Effect of Ag on the Microstructure of Sn-8.5Zn-xAg-0.01Al-0.1Ga Solders Under High-Temperature and High-Humidity Conditions

The effect of Ag on the microstructure and thermal behavior of Sn-Zn and Sn-8.5Zn-xAg-0.01Al-0.1Ga solders (x from 0.1 wt.% to 1 wt.%) under high-temperature/relative humidity conditions (85°C/85% RH) for various exposure times was investigated. Scanning electron microscopy (SEM) studies revealed that, in all the investigated solders, the primary α-Zn phases were surrounded by eutectic β-Sn/α-Zn phases, in which fine Zn platelets were dispersed in the β-Sn matrix. SEM micrographs revealed that increase of the Ag content to 1 wt.% resulted in coarsening of the dendritic plates and diminished the Sn-9Zn eutectic phase in the microstructure. Differential scanning calorimetry (DSC) studies revealed that the melting temperature of Sn-8.5Zn-xAg-0.01Al-0.1Ga solder decreased from 199.6°C to 199.2°C with increase of the Ag content in the solder alloy. Both ZnO and SnO₂ along with Ag-Zn intermetallic compound (IMC) were formed on the surface when Sn-8.5Zn-0.5Ag-0.01Al-0.1Ga solder was exposed to high-temperature/high-humidity conditions (85°C/85% RH) for 100 h. The thickness of the ZnO phase increased as the Ag content and exposure time were increased. Sn whiskers of various shapes and lengths varying from 2 μm to 5 μm were extruded from the surface when the investigated five-element solder with Ag content varying from 0.5 wt.% to 1 wt.% was exposed to similar temperature/humidity conditions for 250 h. The length and density of the whiskers increased with further increase of the exposure time to 500 h and the Ag content in the solder to 1 wt.%. The Sn whisker growth was driven by the compressive stress in the solder, which was generated due to the volume expansion caused by ZnO and Ag-Zn intermetallic compound formation at the grain boundaries of Sn.     

The thermal property of lead-free Sn-8.55Zn-1Ag-XAl solder alloys and their wetting interaction with Cu

The wetting behaviors between the quaternary Sn-8.55Zn-1Ag-XAl solder alloys and Cu have been investigated with the wetting balance method. The Al contents, x, of the quaternary solder alloys investigated were 0.01–0.45 wt.%. The results of differential scanning calorimeter (DSC) analysis indicate that the solders exhibit a solid-liquid coexisting range of about 7–10°C. The solidus temperature of the quaternary Sn-8.55Zn-1Ag-XAl solder alloys is about 198.2°C, while the liquidus temperatures are 205–207°C. The experimental results showed that the wettability of the Sn-8.55Zn-1Ag-XAl solder alloys is improved by the addition of Al. The mean maximum wetting force of the solders with Cu is within 0.75–1.18 mN and the mean wetting time is around 1.0–1.1 sec, better than the ∼1.3 sec of eutectic Sn-9Zn and Sn-8.55Zn-1Ag solder alloys. The addition of Al also depresses the formation of ε-Ag-Zn compounds at the interface between Sn-8.55Zn-1Ag-XAl solders and copper.     

Wetting interaction between Sn-Zn-Ag solders and Cu

The wetting interaction of Sn-(7.1–9)Zn-(0–3)Ag solders with Cu was investigated from 230°C to 300°C. The wetting time, wetting forces, and activation energy of the wetting reaction were studied. The wetting time decreases with increasing temperature and increases with Ag content. The wetting force exhibits a disproportional correlation to temperature rise, while no trend was observed with respect to Ag content. The wetting behavior was ascribed to the interaction between Cu and Zn. The AgZn₃ compound was formed at the interface when the solder contains 0.3% Ag and above, while it was formed within the bulk solder at 2% Ag and above.     

Investigation of Dissolution Behavior of Metallic Substrates and Intermetallic Compound in Molten Lead-free Solders

This study investigates the dissolution behavior of the metallic substrates Cu and Ag and the intermetallic compound (IMC)-Ag₃Sn in molten Sn, Sn-3.0Ag-0.5Cu, Sn-58Bi and Sn-9Zn (in wt.%) at 300, 270 and 240°C. The dissolution rates of both Cu and Ag in molten solder follow the order Sn > Sn-3.0Ag-0.5Cu >Sn-58Bi > Sn-9Zn. Planar Cu₃Sn and scalloped Cu₆Sn₅ phases in Cu/solders and the scalloped Ag₃Sn phase in Ag/solders are observed at the metallic substrate/solder interface. The dissolution mechanism is controlled by grain boundary diffusion. The planar Cu₅Zn₈ layer formed in the Sn-9Zn/Cu systems. AgZn₃, Ag5Zn₈ and AgZn phases are found in the Sn-9Zn/Ag system and the dissolution mechanism is controlled by lattice diffusion. Massive Ag₃Sn phases dissolved into the solders and formed during solidification processes in the Ag₃Sn/Sn or Sn-3.0Ag-0.5Cu systems. AgZn₃ and Ag₅Zn₈ phases are formed at the Sn-9Zn/Ag₃Sn interface. Zn atoms diffuse through Ag-Zn IMCs to form (Ag, Zn)Sn₄ and Sn-rich regions between Ag₅Zn₈ and Ag₃Sn.     

Interfacial reaction between multicomponent lead-free solders and Ag,Cu, Ni,and Pd substrates

The interfacial reaction between two prototype multicomponent lead-free solders, Sn-3.4Ag-1Bi-0.7Cu-4In and Sn-3.4Ag-3Bi-0.7Cu-4In (mass%), and Ag, Cu, Ni, and Pd substrates are studied at 250°C and 150°C. The microstructural characterization of the solder bumps is carried out by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis. Ambient temperature, isotropic elastic properties (bulk, shear, and Young’s moduli and Poisson’s ratio) of these solders along with eutectic Sn-Ag, Sn-Bi, and Sn-Zn solders are measured. The isotropic elastic moduli of multicomponent solders are very similar to the eutectic Sn-Ag solder. The measured solubility of the base metal in liquid solders at 250°C agrees very well with the solubility limits reported in assessed Sn-X (X=Ag, Cu, Ni, Pd) phase diagrams. The measured contact angles were generally less than 15° on Cu and Pd substrates, while they were between 25° and 30° on Ag and Ni substrates. The observed intermediate phases in Ag/solder couples were Ag₃Sn after reflow at 250°C and Ag₃Sn and ζ (Ag-Sn) after solid-state aging at 150°C. In Cu/solder and Ni/solder couples, the interfacial phases were Cu₆Sn₅ and (Cu,Ni)₆Sn₅, respectively. In Pd/solder couples, only PdSn₄ after 60-sec reflow, while both PdSn₄ and PdSn₃ after 300-sec reflow, were observed.     

Influence of Ag micro-particle additions on the microstructure, hardness and tensile properties of Sn-9Zn binary eutectic solder alloy

In this study, an addition of Ag micro-particles (8-10 μm) with a content in the range between 0 and 1.5 wt.% to Sn-9Zn eutectic solder, were examined in order to understand the effect of Ag additions as the particulate reinforcement on the microstructural and mechanical properties as well as the thermal behavior of the newly developed composite solders. Here, an approach to prepare a micro-composite solder alloy by mixing Ag micro-particles with a molten Sn-Zn solder alloy was developed. The composite solder was prepared by mechanically mixing Ag micro-particles into the Sn-9Zn alloy melt to ensure a homogeneous distribution of the reinforcing particles. The distribution of the Ag micro-particles in the matrix was found to be fairly uniform. The Ag particles reacted with the Zn and formed ε-AgZn₃ intermetallic compounds (IMC) in the β-Sn matrix. It was found that the more Ag particles added to the Sn-9Zn solder, the more Ag-Zn compound formed. In the Sn-9Zn/XAg composite solder, the microstructure was composed of AgZn₃ IMC and α-Zn phase in the β-Sn matrix. Interestingly, as the Ag particles in the composite solder increased, the α-Zn phase was found to be depleted from the matrix. The average tensile strength of the composite solders increased with the Ag micro-particles content up to a certain limit. Beyond this limit, the addition of Ag particles actually decreased the strength.     

The microstructures and mechanical properties of the Sn-Zn-Ag-Al-Ga solder alloys—the effect of Ag

The microstructures and mechanical properties of Sn-8.55Zn-xAg-0.45 Al-0.5Ga (wt.%) lead-free solders were investigated. The x content of the solders investigated were 0.5–3.0 wt.%. The results indicate that Ag plays an important role not only in the structure but also in the mechanically properties. The mechanical properties and differential scanning calorimetry (DSC) behavior has been compared with that of 63Sn-37Pb solder. Small additions of Ag decreased the melting point of the Sn-8.55Zn-xAg-0.45Al-0.5Ga solders while maintaining the same strength and ductility as the 63Sn-37Pb solder.     

The adhesion strength of A lead-free solder hot-dipped on copper substrate

Eutectic Sn-Zn-Al solder alloy was used [composition: 91Sn-9(5Al-Zn)] to investigate the effects of dipping parameters such as the temperature, rate and time dipping on the adhesion strength between solder and substrate using dimethylammonium chloride (DMAHCl) flux. The optimum conditions for the highest adhesion strength (about 8 MPa) were determined as dipping at 350°C, and a rate of 10.8∼11.8 mm/s for 5∼7.5 min. A poor solder coating was obtained as dipped at 250°C. Some defects by non-wetting were found as dipped at a slow rate (slower than 8.2 mm/s). Quite different from the most tin-based solders for copper substrate, γ-Cu₅Zn₈ intermetallic compound particles were found by x-ray diffraction (XRD) analysis at the interface of solder and substrate as dipped at 300°C after pull-off test by etching out the unreacted solder layer. The morphology of the intermetallic compound formed was observed by scanning electron microscopy (SEM). The elements of Al (near Cu), Zn (near Sn) are enriched at the interface of solder and copper substrate as determined by the line scanning and mapping analysis.     

Effect of Zn Addition on Interfacial Reactions Between Sn-4Ag Solder and Ag Substrates

In this study, the effect of Zn (Zn = 1 wt.%, 3 wt.%, and 7 wt.%) additions to Sn-4Ag solder reacting with Ag substrates was investigated under solid-state and liquid-state conditions. The composition and microstructure of the intermetallic compounds (IMCs) significantly changed due to the introduction of different Zn contents. In the case of Sn-4Ag solder with 1 wt.% Zn, a continuous Ag-Sn IMC layer formed on the Ag substrates; discontinuous Ag-Zn layers and Sn-rich regions formed on the Ag substrates under liquid-state conditions when the Sn-4Ag solders contained 3 wt.% and 7 wt.% Zn. If 3 wt.% Zn was added to Sn-4Ag solder, the Ag-Sn IMC would be transformed into a Ag-Zn IMC with increasing aging time. Rough interfaces between the IMCs and the Ag substrates were observed in Sn-4Ag-7Zn/Ag joints after reflowing at 260°C for 15 min; however, the interfaces between the IMCs and the Ag substrates became smooth for Sn-4Ag-1Zn/Ag and Sn-4Ag-3Zn/Ag joints. The nonparabolic growth mechanism of IMCs was probed in the Sn-4Ag-3Zn/Ag joints during liquid-state reaction, and can be attributed to the detachment of IMCs. On the other hand, the effect of gravity was also taken into account to explain the formation of IMCs at the three different interfaces (bottom, top, and vertical) during the reflow procedure.     

Intermetallic growth kinetics for Sn-Ag, Sn-Cu, and Sn-Ag-Cu lead-free solders on Cu, Ni, and Fe-42Ni substrates

Soldering with the lead-free tin-base alloys requires substantially higher temperatures (∼235–250°C) than those (213–223°C) required for the current tin-lead solders, and the rates for intermetallic compound (IMC) growth and substrate dissolution are known to be significantly greater for these alloys. In this study, the IMC growth kinetics for Sn-3.7Ag, Sn-0.7Cu, and Sn-3.8Ag-0.7Cu solders on Cu substrates and for Sn-3.8Ag-0.7Cu solder with three different substrates (Cu, Ni, and Fe-42Ni) are investigated. For all three solders on Cu, a thick scalloped layer of η phase (Cu₆Sn₅) and a thin layer of ε phase (Cu₃Sn) were observed to form, with the growth of the layers being fastest for the Sn-3.8Ag-0.7Cu alloy and slowest for the Sn-3.7Ag alloy. For the Sn-3.8Ag-0.7Cu solder on Ni, only a relatively uniform thick layer of η phase (Cu,Ni)₆Sn₅ growing faster than that on the Cu substrate was found to form. IMC growth in both cases appears to be controlled by grain-boundary diffusion through the IMC layer. For the Fe-42Ni substrate with the Sn-3.8Ag-0.7Cu, only a very thin layer of (Fe,Ni)Sn₂ was observed to develop.     

Effect of TiO<Subscript>2</Subscript> Nanoparticles Addition on the Thermal,Microstructural and Room-Temperature Creep Behavior of Sn-Zn Based Solder

The effect of adding TiO₂ nanoparticles as well as aging time on the thermal, microstructural and creep properties of Sn-6.5Zn solder was studied. The Sn-6.5Zn composite solders were prepared by mechanically dispersing different weight percentages (0.0 wt.%, 0.25 wt.%, 0.50 wt.%, 0.75 wt.% and 1.0 wt.%) of TiO₂ nanoparticles into Sn-6.5Zn solder. After being solution heat treated at 453 K for 4 h, specimens were cooled by water quenching at 273 K. Specimens were artificially aged at 393 K for durations ranging from 15 to 120 min, followed by water quenching at 273 K to cease further aging. The thermal behavior of the composite solders was investigated using differential scanning calorimetry (DSC). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to observe the microstructure of the solders. The mechanical properties were characterized using tensile creep tests and correlated with microstructural features. The investigation revealed that the minimum creep rate of solders decreased with the increase in the content of TiO₂, while it increased with increasing aging time. The data from microstructure-properties analysis showed that the nano-TiO₂ particles had significantly refined the microstructure and improved the creep resistance in comparison with the Sn-Zn solder. The calculated stress exponent values were close to 7.     

Effect of small Sn–3.5Ag–0.5Cu additions on the structure and properties of Sn–9Zn solder in ball grid array packages

Sn–9Zn with various additions of Sn–3.5Ag–0.5Cu powder was prepared by mechanically dispersing different weight percentages (1, 3, 5 and 7) of Sn–Ag–Cu powder into Sn–9Zn solder paste. In the Sn–Zn solder, scallop-shaped AuZn₃ intermetallic compound was found at the interfaces. On the other hand, in the Sn–3.5Ag–0.5Cu content solders, an additional ε-AgZn₃ intermetallic compound layer was found to be well adhered on the top surface of the AuZn₃ layer and the ε-AgZn₃ layer thickness increased with the number of reflow cycles. In addition, fine spherical-shaped ε-AgZn₃ intermetallic compound particles as well as an acicular-shaped Zn-rich phase was clearly observed in the β-Sn matrix. On increasing the Sn–Ag–Cu content, the shear load was increased from 1.80 to 2.03 kg after one reflow cycle. In the Sn–3.5Ag–0.5Cu content solders, the fracture surfaces exhibited typical ductile behavior with very rough dimpled surfaces while the fracture surface in the Sn–Zn solder gave fractures with a brittle appearance. In the fracture surface of the Sn–3.5Ag–0.5Cu content solders, some dimples were clearly observed associated with the formation of spherical-shaped ε-AgZn₃ intermetallic compound particles.     

The microstructures and mechanical properties of the Sn-Zn-Ag-Al-Ga solder alloys—The effect of Ga

The microstructures and mechanical properties of Sn-8.55Zn-0.5Ag-0.45Al-yGa (wt.%) lead-free solders were investigated. The y content of the solders investigated was 0.5–3.0 wt.%. The results indicate that Ga exhibits prominent influence in the microstructure as well as mechanical properties of the solders. By increasing Ga, the fraction of the Sn/Zn eutectic region decreases and the Sn-matrix region increases. An increase in the Ga content from 0.5 wt.% to 2.0 wt.% enhances the tensile strength while degrading the ductility. The mechanical properties and differential scanning calorimetry (DSC) behavior have been compared with that of the 63Sn-37Pb solder. Gallium lowers the melting point of the Sn-8.55Zn-0.5Ag-0.45Al-yGa solders. The Sn-8.55Zn-0.5Ag-0.45Al-0.5Ga solders exhibit greater tensile strength and better ductility than the 63Sn-37Pb solder.     

Role of Ag in the formation of interfacial intermetallic phases in Sn-Zn soldering

This study explored the effect of Ag as the substrate or alloying element of solders on the interfacial reaction in Sn-Zn soldering. Results show that instead of Ag-Sn compounds, ζ-AgZn and γ-Ag₅Zn₈ form at the Sn-Zn/Ag interface. The addition of Ag in Sn-Zn solders leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics. The morphology of this additional AgZn₃ is closely related to the solidification process of Ag-Zn intermetallics and the under intermetallic layer.     

Interfacial Reactions and Joint Strengths of Sn-<Emphasis Type="Italic">x</Emphasis>Zn Solders with Immersion Ag UBM

The solder joint microstructures of immersion Ag with Sn-xZn (x = 0 wt.%, 1 wt.%, 5 wt.%, and 9 wt.%) solders were analyzed and correlated with their drop impact reliability. Addition of 1 wt.% Zn to Sn did not change the interface microstructure and was only marginally effective. In comparison, the addition of 5 wt.% or 9 wt.% Zn formed layers of AgZn₃/Ag₅Zn₈ at the solder joint interface, which increased drop reliability significantly. Under extensive aging, Ag-Zn intermetallic compounds (IMCs) transformed into Cu₅Zn₈ and Ag₃Sn, and the drop impact resistance at the solder joints deteriorated up to a point. The beneficial role of Zn on immersion Ag pads was ascribed to the formation of Ag-Zn IMC layers, which were fairly resistant to the drop impact, and to the suppression of the brittle Cu₆Sn₅ phase at the joint interface.     

Reliability investigation and interfacial reaction of ball-grid-array packages using the lead-free Sn-Cu solder

The interfacial reactions between two Sn-Cu (Sn-0.7Cu and Sn-3Cu, wt.%) ball-grid-array (BGA) solders and the Au/Ni/Cu substrate by solid-state isothermal aging were examined at temperatures between 70°C and 170°C for 0 to 100 days. For the Sn-0.7Cu solder, a (Cu,Ni)₆Sn₅ layer was observed in the samples aged at 70–150°C. After isothermal aging at 170°C for 50 days, the solder/Ni interface exhibited a duplex structure of (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄. For the Sn-3Cu solder, only the (Cu,Ni)₆Sn₅ layer was formed in all aged samples. Compared to these two Sn-Cu solders, the Cu content in the (Cu,Ni)₆Sn₅ layer formed at the interface increased with the Cu concentration in the Sn-xCu solders. And, the shear strength was measured to evaluate the effect of the interfacial reactions on the mechanical reliability as a function of aging conditions. The shear strength significantly decreased after aging for 1 day and then remained nearly unchanged by further prolonged aging. In all the samples, the fracture always occurred in the bulk solder. Also, we studied the electrical property of Cu/Sn-3Cu/Cu BGA packages with the number of reflows. The electrical resistivity increased with the number of reflows because of an increase of intermetallic compound (IMC) thickness.     

Soldering reactions between In49Sn and Ag thick films

The interfacial reactions between In49Sn solders and Ag thick films at temperatures ranging from 200°C to 350°C have been studied. The intermetallic compound formed at the Ag/In49Sn interface is Ag₂In enveloped in a thin layer of AgIn₂. Through the measurement of the thickness decrease of Ag thick films, it has been determined that the reaction kinetics of Ag₂In has a linear relation to reaction time. Morphology observations indicated that the linear reaction of Ag₂In was caused by the floating of Ag₂In into the In49Sn solder as a result of the In49Sn solder penetrating into the porous Ag thick film. A sound joint can be obtained when a sufficient thickness of the Ag thick film (over 19.5 μm) reacts with the In49Sn solder. In this case, the tensile tested specimens fracture in the In49Sn matrix.     

Microstructure and Creep Deformation of Sn-Ag-Cu-Bi/Cu Solder Joints

Sn-Ag-Cu solder is one of the candidate alternatives to Sn-Pb-based solders. In order to improve its performance, different materials have been added to Sn-Ag-Cu-based solders. Several studies on Sn-Ag-Cu-based solders with Bi additions have shown Sn-Ag-Cu-Bi to be a class of solders with good wetting behavior and good performance that show great promise for use in the electronics assembly and packaging industry. To investigate the mechanical reliability of the Sn-Ag-Cu-Bi solders further, single-lap shear creep characteristics have been studied in this work. Dog-bone-type solder joint specimens were formed using five types of solder alloys, Sn-3.0Ag-0.5Cu and Sn-3.0 Ag-0.5Cu-xBi (x = 1 wt.% to 4 wt.%) with Cu substrates, and creep tests were performed at temperatures of 120°C and 150°C under stresses of 5 MPa to 10 MPa. Results indicate that the rupture times for Sn-3.0Ag-0.5Cu-xBi solder joints up to 4 wt.% of Bi are longer than the rupture time for Sn-3.0Ag-0.5Cu. Stress exponents ranged from 3 to 7 for temperatures of 150°C and 120°C with stresses under 10 MPa. Microstructural analyses using scanning electron microscopy (SEM) were performed and related to the creep behavior of the solder joints.     

Intermetallic reactions in reflowed and aged Sn-9Zn solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflowing of Sn-9Zn solder ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the surface-finished Au and Ag film dissolved rapidly and reacted with the Sn-9Zn solder to form a γ₃-AuZn₄/γ-Au₇Zn₁₈ intermetallic double layer and ε-AgZn₆ intermetallic scallops, respectively. The growth of γ₃-AuZn₄ is prompted by further aging at 100°C through the reaction of γ-Au₇Zn₁₈ with the Zn atoms dissolved from the Zn-rich precipitates embedded in the β-Sn matrix of Sn-9Zn solder BGA with Au/Ni/Cu pads. No intermetallic compounds can be observed at the solder/pad interface of the Sn-9Zn BGA specimens aged at 100°C. However, after aging at 150°C, a Ni₄Zn₂₁ intermetallic layer is formed at the interface between Sn-9Zn solder and Ni/Cu pads. Aging the immersion Ag packages at 100°C and 150°C caused a γ-Cu₅Zn₈ intermetallic layer to appear between ε-AgZn₆ intermetallics and the Cu pad. The scallop-shaped ε-AgZn₆ intermetallics were found to detach from the γ-Cu₅Zn₈ layer and float into the solder ball. Accompanied with the intermetallic reactions during the aging process of reflowed Sn-9Zn solder BGA packages with Au/Ni/Cu and Ag/Cu pads, their ball shear strengths degrade from 8.6 N and 4.8 N to about 7.2 N and 2.9 N, respectively.     

Solid state intermetallic compound growth between copper and high temperature,tin-rich solders—part I: Experimental analysis

An experimental study was performed which examined the solid state growth kinetics of the interfacial intermetallic compound layers formed between copper and the high temperature, tin-rich solders 96.5Sn-3.5Ag (wt.%) and 95Sn-5Sb. These results were compared with baseline data from the 100Sn/copper system. Both the 96.5Sn-3.5Ag and 95Sn-5Sb solders exhibited the individual Cu₃Sn and Cu₆Sn₅ layers at the interface; the thickness of the Cu₃Sn layer being a function of the aging time and temperature. The total thickness of the intermetallic compound layer formed in the 96.5Sn-3.5Ag solder/copper couple showed a mixture of linear and √t dependencies at the lower temperatures of 70,100, and 135°C, and a t^0.42 dependence at 170 and 205°C. The combined apparent activation energy was 59 kJ/mol, the Arrhenius plot showed a knee between the low and high temperature data. The total layer thickness of the 95Sn-5Sb/copper system exhibited √t dependence at the three lower temperatures and t^0.42 growth kinetics at 170 and 205°C. The combined apparent activation energy was 61 kJ/mol.