cu substrate was characterized. After soldering, the additive couples, Co-Ni, were all detected at the intermetallic region. The microstructure of intermetallic was identified as (Cu, Ni, Co)₆Sn₅ by electron probe microanalysis (EPMA) and x-ray diffraction (XRD). However, the morphology of (Cu, Ni, Co)₆Sn₅ was converted to columnar like and was not as dense as the typical scallop-like Cu₆Sn₅. A duplex structure of (Cu, Ni, Co)₆Sn₅, namely, two distinct regions bearing different concentrations of Ni and Co, was observed. Much higher Ni and Co concentrations were probed in the outer intermetallic region adjacent to the solder matrix, while lower concentration at the inner region was verified. After aging, the intermetallic (Cu, Ni, Co)₆Sn₅ tended to be dense, while the growth rate was depressed at the early stage. In addition, the Cu₃Sn phase was not detected after aging at 110°C, while it appeared at 130°C and 150°C for 504 h. Using the nanoindentation technique, some mechanical properties of (Cu, Ni, Co)₆Sn₅ were investigated. The lower hardness and Young’s modulus of the outer intermetallic region was revealed. After aging treatment, both the hardness and Young’s modulus values were elevated.     

Study of interfacial reactions between Sn3.5Ag0.5Cu composite alloys and Cu substrate

For development of a lead-free composite solder for advance electrical components, lead-free Sn3.5Ag0.5Cu solder was produced by mechanically mixing 0.5 wt.% TiO₂ nanopowder with Sn3.5Ag0.5Cu solder. The morphology and growth kinetics of the intermetallic compounds that formed during the soldering reactions between Sn3.5Ag0.5Cu solder with intermixed TiO₂ nanopowder and Cu substrates at various temperatures ranging from 250 to 325 °C were investigated. A scanning electron microscope (SEM) was used to quantify the interfacial microstructure at each processing condition. The thickness of interfacial intermetallic layers was quantitatively evaluated from SEM micrographs using imaging software. Experimental results show that a discontinuous layer of scallop-shaped Cu-Sn intermetallic compounds formed during the soldering. Kinetics analysis shows that the growth of such interfacial Cu-Sn intermetallic compounds is diffusion controlled with an activation energy of 67.72 kJ/mol.     

Revealing the nucleation and growth mechanism of a novel solder developed from Sn-3.5Ag-0.5Cu nanoparticles by a chemical reduction method

Sn-3.5Ag-0.5Cu nanoparticles were synthesized by chemical precipitation with NaBH₄. By using x-ray diffraction and transmission and scanning electron microscopy, the microstructural characteristics of particle growth were evaluated. The results indicated that the primary particles after precipitation were (Ag,Cu)₄Sn, with a size of 4.9 nm. (Ag,Cu)₄Sn was transformed into (Ag,Cu)₃Sn, when the total amount of Sn contributed from both (Ag,Cu)₄Sn and Sn covering the (Ag,Cu)₄Sn overtook that of (Ag,Cu)₃Sn. The final particle size of polycrystalline particles was 42.1 nm owing to the depletion of Sn atoms in the solution. Nucleation and growth mechanisms of Sn-3.5Ag-0.5Cu nanoparticles are also discussed and proposed.     

Effects of cooling rate on the microstructure and tensile behavior of a Sn-3.5wt.%Ag solder

The tensile behavior and microstructure of bulk, Sn-3.5Ag solders as a function of cooling rate were studied. Cooling rate is an important processing parameter that affects the microstructure of the solder and, therefore, significantly influences mechanical behavior. Controlled cooling rates were obtained by cooling specimens in different media: water, air, and furnace. Cooling rate significantly affected secondary dendrite-arm size and spacing of the Sn-rich phase, as well as the aspect ratio of Ag₃Sn. The Sn-rich dendrite-arm size and spacing were smaller for water-cooled specimens than for air-cooled specimens. Furnace cooling yielded a nearly eutectic microstructure because the cooling rate approached equilibrium cooling. The morphology of Ag₃Sn also changed from spherical, at a fast cooling rate, to a needlelike morphology for slower cooling. The changes in the microstructure induced by the cooling rate significantly affected the mechanical behavior of the solder. Yield strength was found to increase with increasing cooling rate, although ultimate tensile strength and strain-to-failure seemed unaffected by cooling rate. Cooling rate did not seem to affect Young’s modulus, although a clear coorelation between modulus and porosity was obtained. The mechanical behavior was correlated with the observed microstructure, and fractographic analysis was employed to elucidate the underlying damage mechanisms.     

Scanning electron microscope in-situ investigation of fracture behavior in 96.5Sn3.5Ag lead-free solder

In-situ tensile tests of as-cast 96.5Sn3.5Ag eutectic solder were performed under the scanning electron microscope (SEM) using different strain rates at room temperature, and various crack initiation and propagation behavior was observed on the specimen surface. It was found that, due to the existence of Ag₃Sn intermetallic particles and the special microstructure of β-Sn phases in Sn3.5Ag solder, grain boundary sliding (GBS) was no longer the dominant mechanism for this Pb-free solder. In the lower strain rate regime, accompanied by partial intragranular cracks, intergranular fracture along the grain boundaries in Sn-Ag eutectic structure or along the interphase boundaries between Sn-rich dendrites and Sn-Ag eutectic phases occurred primarily for the Sn3.5Ag solder in the early tensile stage. However, significant plastic deformation was observed in large areas for the specimens tested at higher strain rates, and cracks propagated in a transgranular manner across the Sn dendrites and Sn-Ag eutectic structure.     

Effect of cooling rate on microstructure and shear strength of pure Sn,Sn-0.7Cu,Sn-3.5Ag,and Sn-37Pb solders

The microstructure and shear strength characteristics of pure Sn and the eutectic compositions of Sn-37Pb, Sn-0.7Cu, and Sn-3.5Ag prepared under identical reflow conditions but subjected to two different cooling conditions were evaluated at room temperature. For the four solders, the ultimate shear strength increased with increasing strain rate from 10⁻⁵ s⁻¹ to 10⁻¹ s⁻¹. Decreasing the cooling rate tended to decrease the ultimate shear strength for both the Sn-0.7Cu and Sn-3.5Ag solders. The effects of work hardening resulting from increased strain rate were more prevalent in quench-cooled (QC) samples.     

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 cooling rate on creep behavior of a Sn-3.5Ag alloy

The effect of cooling rate on microstructure and creep behavior of bulk, eutectic Sn-3.5Ag solders was studied. The cooling rate is an important processing variable that significantly affects the microstructure of the solder and therefore determines its mechanical behavior. Controlled cooling rates were obtained by cooling specimens in different media: water, air, and furnace, which resulted in cooling rates of 24°C/s, 0.5°C/s, and 0.08°C/s, respectively. The cooling rate decreased the secondary dendrite arm size and the spacing of the Sn-rich phase, as well as the morphology of Ag₃Sn. The Sn-dendrite arm size and spacing were smaller at fast cooling rates, while slower cooling rates yielded a nearly eutectic microstructure. The morphology of Ag₃Sn also changed from relatively spherical, at faster cooling rates, to needlelike for slower cooling. The effect of cooling rate on creep behavior was studied at 25°C, 60°C, 95°C, and 120°C. Faster cooling rates were found to increase the creep strength of the solder due to the refinement of the solder microstructure. Stress exponents, n, indicated that dislocation climb was the controlling mechanism. Activation energies, for all cooling rates, indicated that the dominant diffusional mechanism corresponded to dislocation pipe diffusion of Sn. Grain boundary sliding (GBS) measurements were conducted, using both scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was observed that GBS had a very small contribution to the total creep strain.     

42Sn58Bi—96.5Sn3.5Ag系焊点疲劳性能的研究

本文研究了热处理时间对不同组分的４２Ｓｎ５８Ｂｉ－９６．５Ｓｎ３．５Ａｇ焊料疲劳性能的影响,研究发现适当的热处理时间能提高焊点的机械强度,延长焊点的疲劳寿命。     

Intermetallic reactions in Sn-3.5Ag solder ball grid array packages with Ag/Cu and Au/Ni/Cu pads

During the reflow process of Sn-3.5Ag solder ball grid array (BGA) packages with Ag/Cu and Au/Ni/Cu pads, Ag and Au thin films dissolve rapidly into the liquid solder, and the Cu and Ni layers react with the Sn-3.5Ag solder to form Cu₆Sn₅ and Ni₃Sn₄ intermetallic compounds at the solder/pad interfaces, respectively. The Cu₆Sn₅ intermetallic compounds also appear as clusters in the solder matrix of Ag surface-finished packages accompanied by Ag₃Sn dispersions. In the solder matrix of Au/Ni surface-finished specimens, Ag₃Sn and AuSn₄ intermetallics can be observed, and their coarsening coincides progressively with the aging process. The interfacial Cu₆Sn₅ and Ni₃Sn₄ intermetallic layers grow by a diffusion-controlled mechanism after aging at 100 and 150°C. Ball shear strengths of the reflowed Sn-3.5Ag packages with both surface finishes are similar, displaying the same degradation tendencies as a result of the aging effect.     

Low-cycle fatigue prediction model for pb-free solder 96.5Sn-3.5Ag

Low-cycle fatigue (LCF) data of Sn-Ag eutectic solder (96.5Sn-3.5Ag) under various temperatures and frequencies has been described using three different prediction models, i.e., Coffin-Manson model, Smith-Watson-Topper (SWT) model, and Morrow energy model. The LCF behavior represented by the present prediction models showed temperature and frequency dependences, i.e., the fatigue ductility coefficient increased with increasing frequency and decreasing temperature. In order to better correlate the LCF data, a flow stress and/or frequency-dependent modifications were introduced to the Coffin-Manson and Morrow energy models. The frequency-modified Coffin-Manson model could not describe the influence of temperature on LCF behavior, while the flow stress-modified frequency-modified Morrow energy model, into which the metallurgical response (flow stress and frequency) was introduced to account for the effect of temperature and frequency on LCF behavior, gave reasonable predictions of LCF data under various temperatures and frequencies.     

Influence of current density on mechanical reliability of Sn-3.5Ag BGA solder joint

In this study, we investigated the effect of the current density on the interfacial reaction and mechanical reliability of an electroless Ni/immersion Au (ENIG) substrate with Sn-3.5Ag solder. We first evaluated the interfacial reactions of the solder joint under aging for up to 800 h and current stressing with current densities of 3 × 10² A/cm² and 5 × 10³ A/cm². Also, we successfully revealed the correlation between the interfacial reaction behavior and mechanical reliability under current stressing. With increasing aging time, the thickness of the Ni₃Sn₄ layer increased. At both low and high current densities, the thickness of the Ni₃Sn₄ layer increased up to 400 h and decreased thereafter at the cathode, while that of the IMC increased up to 800 h at the anode. After the die shear test, the ductile fracture was observed in the as-reflowed joint without current stressing. The fracture mode changed from ductile fracture to brittle fracture when thermal aging and current flow were simultaneously applied. The combination of the current stressing and isothermal aging at high temperature significantly deteriorated the mechanical reliability of the solder joint.