Interfacial Reaction Effect on Electrical Reliability of Cu Pillar/Sn Bumps

Thermal annealing and electromigration (EM) tests were performed with Cu pillar/Sn bumps to understand the growth mechanism of intermetallic compounds (IMCs). Annealing tests were carried out at both 100°C and 150°C. At 150°C, EM tests were performed using a current density of 3.5 × 10⁴ A/cm². The electrical failure mechanism of the Cu pillar/Sn bumps was also investigated. Cu₃Sn formed and grew at the Cu pillar/Cu₆Sn₅ interface with increasing annealing and current-stressing times. The growth mechanism of the total (Cu₆Sn₅ + Cu₃Sn) IMC changed when the Sn phase in the Cu pillar/Sn bump was exhausted. The time required for complete consumption of the Sn phase was shorter during the EM test than in the annealing test. Both IMC growth and phase transition from Cu₆Sn₅ to Cu₃Sn had little impact on the electrical resistance of the whole interconnect system during current stressing. Electrical open failure in the Al interconnect near the chip-side Cu pillar edge implies that the Cu pillar/Sn bump has excellent electrical reliability compared with the conventional solder bump.     

Effects of Surface Finishes and Current Stressing on Interfacial Reaction Characteristics of Sn-3.0Ag-0.5Cu Solder Bumps

The effects of surface finishes on the in situ interfacial reaction characteristics of ball grid array (BGA) Sn-3.0Ag-0.5Cu lead-free solder bumps were investigated under annealing and electromigration (EM) test conditions of 130°C to 175°C with 5.0 × 10³ A/cm². During reflow and annealing, (Cu,Ni)₆Sn₅ intermetallic compound (IMC) formed at the interface of electroless nickel immersion gold (ENIG) finish. In the case of both immersion Sn and organic solderability preservative (OSP) finishes, Cu₆Sn₅ and Cu₃Sn IMCs formed. Overall, the IMC growth velocity of ENIG was much lower than that of the other finishes. The activation energies of total IMCs were found to be 0.52 eV for ENIG, 0.78 eV for immersion Sn, and 0.72 eV for OSP. The ENIG finish appeared to present an effective diffusion barrier between the Cu substrate and the solder, which leads to better EM reliability in comparison with Cu-based pad systems. The failure mechanisms were explored in detail via in situ EM tests.     

Kinetics of Intermetallic Compound Formation at the Interface Between Sn-3.0Ag-0.5Cu Solder and Cu-Zn Alloy Substrates

The growth kinetics of an intermetallic compound (IMC) layer formed between Sn-3.5Ag-0.5Cu (SAC) solders and Cu-Zn alloy substrates was investigated for samples aged at different temperatures. Scallop-shaped Cu₆Sn₅ formed after soldering by dipping Cu or Cu-10 wt.%Zn wires into the molten solder at 260°C. Isothermal aging was performed at 120°C, 150°C, and 180°C for up to 2000 h. During the aging process, the morphology of Cu₆Sn₅ changed to a planar type in both specimens. Typical bilayer of Cu₆Sn₅ and Cu₃Sn and numerous microvoids were formed at the SAC/Cu interfaces after aging, while Cu₃Sn and microvoids were not observed at the SAC/Cu-Zn interfaces. IMC growth on the Cu substrate was controlled by volume diffusion in all conditions. In contrast, IMC growth on Cu-Zn specimens was controlled by interfacial reaction for a short aging time and volume diffusion kinetics for a long aging time. The growth rate of IMCs on Cu-Zn substrates was much slower due to the larger activation energy and the lower layer growth coefficient for the growth of Cu-Sn IMCs. This effect was more prominent at higher aging temperatures.     

Influence of Dopant on Growth of Intermetallic Layers in Sn-Ag-Cu Solder Joints

The interfacial interaction between Cu substrates and Sn-3.5Ag-0.7Cu-xSb (x = 0, 0.2, 0.5, 0.8, 1.0, 1.5, and 2.0) solder alloys has been investigated under different isothermal aging temperatures of 100°C, 150°C, and 190°C. Scanning electron microscopy (SEM) was used to measure the thickness of the intermetallic compound (IMC) layer and observe the microstructural evolution of the solder joints. The IMC phases were identified by energy-dispersive x-ray spectroscopy (EDX) and x-ray diffractometry (XRD). The growth of both the Cu₆Sn₅ and Cu₃Sn IMC layers at the interface between the Cu substrate and the solder fits a power-law relationship with the exponent ranging from 0.42 to 0.83, which suggests that the IMC growth is primarily controlled by diffusion but may also be influenced by interface reactions. The activation energies and interdiffusion coefficients of the IMC formation of seven solder alloys were determined. The addition of Sb has a strong influence on the growth of the Cu₆Sn₅ layer, but very little influence on the formation of the Cu₃Sn IMC phase. The thickness of the Cu₃Sn layer rapidly increases with aging time and temperature, whereas the thickness of the Cu₆Sn₅ layer increases slowly. This is probably due to the formation of Cu₃Sn at the interface between two IMC phases, which occurs with consumption of Cu₆Sn₅. Adding antimony to Sn-3.5Ag-0.7Cu solder can evidently increase the activation energy of Cu₆Sn₅ IMC formation, reduce the atomic diffusion rate, and thus inhibit excessive growth of Cu₆Sn₅ IMCs. This study suggests that grain boundary pinning is one of the most important mechanisms for inhibiting the growth of Cu₆Sn₅ IMCs in such solder joints when Sb is added.     

Measurement of Sn and In Solidification Undercooling and Lattice Expansion Using <Emphasis Type="Italic">In Situ</Emphasis> X-Ray Diffraction

The solidification behavior of two low-melting-point metals, Sn and In, on three substrates has been examined using in situ x-ray diffraction. Undercoolings of up to 56.1°C were observed for Sn solidified on graphite, which is a nonwetting substrate, while lower undercoolings were observed for Sn on Au/Ni/Cu (17.3°C) and on Cu (10.5°C). Indium behaved quite differently, showing undercoolings of less than 4°C on all three substrates. The lattice expansion/contraction behavior of Sn, In, and intermetallic compounds (IMCs) that formed during the reaction of Sn with Au/Ni/Cu surfaces were also measured during heating and cooling. Results showed anisotropic and nonlinear expansion of both Sn and In, with a contraction, rather than expansion, of the basal planes of In during heating. The principal IMC that formed between Sn and the Au/Ni/Cu surface was characterized as Cu₆Sn₅, having an average expansion coefficient of 13.6 × 10⁻⁶/°C, which is less than that of Sn or Cu.     

A Study on the Thermal Reliability of Cu/SnAg Double-Bump Flip-Chip Assemblies on Organic Substrates

The Cu/SnAg double-bump structure is a promising candidate for fine-pitch flip-chip applications. In this study, the interfacial reactions of Cu (60 μm)/SnAg (20 μm) double-bump flip chip assemblies with a 100 μm pitch were investigated. Two types of thermal treatments, multiple reflows and thermal aging, were performed to evaluate the thermal reliability of Cu/SnAg flip-chip assemblies on organic printed circuit boards (PCBs). After these thermal treatments, the resulting intermetallic compounds (IMCs) were identified with scanning electron microscopy (SEM), and the contact resistance was measured using a daisy-chain and a four-point Kelvin structure. Several types of intermetallic compounds form at the Cu column/SnAg solder interface and the SnAg solder/Ni pad interface. In the case of flip-chip samples reflowed at 250°C and 280°C, Cu₆Sn₅ and (Cu, Ni)₆Sn₅ IMCs were found at the Cu/SnAg and SnAg/Ni interfaces, respectively. In addition, an abnormal Ag₃Sn phase was detected inside the SnAg solder. However, no changes were found in the electrical contact resistance in spite of severe IMC formation in the SnAg solder after five reflows. In thermally aged flip-chip samples, Cu₆Sn₅ and Cu₃Sn IMCs were found at the Cu/SnAg interface, and (Cu, Ni)₆Sn₅ IMCs were found at the SnAg/Ni interface. However, Ag₃Sn IMCs were not observed, even for longer aging times and higher temperatures. The growth of Cu₃Sn IMCs at the Cu/SnAg interface was found to lead to the formation of Kirkendall voids inside the Cu₃Sn IMCs and linked voids within the Cu₃Sn/Cu column interfaces. These voids became more evident when the aging time and temperature increased. The contact resistance was found to be nearly unchanged after 2000 h at 125°C, but increases slightly at 150°C, and a number of Cu/SnAg joints failed after 2000 h. This failure was caused by a reduction in the contact area due to the formation of Kirkendall and linked voids at the Cu column/Cu₃Sn IMC interface.     

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.     

Coupling Effect of the Interfacial Reaction in Co/Sn/Cu Diffusion Couples

Co/Sn/Cu sandwich couples formed by electroplating were examined to investigate the interaction between Cu and Co across the Sn layer for various Sn thicknesses from 75 μm to 580 μm. At the Sn/Cu interface, both Cu₆Sn₅ and Cu₃Sn are formed. Unlike in a binary Sn/Cu couple, Cu₆Sn₅ has a spiked structure for couples with a thinner Sn layer. At the Co/Sn interface, two phases, CoSn₃ and (Cu,Co)₆Sn₅, were simultaneously observed after reaction at 200°C. Remarkably, the CoSn₃ reaction layer was much thinner than that in the binary Sn/Co couple. Furthermore, only the (Cu,Co)₆Sn₅ phase was formed at 150°C. This finding indicates that CoSn₃ growth is significantly inhibited in Co/Sn/Cu sandwich couples due to the Cu substrate.     

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.     

Solid-state intermetallic compound layer growth between copper and 95.5Sn-3.9Ag-0.6Cu solder

Long-term, solid-state intermetallic compound (IMC) layer growth was examined in 95.5Sn-3.9Ag-0.6Cu (wt.%)/copper (Cu) couples. Aging temperatures and times ranged from 70°C to 205°C and from 1 day to 400 days, respectively. The IMC layer thicknesses and compositions were compared to those investigated in 96.5Sn-3.5Ag/Cu, 95.5Sn-0.5Ag-4.0Cu/Cu, and 100Sn/Cu couples. The nominal Cu₃Sn and Cu₆Sn₅ stoichiometries were observed. The Cu₃Sn layer accounted for 0.4–0.6 of the total IMC layer thickness. The 95.5Sn-3.9Ag-0.6Cu/Cu couples exhibited porosity development at the Cu₃Sn/Cu interface and in the Cu₃Sn layer as well as localized “plumes” of accelerated Cu₃Sn growth into the Cu substrate when aged at 205°C and t>150 days. An excess of 3–5at.%Cu in the near-interface solder field likely contributed to IMC layer growth. The growth kinetics of the IMC layer in 95.5Sn-3.9Ag-0.6Cu/Cu couples were described by the equation x=x_o+Atⁿexp [−ΔH/RT]. The time exponents, n, were 0.56±0.06, 0.54±0.07, and 0.58±0.07 for the Cu₃Sn layer, the Cu₆Sn₅, and the total layer, respectively, indicating a diffusion-based mechanism. The apparent-activation energies (ΔH) were Cu₃Sn layer: 50±6 kJ/mol; Cu₆Sn₅ layer: 44±4 kJ/mol; and total layer: 50±4 kJ/mol, which suggested a fast-diffusion path along grain boundaries. The kinetics of Cu₃Sn growth were sensitive to the Pb-free solder composition while those of Cu₆Sn₅ layer growth were not so.     

EBSD Investigation of Cu-Sn IMC Microstructural Evolution in Cu/Sn-Ag/Cu Microbumps During Isothermal Annealing

The microstructural evolution of Cu/Sn-Ag (~5 μm)/Cu Cu-bump-on-line (CuBOL) joints during isothermal annealing at 180°C was examined using a field-emission scanning electron microscope equipped with an electron backscatter diffraction (EBSD) system. Cu₆Sn₅ and Cu₃Sn were the two key intermetallic compound (IMC) species that appeared in the CuBOL joints. After annealing for 24 h (= t), the solder had completely converted to Cu-Sn IMCs, forming an “IMC” joint with Cu/Cu₃Sn/Cu₆Sn₅/Cu₃Sn/Cu structure. EBSD analyses indicated that the preferred orientation of the hexagonal Cu₆Sn₅ (η) was $ (2\bar{1}\bar{1}3) $ , while the preferred orientation was (100) for the monoclinic Cu₆Sn₅ structure (η′). Upon increasing t to 72 h, Cu₆Sn₅ entirely transformed into Cu₃Sn, and the IMC joint became Cu/Cu₃Sn/Cu accordingly. Interestingly, the grain size and crystallographic orientation of Cu₃Sn displayed location dependence. Detailed EBSD analyses in combination with transmission electron microscopy on Cu₃Sn were performed in the present study. This research offers better understanding of crystallographic details, including crystal structure, grain size, and orientation, for Cu₆Sn₅ and Cu₃Sn in CuBOL joints after various annealing times.     

Electromigration-Induced Interfacial Reactions in Cu/Sn/Electroless Ni-P Solder Interconnects

The effect of electromigration (EM) on the interfacial reaction in a line-type Cu/Sn/Ni-P/Al/Ni-P/Sn/Cu interconnect was investigated at 150°C under 5.0 × 10³ A/cm². When Cu atoms were under downwind diffusion, EM enhanced the cross-solder diffusion of Cu atoms to the opposite Ni-P/Sn (anode) interface compared with the aging case, resulting in the transformation of interfacial intermetallic compound (IMC) from Ni₃Sn₄ into (Cu,Ni)₆Sn₅. However, at the Sn/Cu (cathode) interface, the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.2 wt.% Ni) and Cu₃Sn. When Ni atoms were under downwind diffusion, only a very small quantity of Ni atoms diffused to the opposite Cu/Sn (anode) interface and the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.6 wt.% Ni) and Cu₃Sn. EM significantly accelerated the dissolution of Ni atoms from the Ni-P and the interfacial Ni₃Sn₄ compared with the aging case, resulting in fast growth of Ni₃P and Ni₂SnP, disappearance of interfacial Ni₃Sn₄, and congregation of large (Ni,Cu)₃Sn₄ particles in the Sn solder matrix. The growth kinetics of Ni₃P and Ni₂SnP were significantly accelerated after the interfacial Ni₃Sn₄ IMC completely dissolved into the solder, but still followed the t ^1/2 law.     

Cu Substrates with Different Grain Sizes

Cu₆Sn₅ and Cu₃Sn are easily formed at the interface between Sn and Cu during reflow and aging processes. Thick Cu-Sn compounds at the interface become brittle, reducing the mechanical strength of solder joints and increasing the consumption of under bump metallization (UBM). It is noted that intermetallic compound (IMC) growth and substrate consumption are affected by factors such as substrate fabrication, substrate orientation, and substrate microstructure. In this study, to determine the effects of substrate grain size on IMC growth and substrate consumption, pure Sn solder was reflowed on annealed Cu substrates with different grain sizes at 250°C for 30 s to 600 s. It was revealed that Cu substrates with smaller grain sizes exhibited reduced IMC growth. In addition, the interdiffusion coefficients of Cu₆Sn₅ and Cu₃Sn were decreased for the Cu substrate with the smaller grain size. The influence of the Cu substrate grain size on IMC growth and substrate consumption is discussed.     

Effects of solid-state annealing on the interfacial intermetallics between tin-lead solders and copper

The interfacial intermetallics between Cu and solder were studied for four Sn-Pb compositions at the annealing temperatures of 125°C, 150°C, and 175°C for up to 30 days. The η-phase (Cu₆Sn₅) layer formed during reflow continues to grow during annealing. An additional layer of ɛ-phase (Cu₃Sn) forms at the η/Cu interface after an incubation annealing time. The thickness results fit a power-law relationship against time with average exponents 0.69 and 0.44 for the η phase and the ɛ phase, respectively. On prolonged annealing, the proportions of the individual phases in the total layer reach a steady state.     

Non-conductive film with Zn-nanoparticles (Zn-NCF) for 40 μm pitch Cu-pillar/Sn–Ag bump interconnection

Non-conductive film with Zn nano-particles (Zn-NCF) is an effective solution for fine-pitch Cu-pillar/Sn–Ag bump interconnection in terms of manufacturing process and interfacial reliability. In this study, NCFs with Zn nano-particles of different acidity, viscosity, and curing speed were formulated and diffused Zn contents in the Cu pillar/Sn–Ag bumps were measured after 3D TSV chip-stack bonding. Amount of Zn diffusion into the Cu pillar/Sn–Ag bumps increased as the acidity of resin increased, as the viscosity of resin decreased, as the curing speed of resin decreased, and as the bonding temperature increased. Diffusion of Zn nano-particles into the Cu pillar/Sn–Ag bumps are maximized when the resin viscosity became lowered and the solder oxide layer was removed. To analyze the effects of Zn-NCF on IMC reduction, IMC height depending on aging time was measured and corresponding activation energies for IMC growth were calculated. For the evaluation of joint reliabilities, test vehicles were bonded using NCFs with 0 wt%, 1 wt%, 5 wt%, and 10 wt% of Zn nano-particles and aged at 150 °C up to 500 h. NCF with 10 wt% Zn nano-particle showed remarkable suppression in Cu₆Sn₅ and (Cu,Ni)₆Sn₅ IMC compared to NCFs with 0 wt%, 1 wt%, and 5 wt% of Zn nano-particles. However, in terms of Cu₃Sn IMC suppression, which is the most critical goal of this experiment NCFs with 1 wt%, 5 wt%, and 10 wt% showed an equal amount of IMC suppression. As a result, it was successfully demonstrated that the suppression of Cu–Sn IMCs was achieved by the addition of Zn nano-particles in the NCFs resulting an enhanced reliability performance in the Cu/Sn–Ag bumps bonding in 3D TSV interconnection.     

Intermetallic Compound Growth and Reliability of Cu Pillar Bumps Under Current Stressing

Fine-pitch Cu pillar bumps have been adopted for flip-chip bonding technology. Intermetallic compound (IMC) growth in Cu pillar bumps was investigated as a function of annealing or current stressing by in situ observation. The effect of IMC growth on the mechanical reliability of the Cu pillar bumps was also investigated. It is noteworthy that Sn exhaustion was observed after 240 h of annealing when current stressing was not applied, and IMC growth rates were changed remarkably. As the applied current densities increased, the time required for complete Sn consumption became shorter. In addition, Kirkendall voids, which would be detrimental to the mechanical reliability of Cu pillar bumps, were observed in both Cu₃Sn/Cu pillars and Cu₃Sn/Cu under-bump metallization interfaces. Die shear force was measured for Cu pillar samples prepared with various annealing times, and degradation of mechanical strength was observed.     

Electromigration Reliability and Morphologies of Cu Pillar Flip-Chip Solder Joints with Cu Substrate Pad Metallization

The Cu pillar is a thick underbump metallurgy (UBM) structure developed to alleviate current crowding in a flip-chip solder joint under operating conditions. We present in this work an examination of the electromigration reliability and morphologies of Cu pillar flip-chip solder joints formed by joining Ti/Cu/Ni UBM with largely elongated ∼62 μm Cu onto Cu substrate pad metallization using the Sn-3Ag-0.5Cu solder alloy. Three test conditions that controlled average current densities in solder joints and ambient temperatures were considered: 10 kA/cm² at 150°C, 10 kA/cm² at 160°C, and 15 kA/cm² at 125°C. Electromigration reliability of this particular solder joint turns out to be greatly enhanced compared to a conventional solder joint with a thin-film-stack UBM. Cross-sectional examinations of solder joints upon failure indicate that cracks formed in (Cu,Ni)₆Sn₅ or Cu₆Sn₅ intermetallic compounds (IMCs) near the cathode side of the solder joint. Moreover, the ~52-μm-thick Sn-Ag-Cu solder after long-term current stressing has turned into a combination of ~80% Cu-Ni-Sn IMC and ~20% Sn-rich phases, which appeared in the form of large aggregates that in general were distributed on the cathode side of the solder joint.     

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.     

Effect of Isothermal Aging and Thermal Cycling on Interfacial IMC Growth and Fracture Behavior of SnAgCu/Cu Joints

The growth behavior of interfacial intermetallic compounds (IMCs) of SnAgCu/Cu soldered joints was investigated during the reflow process, isothermal aging, and thermal cycling with a focus on the influence of these parameters on growth kinetics. The SnAgCu/Cu soldered joints were isothermally aged at 125°C, 150°C, and 175°C while the thermal cycling was performed within the temperature ranges from −25°C to 125°C and −40°C to 125°C. It was observed that a Cu₆Sn₅ layer formed, followed by rapid coarsening at the solder/Cu interface during reflowing. The grain size of the interfacial Cu₆Sn₅ was found to increase with aging time, and the morphology evolved from scallop-like to needle-like to rod-like and finally to particles. The rod-like Ag₃Sn phase was formed on the solder side in front of the previously formed Cu₆Sn₅ layer. However, when subject to an increase of the aging time, the Cu₃Sn phase was formed at the interface of the Cu₆Sn₅ layer and Cu substrate. The IMC growth rate increased with aging temperature for isothermally aged joints. During thermal cycling, the thickness of the IMC layer was found to increase with the number of thermal cycles, although the growth rate was slower than that for isothermal aging. The dwell time at the high-temperature end of the thermal cycles was found to significantly influence the growth rate of the IMCs. The growth of the IMCs, for both isothermal aging and thermal cycling, was found to be Arrhenius with aging temperature, and the corresponding diffusion factor and activation energy were obtained by data fitting. The tensile strength of the soldered joints decreased with increasing aging time. Consequently, the fracture site of the soldered joints migrated from the solder matrix to the interfacial Cu₆Sn₅ layer. Finally, the shear strength of the joints was found to decrease with both an increase in the number of thermal cycles and a decrease in the dwell temperature at the low end of the thermal cycle.     

Influences of Substrate Alloying and Reflow Temperature on Bi Segregation Behaviors at Sn-Bi/Cu Interface

In this study, the influences of substrate alloying and reflow temperature on the Bi segregation behaviors at the Sn-Bi/Cu interface were investigated. Cu and Cu-Ag alloys with different Ag contents were reflowed with Sn-Bi solder at 180°C, 200°C or 220°C, and then aged at 120°C for different times. The evolution of their interfacial morphologies during the aging process was observed, and tensile tests of some solder joints were conducted. The experimental results reveal that the Bi atoms that dissolved in the Cu₆Sn₅ during the reflow process are expelled when the Cu₆Sn₅ transforms into Cu₃Sn and then segregate around the Cu₃Sn/Cu interface, inducing interfacial embrittlement. Alloying the Cu substrate with Ag can alleviate the Bi segregation by suppressing Cu₃Sn formation and dissolving the Bi atoms in the Cu-Ag substrate; the critical Ag content to eliminate the Bi segregation is about 1 at.% for the interface reflowed at 200°C. For interfaces reflowed at 180°C, the Bi segregation is less serious because less Bi is dissolved in the Cu₆Sn₅, and 0.6 at.% Ag can eliminate it. Tensile tests demonstrate that the embrittlement will not occur at Sn-Bi/Cu-Ag joints once the Bi segregation is eliminated. Based on this understanding, aging embrittlement of Sn-Bi/Cu solder joints can be prevented by decreasing the reflow temperature and adding a small amount of Ag to the Cu substrate.