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.     

Microstructural evolution of lead-free Sn-Bi-Ag-Cu SMT joints during aging

It was reported in a previous study that the Sn-6Bi-2Ag-0.5Cu solder alloy had great potential to replace leaded alloys. This alloy was prepared by mechanical alloying, and had the advantage of providing a high percentage of supersaturate solution of bismuth in tin. In the present paper, the microstructural evolution of surface-mount joints during aging was examined. In the as-soldered joints, small bismuth and Ag₃Sn particles of about 1 mum in size were found to be finely dispersed in a nearly pure tin matrix with a small amount of eta-Cu₆Sn₅ phase in the bulk of solder. During aging, microstructural evolution of solder joints occurred. These include Cu-Sn intermetallic compound (IMC) layer growth at the interface between solder and copper pad on the printed circuit board, as well as bismuth phase and Ag₃Sn phase coarsening. The shear strength of the solder joints decreased parabolically with the increase in IMC layer thickness, such that tau_s=22.22-radic22.05(t-1.88), where tau_s is the shear strength in MPa and t (>1.88) is the total IMC layer thickness in micrometers. The microstructure of solder appeared to be stable under aging at elevated temperatures up to about 160degC. Above this temperature, brittle and porous IMC epsiv-Cu₃Sn appeared at the copper/eta-Cu₆Sn ₅ interface. Fracture was found to occur at the Cu-Sn IMC layer-solder interface and in the bulk of solder     

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.     

Effect of Ag Content and the Minor Alloying Element Fe on the Mechanical Properties and Microstructural Stability of Sn-Ag-Cu Solder Alloy Under High-Temperature Annealing

This study compares the high-Ag-content Sn-3Ag-0.5Cu with the low- Ag-content Sn-1Ag-0.5Cu solder alloy and the three quaternary solder alloys Sn-1Ag-0.5Cu-0.1Fe, Sn-1Ag-0.5Cu-0.3Fe, and Sn-1Ag-0.5Cu-0.5Fe to understand the beneficial effects of Fe on the microstructural stability, mechanical properties, and thermal behavior of the low-Ag-content Sn-1Ag-0.5Cu solder alloy. The results indicate that the Sn-3Ag-0.5Cu solder alloy possesses small primary β-Sn dendrites and wide interdendritic regions consisting of a large number of fine Ag₃Sn intermetallic compound (IMC) particles. However, the Sn-1Ag-0.5Cu solder alloy possesses large primary β-Sn dendrites and narrow interdendritic regions of sparsely distributed Ag₃Sn IMC particles. The Fe-bearing SAC105 solder alloys possess large primary β-Sn dendrites and narrow interdendritic regions of sparsely distributed Ag₃Sn IMC particles containing a small amount of Fe. Moreover, the addition of Fe leads to the formation of large circular FeSn₂ IMC particles located in the interdendritic regions. On the one hand, tensile tests indicate that the elastic modulus, yield strength, and ultimate tensile strength (UTS) increase with increasing Ag content. On the other hand, increasing the Ag content reduces the total elongation. The addition of Fe decreases the elastic modulus, yield strength, and UTS, while the total elongation is still maintained at the Sn-1Ag-0.5Cu level. The effect of aging on the mechanical behavior was studied. After 720 h and 24 h of aging at 100°C and 180°C, respectively, the Sn-1Ag-0.5Cu solder alloy experienced a large degradation in its mechanical properties after both of the aging conditions, whereas the mechanical properties of the Sn-3Ag-0.5Cu solder alloy degraded more dramatically after 24 h of aging at 180°C. However, the Fe-bearing SAC105 solder alloys exhibited only slight changes in their mechanical properties after both aging procedures. The inclusion of Fe in the Ag₃Sn IMC particles suppresses their IMC coarsening, which stabilizes the mechanical properties of the Fe-bearing SAC105 solder alloys after aging. The results from differential scanning calorimetry (DSC) tests indicate that the addition of Fe has a negligible effect on the melting behavior. However, the addition of Fe significantly reduces the solidification onset temperature and consequently increases the degree of undercooling. In addition, fracture surface analysis indicates that the addition of Fe to the Sn-1Ag-0.5Cu alloy does not affect the mode of fracture, and all tested alloys exhibited large ductile dimples on the fracture surface.     

A Study on the Physical Properties and Interfacial Reactions with Cu Substrate of Rapidly Solidified Sn-3.5Ag Lead-Free Solder

A rapidly solidified Sn-3.5Ag eutectic alloy produced by the melt-spinning technique was used as a sample in this research to investigate the microstructure, thermal properties, solder wettability, and inhibitory effect of Ag₃Sn on Cu₆Sn₅ intermetallic compound (IMC). In addition, an as-cast Sn-3.5Ag solder was prepared as a reference. Rapidly solidified and as-cast Sn-3.5Ag alloys of the same size were soldered at 250°C for 1 s to observe their instant melting characteristics and for 3 s with different cooling methods to study the inhibitory effect of Ag₃Sn on Cu₆Sn₅ IMC. Experimental techniques such as scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectrometry were used to observe and analyze the results of the study. It was found that rapidly solidified Sn-3.5Ag solder has more uniform microstructure, better wettability, and higher melting rate as compared with the as-cast material; Ag₃Sn nanoparticles that formed in the rapidly solidified Sn-3.5Ag solder inhibited the growth of Cu₆Sn₅ IMC during aging significantly much strongly than in the as-cast material because their number in the rapidly solidified Sn-3.5Ag solder was greater than in the as-cast material with the same soldering process before aging. Among the various alternative lead-free solders, this study focused on comparison between rapidly solidified and as-cast solder alloys, with the former being observed to have better properties.     

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.     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Computational Investigation of the Evolution of Intermetallic Compounds Affected by Microvoids During the Solid-State Aging Process in the Cu-Sn System

In this work, the impact of microvoids on the microstructural evolution of η-Cu₆Sn₅ and ?-Cu₃Sn in the Cu-Sn system is evaluated numerically. Through the use of the multiphase-field method, the systems of interest are allowed to evolve using a solid-state aging temperature of 453 K in conjunction with material parameters and reaction conditions adopted from previous research. The simulation results are then analyzed and compared with previous experiments in terms of the morphological evolution of the intermetallic compounds (IMCs), the IMC layer thicknesses, and the corresponding interfacial roughness. It is shown that the presence of microvoids at the ?/Cu interface interferes with the flow of mass throughout the phases, impeding phase transformations and grain coarsening. This ultimately affects the IMC coarsening rate and overall IMC layer thicknesses. Additionally, it was observed that the presence of microvoids at the ?/Cu interface affects the formation of both IMC layers and their corresponding interfaces, and the changes in roughness for the interfaces are quantitatively provided. Overall, the simulations are found to be within the range of accepted experimental values for the morphology of the IMC grains, the evolution of IMC layer thicknesses, and the evolution of interface roughness.     

An investigation of effects of Sb on the intermetallic formation in Sn-3.5Ag-0.7Cu solder joints

This study investigates the microstructural evolution and kinetics of intermetallic (IMC) formation in Sn-3.5Ag-0.7Cu lead-free solder joints with different percentages of Sb element, namely, Sn-3.5Ag-0.7Cu-xSb (x=0, 0.2, 0.5, 0.8, 1.0, 1.5, and 2.0). To investigate the elemental interdiffusion and growth kinetics of IMC formation, isothermal aging test is performed at temperatures of 100/spl deg/C, 150/spl deg/C, and 190/spl deg/C, respectively. Scanning electron microscope (SEM) is used to measure the thickness of intermetallic layer and observe the microstructural evolution of solder joint. The IMC phases are identified by EDX and XRD. Results show that some of the antimony powders are dissolved in the /spl beta/-Sn matrix (Sn-rich phase), some of them participate in the formation of Ag/sub 3/(Sn,Sb) and the rest dissolves in the Cu/sub 6/Sn/sub 5/ IMC layer. There is a significant drop in IMC thickness when Sb is added to 0.8 wt%. Over this amount the thickness of the IMC increases slightly again. The activation energy and growth rate of the IMC formation are determined. Results reveal that adding antimony in Sn-3.5Ag-0.7Cu solder system can increase the activation energy, and thus reduce the atomic diffusion rate, so as to inhibit the excessive growth of the IMC. The solder joint containing 0.8 wt% antimony has the highest activation energy. SEM images reveal that the number of small particles precipitating in the solder matrix increases with the increase in Sb composition. Based on the observation of the microstructural evolution of the solder joints, a grain boundary pinning mechanism for inhibition of the IMC growth due to Sb addition is proposed.     

SnAgCu无铅焊点的电迁移行为研究

电迁移引发的焊点失效已经成为当今高集成度电子封装中的最严重的可靠性问题之一。应用SnAgCu无铅焊膏焊接微米级铜线,进行电迁移实验。结果表明:焊点形貌从原来的光滑平整变得凹凸不平,阴极处出现了裂纹和孔洞,并且在铜基板和Cu6Sn5金属间化合物(IMC)之间出现薄薄的一层Cu3Sn金属间化合物,由ImageJ软件测量其平均厚度约为2.11μm;而在阳极附近没有明显的Cu3Sn金属间化合物形成。     

无铅焊点在热疲劳和电迁移作用下的组织演变

研究了Cu/Sn-58Bi/Cu焊点接头在室温和55℃下通电过程中阴极和阳极界面处微观组织的演变,电流密度均采用104A/cm2。结果表明,室温条件下通电达到25 d,Bi原子由阴极向阳极发生了扩散迁移,在阳极界面处形成了厚度约22.4μm的均匀Bi层,而阴极出现了Sn的聚集。加载55℃通电2 d后,焊点发生了熔融,阴极界面处形成了厚度为34.3μm的扇贝状IMC,而阳极界面IMC的厚度仅为9.7μm。在IMC层和钎料基体之间形成了厚度约7.5μm的Bi层,它的形成阻碍了Sn原子向阳极界面的扩散迁移,进而阻碍了阳极界面IMC的生长,导致了异常极化效应的出现。     

Effect of reflow and thermal aging on the microstructure and microhardness of Sn-3.7Ag-xBi solder alloys

This work investigates the effect of reflow and the thermal aging process on the microstructural evolution and microhardness of five types of Sn-Ag based lead-free solder alloys: Sn-3.7Ag, Sn-3.7Ag-1Bi, Sn-3.7Ag-2Bi, Sn-3.7Ag-3Bi, and Sn-3.7Ag-4Bi. The microhardness and microstructure of the solders for different cooling rates after reflow at 250°C and different thermal aging durations at 150°C for air-cooled samples have been studied. The effect of Bi is discussed based on the experimental results. It was found that the microhardness increases with increasing Bi addition to Sn-3.7Ag solder regardless of reflow or thermal aging process. Scanning electron microscopy images show the formation of Ag₃Sn particles, Sn-rich phases, and precipitation of Bi-rich phases in different solders. The increase of microhardness with Bi addition is due to the solution strengthening and precipitation strengthening provided by Bi in the solder. The trend of decrease in microhardness with increasing duration of thermal aging was observed.     

波峰焊及再流焊无铅焊点组织演变规律的研究

以电子封装线上的波峰焊无铅焊点Sn-0.7Cu/Cu、回流焊无铅焊点Sn-3Ag-0.5Cu/Cu为对象,研究了150 ℃时效过程中无铅焊点处金属间化合物(IMC)、焊料合金组织的演化规律及界面处金属间化合物生长的动力学.试验结果表明:两种无铅焊点处IMC层的厚度随着时效时间的延长而增加,IMC层的生长基本上符合抛物线规律,因此IMC层的长大受元素扩散控制;且两种无铅焊点处IMC层的生长速率常数相近,但Sn-0.7Cu焊料中Sn的晶粒尺寸较Sn-3Ag-0.5Cu中的大;长期时效后,在试样的IMC层内发现有孔洞产生.     

Effect of thermal cycling on the growth of intermetallic compounds at the Sn-Zn-Bi-In-P lead-free solder/Cu interface

The low-temperature Sn-9Zn-1.5Bi-0.5In-0.01P lead-free solder alloy is used to investigate the intermetallic compounds (IMCs) formed between solder and Cu substrates during thermal cycling. Metallographic observation, scanning electron microscopy, transmission electron microscopy, and electron diffraction analysis are used to study the IMCs. The γ-Cu₅Zn₈ IMC is found at the Sn-9Zn-1.5Bi-0.5In-0.01P/Cu interface. The IMC grows slowly during thermal cycling. The fatigue life of the Sn-9Zn-1.5Bi-0.5In-0.01P solder joint is longer than that of Pb-Sn eutectic solder joint because the IMC thickness of the latter is much greater than that of the former. Thermodynamic and diffusivity calculations can explain the formation of γ-Cu₅Zn₈ instead of Cu-Sn IMCs. The growth of IMC layer is caused by the diffusion of Cu and Zn elements. The diffusion coefficient of Zn in the Cu₅Zn₈ layer is determined to be 1.10×10⁻¹² cm²/sec. A Zn-rich layer is found at the interface, which can prevent the formation of the more brittle Cu-Sn IMCs, slow down the growth of the IMC layer, and consequently enhance the fatigue life of the solder joint.     

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.     

Microstructure and shear strength evolution of Sn-Ag-Cu solder bumps during aging at different temperatures

Flip-chip devices with Sn-3.8Ag-0.7Cu solder on electroless Ni (EN) without immersion Au were studied after aging at different temperatures. The (Cu,Ni)₆Sn₅ intermetallics (IMCs) growth was volume diffusion controlled and Kirkendall voids were found in the Ni₃P layer even at the initial stage of high-temperature aging due to the faster diffusion of Ni in the Ni₃P layer via its column structure boundaries. The Ag₃Sn IMCs were distributed in the bulk solder, existing as plate- or lamella-like phases or as small particles around the β-Sn dendrites, and the (Cu,Ni)₆Sn₅ IMCs existed as facet-like phases. The plate- and lamella-like Ag₃Sn phases break up into small parts and these broken parts, together with small Ag₃Sn particles, coarsen into pebble-like phases during high-temperature aging. Shear tests showed that all the solder bumps fractured in the bulk solder. The shear strength of solder bumps decreases at the initial stage of aging at 150°C and 175°C, and the strength degradation during aging may be caused by the coarsening of small Ag₃Sn particles.     

Effects of microstructural evolution and intermetallic layer growth on shear strength of ball-grid-array Sn-Cu solder joints

The shear strength of ball-grid-array (BGA) solder joints on Cu bond pads was studied for Sn-Cu solder containing 0, 1.5, and 2.5 wt.% Cu, focusing on the effect of the microstructural changes of the bulk solder and the growth of intermetallic (IMC) layers during soldering at 270°C and aging at 150°C. The Cu additions in Sn solder enhanced both the IMC layer growth and the solder/IMC interface roughness during soldering but had insignificant effects during aging. Rapid Cu dissolution from the pad during reflow soldering resulted in a fine dispersion of Cu₆Sn₅ particles throughout the bulk solder in as-soldered joints even for the case of pure Sn solder, giving rise to a precipitation hardening of the bulk solder. The increased strength of the bulk solder caused the fracture mode of as-soldered joints to shift from the bulk solder to the solder/IMC layer as the IMC layer grew over a critical thickness about 1.2 m for all solders. The bulk solder strength decreased rapidly as the fine Cu₆Sn₅ precipitates coarsened during aging. As a consequence, regardless of the IMC layer thickness and the Cu content of the solders, the shear strength of BGA solder joints degraded significantly after 1 day of aging at 150°C and the shear fracture of aged joints occurred in the bulk solder. This suggests that small additions of Cu in Sn-based solders have an insignificant effect on the shear strength of BGA solderjoints, especially during system use at high temperatures.     

Influence of Dopant on Growth of Intermetallic Layers in Sn-Ag-Cu Solder Joints

The interfacial interaction between Cu substrates and Sn-3.5Ag-0.7Cu-xSb (x = 0, 0.2, 0.5, 0.8, 1.0, 1.5, and 2.0) solder alloys has been investigated under different isothermal aging temperatures of 100°C, 150°C, and 190°C. Scanning electron microscopy (SEM) was used to measure the thickness of the intermetallic compound (IMC) layer and observe the microstructural evolution of the solder joints. The IMC phases were identified by energy-dispersive x-ray spectroscopy (EDX) and x-ray diffractometry (XRD). The growth of both the Cu₆Sn₅ and Cu₃Sn IMC layers at the interface between the Cu substrate and the solder fits a power-law relationship with the exponent ranging from 0.42 to 0.83, which suggests that the IMC growth is primarily controlled by diffusion but may also be influenced by interface reactions. The activation energies and interdiffusion coefficients of the IMC formation of seven solder alloys were determined. The addition of Sb has a strong influence on the growth of the Cu₆Sn₅ layer, but very little influence on the formation of the Cu₃Sn IMC phase. The thickness of the Cu₃Sn layer rapidly increases with aging time and temperature, whereas the thickness of the Cu₆Sn₅ layer increases slowly. This is probably due to the formation of Cu₃Sn at the interface between two IMC phases, which occurs with consumption of Cu₆Sn₅. Adding antimony to Sn-3.5Ag-0.7Cu solder can evidently increase the activation energy of Cu₆Sn₅ IMC formation, reduce the atomic diffusion rate, and thus inhibit excessive growth of Cu₆Sn₅ IMCs. This study suggests that grain boundary pinning is one of the most important mechanisms for inhibiting the growth of Cu₆Sn₅ IMCs in such solder joints when Sb is added.     

Growth of an intermetallic compound layer with Sn-3.5Ag-5Bi on Cu and Ni-P/Cu during aging treatment

Growth kinetics of intermetallic compound (IMC) layers formed between the Sn-3.5Ag-5Bi solder and the Cu and electroless Ni-P substrates were investigated at temperatures ranging from 70°C to 200°C for 0–60 days. With the solder joints between the Sn-Ag-Bi solder and Cu substrates, the IMC layer consisted of two phases: the Cu₆Sn₅ (η phase) adjacent to the solder and the Cu₃Sn (ε phase) adjacent to the Cu substrate. In the case of the electroless Ni-P substrate, the IMC formed at the interface was mainly Ni₃Sn₄, and a P-rich Ni (Ni₃P) layer was also observed as a by-product of the Ni-Sn reaction, which was between the Ni₃Sn₄ IMC and the electroless Ni-P deposit layer. With all the intermetallic layers, time exponent (n) was approximately 0.5, suggesting a diffusion-controlled mechanism over the temperature range studied. The interface between electroless Ni-P and Ni₃P was planar, and the time exponent for the Ni₃P layer growth was also 0.5. The Ni₃P layer thickness reached about 2.5 μm after 60 days of aging at 170°C. The activation energies for the growth of the total Cu-Sn compound layer (Cu₆Sn₅ + Cu₃Sn) and the Ni₃Sn₄ IMC were 88.6 kJ/mol and 52.85 kJ/mol, respectively.     

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.