Intermetallics Evolution in Sn-3.5Ag Based Lead-Free Solder Matrix on an OSP Cu Finish

The 0.2Co + 0.1Ni dual additives were used to dope a Sn-3.5Ag solder matrix to modify the alloy microstructure and the solder joint on an organic solderability preservative (OSP) Cu pad. The refined microstructure of the Sn-3.5Ag-0.2Co-0.1Ni solder alloy or the reduced β-Sn size was attributed to the depressed undercooling achieved by the Co-Ni addition. After soldering on the OSP Cu pad, a large Ag₃Sn plate was formed at the Sn-3.5Ag/OSP solder joint, whereas it was absent at the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joints. With isothermal aging at 150°C, large Ag₃Sn plates formed at the Sn-3.5Ag/OSP solder joint were still observed. A coarsened and dispersed Ag₃Sn phase was found in the solder joints with Co-Ni additions as well. Compared to Cu₆Sn₅, the (Co,Ni)Sn₂ intermetallic compound showed much lower microhardness values. However, (Co,Ni)Sn₂ hardness was comparable to that of the Ag₃Sn phase. Pull strength testing of Sn-3.5Ag-0.2Co-0.1Ni/OSP revealed slightly lower values than for Sn-3.5Ag/OSP during aging. Such results are thought be due to the phase transformation of (Co,Ni)Sn₂ to (Cu,Co,Ni)₆Sn₅.     

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.     

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.     

Reliability testing of WLCSP lead-free solder joints

The interfacial reactions of solder joints between Sn-4Ag-0.5Cu solder ball and a couple of presoldered pastes (Sn-7Zn-Al(30ppm) and Sn-3Ag-0.5Cu) were investigated in wafer-level chip-scale package (WLCSP). After appropriate surface mount technology reflow processes on printed circuit boards with a Cu/OSP (organic solderability preservative) surface finish, samples were subjected to 150°C high-temperature storage (HTS) for 1,000 h of aging or 1,000 cycles of a thermal cycling test (TCT). Sequentially, cross-section analysis is scrutinized by scanning electron microscopy/energy dispersive spectrometry and energy probe microanalysis to observe metallurgical evolution in the interface and solder buck itself. It was found that the degradation of the joint shear strength after TCT is more pronounced than that of the shear strength after HTS. Fracture surface analyses of the shear tests show that the degradation of the joint strength for HTS is solely due to the influence of the interfacial IMC grain growth, while the shear strength degradation for TCT is mainly due to the coefficient thermal expansion mismatch from the thermal cycling at the chip-solder interface and can lead to the occurrence of the crack.     

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.     

Interfacial microstructure and bonding strength of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder BGA packages with immersion Ag surface finish

Although it has been verified that tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder, no detailed studies have been conducted on interfacial reactions and mechanical properties of Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with an immersion Ag surface finish. The intermetallic compounds formed during the reflow and aging of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder ball grid array (BGA) packages were investigated. Because more heterogeneous nucleation sites, provided by CeSn₃ intermetallics and Zn atoms, formed in the Sn-3Ag-0.5Cu-0.5Ce-xZn solder matrix, and Cu and Zn have a stronger affinity than Cu and Sn, the Cu-Sn intermetallics growth in Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with Ag/Cu pads was suppressed. The 0.2% Zn addition for inhibiting rapid whisker growth in RE-doped Sn-Ag-Cu solder joints is more appropriate than 0.5 wt.% additions, as excess Zn addition causes poor oxidation resistance and inferior bonding strength.     

Effect of Ag and Cu Concentrations on the Creep Behavior of Sn-Based Solders

The creep behavior of Sn-1Ag-0.5Cu, Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu ball grid array (BGA) solder balls and 99.99% pure polycrystalline bulk Sn was studied using impression creep and related to the microstructure. Sn-Ag-Cu solders generally consist of primary dendrites/grains of β-Sn, and a eutectic microconstituent comprising fine Ag₃Sn and Cu₆Sn₅ particles in β phase. With increasing concentrations of Ag and Cu in the alloy, the proportion of the eutectic microconstituent in relation to the primary β phase increases. In pure Sn and Sn-1Ag-0.5Cu, the β grains form the continuous matrix, whereas in Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu, the eutectic microconstituent forms a continuous network around the β grains, which form isolated islands within the eutectic. The steady-state creep behavior of the alloys was dominated by the response of the continuous microstructural constituent (β-Sn or solid solution β for pure Sn and Sn-1Ag-0.5Cu, and the eutectic microconstituent for Sn-2.5Ag-0.5Cu and Sn-4Ag-0.5Cu). In general, the steady-state creep rate decreased with increasing alloy content, and in particular, the volume fraction of Ag₃Sn and Cu₆Sn₅ precipitates. The rate-limiting creep mechanism in all the materials investigated here was core diffusion controlled dislocation climb. However, subtle changes in the stress exponent n and activation energy Q were observed. Pure Sn shows n = 5, Q = 42 kJ/mol, Sn-1Ag-0.5Cu shows n = 5, Q = 61 kJ/mol, whereas both Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu show n = 6 and Q = 61 kJ/mol. Rationalizations for the observed changes of n and Q are provided, based on the influence of the microstructure and the solute concentrations.     

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.     

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.     

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.     

Interfacial microstructure evolution in Pb-free solder systems

The Sn-3.5Ag and Sn-3.0Ag-0.5Cu ball-grid-array solder balls bonded onto Ni/Au metallization exhibited different interfacial morphology after both wetting and solid-state reactions. In contrast to the eutectic-SnPb solder system, both Pb-free systems showed higher solder-ball shear strength after annealing. Reprecipitation of Au as (Au,Ni)Sn₄ at the interface, as shown in the eutectic-SnPb solder system, was not observed in both Pb-free solder systems. Instead, Ni₃Sn₄ and Cu-Sn-Ni-Au intermetallic compounds (IMCs) were found in the SnAg and SnAgCu systems, respectively. In the SnAgCu system, a thick, acicular-Cu-Sn-Ni IMC formed after wetting, but a faceted-Cu-Sn-Ni-Au phase was found with longer annealing. The growth of this interfacial phase in the Sn-3.0Ag-0.5Cu solder system was also slightly inhibited by the addition of Cu, with a formation energy of about 200 kJ/mol.     

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.     

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.     

Effect of Ionization Characteristics on Electrochemical Migration Lifetimes of Sn-3.0Ag-0.5Cu Solder in NaCl and Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> Solutions

Anodic dissolution characteristics and electrochemical migration (ECM) behavior of Sn-3.0Ag-0.5Cu solder in NaCl and Na₂SO₄ solutions were investigated using anodic polarization tests and water drop tests (WDT). The ECM lifetime of Sn-3.0Ag-0.5Cu solder in NaCl solution (42.4 s) was longer than that in Na₂SO₄ solution (34.8 s). The pitting potential of Sn-3.0Ag-0.5Cu solder in NaCl solution (135 mV, SCE) was higher than that in Na₂SO₄ solution (−367 mV, SCE). The passivity film (SnO₂) formed on Sn-3.0Ag-0.5Cu solder during WDTs in NaCl solution was thicker than that formed in Na₂SO₄ solution. Therefore, the longer ECM lifetime of Sn-3.0Ag-0.5Cu solder in NaCl solution than in Na₂SO₄ solution can be attributed to the higher pitting potential in the NaCl solution, which is ascribed to the formation of a thicker passivity film (SnO₂) in the former. It was confirmed that microelements such as Ag and Cu do not take part in ECM because they form chemically stable intermetallic compounds with Sn. We believe that Sn is the only element that contributes to ECM, and dissolution of Sn at the anode is possibly the rate-determining step of ECM of Sn-3.0Ag-0.5Cu solder.     

Interfacial Reactions of Sn-3.5Ag-<Emphasis Type="Italic">x</Emphasis>Zn Solders and Cu Substrate During Liquid-State Aging

The effects of Zn (1 wt.%, 3 wt.%, and 7 wt.%) additions to Sn-3.5Ag solder and various reaction times on the interfacial reactions between Sn-3.5Ag-xZn solders and Cu substrates a during liquid-state aging were investigated in this study. The composition and morphological evolution of interfacial intermetallic compounds (IMCs) changed significantly with the Zn concentration and reaction time. For the Sn-3.5Ag-1Zn/Cu couple, CuZn and Cu₆Sn₅ phases formed at the interface. With increasing aging time, the Cu₆Sn₅ IMC layer grew thicker, while the CuZn IMC layer drifted into the solder and decomposed gradually. Cu₅Zn₈ and Ag₅Zn₈ phases formed at the interfaces of Sn-3.5Ag-3Zn/Cu and Sn-3.5Ag-7Zn/Cu couples. With increasing reaction time, the Cu₅Zn₈ layer grew and Cu atoms diffused from the substrate to the solder, which transformed the Ag₅Zn₈ to (Cu,Ag)₅Zn₈. The Cu₆Sn₅ layer that formed between the Cu₅Zn₈ layer and Cu was much thinner at the Sn-3.5Ag-7Zn/Cu interface than at the Sn-3.5Ag-3Zn/Cu interface. Additionally, we measured the thickness of interfacial IMC layers and found that 3 wt.% Zn addition to the solder was the most effective for suppressing IMC growth at the interfaces.     

Effect of cooling rate on growth of the intermetallic compound and fracture mode of near-eutectic Sn-Ag-Cu/Cu pad: Before and after aging

Several near-eutectic solders of (1) Sn-3.5Ag, (2) Sn-3.0Ag-0.7Cu, (3) Sn-3.0Ag-1.5Cu, (4) Sn-3.7Ag-0.9Cu, and (5) Sn-6.0Ag-0.5Cu (in wt.% unless specified otherwise) were cooled at different rates after reflow soldering on the Cu pad above 250°C for 60 sec. Three different media of cooling were used to control cooling rates: fast water quenching, medium cooling on an aluminum block, and slow cooling in furnace. Both the solder composition and cooling rate after reflow have a significant effect on the intermetallic compound (IMC) thickness (mainly Cu₆Sn₅). Under fixed cooling condition, alloys (1), (3), and (5) revealed larger IMC thicknesses than that of alloys (2) and (4). Slow cooling produced an IMC buildup of thicker than 10 μm, while medium and fast cooling produced a thickness of thinner than 5 μm. The inverse relationship between IMC thickness and shear strength was confirmed. All the fast- and medium-cooled joints revealed a ductile mode (fracture surface was composed of the β-Sn phase), while the slow-cooled joints were fractured in a brittle mode (fracture surface was composed of Cu₆Sn₅ and Cu₃Sn phases). The effect of isothermal aging at 130°C on the growth of the IMC, shear strength, and fracture mode is also reported.     

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.     

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.     

Intermetallic growth kinetics for Sn-Ag, Sn-Cu, and Sn-Ag-Cu lead-free solders on Cu, Ni, and Fe-42Ni substrates

Soldering with the lead-free tin-base alloys requires substantially higher temperatures (∼235–250°C) than those (213–223°C) required for the current tin-lead solders, and the rates for intermetallic compound (IMC) growth and substrate dissolution are known to be significantly greater for these alloys. In this study, the IMC growth kinetics for Sn-3.7Ag, Sn-0.7Cu, and Sn-3.8Ag-0.7Cu solders on Cu substrates and for Sn-3.8Ag-0.7Cu solder with three different substrates (Cu, Ni, and Fe-42Ni) are investigated. For all three solders on Cu, a thick scalloped layer of η phase (Cu₆Sn₅) and a thin layer of ε phase (Cu₃Sn) were observed to form, with the growth of the layers being fastest for the Sn-3.8Ag-0.7Cu alloy and slowest for the Sn-3.7Ag alloy. For the Sn-3.8Ag-0.7Cu solder on Ni, only a relatively uniform thick layer of η phase (Cu,Ni)₆Sn₅ growing faster than that on the Cu substrate was found to form. IMC growth in both cases appears to be controlled by grain-boundary diffusion through the IMC layer. For the Fe-42Ni substrate with the Sn-3.8Ag-0.7Cu, only a very thin layer of (Fe,Ni)Sn₂ was observed to develop.     

Interfacial behaviors of Sn-Pb,Sn-Ag-Cu Pb-free and mixed Sn-Ag-Cu/Sn-Pb solder joints during electromigration

SnPb-SnAgCu mixed solder joints with Sn-Pb soldering Sn-Ag-Cu Pb-free components are inevitably occurred in the high reliability applications. In this study, the interfacial behaviors in Sn-37Pb and Sn-3.0Ag-0.5Cu mixed solder joints was addressed and compared with Sn-37Pb solder joints and Sn-3.0Ag-0.5Cu solder joints with the influence from isothermal aging and electromigration. Considering the difference on the melting point between Sn-3.0Ag-0.5Cu and Sn-37Pb solder, two mixed solder joints: partial mixing and full mixing between Sn-Pb and Sn-Ag-Cu solders were reached with the peak reflowing temperature of 190 and 250 °C, respectively. During isothermal aging, the intermetallic compound (IMC) layer increased with aging time and its growth was diffusion controlled. There was also no obvious affect from the solder composition on IMC growth. After electromigration with the current density of 2.0 × 10³ A/cm², Sn-37Pb solder joints showed the shortest lifetime with the cracks observed at the cathode for the stressing time < 250 h. In Sn-3.0Ag-0.5Cu Pb-free solder joints, current stressing promoted the growth of IMC layer at the interfaces, but the growing rate of IMC at the anode interface was far faster than that at the cathode interface. Therefore, there existed an obvious polarity effect on IMC growth in Sn-Ag-Cu Pb-free solder joints. After Sn-37Pb was mixed with Sn-3.0Ag-0.5Cu Pb-free solder, whether the partial mixing or the full mixing between Sn-Pb and Sn-Ag-Cu can obviously depress both the crack formation at the cathode side and the IMC growth at the anode.