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.     

Mechanisms for the intermetallic formation during the Sn-20In-2.8Ag/Ni soldering reactions

The morphology and growth kinetics of intermetallic compounds formed during the interfacial reactions between liquid Sn-20In-2.8Ag solder and Ni substrates are investigated. Energy-dispersive x-ray (EDX) analysis identifies the composition of the interfacial intermetallics as Ni₃(In_0.99In_0.01)₄. The soldering reactions at lower temperatures (225–275°C) result in the predominant formation of a homogeneous intermetallic layer whose growth is diffusion controlled. At higher soldering temperatures (300–350°C), the interfacial intermetallics appear to be long needlelike crystals, and the grooves in between the intermetallics provide fast-diffusion paths for Ni atoms to react with Sn atoms at the intermetallic front, which leads to interface-controlled growth kinetics. The intermetallic needles turned out to be flat slablike after selective etching of the unreacted solder. Kinetics analysis showed that they not only lengthened in the longitudinal direction, but also coarsened transversely by the Ostwald ripening mechanism.     

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 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.     

Effect of soldering and aging time on interfacial microstructure and growth of intermetallic compounds between Sn-3.5Ag solder alloy and Cu substrate

The formation and the growth of the intermetallic compound (IMC, hereafter) at the interface between the Sn-3.5Ag (numbers are all in wt.% unless otherwise specified) solder alloy and the Cu substrate were investigated. Solder joints were prepared by changing the soldering time at 250°C from 30 sec to 10 h and the morphological change of IMCs with soldering time was observed. It resulted from the competition between the growth of IMC and the dissolution of Cu from the substrate and IMCs. They were further aged at 130°C up to 800 h. During aging, the columnar morphology of IMCs changed to a more planar type while the scallop morphology remained unchanged. It was observed that the growth behavior of IMCs was closely related with the initial soldering condition.     

Mechanical and Electrical Properties of Cu/Sn-3.5Ag/Cu Ball Grid Array (BGA) Solder Joints after Multiple Reflows

The microstructural evolution, die shear strength, and electrical resistivity of Cu/Sn-3.5Ag (wt.%)/Cu ball grid array (BGA) solder joints were investigated after 1 to 10 reflows using scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron probe microanalysis (EPMA), bonding testing, and a four-point probe station. A Cu₆Sn₅ intermetallic compound (IMC) was formed at both the upper and lower interfaces after one reflow. The IMC thickness increased at the lower interface with increasing reflow number, whereas the IMC morphology and thickness remained virtually unchanged at the upper interface, irrespective of the reflow number. The amount of Cu₆Sn₅ IMC contained in the solder ball increased with increasing reflow number. These microstructural evolutions with increasing reflow number strongly affected the mechanical and electrical properties of the solder joint.     

Effect of cooling rate on microstructure and shear strength of pure Sn,Sn-0.7Cu,Sn-3.5Ag,and Sn-37Pb solders

The microstructure and shear strength characteristics of pure Sn and the eutectic compositions of Sn-37Pb, Sn-0.7Cu, and Sn-3.5Ag prepared under identical reflow conditions but subjected to two different cooling conditions were evaluated at room temperature. For the four solders, the ultimate shear strength increased with increasing strain rate from 10⁻⁵ s⁻¹ to 10⁻¹ s⁻¹. Decreasing the cooling rate tended to decrease the ultimate shear strength for both the Sn-0.7Cu and Sn-3.5Ag solders. The effects of work hardening resulting from increased strain rate were more prevalent in quench-cooled (QC) samples.     

Interdiffusion analysis of the soldering reactions in Sn-3.5Ag/Cu couples

Extensive microstructural and kinetic studies on the formation and growth of the intermetallics of Sn-rich solder/Cu couples have been reported. However, experimental data on the interdiffusion mechanisms during soldering reactions are limited and in conflict. The interdiffusion processes for soldering of Sn-3.5Ag alloy/Cu couples were investigated by using the Cr-evaporated surface as a reference line. At the beginning of soldering, Cu was observed to outdiffuse to the molten Sn−3.5Ag alloy until saturation, and the Sn−Ag solder dissolved with Cu collapsed below the reference line. As a result, the scallop-shaped Cu₆Sn₅ intermetallic compound was formed at the newly-formed Sn−Ag−Cu solder/Cu interface below the original Cu surface. When the soldered joint was reflowed at the lower temperature to suppress the Cu dissolution, the Cu₆Sn₅/Cu interface moved into the Cu substrate. Therefore, Sn is the dominant diffusing species for the intermetallic formation during the soldering process, although the extensive Cu dissolution occurs at the early stage of soldering.     

Kinetics of intermetallic formation at Sn-37Pb/Cu interface during reflow soldering

The kinetics of the intermetallic layer formation at Sn-37wt.%Pb solder/Cu pad interface during reflow soldering were studied. The growth kinetics were analyzed theoretically by assuming that the mass flux of Cu through channels between scalloplike grains primarily contributes to the growth. Rate-controlling steps considered for the mass flux were the Cu dissolution from the bottom of the channels, diffusion through the channel, and the formation reaction of the intermetallic layer. These results indicated that a transition in the growth rate observed around 120–150 sec of reflow time may be associated with transition of the rate-controlling step from the Cu dissolution to the Cu diffusion through the channel.     

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.     

Selective formation of intermetallic compounds in Sn-20In-0.8Cu ball grid array solder joints with Au/Ni surface finishes

After Sn-20In-0.8Cu solder balls are reflowed on a ball grid array (BGA) substrate (substrate A) with an Au/Ni surface finish, scallop-shaped intermetallic compounds with a composition of 0.83[Cu₆(Sn_0.87In_0.13)₅] + 0.17[Ni₃(Sn_0.87In_0.13)₄] are formed at the solder/pad interface. The distribution of the intermetallics is not altered by gravity or by multiple reflows of the solder joints. As another substrate (substrate B) is further attached onto the primary reflowed BGA assembly to form a sandwich structure subjected to subsequent multiple reflows, the Cu₆(Sn_0.87In_0.13)₅ interfacial intermetallic scallops remain still on the side of substrate A while many Au(In_0.91Sn_0.09)₂ intermetallics of cubic shape appear near the solder/Ni interface on the side of substrate B. When the Sn-20In-0.8Cu solder balls are assembled simultaneously in between two substrates (A and B), Au(In_0.91Sn_0.09)₂ intermetallic cubes of equal proportion are observed to form on both sides of the assembly. In summarizing the results, it is proposed that the diffusion of Cu atoms in the Sn-20In-0.8Cu solder toward the Ni layers after Au thin-film dissolution on Au/Ni surface finishes led to the formation of Cu₆(Sn_0.87Zn_0.17)₅ intermetallic compounds, which prevailed over the gravitational effect so that no intermetallic sedimentation in the liquid solder would occur. The appearance of Au(In_0.91Sn_0.09)₂ at the Ni/Sn-20In-0.8Cu interfaces was hindered by the preferential formation of Cu₆(Sn_0.87Zn_0.17)₅ until the Cu atoms in the Sn-20In-0.8Cu solder matrix were consumed to a lower content via the attachment of a second substrate to the assembly.     

Microstructural effect on the creep strength of a Sn-3.5%Ag solder alloy

The effect of microstructure obtained by rapid or slow solidification and cooling of a Sn-3.5%Ag lead-free solder alloy on the creep strength has been investigated. The rapidly cooled alloy showed that the microstructure consisted of the primarily crystallized Sn phase and the quasi-eutectic phase, where fine Ag₃Sn particles dispersed in the Sn matrix. In the slowly cooled alloy, large platelets of Ag₃Sn were formed sparsely in the Sn matrix. A difference of about 2.5 orders of magnitude in the cooling rate translates to about 1.5 orders of magnitude in the creep-rupture time. Accordingly, fine particle dispersion of Ag₃Sn is considered to be very beneficial for the restraining of creep deformation, that is, for the decreasing of creep rate of the Sn-3.5%Ag alloy, compared with the effect of large platelets of Ag₃Sn sparsely formed in the Sn matrix.     

The effect of substrate surface roughness on the fracture toughness of Cu/96.5Sn-3.5Ag solder joints

The effects of substrate surface roughness, joint thickness, time above liquidus, and testing temperature on the chevron notch fracture toughness of Cu/96.5Sn-3.5Ag solder joints are investigated. Of these four variables,only the surface roughness of the copper surfaces to be soldered has a significant effect. A minimum fracture toughness is obtained when the average surface roughness, R_a, is between 0.2 and 1.0 μm. This encompasses the surface roughnesses produced by many cold forming operations. Decreasing the roughness to 0.04 μm increases the fracture toughness from 4.7 to 11.0 MPa√m, an improvement of 135%. Increasing the roughness to 2.0 μm increases the fracture toughness to 8.8 MPa√m, an improvement of 80%. We attribute these effects to the increased growth stresses that develop in the brittle intermetallic layer when the size scale of individual intermetallic particles is comparable to the size of the roughness features of the substrate. Two models that describe how these growth stresses might develop are provided.     

Effects of strain ratio and tensile hold time on low-cycle fatigue of lead-free Sn-3.5Ag-0.5Cu solder

Low-cycle fatigue (LCF) behavior of a lead-free Sn-3.5Ag-0.5Cu solder alloy was investigated at various combinations of strain ratio (R = −1, 0, and 0.5) and tensile hold time (0, 10, and 100 sec). Results showed that the LCF life of the given solder, at each given combination of testing conditions, could be individually described by a Coffin-Manson relationship. An increase of strain ratio from R=−1 to 0 and to 0.5 would cause a significant reduction of LCF life due to a mean strain effect instead of mean stress effect. LCF life was also markedly reduced when the hold time at tensile peak strain was increased from 0 to 100 sec, as a result of additional creep damage generated during LCF loading. With consideration of the effects of strain ratio and tensile hold time, a unified LCF lifetime model was proposed and did an excellent job in describing the LCF lives for all given testing conditions.     

Morphological Evolution of the Reaction Product at the Sn-9wt.%Zn/Thin-Film Cu Interface

The morphological evolution of the reaction product formed at the Sn-9wt.%Zn/thin-film Cu interface under reflow and solid-state aging was investigated. The Cu thin film was rapidly consumed and converted to CuZn₅ and Cu₅Zn₈ at the interface after reflow for 1 min. Upon increasing reflow time, the Cu₅Zn₈ compound was transformed into CuZn₅, followed by grain ripening. CuZn₅ grains grew bigger and the number of grains decreased. During the reflow process, CuZn₅ grains showed a round and convex surface morphology. During solid-state aging, a different morphological evolution of CuZn₅ grains was observed. The surface morphology of the grains became more planar after solid-state aging for 24 h. In addition, the grain surface fractured severely, implying that a compressive stress was created at the interface. After a longer duration of solid-state aging, the grain surface changed into a more faceted morphology. Potential mechanisms of the morphological evolution and fracture of the CuZn₅ grains are also discussed.     

Effect of thermal cycles on the mechanical strength of quad flat pack leads/Sn-3.5Ag-X (X=Bi and Cu) solder joints

Quad Flat Pack (QFP) Leads/Sn-3.5Ag-X (X=Bi and Cu) joint was thermally cycled between 243 K and 403 K or 273 K and 373 K, and both metallographic examination and mechanical pull test were performed to evaluate thermal fatigue damage of the joint. The addition of bismuth drastically degrades the thermal fatigue resistance of Sn-3.5Ag solder. On the other hand, the pull strength of Sn-3.5Ag-Cu solder joints slightly decreased with increasing number of thermal cycles, though it still remains higher in comparison to that for conventional Sn-37Pb or bismuth containing solder joint. The behavior observed here reflects the isothermal fatigue properties of bulk solder, because thermal fatigue crack initiates at the surface of solder fillet and propagates within the fillet in an early stage of fatigue damage. Furthermore, the lead phases lying at the interface between lead-frame and bismuth containing solder joint may promote the crack propagation at the interface, resulting in the extremely low thermal fatigue resistance of the joint.     

The effect of isothermal aging on the thickness of intermetallic compound layer growth between low melting point solders and Ni-plated Cu substrate

The growth kinetics of the intermetallic compound (IMC) layer formed between two low melting point solders and electrolytic Ni/Cu substrate by solid-state isothermal aging were examined. The solders were 100 In and In-48Sn. A quantitative analysis of the IMC layer thickness as a function of aging time and aging temperature was performed. Experimental results showed that the IMCs, such as In₂₇Ni₁₀ and Ni₃(In, Sn)₄), were observed for different solders. Additionally, the growth rate of these IMCs increased with the aging temperature and time. The layer growth of the IMC in the couples of indium solder alloy/electrolytic Ni system satisfied the parabolic law at a given temperature range. As a whole, because the values of the time exponent (n) are approximately 0.5, the layer growth of the IMC was mainly controlled by the diffusion mechanism over the temperature range studied. The apparent activation energies for IMC growth were 60.03 kJ/mol for In₂₇Ni₁₀ and 72.84 kJ/mol for Ni₃(In, Sn)₄.     

Effect of intermetallic compound formation on electrical properties of Cu/Sn interface during thermal treatment

Cu₆Sn₅ and Cu₃Sn intermetallic compounds are commonly found in the Sn-Cu bimetallic system. Due to the distinct resistivity of these two compounds, the electrical properties of Cu/Sn interfaces, e.g., solder joints on Cu metallization, may be impacted by the formation of Cu-Sn compounds. In this study, the kinetics of Sn-Cu compound formation was investigated by in-situ resistivity measurement, x-ray diffraction, and scanning electron microscopy (SEM). The interfacial reaction of the Cu-Sn bimetallic thin film specimen was monitored by the resistivity change of the specimen during thermal treatment. The activation energy of formation of Cu-Sn compounds was determined to be 0.97±0.07 eV. It is proposed that the Cu₆Sn₅ compound first forms at Sn/Cu interfaces and then reacts with Cu, forming the Cu₃Sn compound at elevated temperatures during the thermal ramping process. The effect of thin film thickness on the sequential formation of Sn-Cu compounds is also discussed.     

微量Ni对Sn-3.0Ag-0.5Cu钎料及焊点界面的影响

研究了Ni的含量对无铅钎料Sn-3.0Ag-0.5Cu润湿性、熔点、重熔及老化条件下界面化合物(IMC)的影响。结果表明:微量Ni的加入使SnAgCu润湿力增加6%;使合金熔点略升高约3℃;重熔时在界面形成了(Cu,Ni)6Sn5IMC层,且IMC厚度远高于SnAgCu/Cu的Cu6Sn5IMC厚度。在150℃老化过程中,SnAgCuNi/Cu重熔焊点IMC随着时间的增加,其增幅小于SnAgCu/Cu的增幅,此时Ni对IMC的增长有一定抑制作用。     

An improved numerical method for predicting intermetallic layer thickness developed during the formation of solder joints on Cu substrates

An improved numerical method has been developed for calculating the thickness of intermetallic layers formed between Cu substrates and solders during the soldering process. The improved method takes into account intermetallic dissolution during heating and intermetallic precipitation during cooling and requires as input (1) the temperature-time profile for the soldering process, (2) the experimentally determined isothermal growth parameters for the growth of the intermetallic layer into Cu saturated molten solder, (3) the experimentally determined Nernst-Brunner parameters for the dissolution of Cu into molten solder, (4) the experimentally determined solubility of Cu in molten solder and (5) assumptions about the thickness of the boundary layer in the liquid ahead of the growing intermetallic. Calculations show that the improved method predicts intermetallic growth between Cu substrates and 96.5Sn-3.5Ag solder during reflow soldering better than a previously developed method, which did not take into account dissolution during heating and precipitation during cooling. Calculations further show that dissolution has a significant effect on growth, while precipitation does not.