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.     

Growth of intermetallic compounds in the Sn-9Zn/Cu joint

We have studied the microstructure of the Sn-9Zn/Cu joint in soldering at temperatures ranging from 230°C to 270°C to understand the growth of the mechanism of intermetallic compound (IMC) formation. At the interface between the Sn-9Zn solder and Cu, the results show a scallop-type ε-CuZn₄ and a layer-type γ-Cu₅Zn₈, which grow at the interface between the Sn-9Zn solder and Cu. The activation energy of scallop-type ε-CuZn₄ is 31 kJ/mol, and the growth is controlled by ripening. The activation energy of layer-type γ-Cu₅Zn₈ is 26 kJ/mol, and the growth is controlled by the diffusion of Cu and Zn. Furthermore, in the molten Sn-9Zn solder, the results show η-CuZn grains formed in the molten Sn-9Zn solder at 230°C. When the soldering temperature increases to 250°C and 270°C, the phase of IMCs is ε-CuZn₄.     

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.     

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.     

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.     

Interfacial microstructure between Sn-3Ag-xBi alloy and Cu substrate with or without electrolytic Ni plating

The microstructure of the interfacial phase of Sn-3Ag-xBi alloy on a Cu substrate with or without electrolytic Ni plating was evaluated. Bismuth additions into Sn-Ag alloys do not affect interfacial phase formations. Without plating, η-Cu₆Sn₅/ε-Cu₃Sn interfacial phases developed as reaction products in the as-soldered condition. The η-phase Cu₆Sn₅ with a hexagonal close-packed structure grows about 1-μm scallops. The ε-phase Cu₃Sn with an orthorhombic structure forms with small 100-nm grains between η-Cu₆Sn₅ and Cu. For Ni plating, a Ni₃Sn₄ layer of monoclinic structure formed as the primary reaction product, and a thin η-Ni₃Sn₂ layer of hexagonal close-packed structure forms between the Ni₃Sn₄ and Ni layer. In the Ni layer, Ni-Sn compound particles of nanosize distribute by Sn diffusion into Ni. On the total thickness of interfacial reaction layers, Sn-3Ag-6Bi joints are thicker by about 0.9 μm for the joint without Ni plating and 0.18 μm for the joint with Ni plating than Sn-3Ag joints, respectively. The thickening of interfacial reaction layers can affect the mechanical properties of strength and fatigue resistance.     

Effect of Cu Thickness on the Evolution of the Reaction Products at the Sn-9wt.%Zn Solder/Cu Interface During Reflow

Interfacial reactions between Sn-9wt.%Zn solder and Cu substrates at 230°C were investigated. The substrate thickness was found to have noticeable effects on the evolution of the reaction products formed at the solder/Cu interface. The CuZn₅ and Cu₅Zn₈ phases were formed at the early stage of reflow, regardless of the Cu thickness, while, with increasing reflow time, the two phases displayed different growth behaviors on the Cu substrates with various thicknesses. For the thicker Cu substrates with a thickness of 6 μm, 10 μm, and 0.5 mm, CuZn₅ disappeared but Cu₅Zn₈ kept on growing after a longer reflow time. In contrast, for the thinner Cu substrates with a thickness less than 3 μm, Cu₅Zn₈ shrank with increasing reflow time but CuZn₅ grew dominantly. A different evolution of the grain morphology of CuZn₅ was also observed between the thicker and thinner Cu substrates. When the reflow time was increased, the CuZn₅ grains retained a rounded shape on the thinner Cu substrates; however, the grain structure became faceted on the thicker Cu substrates.     

Interfacial Reactions of Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Cu (<Emphasis Type="Italic">x</Emphasis> = 1, 4, 7, 10) Solders with Ni Substrates

This study investigates the effects of various reaction times and Cu contents on the interfacial reactions between Sn-9Zn-xCu alloys and Ni substrates. After aging at 255°C for 1 h to 3 h, the Ni₅Zn₂₁ and Cu₅Zn₈ phases formed at the interface of Sn-9Zn/Ni and Sn-9Zn-1wt.%Cu/Ni couples, respectively. The (Ni,Zn)₃Sn₄ phase was found in the Sn-9Zn-4wt.%Cu/Ni couple, and the (Cu,Ni)₆Sn₅ and Cu₆Sn₅ phases formed, respectively, in the Sn-9Zn-7wt.%Cu/Ni and Sn-9Zn-10wt.%Cu/Ni couples. As the reaction time was increased from 5 h to 24 h, the (Cu₅Zn₈ + Ni₅Zn₂₁) phases replaced the Cu₅Zn₈ phase to form in the Sn-9Zn-1wt.%Cu/Ni couple; the (Ni,Zn)₃Sn₄ phase formed in the Sn-9Zn-4wt.%Cu/Ni couple, and (CuZn + Cu₆Sn₅) formed in the Sn-9Zn-10wt.%Cu alloys. Experimental results indicate that intermetallic compound (IMC) formation in Sn-9Zn-xCu/Ni couples changes dramatically with reaction time and Cu content. The Sn-Zn-Ni, Sn-Cu-Ni, and Sn-Zn-Cu ternary isothermal sections greatly help us to understand the IMC evolutions in the Sn-9Zn-xCu/Ni couples.     

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 bismuth on the isothermal fatigue properties of Sn-3.5mass%Ag solder alloy

Sn-3.5mass%Ag eutectic solder is selected as a candidate base alloy for replacing the eutectic Sn-Pb, and the effect of bismuth (2, 5, 10mass%) on the fatigue life of bulk Sn-3.5mass%Ag eutectic at room temperature has been studied over the total strain range from 0.3 to 3 percent in tension-tension mode. Fatigue life is defined as the number of cycles at which the load decreases to a half of the initial value. The fatigue life dramatically decreases with increasing contents of bismuth and adding this element over 2% makes fatigue life shorter than that of tin-lead eutectic alloy. Tensile strength of the alloy significantly increases with an increase in bismuth contents due to solid solution hardening (<5%Bi) or dispersion strengthning of fine bismuth particles, while ductility of this system dramatically decreases with increasing bismuth contents. Fatigue life of these alloys depends on ductility obtained by tensile test. The fatigue life of Bi containing Sn-3.5%Ag alloys can be described by, (Δε_p/2D)·N _f ^0.59 =0.66 where N_f is fatigue life defined by number of cycles to one-half load reduction, Δε_p is the plastic strain range for initial cycles, D is the ductility as measured by reduction in area.     

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.     

Electrochemical Properties of Joints Formed Between Sn-9Zn-1.5Ag-1Bi Alloys and Cu Substrates in a 3.5 wt.% NaCl Solution

The electrochemical properties of the joints formed between Sn-9Zn-1.5Ag-1Bi alloys and Cu substrates in a 3.5 wt.% NaCl solution have been investigated by potentiodynamic polarization, X-ray diffraction, and scanning electron microscopy. For the Sn-9Zn-1.5Ag-1Bi/Cu joints in a 3.5 wt.% NaCl solution, corrosion current (I _corr), corrosion potential (E _corr) and corrosion resistance (R _p) are 2.46 × 10⁻⁶ A/cm², −1.18 V, and 7.54 × 10³ Ωcm², respectively. Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn are formed at the interface between the Sn-9Zn-1.5Ag-xBi solder alloy and Cu substrate. The corrosion products of ZnCl₂, SnCl₂ and ZnO are formed at the Sn-9Zn-1.5Ag-xBi/Cu joints after polarization in a 3.5 wt.% NaCl solution. Pits are also formed on the surface of the solder alloys.     

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.     

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.     

Mechanical properties and intermetallic compound formation at the Sn/Ni and Sn-0.7wt.%Cu/Ni joints

The Ni/Sn/Ni and Ni/Sn-0.7wt.%Cu/Ni couples are reacted at 200°C for various lengths of time. The tensile strengths of these annealed specimens are determined at room temperature. In addition, the interfacial reactions and fracture surfaces of the specimens are examined as well. These properties are important for the evaluation of the usage of Sn-0.7wt.%Cu lead-free solders, which has been not available in the literature. Only the Ni₃Sn₄ phase is formed at the Sn/Ni interface, but both the Cu₆Sn₅ and Ni₃Sn₄ phases are formed at the Sn-0.7wt.%Cu/Ni interface. The thickness of the intermetallic compound layers grows, while the joint strength decreases with longer reaction time. With a 1-h reaction at 200°C, the fracture surface is in the solder matrix for both of the two kinds of couples. Shifting toward the compound layer with longer reaction time, the fracture surface is in the Ni₃Sn₄ layer in the Sn/Ni couple and is at the interface between the Cu₆Sn₅ and Ni₃Sn₄ in the Sn-0.7wt.%Cu/Ni after reacting at 200°C for 240 h.     

Influence of interfacial reaction layer on reliability of chip-scale package joint from using Sn-37Pb and Sn-8Zn-3Bi solder

The microstructure of Sn-37Pb and Sn-8Zn-3Bi solders and the full strength of these solders with an Au/Ni/Cu pad under isothermal aging conditions were investigated. The full strengths tended to decrease as the aging temperature and time increased, regardless of the properties of the solders. The Sn-8Zn-3Bi had higher full strength than Sn-37Pb. In the Sn-37Pb solder, Ni₃Sn₄ compounds and irregular-shaped Pb-rich phase were embedded in a β-Sn matrix. The Ni₃Sn₄ compounds were observed at the interface between the solder and pad. The microstructure of the as-reflowed Sn-8Zn-3Bi solder mainly consists of the β-Sn matrix scattered with Zn-rich phase. Zinc first reacted with Au and then was transformed to the AuZn compound. With aging, Ni₅Zn₂₁ compounds were formed at the Ni layer. Finally, a Ni₅Zn₂₁ phase, divided into three layers, was formed with column-shaped grains, and the thicknesses of the layers were changed.     

Interfacial Reactions in Sn-0.7wt.%Cu/Ni-V Couples at 250°C

The Delco process is a major flip chip under-bump metallurgy process and its contact is soldered with the Ni-7wt.%V substrate; there are, however, only a few studies on the interfacial reactions between solders and Ni-V alloys. This study examines the interfacial reactions of the Sn-0.7wt.%Cu alloy with the Ni-7wt.%V, Ni-5wt.%V, and Ni-3wt.%V substrates at 250°C. It is found that the interfacial reactions between Sn-0.7wt.%Cu and Ni-V alloys are different from those between Sn-0.7wt.%Cu and pure Ni. In addition to the formation of the Cu₆Sn₅ phase, a new Sn-rich phase, denoted the Q phase, is found in the Ni-V substrate couples. Nucleation of the Ni₃Sn₄ phase is at a much earlier stage and the rates of consumption of Ni are much higher in Ni-V substrate couples than in Ni substrate couples. Knowledge of these different reactions is important for proper assessment of the flip chip products.     

Interfacial reactions in Ag-Sn/Cu couples

Interfacial reactions between Sn-3.5 wt.%Ag, Sn-25 wt.%Ag, and Sn-74 wt.%Ag alloys with Cu substrate at 240°C and 450°C have been studied here by examining the reaction couples. It is found that Sn is the fastest diffusion species among the three elements during the reaction, while Ag is the slowest. The reaction path is liquid/η/ɛ₁/Cu for the Sn-3.5 wt.%Ag/Cu couples reacted at 240°C. The paths are liquid/ɛ₁/δ/Cu, liquid/ɛ₁/δ/Cu, ɛ₂/ζ/ɛ₁/δ/Cu, for the Sn-3.5 wt.%Ag/Cu, Sn-25 wt.%Ag/Cu, and Sn-74 wt.%Ag/Cu couples at 450°C, respectively. These reaction paths are in agreement with the isothermal sections of the Ag-Sn-Cu ternary system at 240°C and 450°C. The isothermal sections are proposed based on the limited ternary phase equilibria data and the phase diagrams of its three constituent binary systems, Ag-Sn, Cu-Sn, and Ag-Cu.     

Three-dimensional analysis of the interface between an Sn-8wt.%Zn-3wt.%Bi solder and a substrate by using an angle-lapping method

The validity of application of the angle-lapping method to investigate the microstructure between an Sn-8wt.%Zn-3wt.%Bi Pb-free solder and an Auimmersed Ni-7.0%P plate or a Cu substrate was studied using transmission electron microscopy. The method enabled a three-dimensional analysis of the interface layers. The morphology of the Au layer was clarified as an intermetallic compound with Zn with numerous voids that looked like cracks spreading in all directions. Sn and Bi could diffuse into the interface layer only when the Ni-P plate was used, but Ni did not diffuse actively and formed a narrow interface layer. When a Cu substrate was used, Cu diffused, rather than Sn or Bi, and formed a relatively wide interface layer. These results were obtained with the angle-lapping method.     

Interfacial Reactions in Sn-Pb/Ni-8.0 at.%V Couples

The Ni-8.0 at.%V (Ni-7.0 wt.%V) substrate is an important diffusion barrier layer material in flip-chip technology. This study examines interfacial reactions in couples prepared using Ni-8.0 at.%V substrate and Sn-6.0 at.%Pb, Sn-27.6 at.%Pb, and Sn-83.8 at.%Pb solders, at temperatures between 210°C and 450°C. In the Sn-27.6 at.%Pb/Ni-8.0 at.%V and Sn-83.8 at.%Pb/Ni-8.0 at.%V couples, the reaction products are the Ni₃Sn₄ phase and a T phase with limited Pb solubility, being similar to those in the Sn/Ni-8.0 at.%V couples. However, the Ni₃Sn₄ phase is formed at an earlier stage and the T phase is formed later. The phase formation sequences are different from those in Sn/Ni-8.0 at.%V couples. In Sn-6.0 at.%Pb/Ni-8.0 at.%V couples, a “Pb-rich” phase is formed, in addition to the T phase and the Ni₃Sn₄ phase, and the T phase and Ni₃Sn₄ phase are formed almost simultaneously. Although Pb does not participate actively in the interfacial reactions, the phase formation sequences are changed when Pb alloys in the solder, due to the reduced Sn flux from the solder into the Ni-8.0 at.%V substrate.