Intermetallic reactions in reflowed and aged Sn-9Zn solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflowing of Sn-9Zn solder ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the surface-finished Au and Ag film dissolved rapidly and reacted with the Sn-9Zn solder to form a γ₃-AuZn₄/γ-Au₇Zn₁₈ intermetallic double layer and ε-AgZn₆ intermetallic scallops, respectively. The growth of γ₃-AuZn₄ is prompted by further aging at 100°C through the reaction of γ-Au₇Zn₁₈ with the Zn atoms dissolved from the Zn-rich precipitates embedded in the β-Sn matrix of Sn-9Zn solder BGA with Au/Ni/Cu pads. No intermetallic compounds can be observed at the solder/pad interface of the Sn-9Zn BGA specimens aged at 100°C. However, after aging at 150°C, a Ni₄Zn₂₁ intermetallic layer is formed at the interface between Sn-9Zn solder and Ni/Cu pads. Aging the immersion Ag packages at 100°C and 150°C caused a γ-Cu₅Zn₈ intermetallic layer to appear between ε-AgZn₆ intermetallics and the Cu pad. The scallop-shaped ε-AgZn₆ intermetallics were found to detach from the γ-Cu₅Zn₈ layer and float into the solder ball. Accompanied with the intermetallic reactions during the aging process of reflowed Sn-9Zn solder BGA packages with Au/Ni/Cu and Ag/Cu pads, their ball shear strengths degrade from 8.6 N and 4.8 N to about 7.2 N and 2.9 N, respectively.     

Intermetallic reactions in Sn-8Zn-20In solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflow process of Sn-8Zn-20In solder joints in the ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the Au and Ag thin films react with liquid solder to form γ₃-AuZn₄/γ-Au₇Zn₁₈ and ε-AgZn₆ intermetallics, respectively. The γ₃/γ intermetallic layer is prone to floating away from the solder/Ni interface, and the appearance of any interfacial intermetallics cannot be observed in the Au/Ni surface finished Sn-8Zn-20In packages during further aging treatments at 75°C and 115°C. In contrast, ε-CuZn₅/γ-Cu₅Zn₈ intermetallics are formed at the aged Sn-8Zn-20In/Cu interface of the immersion Ag BGA packages. Bonding strengths of 3.8N and 4.0N are found in the reflowed Sn-8Zn-20In solder joints with Au/Ni/Cu and Ag/Cu pads, respectively. Aging at 75°C and 115°C gives slight increases of ball shear strength for both cases.     

Interfacial Reactions of Sn-8wt.%Zn-3wt.%Bi Solder with Cu,Ag, and Ni Substrates

Sn-Zn-Bi alloys are promising Pb-free solders. Interfacial reactions between the Sn-8wt.%Zn-3wt.%Bi (Sn-13.80at.%Zn-1.62at.%Bi) alloy and the Cu, Ag, and Ni substrates are examined. Two different kinds of substrates, the bulk plate and the electroplating layer, are used, and the reactions are carried out at 250°C and 220°C. Although the Zn content is only 13.8 at.%, two Zn-Cu compounds, γ-Cu₅Zn₈ and ε-CuZn₅ phases, are formed in the Sn-13.80at.%Zn-1.62at.%Bi/Cu couples. The ε-CuZn₅ phase is scallop shaped, and the γ-Cu₅Zn₈ phase is planar. In the Sn-13.80at.%Zn-1.62at.%Bi/Ag couples, three Zn-Ag compounds are observed, and they are ε-AgZn₃, γ-Ag₅Zn₈, and ζ-AgZn phases. In the Sn-13.80at.%Zn-1.62at.%Bi/Ni couples, a Zn-Ni compound, γ-Ni₅Zn₂₁ phase, is formed. Similar results are found in the couples prepared with an electroplating layer: the reaction phases are the same, but the growth rates are different.     

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.     

Effects of Co Alloying and Size on Solidification and Interfacial Reactions in Sn-57 wt.%Bi-(Co)/Cu Couples

Solidification and interfacial reactions in Sn-57 wt.%Bi-(Co)/Cu couples are investigated. The addition of 0.05 wt.% Co and 0.5 wt.% Co and changes between 2 g and 20 mg solder sizes have no significant effects on the undercooling of Sn-57 wt.%Bi solders. Both η-Cu₆Sn₅ and ε-Cu₃Sn phases are formed in Sn-57 wt.%Bi/Cu couples reacted at 80°C, 100°C, and 100°C, whereas only η-Cu₆Sn₅ is formed at 160°C. The formation of ε-Cu₃Sn is suppressed and only η-Cu₆Sn₅ is found in the couple with 0.05 wt.% Co and 0.5 wt.% Co addition in Sn-57 wt.%Bi solder. Both the growth rate of η-Cu₆Sn₅ and the dissolution rate of the Cu substrate increase with Co addition. The morphology of η-Cu₆Sn₅ is also altered with Co addition, becoming a porous structure with solder trapped in the voids.     

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.     

The adhesion strength of A lead-free solder hot-dipped on copper substrate

Eutectic Sn-Zn-Al solder alloy was used [composition: 91Sn-9(5Al-Zn)] to investigate the effects of dipping parameters such as the temperature, rate and time dipping on the adhesion strength between solder and substrate using dimethylammonium chloride (DMAHCl) flux. The optimum conditions for the highest adhesion strength (about 8 MPa) were determined as dipping at 350°C, and a rate of 10.8∼11.8 mm/s for 5∼7.5 min. A poor solder coating was obtained as dipped at 250°C. Some defects by non-wetting were found as dipped at a slow rate (slower than 8.2 mm/s). Quite different from the most tin-based solders for copper substrate, γ-Cu₅Zn₈ intermetallic compound particles were found by x-ray diffraction (XRD) analysis at the interface of solder and substrate as dipped at 300°C after pull-off test by etching out the unreacted solder layer. The morphology of the intermetallic compound formed was observed by scanning electron microscopy (SEM). The elements of Al (near Cu), Zn (near Sn) are enriched at the interface of solder and copper substrate as determined by the line scanning and mapping analysis.     

Mechanisms for interfacial reactions between liquid Sn-3.5Ag solders and cu substrates

Intermetallic compounds formed during the soldering reactions between Sn-3.5Ag and Cu at temperatures ranging from 250°C to 375°C are investigated. The results indicate that scallop-shaped η-Cu₆(Sn_0.933 Ag_0.007)₅ intermetallics grow from the Sn-3.5Ag/Cu interface toward the solder matrix accompanied by Cu dissolution. Following prolonged or higher temperature reactions, ɛ-Cu₃ (Sn_0.996 Ag_0.004) intermetallic layers appear behind the Cu₆(Sn_0.933 Ag_0.007)₅ scallops. The growth of these interfacial intermetallics is governed by a kinetic relation: ΔX=tⁿ, where the n values for η and ɛ intermetallics are 0.75 and 0.96, respectively. The mechanisms for such nonparabolic growth of interfacial intermetallics during the liquid/solid reactions between Sn-3.5Ag solders and Cu substrates are probed.     

Interfacial Reaction Between Cu Substrates and Zn-Al Base High-Temperature Pb-Free Solders

Chemical reactions between Cu substrates and Zn-Al high-temperature solder alloys, Zn-4Al and Zn-4Al-1Cu (mass%), at temperatures ranging from 420°C to 530°C were experimentally investigated by a scanning electron microscope using backscattered electrons (SEM-BSE) and an electron probe microanalyzer (EPMA). Intermediate phases (IMPs), β(A2) or β′(B2), γ(D8₂), and ε(A3) phases formed and grew during the soldering and aging treatments. The consumption rate of the IMP for Cu substrates is described by the square root of t in both the alloys, while the additional Cu in the molten Zn-Al alloy slightly suppresses the consumption of Cu substrates. The growth of IMPs during soldering treatment is controlled by the volume diffusion of constituent elements, and its activation energy increases in the order of Q _ε < Q _γ < Q _β. In view of the aging process, the growth of IMPs is considered to be controlled by the volume diffusion. In particular, the layer thickness of γ rapidly grows over 200°C, although the thickness of the β layer grows very slowly.     

Intermetallic compounds and adhesion strength between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder and unfluxed Cu substrate

The intermetallic compounds (IMCs) formed at the interface between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder alloy and unfluxed Cu substrate have been investigated by x-ray diffraction, optical microscopy, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The melting point and melting range of the Sn-9Zn-1.5Ag-0.5Bi solder alloy are determined as 195.9°C and 10°C, respectively, by differential scanning calorimetry (DSC). Cu₆Sn₅ and Cu₅Zn₈ IMCs are formed between the Sn-9Zn-1.5Ag-0.5Bi/unfluxed Cu substrate wetted at 250°C for 10 sec. The interfacial adhesion strength changes from 10.27±0.68 MPa to 8.58±0.59 MPa when soldering time varies from 10 sec to 30 sec at 250°C.     

The thermal property of lead-free Sn-8.55Zn-1Ag-XAl solder alloys and their wetting interaction with Cu

The wetting behaviors between the quaternary Sn-8.55Zn-1Ag-XAl solder alloys and Cu have been investigated with the wetting balance method. The Al contents, x, of the quaternary solder alloys investigated were 0.01–0.45 wt.%. The results of differential scanning calorimeter (DSC) analysis indicate that the solders exhibit a solid-liquid coexisting range of about 7–10°C. The solidus temperature of the quaternary Sn-8.55Zn-1Ag-XAl solder alloys is about 198.2°C, while the liquidus temperatures are 205–207°C. The experimental results showed that the wettability of the Sn-8.55Zn-1Ag-XAl solder alloys is improved by the addition of Al. The mean maximum wetting force of the solders with Cu is within 0.75–1.18 mN and the mean wetting time is around 1.0–1.1 sec, better than the ∼1.3 sec of eutectic Sn-9Zn and Sn-8.55Zn-1Ag solder alloys. The addition of Al also depresses the formation of ε-Ag-Zn compounds at the interface between Sn-8.55Zn-1Ag-XAl solders and copper.     

Morphological stability of solder reaction products in flip chip technology

We have studied two kinds of solder reactions between eutectic SnPb and Cu. The first is wetting reaction above the melting point of the solder, and the second is solid state aging below the melting point of the solder. In wetting reaction, the intermetallic compound (IMC) formation has a scallop-type morphology. There are channels between the scallops. In solid state aging, the IMC formation has a layer-type morphology. There are no channels but grain boundaries between the IMC grains. Why scallops are stable in wetting reactions has been an unanswered question of fundamental interest. We have confirmed that the scallop-type morphology is stable in wetting reaction by re-wetting the layer-type IMC by molten eutectic SnPb solder. In less than 1 min, a layer-type Cu₆Sn₅ is transformed back to scallops by the molten solder at 200 C. In analyzing these reactions, we conclude that the scallop-type morphology is thermodynamically stable in wetting reaction, but the layer-type morphology is thermodynamically stable in solid state aging, due to minimization of interfacial and grain boundary energies.     

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.     

Wetting interaction between Sn-Zn-Ag solders and Cu

The wetting interaction of Sn-(7.1–9)Zn-(0–3)Ag solders with Cu was investigated from 230°C to 300°C. The wetting time, wetting forces, and activation energy of the wetting reaction were studied. The wetting time decreases with increasing temperature and increases with Ag content. The wetting force exhibits a disproportional correlation to temperature rise, while no trend was observed with respect to Ag content. The wetting behavior was ascribed to the interaction between Cu and Zn. The AgZn₃ compound was formed at the interface when the solder contains 0.3% Ag and above, while it was formed within the bulk solder at 2% Ag and above.     

Effects of Ce and La Additions on the Microstructure and Mechanical Properties of Sn-9Zn Solder Joints

The effects of rare-earth elements on the microstructure and mechanical properties of Sn-9Zn alloys and solder joints in ball grid array packages with Ni/Au(ENIG) surface finishes have been investigated. Metallographic observations showed that (Ce_0.8Zn_0.2)Sn₃ and (La_0.9Zn_0.1)Sn₃ intermetallic compounds appeared in the solder matrix of Sn-9Zn-0.5Ce and Sn-9Zn-0.5La alloys, respectively. Both fiber- and hillock-shaped tin whiskers were inhibited in the Sn-9Zn-0.5Ce solder, while tin fibers were still observed on the surface of oxidized (La_0.9Zn_0.1)Sn₃ intermetallics in Sn-9Zn-0.5La after air exposure at room temperature. Mechanical testing indicated that the tensile strength of Sn-9Zn alloys doped with Ce and La increased significantly, and the elongation decreased, in comparison with the undoped Sn-9Zn. The bonding strengths of the as-reflowed Sn-9Zn-0.5Ce and Sn-9Zn-0.5La solder joints were also improved. However, aging treatment at 100°C and 150°C caused degradation of ball shear strength in all specimens. During the reflowing and aging processes, AuZn₈ intermetallic phases appeared at the interfaces of all solder joints. In addition, Zn-rich phases were observed to migrate from the solder matrix to the solder/pad interfaces of the aged specimens.     

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.     

Intermetallic formation in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with immersion Ag surface finish

The intermetallic compounds formed in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Ag/Cu pads are investigated. After reflow, scallop-shaped η-Cu₆Sn₅ and continuous planar η-(cu_0.9Ni_0.1)₆Sn₅ intermetallics appear at the interfaces of the Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder joints, respectively. In the case of the Sn3Ag0.5Cu specimens, an additional ε-Cu₃Sn intermetallic layer is formed at the interface between the η-Cu₆Sn₅ and Cu pads after aging at 150°C, while the same type of intermetallic formation is inhibited in the Sn3Ag0.5Cu0.06Ni0.01Ge packages. In addition, the coarsening of Ag₃Sn precipitates also abates in the solder matrix of the Sn3Ag0.5Cu0.06Ni0.01Ge packages, which results in a slightly higher ball shear strength for the specimens.     

Interfacial Microstructure Evolution Between Sn-Zn Solders and Ag Substrate During Solid-State Annealing

In this study, solid-state interfacial reactions between Ag and Sn-Zn alloys with varying Zn content (0.1 wt.% to 9 wt.%) were investigated at 170°C. The reaction couples were prepared by electroplating Ag on the Sn-Zn alloy to avoid dissolution of Ag into the molten solder during soldering. The Zn content greatly influenced the reaction products and the interfacial microstructures. When the Zn content was less than 4 wt.%, Ag₃Sn and AgZn layers were simultaneously formed. Notably, Zn could actively diffuse through the Ag₃Sn layer and react with Ag to form the AgZn phase. With the proceeding reaction, small α-Ag particulates were produced within the AgZn phase. With 9 wt.% Zn, the dominant reactions formed Ag₅Zn₈ and AgZn layers. The interfacial microstructure evolved significantly with reaction time. Interface instability due to Zn depletion in the solder resulted in massive spalling of the Ag₅Zn₈ layer. The Ag₃Sn phase was then produced next to the AgZn layer. Moreover, another reaction couple, Sn-9 wt.%Zn/Sn(15 μm)/Ag, was prepared, in which fast interdiffusion between Zn and Ag across the Sn layer was demonstrated due to the strong chemical affinity of Zn.     

The formation and growth of intermetallic compounds in Sn-Zn and Sn-Zn-Al solder with Ni/Au surface finish bond pad

In this study, we used microstructure evolution and electron microprobe analysis (EPMA) to investigate the interfacial reactions in Sn-Zn and Sn-Zn-Al solder balls with Au/Ni surface finish ball-grid-array (BGA) bond pad over a period of isothermal aging at 150°C. During reflow, Au dissolved into the solder balls and reacted with Zn to form γ-Au₃Zn₇ and γ₂-AuZn₃. As aging progressed, γ and γ₂ transformed into γ₃-AuZn₄. Finally, Zn precipitated out next to γ₃-AuZn₄. The Zn reacted with the Ni layer to form Ni₅Zn₂₁. A thin layer (Al, Au, Zn) intermetallic compound (IMC) formed at the interface of the Sn-Zn-Al solder balls, inhibiting the reaction of Ni with Zn. Even after 50 days of aging, no Ni₅Zn₂₁ was observed. Instead, fine (Al, Au, Zn) particles similar to Al₂ (Au, Zn) in composition formed and remained stable in the solder. The lower ball shear strength corresponded with the brittle fracture morphology in Sn-Zn-Al solder ball samples.     

Morphology of intermetallic compounds formed between lead-free Sn-Zn based solders and Cu substrates

The morphologies of intermetallic compounds formed between Sn-Zn based solders and Cu substrates were investigated in this study. The investigated solders were Sn-9Zn, Sn-8.55Zn-0.45Al, and Sn-8.55Zn-0.45Al-0.5Ag. The experimental results indicated that the Sn-9Zn solder formed Cu₅Zn₈ and CuZn₅ compounds on the Cu substrate, while the Al-containing solders formed the Al_4.2Cu_3.2Zn_0.7 compound. The addition of Ag to the Sn-8.55Zn-0.45Al solder resulted in the formation of the AgZn₃ compound at the interface between the Al_4.2Cu_3.2Zn_0.7 compound and the solder. Furthermore, it was found that the cooling rate of the specimen after soldering had an effect on the quantity of AgZn₃ compound formed at the interface. The AgZn₃ compound formed with an air-cooling condition exhibited a rougher surface and larger size than with a water-quenched condition. It was believed that the formation of the AgZn₃ compound at the interface occurs through heterogenous nucleation during solidification.