Electromigration Study on Sn(Cu) Solder/Ni(P) Joint Interfaces

This study investigates the electromigration (EM) effect under a high current density (10⁴?A/cm²) on the different interfacial compound phases at Sn(Cu) solder/electroless nickel immersion gold (ENIG) interfaces. The interfacial Ni₃Sn₄ phase at the Sn-0.7?wt.%Cu/ENIG joint interface was quickly depleted after a short period (50?h) of current stressing. The inference drawn is that the Ni atoms in the Ni₃Sn₄ phase at the joint interface are likely forced out under current stressing; however, the ternary (Cu,Ni)₆Sn₅ compound effectively reduces the EM-driven Ni flux into the Sn bump; thus, a significantly lower Ni(P) consumption was observed at the Sn-1?wt.%Cu/ENIG interface. The EM-induced Ni(P) dissolution rates in the Sn-0.2?wt.%Cu/ENIG and Sn-1?wt.%Cu/ENIG cases were calculated to be 0.028?μm/h and 0.018?μm/h, respectively. In addition, significant EM-assisted Ni₃P formation was observed for the current-stressed Sn-0.2?wt.%Cu/ENIG and Sn-0.7?wt.%Cu/ENIG cases; however, for the Sn-1?wt.%Cu/ENIG case, formation of a Ni₃P layer was scarcely observed. Moreover, the initial (Cu,Ni)₆Sn₅ that formed at the interface appeared compact with a layer-type structure, which reduced the EM-driven Ni diffusion.     

Interfacial Reactions Between Pb-Free Solders and In/Ni/Cu Multilayer Substrates

This study investigates the interfacial reactions between Sn-3.0wt.% Ag-0.5wt.%Cu (SAC) and Sn-0.7wt.%Cu (SC) on In/Ni/Cu multilayer substrates using the solid–liquid interdiffusion bonding technique. Samples were reflowed first at 160°C, 180°C, and 200°C for various periods, and then aged at 100°C for 100 h to 500 h. The scalloped Cu₆Sn₅ phase was formed at the SAC/In/Ni/Cu and SC/In/Ni/Cu interfaces. When the reflowing temperatures were 160°C and 180°C, a ternary Ni-In-Sn intermetallic compound (IMC) was formed when the samples were further aged at 100°C. This ternary Ni-In-Sn IMC could be the binary Ni₃Sn₄ phase with extensive Cu and In solubilities, or the ternary Sn-In-Ni compound with Cu solubility, or even a quaternary compound. As the reflow temperature was increased to 200°C, only one Cu₆Sn₅ phase was formed at the solder/substrate interface with the heat treatment at 100°C for 500 h. Mechanical test results indicated that the formation of the Ni-In-Sn ternary IMC weakened the mechanical strength of the solder joints. Furthermore, the solid–liquid interdiffusion (SLID) technique in this work effectively reduced the reflow temperature.     

Interfacial reactions in the Sn-(Cu)/Ni,Sn-(Ni)/Cu,and Sn/(Cu,Ni) systems

Specimens with the Sn/Cu/Sn/Ni/Sn/Cu/Sn structure reacted at 200°C are prepared and examined. The Cu₆Sn₅ and Cu₃Sn phases are formed at the Sn/Cu interface, and the Cu₆Sn₅ and Ni₃Sn₄ phases at the Sn/Ni interface. The reaction path in the original Cu/Sn/Ni part of the specimen is Cu/Cu₃Sn/Cu₆Sn₅/Sn/Cu₆Sn₅/Ni₃Sn₄/Ni. The peculiar phenomenon of the Cu₆Sn₅ phase forming at both sides of the Sn phase is illustrated using the Sn-Cu-Ni phase diagram with a very wide compositional-homogeneity range of the Cu₆Sn₅ phase. Interfacial reactions at 240°C between pure Sn and (Cu,Ni) alloys of various compositions are determined. The Cu₆Sn₅ phase is formed when the NI content is less than 30 wt.%, and the Ni₃Sn₄ phase is formed when the Ni content is higher than 40 wt.%. When the Ni content is between 35 wt.% and 40 wt.%, both Cu₆Sn₅ and Ni₃Sn₄ phases are formed. It is also noticed that the formation of the Cu₃Sn phase at the Sn/(Cu,Ni) interface is suppressed with more than 1wt.%Ni addition in the substrate.     

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.     

Inhibiting the formation of (Au1−xNix)Sn4 and reducing the consumption of Ni metallization in solder joints

The effects of adding a small amount of Cu into eutectic PbSn solder on the interfacial reaction between the solder and the Au/Ni/Cu metallization were studied. Solder balls of two different compositions, 37Pb-63Sn (wt.%) and 36.8Pb-62.7Sn-0.5Cu, were used. The Au layer (1 ± 0.2 μm) and Ni layer (7 ± 1 μm) in the Au/Ni/Cu metallization were deposited by electroplating. After reflow, the solder joints were aged at 160°C for times ranging from 0 h to 2,000 h. For solder joints without Cu added (37Pb-63Sn), a thick layer of (Au_1−xNi_x)Sn₄ was deposited over the Ni₃Sn₄ layer after the aging. This thick layer of (Au_1−xNi_x)Sn₄ can severely weaken the solder joints. However, the addition of 0.5wt.%Cu (36.8Pb-62.7Sn-0.5Cu) completely inhibited the deposition of the (Au_1−xNi_x)Sn₄ layer. Only a layer of (Cu_1-p-qAu_pNi_q)₆Sn₅ formed at the interface of the Cu-doped solder joints. Moreover, it was discovered that the formation of (Cu_1-p-qAu_pNi_q)₆Sn₅ significantly reduced the consumption rate of the Ni layer. This reduction in Ni consumption suggests that a thinner Ni layer can be used in Cu-doped solder joints. Rationalizations for these effects are presented in this paper.     

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.     

Co Solubility in Sn and Interfacial Reactions in Sn-Co/Ni Couples

It has been reported that minute Co additions to Sn-based solders are very effective for reducing undercooling, probably due to low Co solubility in Sn. In this study, Co solubility in molten Sn was determined experimentally. According to results of metallographic analysis, Co solubility in molten Sn is as low as 0.04 wt.% at 250°C. Interfacial reactions in Sn-Co/Ni couples at 250°C were examined for Co contents from 0.01 wt.% to 0.4 wt.%. The Ni₃Sn₄ phase was the only interfacial reaction phase in almost the entire Sn-0.01 wt.%Co/Ni couple. For Sn-Co/Ni couples with a Co content higher than 0.01 wt.%, a thin, continuous Ni₃Sn₄ layer and a discontinuous decahedron (Ni,Co)Sn₄ phase were formed in the initial stage of reaction. The reaction products evolved with time. With longer reaction time, the Sn content in the decahedron (Ni,Co)Sn₄ phase decreased, and the (Ni,Co)Sn₄ phase transformed into the (Ni,Co)Sn₂ phase and cleaved into a sheet, which then detached from the interface, after which Ni₃Sn₄ began to grow significantly with longer reaction times.     

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

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

Effect of Cross-Interaction between Ni and Cu on Growth Kinetics of Intermetallic Compounds in Ni/Sn/Cu Diffusion Couples during Aging

The solid-state, cross-interaction between the Ni layer on the component side and the Cu pad on the printed circuit board (PCB) side in ball grid array (BGA) solder joints was investigated by employing Ni(15 μm)/Sn(65 μm)/Cu ternary diffusion couples. The ternary diffusion couples were prepared by sequentially electroplating Sn and Ni on a Cu foil and were aged isothermally at 150, 180, and 200°C. The growth of the intermetallic compound (IMC) layer on the Ni side was coupled with that on the Cu side by the mass flux across the Sn layer that was caused by the difference in the Ni content between the (Cu_1−x Ni _x )₆Sn₅ layer on the Ni side and the (Cu_1−y Ni _y )₆Sn₅ layer on the Cu side. As the consequence of the coupling, the growth rate of the (Cu_1−x Ni _x )₆ Sn₅ layer on the Ni side was rapidly accelerated by decreasing Sn layer thickness and increasing aging temperature. Owing to the cross-interaction with the top Ni layer, the growth rate of the (Cu_1−y Ni _y )₆Sn₅ layer on the Cu side was accelerated at 150°C and 180°C but was retarded at 200°C, while the growth rate of the Cu₃Sn layer was always retarded. The growth kinetic model proposed in an attempt to interpret the experimental results was able to reproduce qualitatively all of the important experimental observations pertaining to the growth of the IMC layers in the Ni/Sn/Cu diffusion couple.     

Interfacial Reactions of Sn, Sn-3.0Ag-0.5Cu, and Sn-9Zn Lead-Free Solders with Fe-42Ni Substrates

Interfacial reactions between Sn, Sn-3.0 wt.%Ag-0.5 wt.%Cu (SAC), and Sn-9 wt.%Zn (SZ) lead-free solders and Fe-42 wt.%Ni (alloy 42) substrates at 240°C, 255°C, and 270°C were investigated in this study. FeSn₂, (Fe,Ni, Cu)Sn₂, and (Ni,Fe)₅Zn₂₁ phases were formed, respectively, at the interface in the Sn/alloy 42, SAC/alloy 42, and SZ/alloy 42 couples. As the reaction time and temperature were increased, the layered intermetallic compound (IMC) assumed two distinct structures, i.e., a thicker layer and a pillar-shaped IMC, in all couples. The IMC thickness of these couples increased with the increase of reaction time and temperature. The IMC thickness was also proportional to the square root of the reaction time. The interfacial reaction mechanism of these couples was diffusion controlled.     

Effect of Ni layer thickness and soldering time on intermetallic compound formation at the interface between molten Sn-3.5Ag and Ni/Cu substrate

The binary eutectic Sn-3.5wt.%Ag alloy was soldered on the Ni/Cu plate at 250°C, the thickness of the Ni layer changing from 0 through 2 and 4 μm to infinity, and soldering time changing from 30 to 120 s at intervals of 30 s. The infinite thickness was equivalent to the bare Ni plate. The morphology, composition and phase identification of the intermetallic compound (IMC, hereafter) formed at the interface were examined. Depending on the initial Ni thickness, different IMC phases were observed at 30 s: Cu₆Sn₅ on bare Cu, metastable NiSn₃ + Ni₃Sn₄ on Ni(2 μm)/Cu, Ni₃Sn₄ on Ni(4 μm)/Cu, and Ni₃Sn + Ni₃Sn₄ on bare Ni. With increased soldering time, a Cu-Sn-based η-(Cu₆Sn₅)_1−xNi_x phase formed under the pre-formed Ni-Sn IMC layer both at 60 s in the Ni(2 μm)/Cu plate and at 90 s in the Ni(4 μm)/Cu plate. The two-layer IMC pattern remained thereafter. The wetting behavior of each joint was different and it may have resulted from the type of IMC formed on each plate. The thickness of the protective Ni layer over the Cu plate was found to be an important factor in determining the interfacial reaction and the wetting behavior.     

The Sn/Ni-7Wt.%V interfacial reactions

Ni-7wt.%V(8at.%V) is an important under bump metallization material, and Sn is the primary element in most solders. This study examines the Sn/Ni-8at.%V interfacial reactions at 160°C, 200°C, 250°C, 300°C, 325°C, 350°C, and 400°C. Unlike the interfacial reactions in the Sn/Ni couples, a ternary T phase and the binary Ni₃Sn₄ phase are formed at 160°C. The vanadium solubility in the Ni₃Sn₄ phase is only 0.2 at.%, while the T phase contains 13.9at.%V. Similar results are found in the couples at 200°C, and the reaction paths are Sn/Ni₃Sn₄/T/Ni-V. The reaction paths are liquid/T/Ni₃Sn₄/Ni-V at 250°C and 300°C and are liquid/Ni₃Sn₄/Ni-V at 350°C and 400°C. Because the reaction products and the reaction rates in the Sn/Ni-8at.%V and Sn/Ni couples are different, reliabilities of the electronic products with the Ni-8at.%V barrier layer should not be assessed based only on the results of the Sn/Ni couples.     

Fast Concurrent Growth of Ni3Sn4 and Voids During Solid-State Reaction Between Sn-Rich Solder and Ni Substrates

To simulate the growth of Ni₃Sn₄ phase layers in Sn-based solder joints with Ni substrates during solid-state aging, Sn/(Cu_1−x Ni _x )₆Sn₅/Ni and Sn/Ni diffusion couples were aged isothermally at 180°C and 200°C, and the growth kinetics of the (Ni,Cu)₃Sn₄ and Ni₃Sn₄ layers in the respective couples were monitored during the isothermal aging. Once the (Ni,Cu)₃Sn₄ layer was formed at the (Cu,Ni)₆Sn₅/Ni interface, it grew unexpectedly fast with concurrent growth of voids formed in the Sn layer during prolonged aging at both temperatures. The results obtained from the various types of diffusion couples revealed that the voids formed in the Sn layer were Kirkendall voids, due to the (Ni,Cu)₃Sn₄ layer growing predominantly at the (Ni,Cu)₃Sn₄/Ni interface by fast diffusion of Sn across the (Ni,Cu)₃Sn₄ layer. It is proposed that the accelerated growth of the (Ni,Cu)₃Sn₄ and Ni₃Sn₄ layers after the formation of voids in the Sn layer is due to the relaxation of vacancy oversaturation and the enhanced annihilation rate of incoming vacancies in the presence of the voids in the Sn layer.     

Diffusion behavior of Cu in Cu/electroless Ni and Cu/electroless Ni/Sn-37Pb solder joints in flip chip technology

For Cu pads used as under bump metallization (UBM) in flip chip technology, the diffusion behavior of Cu in the metallization layer is an important issue. In this study, isothermal interdiffusion experiments were performed at 240°C for different times with solid-solid and liquid-solid diffusion couples assembled in Cu/electroless-Ni (Ni-10 wt.% P) and Cu/electroless Ni (Ni-10 wt.% P)/ Sn-37Pb joints. The diffusion structure and concentration profiles were examined by scanning electron microscopy and electron microprobe analysis. The interdiffusion fluxes of Cu, Ni and P were calculated from the concentration profiles with the aid of Matano plane evaluation. The values of J_Cu, J_Ni, and J_P decreased with increasing annealing time. The average effective interdiffusion coefficients on the order of 10⁻¹⁴ cm²/s were also evaluated within the diffusion zone. The amounts of Cu dissolved in the intermetallic compounds (IMCs) Ni₃Sn₄ and Ni₃P that precipitate after annealing the Cu/electroless Ni/Sn-37Pb joints were about 0.25 at.% and 0.5 at.%, respectively. For the short period of annealing, it appears that the presence of electroless Ni (EN) with the Sn-Pb soldering reaction assisted the diffusion of Cu through the EN layer.     

Electric current effects upon the Sn/Cu and Sn/Ni interfacial reactions

Electromigration-induced failures in integrated circuits have been intensively studied recently; however, electromigration effects upon interfacial reactions have not been addressed. These electromigration effects in the Sn/Cu and Sn/Ni systems were investigated in this study by analyzing their reaction couples annealed at 200°C with and without the passage of electric current. The intermetallics formed were ε-(Cu₃Sn) and η-(Cu₆Sn₅) phases in the Sn/Cu couples and Ni₃Sn₄ phase in the Sn/Ni couples. The same intermetallics were formed in the two types of couples with and without the passage of electric current. The thickness of the reaction layers was about the same in the two types of couples of the Sn/Cu system. In the Sn/Ni system, the growth of the intermetallic compound was enhanced when the flow direction of electrons and that of diffusion of Sn were the same. But the effect became inhibiting if the directions of these two were opposite. Theoretical calculation indicated that in the Sn/Ni system, the electromigration effect was significant and was 28% of the chemical potential effect for the Sn element flux when the Ni₃Sn₄ layer was 10 μm thick. For the Sn and Cu fluxes in the Sn/Cu reaction couples, similar calculations showed that the electromigration effects were only 2 and 4% of the chemical potential effects, respectively. These calculated results were in good agreement with the experimental observations that in the Sn/Cu system the electric current effects were insignificant upon the interfacial reactions.     

Interfacial reactions in In-Sn/Ni couples and phase equilibria of the In-Sn-Ni system

The In-Sn-Ni alloys of various compositions were prepared and annealed at 160°C and 240°C. No ternary compounds were found; however, most of the binary compounds had extensive ternary solubility. There was a continuous solid solution between the Ni₃Sn phase and Ni₃In phase. The Sn-In/Ni couples, made of Sn-In alloys with various compositions, were reacted at 160°C and 240°C and formed only one compound for all the Sn-In alloys/Ni couples reacted up to 8 h. At 240°C, Ni₂₈In₇₂ phase formed in the couples made with pure indium, In-10at.%Sn and In-11at.%Sn alloys, while Ni₃Sn₄ phase formed in the couples made of alloys with compositions varied from pure Sn to In-12at.%Sn. At 160°C, except in the In/Ni couple, Ni₃Sn₄ formed by interfacial reaction.     

Intermetallic Reactions in Sn-0.4Co-0.7Cu Solder BGA Packages with an ENIG Surface Finish

As-cast Sn-0.4Co-0.7Cu solder contains both (Cu_0.98Co_0.02)₆Sn₅ and (Co_0.85Cu_0.15) Sn₃ intermetallic phases in the matrix. After reflowing, the Au thin film in the electroless Ni/immersion Au (ENIG) surface-finished Sn-0.4Co-0.7Cu solder ball grid array (BGA) packages dissolved rapidly into the solder matrix to form AuSn₄ intermetallics, and a thin layer of (Cu_0.57Ni_0.35Au_0.08)₆Sn₅ intermetallic compound appeared at the solder/pad interface, growing very slowly during aging at 100°C. Increasing the aging temperature to 150°C caused the formation of a new intermetallic layer, (Ni_0.79Cu_0.21)₃Sn₄, at the (Cu_0.57Ni_0.35Au_0.08)₆Sn₅/Ni interface. The reflowed Sn-0.4Co-0.7Cu BGA packages have a ball shear strength of 6.8 N, which decreases to about 5.7 N and 5.5 N after aging at 100°C and 150°C, respectively. The reflowed and aged solder joints fractured across the solder balls with ductile characteristics in ball shear tests.     

Reactive interdiffusion between a lead-free solder and Ti/Ni/Ag thin-film metallizations

The reactive interdiffusion between a Sn-3.0wt.%Ag-0.7wt.%Cu solder and thin-film Ti/Ni/Ag metallizations on two semiconductor devices, a diode and a metal-oxide-semiconductor field-effect transistor (MOSFET), and a Au-layer on the substrates are studied. Comprehensive microanalytical techniques, scanning electron microscopy, transmission electron microscopy (TEM), and analytical electron microscopy (AEM) are employed to identify the interdiffusion processes during fabrication and service of the devices. During the reflow process of both diode and MOSFET devices, (1) the Ag layer dissolves in the liquid solder; (2) two intermetallics, (Ni,Cu)₃Sn₄ and (Cu,Ni)₆Sn₅, form near the back metal/solder interface; and (3) the Au metallization in the substrate side dissolves in the liquid solder, resulting in precipitation of the (Au,Ni,Cu)Sn₄ intermetallic during solidification. During solid-state aging of both diode and MOSFET solder joints at 125°C and 200°C, the following atomic transport processes occur: (1) interdiffusion of Cu, Ni, and Sn, leading to the growth of a (Ni,Cu)₃Sn₄ layer until the Ni layer is completely consumed; (2) interdiffusion of Au, Cu, Ni, and Sn through the (Ni,Cu)₃Sn₄ layer and unconsumed Ni layer to the Ti layer to form a solid solution; and (3) further interdiffusion of Au, Cu, Ni, and Sn through the (Ni,Cu)₃Sn₄ layer to from an (Au,Ti,Ni,Cu)Sn₄ layer. The growth of the latter layer continues until the entire Ti layer is consumed.     

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.     

A comparative study of the kinetics of interfacial reaction between eutectic solders and Cu/Ni/Pd metallization

A comparative study of the kinetics of interfacial reaction between the eutectic solders (Sn-3.5Ag, Sn-57Bi, and Sn-38Pb) and electroplated Ni/Pd on Cu substrate (Cu/Ni/NiPd/Ni/Pd) was performed. The interfacial microstructure was characterized by imaging and energy dispersive x-ray analysis in scanning electron microscope (SEM). For a Pd-layer thickness of less than 75 nm, the presence or the absence of Pd-bearing intermetallic was found to be dependent on the reaction temperature. In the case of Sn-3.5Ag solder, we did not observe any Pd-bearing intermetallic after reaction even at 230°C. In the case of Sn-57Bi solder the PdSn₄ intermetallic was observed after reaction at 150°C and 180°C, while in the case of Sn-38Pb solder the PdSn₄ intermetallic was observed after reaction only at 200°C. The PdSn₄ grains were always dispersed in the bulk solder within about 10 μm from the solder/substrate interface. At higher reaction temperatures, there was no Pd-bearing intermetallic due to increased solubility in the liquid solder. The presence or absence of Pd-bearing intermetallic was correlated with the diffusion path in the calculated Pd-Sn-X (X=Ag, Bi, Pb) isothermal sections. In the presence of unconsumed Ni, only Ni₃Sn₄ intermetallic was observed at the solder-substrate interface by SEM. The presence of Ni₃Sn₄ intermetallic was consistent with the expected diffusion path based on the calculated Ni-Sn-X (X=Ag, Bi, Pb) isothermal sections. Selective etching of solders revealed that Ni₃Sn₄ had a faceted scallop morphology. Both the radial growth and the thickening kinetics of Ni₃Sn₄ intermetallic were studied. In the thickness regime of 0.14 μm to 1.2 μm, the growth kinetics always yielded a time exponent n >3 for liquid-state reaction. The temporal law for coarsening also yielded time exponent m >3. The apparent activation energies for thickening were: 16936J/mol for the Sn-3.5Ag solder, 17804 J/mol for the Sn-57Bi solder, and 25749 J/mol for the Sn-38Pb solder during liquid-state reaction. The corresponding activation energies for coarsening were very similar. However, an apparent activation energy of 37599 J/mol was obtained for the growth of Ni₃Sn₄ intermetallic layer during solid-state aging of the Sn-57Bi/substrate diffusion couples. The kinetic parameters associated with thickening and radial growth were discussed in terms of current theories.