Sn–In–Ag phase equilibria and Sn–In–(Ag)/Ag interfacial reactions

Experimental verifications of the Sn–In and Sn–In–Ag phase equilibria have been conducted. The experimental measurements of phase equilibria and thermodynamic properties are used for thermodynamic modeling by the CALPHAD approach. The calculated results are in good agreement with experimental results. Interfacial reactions in the Sn–In–(Ag)/Ag couples have been examined. Both Ag₂In and AgIn₂ phases are formed in the Sn–51.0 wt%In/Ag couples reacted at 100 and 150 °C, and only the Ag₂In phase is formed when reacted at 25, 50 and 75 °C. Due to the different growth rates of different reaction phases, the reaction layer at 100 °C is thinner than those at 25 °C, 50 °C, and 75 °C. In the Sn–20.0 wt%In/Ag couples, the ζ phase is formed at 250 °C and ζ/AgIn₂ phases are formed at 125 °C. Compared with the Sn–20 wt%In/Ag couples, faster interfacial reactions are observed in the Sn–20.0 wt%In–2.8 wt%Ag/Ag couples, and minor Ag addition to Sn–20 wt%In solder increases the growth rates of the reaction phases.     

Surface and transport properties of liquid Ag–Sn alloys and a case study of Ag–Sn eutectic solder

This review represents the state of the art in the thermophysical properties of liquid Ag–Sn alloys highlighting the surface and wetting properties of Ag–Sn eutectic solder. It includes an atomistic approach developed within the framework of statistical mechanical theory in conjunction with a Quasi Lattice Theory that, through a rigorous mathematical formalism, provides exact relationships between the properties in terms of classical thermodynamics. The model predicted property values are substantiated by available experimental data. Based on the phase diagram evidence about the existence of ε-Ag₃Sn intermetallic compound, the surface (surface tension and surface composition), transport (viscosity and diffusivity) properties and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) have been studied using the Compound Formation Model in a weak interaction approximation and Quasi Chemical Approximation for regular solutions. A case study of Ag–Sn eutectic alloy is presented. Taking into account its importance for design and development of lead free solder alternatives, the literature data on the wettability and the phases formed at the interface between Ag–Sn eutectic alloy and different substrates (Cu, Ni, Au, Pd) have also been analysed.     

Thermophysical Properties of Sn–Ag–Cu Based Pb-Free Solders

Lead–tin (Pb–Sn) alloys are the dominant solders used for electronic packaging because of their low cost and superior properties required for interconnecting electronic components. However, increasing environmental and health concerns over the toxicity of lead, combined with global legislation to limit the use of Pb in manufactured products, have led to extensive research and development studies of lead-free solders. The Sn–Ag–Cu ternary eutectic alloy is considered to be one of the promising alternatives. Except for thermal properties, much research on several properties of Sn–Ag–Cu alloy has been performed. In this study, five Sn–xAg–0.5Cu alloys with variations of Ag content x of 1.0 mass%, 2.5 mass%, 3.0 mass%, 3.5 mass%, and 4.0 mass% were prepared, and their thermal diffusivity and specific heat were measured from room temperature to 150 °C, and the thermal conductivity was calculated using the measured thermal diffusivity, specific heat, and density values. Also, the linear thermal expansion was measured from room temperature to 170 °C. The results show that Sn–3.5Ag–0.5Cu is the best candidate because it has a maximum thermal conductivity and a low thermal expansion, which are the ideal conditions to be a proper packaging alloy for effective cooling and thermostability.     

Effect of microstructure and Ag3Sn intermetallic compounds on corrosion behavior of Sn–3.0Ag–0.5Cu lead-free solder

In this paper, the effects of microstructure on the corrosion behavior of Sn–3.0Ag–0.5Cu (SAC305) lead-free solder were investigated by potentiodynamic polarization and atmospheric corrosion test. Scanning electron microscopy and X-ray diffraction were used to characterize the samples after the electrochemical and atmospheric corrosion tests. Results showed that commercial SAC305 solder exhibits better corrosion resistance than air-cooled and furnace-cooled SAC305 solders both in 3.5 wt% NaCl solution and at 60 °C/100 % relative humidity condition.     

Effects of reflow atmosphere and flux on Sn whisker growth of Sn–Ag–Cu solders

We evaluated the Sn whisker growth behavior of Sn–Ag–Cu solder fillets on lead frames of quad flat packages (QFPs) upon OSP printed circuit boards that were exposed to 85 °C/85% relative humidity (RH) exposure. Three different concentrations of halogen flux for activated Sn-3.0wt%Ag–0.5wt%Cu were used to solder in air and in an inert N₂ reflow atmosphere. The lead frames of the QFPs consisted of Sn plated Cu and Fe-42wt%Ni (alloy 42). Sn whiskers were observed on the surface of the QFP solder fillet joints that were reflowed with halogen containing flux in an air atmosphere. A substantial amount of Sn oxides were formed in those solder fillets while whisker growth and the amount of Sn oxides increased with the halogen content. Sn oxide formation apparently enhanced whisker formation. The combination of air reflow atmosphere and high halogen flux was the worst combination for solder fillet oxidation resulting in Sn whisker formation regardless of the electrode’s lead frame composition of Cu or alloy 42. In contrast, an inert N₂ reflow atmosphere obviously prevented Sn whisker formation on Sn–Ag–Cu solder fillets under all conditions used in this work.     

Interfacial reactions in Sn–20In–2.8Ag/Cu couples

Interfacial reactions between Sn–20 wt.%In–2.8 wt.%Ag (Sn–20In–2.8Ag) Pb-free solder and Cu substrate at 250, 150, and 100 °C were investigated. A scallop-type η-Cu₆Sn₅ phase layer and a planar ε-Cu₃Sn phase layer formed at the interface at 250 °C. The indium content in the molten solder near the interface was increased with the formation of the η-Cu₆Sn₅ phase; and the η-Cu₆Sn₅, Ag₂In, Cu₂In₃Sn, and γ-InSn₄ phases formed from the solidification of the remaining solder. At 100 and 150 °C, only the η-Cu₆Sn₅ phase was found at the interface. However, unusual liquid/solid reaction-like interfacial morphologies, such as irregular elongated intermetallic layers and isolated intermetallic grains, were observed in the solid-state reactions. These η phase layers had less Sn content than the Sn–20In–2.8Ag alloy, resulting in an excess Sn-rich γ-InSn₄ phase accumulating at the interface and forming porous η layers on top of the initially formed dense η layers at 150 °C. At 100 °C, large elongated η grains were formed, whereas the interfacial layers remained almost unchanged after prolonged reaction. Based on the experimental evidence, the growth of the η phase was proposed to follow a diffusion-controlled mechanism at 250, 150 and 100 °C, while that of the ε phase was probably controlled by the reaction.     

Tensile creep behavior of Sn–Ag–Cu–Ni multicomponent lead-free solder alloy

In the process of electronic packaging, the dissolution of under bump metallizations, such as Cu and Ni, into liquid solder occurs during soldering, which can change the original solder to a multicomponent one. Under the trend of miniaturization, it is quite necessary to evaluate the properties of multicomponent solder with excessive Cu and Ni compositions. In this study, the tensile creep behavior of Sn–3.5Ag–2.0Cu–0.5Ni multicomponent lead-free solder alloy is investigated at three temperatures, i.e., 303, 348 and 393 K. The steady-rate creep rates are obtained in the range of 10^?4–10^?8 s^?1, when the normalized stress, σ/E, is in the range of 10^?4–10^?3. Based on the Dorn equation, the apparent stress exponent (n _a), threshold stress (σ _th), and activation energy of creep (Q _C) are calculated at the three temperatures. It is found that the Sn–3.5Ag–2.0Cu–0.5Ni solder alloy shows a better creep performance than pure tin and eutectic Sn–3.5Ag solder due to the strengthening effect of Ag₃Sn and (Cu,Ni)₆Sn₅ IMC precipitations. The true stress exponent for creep is identified to be 7, indicating that the creep behave is controlled by the dislocation-pipe diffusion in the tin matrix.     

Synthesis of Sn–Ag binary alloy powders by mechanical alloying

Sn–Ag binary powders of 2–5 wt%Ag were synthesized by mechanical alloying. Structural evolutions, morphologies, particle size distributions and melting points of the milled Sn–Ag powders were studied. The results show that the milled Sn–Ag powders consist of a supersaturated solid solution of Ag in Sn, Sn(Ag), and Ag₃Sn. During ball milling, Sn, Ag particles in the Sn–3.5Ag powders are deformed, overlapped and cold-welded together to form the Sn/Ag composite particles with a lamellar structure, and then the composite particles are fractured into small spherical particles. When increasing the Ag content from 2 to 5 wt%, the average particle sizes of the 60 h milled Sn–Ag powders are changed from 2.2 to 5.7 μm, and the morphologies of them are changed from spherical shape to irregular shape, respectively. It indicates that the cold-welding and agglomeration of the Sn–Ag powders increases with the Ag content during MA. The melting point of the 60 h milled Sn–3.5Ag powders was detected to be 224.23 °C, near to the eutectic point of the Sn–Ag binary system (221 °C).     

Characterization of interfacial IMCs in low-Ag Sn–Ag–xCu–Bi–Ni solder joints

This research investigated the effects of Cu content on the interfacial IMCs in low-Ag Sn–0.7Ag–xCu–3.5Bi–0.05Ni (x = 0.3, 0.5, 0.7, and 1.5 wt%, respectively) solder joints by deep-etching method and SEM observation. Experimental results indicated that as Cu content increased in the solder, the grain size of the IMCs increased and the thickness of the IMCs decreased on Cu substrate. When the concentration of Cu in the solder was 0.3 wt%, the IMC on the soldering interface was (Cu, Ni)₆Sn₅. The concentration of Ni in (Cu, Ni)₆Sn₅ IMC was significantly suppressed by the increase of Cu content in the solder. As Cu content increased to 1.5 wt%, the concentration of Ni in the IMC decreased to 0 and the IMC transformed from (Cu, Ni)₆Sn₅ to Cu₆Sn₅. Due to the increase of Cu content, more and more (Cu, Ni)₆Sn₅ grains nucleated on Ni substrate, and the morphology of (Cu, Ni)₆Sn₅ transformed from polyhedrons to tiny prisms.     

The measurement of interfacial energies for solid Sn solution in equilibrium with the Sn–Bi–Ag liquid

The equilibrated grain boundary groove shapes of solid Sn solution in equilibrium with Sn–Bi–Ag liquid were observed from a quenched sample by using a radial heat flow apparatus. The Gibbs–Thomson coefficient, solid–liquid interfacial energy, and grain boundary energy of the solid Sn solution were determined from the observed grain boundary groove shapes. The thermal conductivity of the solid phase for Sn-10 at.%Bi-2 at.%Ag alloy and the thermal conductivity ratio of the liquid phase to the solid phase for Sn-10 at.%Bi-2 at.%Ag alloy at the melting temperature were also measured with a radial heat flow apparatus and a Bridgman-type growth apparatus, respectively. A comparison of present results for solid Sn solution in the Sn–10 at.%Bi–2 at.%Ag alloy with the results obtained in previous works for similar solid Sn in equilibrium with different binary or ternary liquid was made. From the comparison, it can be concluded that for solid Sn solution in equilibrium with different liquid, the Gibbs–Thomson coefficient seems to be constant and does not depend on the composition of liquid but solid–liquid interfacial energy changes little bit with composition of liquid at a constant temperature.     

Annealing effect to constitutive behavior of Sn–3.0Ag–0.5Cu solder

Sn–Ag–Cu based solder alloys are replacing Sn–Pb solders in electronic packaging structures of commercial electric devices. In order to evaluate the structural reliability, the mechanical property of solder material is critical to the numerical simulations. Annealing process has been found to stabilize material properties of Sn–37Pb solder material. In the current study, the annealing effect on tensile behaviour of Sn–3.0Ag–0.5Cu (SAC305) solder material is investigated and compared with Sn–37Pb solder. It is found that the tensile strength for both materials are more stabilized and consistent after the annealing process, nevertheless, the annealing process will improve the plasticity of SAC305 solder dominated by dislocation motion, and impede the occurrence of hardening deformation in Sn–37Pb solder dominated by grain-boundary sliding mechanism. Furthermore, the annealing effect is quantified in the proposed constitutive model based on unified creep–plasticity theory. The parameters are calibrated against the measured stress–strain relationships at the tensile strain rates ranging from 1?×?10^?4 to 1?×?10^?3 s^?1. The numerical regressions for dominant parameters in the proposed model reveal the intrinsic differences between SAC305 and Sn–37Pb solders under annealing treatment.     

Development of a Sn–Ag–Cu solder reinforced with Ni-coated carbon nanotubes

In this study, Ni-coated carbon nanotubes (Ni-CNTs) were incorporated into the 95.8Sn-3.5Ag-0.7Cu solder alloy using the powder metallurgy route. Up to 0.3 wt% of Ni-CNTs were successfully incorporated. The effects of Ni-CNTs on the physical, thermal and mechanical properties of Sn–Ag–Cu solder alloy were investigated. With the addition of increasing weight percentages of Ni-CNTs, the composite solders showed a corresponding decrease in density values and improved wetting properties. The thermomechanical property results showed an improvement in thermal stability for the composite solders. Mechanical characterization revealed an improvement in ultimate tensile strength (up to 12%) and 0.2% yield strength (up to 8%) with the addition of 0.05 wt% Ni-CNTs in the solder.     

Combined effects of Ag content and cooling rate on microstructure and mechanical behavior of Sn–Ag–Cu solders

Sn–0.7 wt%Cu–1.0 wt%Ag and Sn–0.7 wt%Cu–2.0 wt%Ag alloys were directionally solidified under transient conditions undergoing cooling rates varying from 0.1 to 25 K/s. The microstructure was characterized along the castings lengths and the present experimental results include the secondary dendrite arm spacing (λ₂) and its correlation with: the tip cooling rate ($\dot{T}$) during solidification and microhardness (HV), yield tensile strength (σ_y), ultimate tensile strength (σ_u) and elongation to fracture (δ). The aim is to examine the effects of Ag content and tip cooling rate on both the microstructure and mechanical properties. The initiation of tertiary branches within the dendritic arrangement, as well as the distinct morphologies of the intermetallic compounds (IMC) related to the solidification cooling rate was also assessed for both examined alloys. While the Cu₆Sn₅ phase appeared as large faceted crystals along the entire casting length, very fine Ag₃Sn spheroids prevailed at higher cooling rates (>7.5 K/s and > 4.0 K/s for 1.0 wt%Ag and 2.0 wt%Ag alloying, respectively) with a mixture of Ag₃Sn coarser spheroids and fibers predominating at lower cooling rates. The Sn–0.7 wt%Cu–2.0 wt%Ag alloy exhibited smaller dendritic spacings and HV of about two times higher than the corresponding values of the Sn–0.7 wt%Cu–1.0 wt%Ag alloy. A single Hall–Petch equation is proposed relating δ to λ₂ for both alloys, which means that the increase in Ag content from 1.0 to 2.0 wt% does not affect the elongation. It is shown that δ decreases with the increase in λ₂.     

Interfacial reactions with and without current stressing at Sn–Co/Ag and Sn–Co/Cu solder joints

Sn–Co alloys are promising Pb-free solders, while plating layers and substrates of Ag and Cu are commonly encountered in electronic products. This study examines the interfacial reactions between Sn–0.25 wt% Co/Ag and Sn–0.25 wt% Co/Cu at 180 and 210 °C, with and without current stressing. CoSn₃ precipitates are found in the solder matrix in the as-prepared condition. In Sn–0.25 wt% Co/Ag couples, a continuous Ag₃Sn reaction phase layer is observed at the interface and Ag₃Sn phase particles are dispersed in the matrix, with and without current stressing. When there is a 500 A/cm² electrical current, the growth rate of the Ag₃Sn phase is not affected at either the cathode side or the anode side. However, the passage of an electrical current leads to the formation of needle-like Ag₃Sn phase particles in the solder matrix. In Sn–0.25 wt% Co/Cu couples, both Cu₆Sn₅ and Cu₃Sn reaction phases are formed at the interface, with and without current stressing. Cu₆Sn₅ precipitates, with a higher Co content, are found in the matrix, mostly nucleated on CoSn₃ precipitates. When there is a 500 A/cm² electrical current stressing, all the reaction phase layers are thicker and the anode interfaces are nonplanar. It is observed that there is cracking and that there are discontinuous Cu₆Sn₅ layers at the interface and that a significant amount of Cu₆Sn₅ phase in the matrix accompanies 500 A/cm² electrical current stressing.     

Effects of Ga–Ag, Ga–Al and Al–Ag additions on the wetting characteristics of Sn–9Zn–X–Y lead-free solders

The effects of Ga–Al, Ga–Ag and Al–Ag binary additions on the wetting characteristics of Sn–9Zn–X–Y lead-free solders are studied by the wetting balance method. Experimental results show that Sn–9Zn–1.0Ga–0.3Ag, Sn–9Zn–0.005Al–0.3Ag, and Sn–9Zn–0.3Ga–0.002Al possess better wettability than the other alloys tested. The mechanism by which Ga, Al, and Ag additions improve the wettability is also proposed. It appears that dense aluminum oxide film formation and the enrichment of Ga on the surface may protect the bulk liquid solder from further oxidation. Moreover, results also indicate that, AgZn₃ IMCs layer formed at the interface, which may release reaction energy during the wetting, results in improving the wettability of the solder.     

Reliability studies of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu soldered joints with aging treatment

In this study, the interfacial reactions and joint reliabilities of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu were investigated during isothermal aging at 150 °C for aging times of up to 1,000 h. Cu₅Zn₈ IMCs layer is formed at the as-soldered Sn–9Zn/Cu interface. Adding 0.3wt.% Ag results in the adsorption of AgZn₃ on the Cu₅Zn₈ IMCs layer. The as-soldered Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu joints have sufficient pull strength. The thickness of the IMCs layer formed at the interface of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu both increase with increasing aging time. Correspondingly, both the pull forces of the Sn–9Zn and Sn–9Zn–0.3Ag soldered joints gradually decrease as the aging time prolonged. However, the thickness of the IMCs layer of Sn–9Zn–0.3Ag/Cu increases much slower than that of Sn–9Zn/Cu and the pull force of Sn–9Zn–0.3Ag soldered joint decreases much slower than that of Sn–9Zn soldered joint. After aging for 1,000 h, some Cu–Sn IMCs form between the Cu₅Zn₈ IMC and the Cu substrate, many voids form at the interface between the Cu₅Zn₈ layer and solder alloy, and some cracks form in the Cu₅Zn₈ IMCs layer of Sn–9Zn/Cu. The pull force Sn–9Zn soldered joint decreases by 53.1% compared to the pull force measured after as-soldered. Fracture of Sn–9Zn/Cu occurred on the IMCs layer on the whole and the fracture micrograph implies a brittle fracture. While the pull force of Sn–9Zn–0.3Ag soldered joint decreases by 51.7% after aging at 150 °C for 1,000 h. The fracture mode of Sn–9Zn–0.3Ag soldered joint is partially brittle at the IMCs layer, and partially ductile at the outer ring of the solder.     

Liquid-state and solid-state interfacial reactions between Sn–Ag–Cu–Fe composite solders and Cu substrate

The growth kinetics and morphology of the interfacial intermetallic compound (IMC) between Sn–3Ag–0.5Cu–xFe (x = 0, 0.5 wt%, 1 wt%) composite solders and Cu substrate were investigated in the present work. The Sn–Ag–Cu–Fe/Cu solder joint were prepared by reflowing for various durations at 250 °C and then aged at 150 °C. During soldering process, Fe particles quickly deposited in the vicinity of IMC, resulting in the formation of Fe-rich area. Isothermal equation of chemical reaction and phase diagrams were used to explain the effect of Fe on the growth kinetics of IMC during liquid-state interfacial reaction. It was shown that Fe could effectively retard the growth of interfacial Cu₆Sn₅ and Cu₃Sn layers during liquid-state reaction and reduce the size of Cu₆Sn₅ grains. Small cracks were observed in the Cu₆Sn₅ grains after reflowing for 2 min while they were found in the other composite solders reflowing for about 30 min. The Fe tended to suppress the growth of the Cu₃Sn layer during solid-state aging. However, the total thickness of IMCs (Cu₆Sn₅ + Cu₃Sn) for the composite solders with Fe particles was similar to that for SnAgCu without Fe particles.