Influence of Lanthanum Additions on the Microstructure and Microhardness of Sn-3.5Ag Solder

This study evaluates the effects of different amounts of lanthanum (La) additions on the microstructure and microhardness of Sn-3.5Ag solders. Sn-3.5Ag-xLa ternary solders were prepared by adding 0 wt.% to 1.0 wt.% La to Sn-3.5Ag alloy. Copper substrates were then dipped in the molten solders and these samples aged at 150°C for up to 625 h. The microstructure and microhardness of the as-solidified solder and the aged solder/copper samples were investigated. The Sn-3.5Ag-xLa solders comprised β-Sn, Ag₃Sn, and LaSn₃ phases, and their microstructure was refined by La additions. As-cast, the addition of La increased the microhardness of the Sn-Ag solder due to the refining effect of Ag₃Sn particles and increased formation of LaSn₃ compounds. As the aging time was increased, the microhardness of the solders decreased and the Ag₃Sn compounds coarsened. However, the coarsening of Ag₃Sn compounds was retarded by La, and the size and amount of LaSn₃ compounds did not change perceptibly with aging time. Therefore, La additions can improve the microhardness and thermal resistance of solder joints.     

The Crystal Orientation of β-Sn Grains in Sn-Ag and Sn-Cu Solders Affected by Their Interfacial Reactions with Cu and Ni(P) Under Bump Metallurgy

Recently, it has been reported that the crystal orientation and grain size of the β-Sn phase in Sn-rich solders have profound effects on the reliabilities of Pb-free solder joints, such as thermo-mechanical fatigue and electromigration. Additionally, it is also known that the microstructure of the Sn-rich solders is strongly affected by their alloy composition. In this study the grain size and orientation of the β-Sn phase were investigated in terms of their alloy composition and interfacial reactions with two different under bump metallurgies (UBMs), Cu and Ni(P). Solder balls (380 μm in diameter) of pure Sn, Sn-0.5Cu, Sn-0.5Ag, and Sn-1.8Ag (in weight percent) were reflowed on Cu and Ni(P) UBMs. After the reflow at 250°C for 120 s, the microstructure of the solder joints was analyzed by cross-polarization light microscopy and electron backscatter diffraction. For the compositional analysis of solder joints, electron probe micro-analysis was used and thermodynamics calculations were also performed. During reflow on Cu or Ni(P) UBM, Cu and Ni atoms were dissolved quickly and were saturated to their solubility limits in the solders, causing changes in composition and β-Sn grain orientation.     

Microstructural Variation and Phase Evolution in the Reaction of Sn-<Emphasis Type="Italic">x</Emphasis>Ag-Cu Solders and Cu-<Emphasis Type="Italic">y</Emphasis>Zn Substrates During Reflow

This study aims to investigate the reaction of Sn-xAg-0.5Cu (x = 1.0 wt.% and 3.0 wt.%) solders on Cu-yZn (y = 0 wt.%, 15 wt.%, and 30 wt.%) substrates at 250°C for 0.5 min, 2 min, and 10 min, respectively. Cu and Zn atoms dissolve from the Cu-yZn substrates into the molten solders during reflow, leading to variation of the solder composition. It was revealed that such composition variation altered the microstructure of the solders. The coarsening of the eutectic region and the decrease of large-sized Cu₆Sn₅ compounds inside the Sn-1.0Ag-0.5Cu solder on both Cu-15Zn and Cu-30Zn substrates were correlated with this elemental redistribution. In addition to the solder matrix, the interfacial reaction was also affected by Zn dissolution. For a Zn concentration of 15 wt.% to 30 wt.% in the Cu-Zn substrate, formation of Cu₃Sn was suppressed. An increase of the Zn content in Cu₆(Sn,Zn)₅ at the solder/Cu-30Zn interface resulted in the formation of a new Cu(Zn,Sn) phase. It was demonstrated that the microstructural variation and the phase evolution in the solder joints were controlled by the reflow time and the Zn concentration in the Cu-yZn substrate.     

Reaction of Liquid Sn-Ag-Cu-Ce Solders with Solid Copper

Small amounts of the rare-earth element Ce were added to the Sn-rich lead-free eutectic solders Sn-3.5Ag-0.7Cu, Sn-0.7Cu, and Sn-3.5Ag to improve their properties. The microstructures of the solders without Ce and with different amounts (0.1 wt.%, 0.2 wt.%, and 0.5 wt.%) of Ce were compared. The microstructure of the solders became finer with increasing Ce content. Deviation from this rule was observed for the Sn-Ag-Cu solder with 0.2 wt.% Ce, and for the Sn-0.7Cu eutectic alloy, which showed the finest microstructure without Ce. The melting temperatures of the solders were not affected. The morphology of intermetallic compounds (IMC) formed at the interface between the liquid solders and a Cu substrate at temperatures about 40°C above the melting point of the solder for dipping times from 2 s to 256 s was studied for the basic solder and for solder with 0.5 wt.% Ce addition. The morphology of the Cu₆Sn₅ IMC layer developed at the interface between the solders and the substrate exhibited the typical scallop-type shape without significant difference between solders with and without Ce for the shortest dipping time. Addition of Ce decreased the thickness of the Cu₆Sn₅ IMC layer only at the Cu/Sn-Ag-Cu solder interface for the 2-s dipping. A different morphology of the IMC layer was observed for the 256-s dipping time: The layers were less continuous and exhibited a broken relief. Massive scallops were not observed. For longer dipping times, Cu₃Sn IMC layers located near the Cu substrate were also observed.     

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.     

Effects of mechanical deformation and annealing on the microstructure and hardness of Pb-free solders

The microstructure property relations of several Pb-free solders are investigated to understand the microstructural changes during thermal and mechanical processes of Pb-free solders. The Pb-free solder alloys investigated include pure Sn, Sn-0.7% Cu, Sn-3.5% Ag, and Sn-3.8% Ag-0.7% Cu (in weight percent). To reproduce a typical microstructure observed in solder joints, the cooling rate, ingot size, and reflow conditions of cast alloys were carefully controlled. The cast-alloy pellets are subjected to compressive deformation up to 50% and annealing at 150°C for 48 h. The microstructure of Pb-free solders is evaluated as a function of alloy composition, plastic deformation, and annealing. The changes in mechanical property are measured by a microhardness test. The work hardening in Sn-based alloys is found to increase as the amount of alloying elements and/or deformation increases. The changes in microhardness upon deformation and annealing are correlated with the microstructural changes, such as recrystallization or grain growth, in Pb-free solder alloys.     

Mechanical Properties and Electrochemical Corrosion Behavior of Al/Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Ag/Cu Joints

The effect of Ag content on the wetting behavior of Sn-9Zn-xAg on aluminum and copper substrates during soldering, as well as the mechanical properties and electrochemical corrosion behavior of Al/Sn-9Zn-xAg/Cu solder joints, were investigated in the present work. Tiny Zn and coarsened dendritic AgZn₃ regions were distributed in the Sn matrix in the bulk Sn-9Zn-xAg solders, and the amount of Zn decreased while that of AgZn₃ increased with increasing Ag content. The wettability of Sn-9Zn-1.5Ag solder on Cu substrate was better than those of the other Sn-9Zn-xAg solders but worse than that of Sn-9Zn solder. The wettability of Sn-9Zn-1.5Ag on the Al substrate was also better than those of the other Sn-9Zn-xAg solders, and even better than that of Sn-9Zn solder. The Al/Sn-9Zn/Cu joint had the highest shear strength, and the shear strength of the Al/Sn-9Zn-xAg/Cu (x = 0 wt.% to 3 wt.%) joints gradually decreased with increasing Ag content. The corrosion resistance of the Sn-9Zn-xAg solders in Al/Sn-9Zn-xAg/Cu joints in 5% NaCl solution was improved compared with that of Sn-9Zn. The corrosion potential of Sn-9Zn-xAg solders continuously increased with increasing Ag content from 0 wt.% to 2 wt.% but then decreased for Sn-9Zn-3Ag. The addition of Ag resulted in the formation of the AgZn₃ phase and in a reduction of the amount of the eutectic Zn phase in the solder matrix; therefore, the corrosion resistance of the Al/Sn-9Zn-xAg/Cu joints was improved.     

Formation of Intermetallic Compounds Between Liquid Sn and Various CuNi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Metallizations

Interfacial reactions between liquid Sn and various Cu-Ni alloy metallizations as well as the subsequent phase transformations during the cooling were investigated with an emphasis on the microstructures of the reaction zones. It was found that the extent of the microstructurally complex reaction layer (during reflow at 240°C) does not depend linearly on the Ni content of the alloy metallization. On the contrary, when Cu is alloyed with Ni, the rate of thickness change of the total reaction layer first increases and reaches a maximum at a composition of about 10 at.% Ni. The reaction layer is composed of a relatively uniform continuous (Cu,Ni)₆Sn₅ reaction layer (a uniphase layer) next to the NiCu metallizations and is followed by the two-phase solidification structures between the single-phase layer and Sn matrix. The thickness of the two-phase layer, where the intermetallic tubes and fibers have grown from the continuous interfacial (Cu,Ni)₆Sn₅ layer, varies with the Ni-to-Cu ratio of the alloy metallization. In order to explain the formation mechanism of the reaction layers and their observed kinetics, the phase equilibria in the Sn-rich side of the SnCuNi system at 240°C were evaluated thermodynamically utilizing the available data, and the results of the Sn/Cu _x Ni_1−x diffusion couple experiments. With the help of the assessed data, one can also evaluate the minimum Cu content of Sn-(Ag)-Cu solder, at which (Ni,Cu)₃Sn₄ transforms into (Cu,Ni)₆Sn₅, as a function of temperature and the composition of the liquid solders.     

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.     

Intermetallic Formation and Fluidity in Sn-Rich Sn-Cu-Ni Alloys

This paper investigates the phase equilibria and solidification behavior of Sn-Cu-Ni alloys with compositions in the range of 0 wt.% to 1.5 wt.% Cu and 0 wt.% to 0.3 wt.% Ni. The isothermal section at 268°C in the Sn-rich corner was determined. No evidence for a ternary phase was found, and the section is in good agreement with past experimental studies that report wide solubility ranges for (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄. The vacuum fluidity test was applied to compositions that are liquid at 268°C to map the variation in microstructure and flow behavior with composition in this system. Significant variations in fluidity length were measured among the Sn-Cu-Ni alloys, and the variations correlate with the microstructure that develops during solidification. The generated fluidity map enables the selection of Sn-Cu-Ni solder compositions that exhibit good fluidity behavior during solidification and form near-eutectic microstructures.     

Mössbauer studies of β → α phase transition in Sn-rich solder alloys

Hyperfine interactions in tin-base alloys Sn-x%Ag-y%Cu (x = 0, 0.3, 3; y ∈ 0 ÷ 3) were studied using ¹¹⁹Sn Mössbauer spectroscopy in order to detect the conditions that promote α-Sn phase formation in metallic tin (β-Sn). In many engineering applications, so-called grey tin or tin pest (α-Sn) is a parasitic phase that weakens the mechanical properties of solder joints. In particular, the chemical composition of commercially available Sn-rich solders and their working temperature conditions could significantly affect the durability of tin joints. The Mössbauer results confirmed that the above mentioned factors have a significant impact on the growth rate of tin pest. The most visible α-Sn phase increase (28.5%) was observed for alloy containing 1% Cu. In turn, the addition of even a small amount of Ag could effectively suppress tin pest formation, which indicates that the composition of tin solder alloys is still demanding for commercial applications due to their time stability. On the other hand, the temperature dependence of Sn-rich solder degradation is a less dominant factor, although the thermal treatment effect can be measured quite well using Mössbauer spectroscopy.     

Effect of reflow and thermal aging on the microstructure and microhardness of Sn-3.7Ag-xBi solder alloys

This work investigates the effect of reflow and the thermal aging process on the microstructural evolution and microhardness of five types of Sn-Ag based lead-free solder alloys: Sn-3.7Ag, Sn-3.7Ag-1Bi, Sn-3.7Ag-2Bi, Sn-3.7Ag-3Bi, and Sn-3.7Ag-4Bi. The microhardness and microstructure of the solders for different cooling rates after reflow at 250°C and different thermal aging durations at 150°C for air-cooled samples have been studied. The effect of Bi is discussed based on the experimental results. It was found that the microhardness increases with increasing Bi addition to Sn-3.7Ag solder regardless of reflow or thermal aging process. Scanning electron microscopy images show the formation of Ag₃Sn particles, Sn-rich phases, and precipitation of Bi-rich phases in different solders. The increase of microhardness with Bi addition is due to the solution strengthening and precipitation strengthening provided by Bi in the solder. The trend of decrease in microhardness with increasing duration of thermal aging was observed.     

Fabrication and Microstructures of Sequentially Electroplated Sn-Rich Au-Sn Alloy Solders

Three Sn-rich, Au-Sn alloy solders with eutectic, hypoeutectic, and hypereutectic Sn compositions were fabricated by sequential electroplating of Au and Sn and then the dual-layer films were reflowed at 250°C. The microstructures and phase compositions of the deposited Au/Sn dual-layer film and the reflowed Sn-rich Au-Sn alloys were studied. Microhardness values of the different phases or phase zones for the reflowed alloys were also tested. Finally, two Si wafers were bonded together with the eutectic Sn-rich Au-Sn alloy solder. For as deposited Au/Sn dual-layer films, reaction between Au and Sn occurs at room temperature leading to the formation of Au₅Sn, AuSn, and AuSn₂ at the Au/Sn interface. After reflowing at 250°C, two phases remain, Sn and AuSn₄, with the morphology and phase distribution depending on the original solder composition. In the Sn-rich, eutectic Au-Sn alloy, AuSn₄ particles are distributed uniformly in the Sn matrix. In the Sn-rich hypoeutectic/hypereutectic Au-Sn alloys, the proeutectic phase, AuSn₄ (Vickers hardness, Hv 125) or Sn (Hv 14.2), is larger in size and is surrounded by the eutectic zone (Sn + AuSn₄) (Hv 16.1). In all cases, the TiW adhesion and barrier layer remains intact during annealing. After reflowing at 250°C under a pressure of 13 kPa, two Si wafers are joined by the Sn-rich eutectic Au-Sn alloy solder, without crack or void formation at the Si wafer/solder interface or within the solder.     

Specific Heat Capacities of Sn-Zn-Based Solders and Sn-Ag-Cu Solders Measured Using Differential Scanning Calorimetry

The specific heat capacities (C _p) of Sn-Zn-based solders and Sn-Ag-Cu solders have been studied using differential scanning calorimetry. The procedure of measuring the specific heat capacity followed the standard test method designed by the American Society for Testing and Materials (ASTM) E1269-05. The results of this work are lists of specific heat capacities of Sn-9Zn, Sn-9Zn-xAg (x = 0.1, 0.5, 1, 2, and 3), Sn-9Zn-0.5Ag-yAl (y = 0.1, 0.2, and 0.5), Sn-9Zn-0.5Ag-yGa (y = 0.1, 0.2, and 0.5), Sn-8.5Zn-0.5Ag-0.01Al-0.1Ga, and Sn-zAg-0.5Cu (z = 1.0, 2.0, 3.0, and 3.5). The study also found that C _p increased with increasing heating temperature. Furthermore, the lead-free solders investigated have a higher specific heat capacity than the traditional Sn-37Pb solder. Among the studied lead-free solders, Sn-3.5Ag-0.5Cu has the lowest C _p and Sn-9Zn-0.1Ag has the highest C _p. Increased silver content in the Sn-9Zn-xAg and Sn-xAg-0.5Cu solder alloys was also found to effectively lower their C _p.     

Interfacial Reaction and Die Attach Properties of Zn-Sn High-Temperature Solders

Interfacial reaction and die attach properties of Zn-xSn (x = 20 wt.%, 30 wt.%, and 40 wt.%) solders on an aluminum nitride–direct bonded copper substrate were investigated. At the interface with Si die coated with Au/TiN thin layers, the TiN layer did not react with the solder and worked as a good protective layer. At the interface with Cu, CuZn₅, and Cu₅Zn₈ IMC layers were formed, the thicknesses of which can be controlled by joining conditions such as peak temperature and holding time. During multiple reflow treatments at 260°C, the die attach structure was quite stable. The shear strength of the Cu/solder/Cu joint with Zn-Sn solder was about 30 MPa to 34 MPa, which was higher than that of Pb-5Sn solder (26 MPa). The thermal conductivity of Zn-Sn alloys of 100 W/m K to 106 W/m K was sufficiently high and superior to those of Au-20Sn (59 W/m K) and Pb-5Sn (35 W/m K).     

Effects of Ni Additions on the Growth of Cu<Subscript>3</Subscript>Sn in High-Lead Solders

In reactions between solders and Cu, additions of minor alloying elements, such as Fe, Co or Ni, to solders often reduce the Cu₃Sn growth rate. Nevertheless, the mechanism for this effect remains unresolved. To provide more experimental observations that are essential for uncovering this mechanism, growth of Cu₃Sn in the reaction between Cu and high-lead solders with or without Ni additions has been studied. The solders used for this study were 10Sn-90Pb and 5Sn-95Pb doped with 0 wt.%, 0.03 wt.%, 0.06 wt.%, 0.1 wt.% or 0.2 wt.% Ni. Reaction conditions included one reflow at 350°C for 2 min and solid-state aging at 160°C for up to 2000 h. The effect of Ni on the growth of Cu₃Sn is discussed in detail based on the experimental results.     

The Shear Strength and Fracture Behavior of Sn-Ag-<Emphasis Type="Italic">x</Emphasis>Sb Solder Joints with Au/Ni-P/Cu UBM

This study investigates the effects of Sb addition on the shear strength and fracture behavior of Sn-Ag-based solders with Au/Ni-P/Cu underbump metallization (UBM) substrates. Sn-3Ag-xSb ternary alloy solder joints were prepared by adding 0 wt.% to 10 wt.% Sb to a Sn-3.5Ag alloy and joining them with Au/Ni-P/Cu UBM substrates. The solder joints were isothermally stored at 150°C for up to 625 h to study their microstructure and interfacial reaction with the UBM. Single-lap shear tests were conducted to evaluate the mechanical properties, thermal resistance, and failure behavior. The results show that UBM effectively suppressed intermetallic compound (IMC) formation and growth during isothermal storage. The Sb addition helped to refine the Ag₃Sn compounds, further improving the shear strength and thermal resistance of the solders. The fracture behavior evolved from solder mode toward the mixed mode and finally to the IMC mode with increasing added Sb and isothermal storage time. However, SnSb compounds were found in the solder with 10 wt.% Sb; they may cause mechanical degradation of the solder after long-term isothermal storage.     

Mechanical and corrosion resistances of a Sn–0.7 wt.%Cu lead-free solder alloy

Sn–Cu alloys are interesting lead-free solder alternatives, with particular interest in the eutectic/near-eutectic compositions. However, little is known about the corrosion responses of these solders while subjected to corrosive environments. The present study examines the Sn–0.7 wt.%Cu solder alloy and the experimental results include a range of cooling rates and growth rates during solidification, metallography with comprehensive characterization of the distinct dendritic and cellular regions and the resulting corrosion and tensile mechanical parameters (potential, corrosion rate, polarization resistance, tensile strength). A β-Sn phase having a dendritic morphology is shown to characterize regions that are associated with higher cooling rates during solidification, while for lower cooling rates (<0.9 K/s) the prevalence of eutectic cells is observed. It was found that lower corrosion resistance and higher mechanical strength are associated with a microstructure formed by an arrangement of very fine dendritic branches and Cu₆Sn₅ fibrous intermetallic compound (IMC).     

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.