Interfacial Reactions between Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Alloy Underbump Metallurgy and Sn-Ag-<Emphasis Type="Italic">z</Emphasis>Cu Solders

A reaction study of Cu _x Ni _y alloy (x = 0.2–0.95) under bump metallization (UBM) with Sn-Ag-zCu solder (z = 0–0.7) was conducted. Formation and separation of intermetallic compounds (IMCs), effect of Cu addition to the Cu _x Ni _y alloy and the solders, and compatibility of reaction products with currently available phase diagrams are extensively investigated. The increase of Cu content both in the Cu _x Ni _y alloy and in the solder promoted IMC growth and Cu _x Ni _y consumption; though, with regard to solder composition, the reverse trend was true of the solder reactions in the literature. The liquid + Cu₆Sn₅ area in the Sn-rich corner needs to be larger compared to the currently available Cu-Ni-Sn ternary phase diagram, and the maximum simultaneous soluble point of Ni and Cu in Sn needs also to be moved to the Ni-Sn side (e.g., Sn-0.6Cu-0.3Ni).     

Growth Mechanism of a Ternary (Cu,Ni)<Subscript>6</Subscript>Sn<Subscript>5</Subscript> Compound at the Sn(Cu)/Ni(P) Interface

The growth mechanism of an interfacial (Cu,Ni)₆Sn₅ compound at the Sn(Cu) solder/Ni(P) interface under thermal aging has been studied in this work. The activation energy for the formation of the (Cu,Ni)₆Sn₅ compound for cases of Sn-3Cu/Ni(P), Sn-1.8Cu/Ni(P), and Sn-0.7Cu/Ni(P) was calculated to be 28.02 kJ/mol, 28.64 kJ/mol, and 29.97 kJ/mol, respectively. The obtained activation energy for the growth of the (Cu,Ni)₆Sn₅ compound layer was found to be close to the activation energy for Cu diffusion in Sn (33.02 kJ/mol). Therefore, the controlling step for formation of the ternary (Cu,Ni)₆Sn₅ layer could be Cu diffusion in the Sn(Cu) solder matrix.     

The nanoindentation characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> intermetallic compounds in the solder bump

In general, formation and growth of intermetallic compounds (IMCs) play a major role in the reliability of the solder joint in electronics packaging and assembly. The formation of Cu-Sn or Ni-Sn IMCs have been observed at the interface of Sn-rich solders reacted with Cu or Ni substrates. In this study, a nanoindentation technique was employed to investigate nanohardness and reduced elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ IMCs in the solder joints. The Sn-3.5Ag and Sn-37Pb solder pastes were placed on a Cu/Ti/Si substrate and Ni foil then annealed at 240°C to fabricate solder joints. In Sn-3.5Ag joints, the magnitude of the hardness of the IMCs was in the order Ni₃Sn₄>Cu₆Sn₅>Cu₃Sn, and the elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ were 125 GPa, 136 GPa, and 142 GPa, respectively. In addition, the elastic modulus of the Cu₆Sn₅ IMC in the Sn-37Pb joint was similar to that for the bulk Cu₆Sn₅ specimen but less than that in the Sn-3.5Ag joint. This might be attributed to the strengthening effect of the dissolved Ag atoms in the Cu₆Sn₅ IMC to enhance the elastic modulus in the Sn-3.5Ag/Cu joint.     

Inhibiting AuSn<Subscript>4</Subscript> Formation by Controlling the Interfacial Reaction in Solder Joints

Au was used in an electronic package to protect the conductor from oxidation. However, Au dissolved into solders and reacted with the Sn-rich phase to form AuSn₄ during soldering. After aging, Au diffused from AuSn₄ toward the solder/metallization interface. If Ni₃Sn₄ formed at the soldering interface, a layer of AuSn₄ was redeposited on Ni₃Sn₄. In contrast, Au diffused into Cu₆Sn₅-based intermetallic compounds (IMCs) to produce either (Cu,Au)₆Sn₅ or (Cu,Ni,Au)₆Sn₅, while Cu₆Sn₅ or (Cu,Ni)₆Sn₅ was formed at the soldering interface. Gibbs free energy evaluation revealed that both (Ni,Au)₃Sn₄ and (Cu,Au)₆Sn₅ were more thermodynamically stable than AuSn₄. The maximum amount of Au diffused in Ni₃Sn₄ was 4.6 at.%, while the maximum dissolution of Au in Cu₆Sn₅ was 24.3 at.% at 150°C. Thus, dissolution of Au in Ni₃Sn₄ was limited, and residual Au rereacted with Sn to produce the layer-type AuSn₄. If Cu₆Sn₅ formed at the interface, most of the Au in AuSn₄ diffused into Cu₆Sn₅. Consequently, AuSn₄ formation could be inhibited by controlling formation of Cu₆Sn₅ in solder/under-bump metallization (UBM) assemblies.     

Elastic Moduli of (Ni,Cu)<Subscript>3</Subscript>Sn<Subscript>4</Subscript> Ternary Alloys from First-Principles Calculations

Based on first-principles calculations, the effect of Cu solubility on the elastic moduli of Ni₃Sn₄-based intermetallic compound (IMC) is investigated. It is found that the stiffness tensor of a (Ni,Cu)₃Sn₄ single crystal is anisotropic, and the presence of Cu in the crystal compound reduces the moduli of (Ni,Cu)₃Sn₄ due to reduced hybridization between Ni and Sn states. Furthermore, our results show that higher Cu concentration in the (Ni,Cu)₃Sn₄-based IMCs leads to thermodynamically less stable compounds. Based on the single-crystal results, the elastic properties of polycrystalline (Ni,Cu)₃Sn₄ are also obtained.     

Study of Interfacial Reactions Between Sn(Cu) Solders and Ni-Co Alloy Layers

The interfacial reactions between electroplated Ni-yCo alloy layers and Sn(Cu) solders at 250°C are studied. For pure Co layers, CoSn₃ is the only interfacial compound phase formed at the Sn(Cu)/Co interfaces regardless of the Cu concentration. Also, the addition of Cu to Sn(Cu) solders has no obvious influence on the CoSn₃ compound growth at the Sn(Cu)/Co interfaces. For Ni-63Co layers, (Co,Ni,Cu)Sn₃ is the only interfacial compound phase formed at the Sn(Cu)/Ni-63Co interfaces. Unlike in the pure Co layer cases, the Cu additives in the Sn(Cu) solders clearly suppress the growth rate of the interfacial (Co,Ni,Cu)Sn₃ compound layer. For Ni-20Co layers, the interfacial compound formation at the Sn(Cu)/Ni-20Co interfaces depends on the Cu content in the Sn(Cu) solders and the reflow time. In the case of high Cu content in the Sn(Cu) solders (Sn-0.7Cu and Sn-1.2Cu), an additional needle-like interfacial (Ni _x ,Co _y ,Cu_1−x−y )₃Sn₄ phase forms above the continuous (Ni _x ,Cu _y ,Co_1−x−y )Sn₂ compound layer. The Ni content in the Ni-yCo layer can indeed reduce the interfacial compound formation at the Sn(Cu)/Ni-yCo interfaces. With pure Sn solders, the thickness of the compound layer monotonically decreases with the Ni content in the Ni-yCo layer. As for reactions with the Sn(Cu) solders, as the compound thickness decreases, the Ni content in the Ni-yCo layers increases.     

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.     

Thermal Stability Study of Cu(MoN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>) Seed Layer on Barrierless Si

This study reports the good thermal stability of a sputtered Cu(MoN _x ) seed layer on a barrierless Si substrate. A Cu film with a small amount of MoN _x was deposited by reactive co-sputtering of Cu and Mo in an Ar/N₂ gas mixture. After annealing at 560°C for 1 h, no copper silicide formation was observed at the interface of Cu and Si. Leakage current and resistivity evaluations reveal the good thermal reliability of Cu with a dilute amount of MoN _x at temperatures up to 560°C, suggesting its potential application in advanced barrierless metallization. The thermal performance of Cu(MoN _x ) as a seed layer was evaluated when pure Cu is deposited on top. X-ray diffraction, focused ion beam microscopy, and transmission electron microscopy results confirm the presence of an ∼10-nm-thick reaction layer formed at the seed layer/Si interface after annealing at 630°C for 1 h. Although the exact composition and structure of this reaction layer could not be unambiguously identified due to trace amounts of Mo and N, this reaction layer protects Cu from a detrimental reaction with Si. The Cu(MoN _x ) seed layer is thus considered to act as a diffusion buffer with stability up to 630°C for the barrierless Si scheme. An electrical resistivity of 2.5 μΩ cm was obtained for the Cu/Cu(MoN _x ) scheme after annealing at 630°C.     

Nanotribological Characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> Intermetallic Compounds

Nanotribological characteristics, including the coefficient of friction, wear coefficient, and wear resistance, of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ intermetallic compounds developed by the annealing of Sn–Cu or Sn–Ni diffusion couples were investigated in this work. The scratch test conditions combined a constant normal load of 10 mN, 20 mN, or 30 mN and a scratch rate of 0.1 μm/s, 1 μm/s, or 10 μm/s. Experimental results indicated that, as the normal load increases, the pile-up grows taller and the scratch deepens, leading to a greater coefficient of friction and wear coefficient, and reduced wear resistance. Moreover, the scratch rate does not have a significant effect on the nanotribological characteristics except for those of Cu₆Sn₅ and Cu₃Sn under a normal load of 10 mN. Though the hardness of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ is similar, Ni₃Sn₄ appears to be more prone to wear damage.     

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.     

Al/Ni : V/Ag metal stacks as rear‐side metallization for crystalline silicon solar cells

Rear sides of crystalline silicon solar cells are usually covered with aluminum on which it is difficult to solder. To ease soldering, we present a durability study for a Ni : V/Ag stack on evaporated Al as rear‐side metallization. We adapt this cost‐effective metallization stack from the microelectronic industry and investigate it as metallization for silicon solar cells. Here, a long‐term stability of the metallization and of the solder joint must be guaranteed for 25 years and is therefore evaluated in detail by thermal aging experiments. During this experiment, the mechanical stability of the solder joints is measured. The chemical stability and the intermetallic compound (IMC) growth within the solder joints are examined by secondary electron microscopy, backscattered electron imaging, and energy dispersive X‐ray analysis. Experiments with either a Sn–Ag‐coated copper tab or pure Sn–Ag solder show two different sorts of IMCs at the Ni : V/Solder interface. With the copper tab, a Cu–Ni–Sn compound, presumably (Cu_{1 ‐ x}Ni_x)₆Sn₅, grows at the Ni/solder interface, whereas in case of a pure Sn–Ag solder, a Ni–Sn compound grows, which is likely to be Ni₃Sn₄. Analysis of the reaction kinetics leads to activation energies of 77 and 42 kJ/mol, respectively, for a diffusion‐controlled IMC growth. By using temperature histograms of PV modules in the field, the necessary minimum Ni : V layer thickness is estimated: without a copper tab up to 1.6 µm Ni and with a copper tab less than 0.2 µm may be consumed by IMC formation during 25 years of lifetime. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Additive Occupancy in the Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>-Based Intermetallic Compound Between Sn-3.5Ag Solder and Cu Studied Using a First-Principles Approach

A Cu₆Sn₅-based intermetallic compound containing a certain amount of Co or Ni is commonly formed at the interface between a Cu substrate and Sn-based solder. The Co or Ni additive is often found to occupy the Cu atom sublattice in the Cu₆Sn₅ crystal structure. In this paper, a first-principles approach based on density-functional theory is employed to explore the most favorable occupancy sites of Ni and Co dopants in the Cu₆Sn₅ crystal structure. It is found that, for up to 27.3 at.% concentration, both Ni and Co atoms tend to substitute for Cu in the Cu₆Sn₅-based structure and form more thermodynamically stable (Cu,Ni)₆Sn₅ and (Cu,Co)₆Sn₅ phases. In comparison, Ni is more effective than Co at stabilizing the Cu₆Sn₅ phase. At a lower concentration level (9.1 at.%), the Ni or Co atoms prefer to occupy the 4e Cu sublattice. At a higher concentration (27.3 at.%), the Ni atoms will likely be located on the 4e + 8f2 Cu sublattice. Analysis of density of states (DOS) and partial density of states (PDOS) indicates that hybridization between Ni-d (or Co-d) and Sn-p states plays a dominant role in structural stability. Compared with Cu₄Ni₂Sn₅, where Ni occupies the 8f2 Cu sublattice, Cu₄Co₂Sn₅ is less stable due to the lower amplitude of the Co-d PDOS peak and its position mismatch with the Sn-p PDOS peak.     

Synthesis of Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Alloy Thin Films Using Ion Implantation and Pulsed Laser Melting (II-PLM)

Ge_1−x Sn _x thin films are interesting for all-group-IV optoelectronics because of a crossover to a direct bandgap with dilute Sn alloying. However, Sn has vanishing room-temperature equilibrium solubility in Ge, making their synthesis very challenging. Herein, we report on our attempts to synthesize Ge_1−x Sn _x films on Ge (001) using ion implantation and pulsed laser melting (II-PLM). A maximum of 2 at.% Sn was incorporated with our experimental conditions in the samples as determined by Rutherford back scattering spectroscopy. A red-shift in the Ge optical phonon branch and increased absorption below the Ge bandgap with increasing Sn concentration indicate Sn-induced lattice- and band-structure changes after II-PLM. However, ion-channeling and electron microscopy show that the films are not of sufficient epitaxial quality for use in devices.     

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.     

Microstructure Changes and Physical Properties of the Intermetallic Compounds Formed at the Interface Between Sn-Cu Solders and a Cu Substrate Due to a Minor Addition of Ni

The influence of Cu content and added Ni on the morphology of the intermetallic compound (IMC) layer formed at the interface between liquid Sn-Cu-based solders and a Cu substrate and on the strength of simulated solder joints was investigated. The reaction of a Sn-0.7Cu alloy with the substrate led to the formation of a thin layer of Cu₆Sn₅ (η-phase) with typical scallop morphology that did not grow with longer reaction times. Higher Cu content such as in the Sn-1.4Cu alloy led to extensive growth with increased reaction time; at long reaction times, Cu₃Sn (ε-phase) was observed at the interface between the Cu substrate and the Cu₆Sn₅ layer. A small nickel addition to the Sn-0.7Cu alloy significantly changed the IMC morphology, accelerated its growth kinetics, prevented formation of the Cu₃Sn layer, and reduced the rate of substrate dissolution.     

Interface Reaction Between Electroless Ni–Sn–P Metallization and Lead-Free Sn–3.5Ag Solder with Suppressed Ni3P Formation

The voids formed in the Ni₃P layer during reaction between Sn-based solders and electroless Ni–P metallization is an important cause of rapid degradation of solder joint reliability. In this study, to suppress formation of the Ni₃P phase, an electrolessly plated Ni–Sn–P alloy (6–7 wt.% P and 19–21 wt.% Sn) was developed to replace Ni–P. The interfacial microstructure of electroless Ni–Sn–P/Sn–3.5Ag solder joints was investigated after reflow and solid-state aging. For comparison, the interfacial reaction in electroless Ni–P/Sn–3.5Ag solder joints under the same reflow and aging conditions was studied. It was found that the Ni–Sn–P metallization is consumed much more slowly than the Ni–P metallization during soldering. After prolonged reaction, no Ni₃P or voids are observed under SEM at the Ni–Sn–P/Sn–3.5Ag interface. Two main intermetallic compounds, Ni₃Sn₄ and Ni₁₃Sn₈P₃, are formed during the soldering reaction. The reason for Ni₃P phase suppression and the overall mechanisms of reaction at the Ni–Sn–P/Sn–3.5Ag interface are discussed.     

Physical Properties of Sn<Subscript>96.5</Subscript>Ag<Subscript>3.5</Subscript>-Based Solders with Additions of Bi,Ge, and In

The melting temperature, electrical resistivity, surface tension, and density of the (Sn_0.965Ag_0.035)_95.17Bi_4.83, (Sn_0.965Ag_0.035)_95.17Bi_4.73Ge_0.1, and (Sn_0.965Ag_0.035)₉₄-Bi₂In₄ alloys have been studied in comparison with the Sn₆₀Pb₄₀ and Sn_96.5Ag_3.5 binary alloys (all wt.%). The electrical conductivity of the solid alloys based on Sn_96.5Ag_3.5 is comparable to that of the Sn₆₀Pb₄₀ alloy. The wetting behavior on Cu and Ni surfaces has been investigated in a wide temperature interval. It is established that the addition of Bi to Sn_96.5Ag_3.5 decreases the surface tension and improves the wetting properties of the alloy. The addition of a small quantity of Ge to the Sn-Ag-Bi alloy did not improve the wetting behavior on either Cu or Ni surfaces. The wetting ability of the (Sn_0.965Ag_0.035)₉₄Bi₂In₄ alloy was slightly worse as compared with (Sn_0.965Ag_0.035)_95.17Bi_4.83.     

Cross-Interaction Study of Cu/Sn/Pd and Ni/Sn/Pd Sandwich Solder Joint Structures

Cross-interactions between Cu/Sn/Pd and Ni/Sn/Pd sandwich structures were investigated in this work. For the Cu/Sn/Pd case, the growth behavior and morphology of the interfacial (Pd,Cu)Sn₄ compound layer was very similar to that of the single Pd/Sn interfacial reaction. This indicates that the growth of the (Pd,Cu)Sn₄ layer at the Sn/Pd interface would not be affected by the opposite Cu/Sn interfacial reaction. We can conclude that there is no cross-interaction effect between the two interfacial reactions in the Cu/Sn/Pd sandwich structure. For the Ni/Sn/Pd case, we observed that: (1) after 300 s of reflow time, the (Pd,Ni)Sn₄ compound heterogeneously nucleated on the Ni₃Sn₄ compound layer at the Sn/Ni interface; (2) the growth of the interfacial PdSn₄ compound layer was greatly suppressed by the formation of the (Pd,Ni)Sn₄ compound at the Sn/Ni interface. We believe that this suppression of PdSn₄ growth is caused by heterogeneous nucleation of the (Pd,Ni)Sn₄ compound in the Ni₃Sn₄ compound layer, which decreases the free energy of the entire sandwich reaction system. The difference in the chemical potential of Pd in the PdSn₄ phase at the Pd/Sn interface and in the (Pd,Ni)Sn₄ phase at the Sn/Ni interface is the driving force for the Pd atomic flux across the molten Sn. The diffusion of Ni into the ternary (Pd,Ni)Sn₄ compound layer controls the Pd atomic flux across the molten Sn and the growth of the ternary (Pd,Ni)Sn₄ compound at the Sn/Ni interface.     

Intermetallic compound formation and morphology evolution in the 95Pb5Sn flip-chip solder joint with Ti/Cu/Ni under bump metallization during reflow soldering

Intermetallic compound formation and morphology evolution in the 95Pb5Sn flip-chip solder joint with the Ti/Cu/Ni under bump metallization (UBM) during 350°C reflow for durations ranging from 50 sec to 1440 min were investigated. A thin intermetallic layer of only 0.4 μm thickness was formed at the 95Pb5Sn/UBM interface after reflow for 5 min. When the reflow was extended to 20 min, the intermetallic layer grew thicker and the phase identification revealed the intermetallic layer comprised two phases, (Ni,Cu)₃Sn₂ and (Ni,Cu)₃Sn₄. The detection of the Cu content in the intermetallic compounds indicated that the Cu atoms had diffused through the Ni layer and took part in the intermetallic compound formation. With increasing reflow time, the (Ni,Cu)₃Sn₄ phase grew at a faster rate than that of the (Ni,Cu)₃Sn₂ phase. Meanwhile, irregular growth of the (Ni,Cu)₃Sn₄ phase was observed and voids formed at the (Ni,Cu)₃Sn₂/Ni interface. After reflow for 60 min, the (Ni,Cu)₃Sn₂ phase disappeared and the (Ni,Cu)₃Sn₄ phase spalled off the NI layer in the form of a continuous layer. The gap between the (Ni,Cu)₃Sn₄ layer and the Ni layer was filled with lead. A possible mechanism for the growth, disappearance, and spalling of the intermetallic compounds at the 95Pb5Sn/UBM interface was proposed.