Interfacial Reactions of Sn-3.5Ag-<Emphasis Type="Italic">x</Emphasis>Zn Solders and Cu Substrate During Liquid-State Aging

The effects of Zn (1 wt.%, 3 wt.%, and 7 wt.%) additions to Sn-3.5Ag solder and various reaction times on the interfacial reactions between Sn-3.5Ag-xZn solders and Cu substrates a during liquid-state aging were investigated in this study. The composition and morphological evolution of interfacial intermetallic compounds (IMCs) changed significantly with the Zn concentration and reaction time. For the Sn-3.5Ag-1Zn/Cu couple, CuZn and Cu₆Sn₅ phases formed at the interface. With increasing aging time, the Cu₆Sn₅ IMC layer grew thicker, while the CuZn IMC layer drifted into the solder and decomposed gradually. Cu₅Zn₈ and Ag₅Zn₈ phases formed at the interfaces of Sn-3.5Ag-3Zn/Cu and Sn-3.5Ag-7Zn/Cu couples. With increasing reaction time, the Cu₅Zn₈ layer grew and Cu atoms diffused from the substrate to the solder, which transformed the Ag₅Zn₈ to (Cu,Ag)₅Zn₈. The Cu₆Sn₅ layer that formed between the Cu₅Zn₈ layer and Cu was much thinner at the Sn-3.5Ag-7Zn/Cu interface than at the Sn-3.5Ag-3Zn/Cu interface. Additionally, we measured the thickness of interfacial IMC layers and found that 3 wt.% Zn addition to the solder was the most effective for suppressing IMC growth at the interfaces.     

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.     

Interfacial reaction and joint reliability of fine-pitch flip-chip solder bump using stencil printing method

This study was focused on the formation and reliability evaluation of solder joints with different diameters and pitches for flip chip applications. We investigated the interfacial reaction and shear strength between two different solders (Sn-37Pb and Sn-3.0Ag-0.5Cu, in wt.%) and ENIG (Electroless Nickel Immersion Gold) UBM (Under Bump Metallurgy) during multiple reflow. Firstly, we formed the flip chip solder bumps on the Ti/Cu/ENIG metallized Si wafer using a stencil printing method. After reflow, the average solder bump diameters were about 130, 160 and 190 μm, respectively. After multiple reflows, Ni₃Sn₄ intermetallic compound (IMC) layer formed at the Sn-37Pb solder/ENIG UBM interface. On the other hand, in the case of Sn-3.0Ag-0.5Cu solder, (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄ IMCs were formed at the interface. The shear force of the Pb-free Sn-3.0Ag-0.5Cu flip chip solder bump was higher than that of the conventional Sn-37Pb flip chip solder bump.     

Optimal phosphorous content selection for the soldering reaction of Ni-P under bump metallization with Sn-Ag-Cu solder

Nickel plating has been used as the under bump metallization (UBM) in the microelectronics industry. The electroplated Ni-P UBM with different phosphorous contents (7 wt.%, 10 wt.%, and 13 wt.%) was used to evaluate the interfacial reaction between Ni-P UBM and Sn-3Ag-0.5Cu solder paste during multiple reflow. (Cu,Ni)₆Sn₅ intermetallic compounds (IMC) formed in the SnAgCu solder/Ni-P UBM interface after the first reflow. For three times reflow, (Ni,Cu)₃Sn₄ IMC formed, while (Cu,Ni)₆Sn₅ IMC spalled into the solder matrix. With further increasing cycles of reflow, the Ni-Sn-P layer formed between (Ni,Cu)₃Sn₄ IMC and Ni-P UBM for Ni-10wt.%P and Ni-13wt.%P UBM. However, almost no Ni-Sn-P layer was revealed for the Ni-7wt.%P UBM even after ten cycles of reflow. In consideration of the wettability of Ni-P UBM, the interfacial reaction of SnAgCu/Ni-P, and dissolution of Ni-P UBM, the optimal phosphorous selection in Ni-P UBM was proposed and also discussed.     

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.     

Interfacial reaction between Sn-0.7Cu (-Ni) solder and Cu substrate

The interfacial reaction between Sn-0.7mass%Cu-(Ni) solders and a Cu substrate was investigated to reveal the effect of the addition of Ni to Sn-Cu solder on the formation of intermetallic compounds (IMCs). Sn-0.7Cu-xNi solders (x=0, 0.05, 0.1, 0.2 mass%) were prepared. For the reflow process, specimens were heated in a radiation furnace at 523 K for 60 sec, 300 sec, and 720 sec to estimate the interfacial reaction between the molten solder and Cu substrate. Then, for the aging process, some specimens were heat-treated in an oil bath at 423 K for 168 h and 504 h. The cross sections of soldered specimens were observed to measure the dissolution thickness of the Cu substrate and the thickness of the IMC and to investigate the microstructures of IMC. The results showed that, just after the reflow process, the dissolution thickness of the Cu substrate increased with the increase of Ni content in the Sn-0.7Cu-xNi solder and the thickness of the IMC between the solder and Cu substrate was the minimum in the Sn-0.7Cu-0.05Ni solder. After the aging process, the IMC grew with the increase of aging time. In the case of 0.05% Ni, the IMC thickness was the thinnest regardless of aging time. It is clear that 0.05% Ni addition to Sn-0.7Cu solder very effectively inhibits the formation and growth of the IMC between solder and Cu substrate. Electron probe microanalysis of the IMC showed that the IMC layer in the Sn-0.7Cu-Ni solder contained Ni, and the IMC was expressed as (Cu_1−y ,Ni _y )₆Sn₅.     

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.     

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 Aluminum Concentration on the Interfacial Reactions of Sn-3.0Ag-<Emphasis Type="Italic">x</Emphasis>Al Solders with Copper and ENIG Metallizations

Aluminum was added into Sn-3.0Ag (wt.%) solder to investigate the effect of aluminum concentration on the interfacial reaction of Sn-3.0Ag-xAl solders with copper or electroless nickel immersion gold (ENIG) metallizations. Four different Sn-3.0Ag-xAl solders (x = 0 wt.%, 0.1 wt.%, 0.5 wt.%, and 1.0 wt.%) were used for comparison. It was found that the composition, morphology, and thickness of interfacial reaction products were strongly dependent on aluminum concentration. At low aluminum concentration (0.1 wt.%), the typical Cu₆Sn₅ layer was formed at the interface. When the aluminum concentration was 0.5 wt.%, a continuous CuAl₂ layer spalled off from the interfacial Cu-Sn intermetallic compound (IMC) layer. Only a planar CuAl₂ layer was observed at the interface when the aluminum concentration was increased to 1.0 wt.%. In Sn-Ag-Al/ENIG reactions, Ni₃Sn₄ was formed and spallation occurred near the interface in the Sn-3.0Ag and Sn-3.0Ag-0.1Al solder joints. When the aluminum concentration was higher than 0.1 wt.%, a thin planar AuAl compound formed at the interface. There was no P-rich phase formation that retarded the spalling phenomenon. The aluminum additive in Sn-Ag solder inhibited the growth of IMCs in the reaction with copper or ENIG metallizations, which was favorable for the reliability of solder joints.     

Influence of Cu content on compound formation near the chip side for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump during aging

Sn-Ag-Cu solder is a promising candidate to replace conventional Sn-Pb solder. Interfacial reactions for the flip-chip Sn-3.0Ag-(0.5 or 1.5)Cu solder joints were investigated after aging at 150°C. The under bump metallization (UBM) for the Sn-3.0Ag-(0.5 or 1.5)Cu solders on the chip side was an Al/Ni(V)/Cu thin film, while the bond pad for the Sn-3.0Ag-0.5Cu solder on the plastic substrate side was Cu/electroless Ni/immersion Au. In the Sn-3.0Ag-0.5Cu joint, the Cu layer at the chip side dissolved completely into the solder, and the Ni(V) layer dissolved and reacted with the solder to form a (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). For the Sn-3.0Ag-1.5Cu joint, only a portion of the Cu layer dissolved, and the remaining Cu layer reacted with solder to form Cu₆Sn₅ IMC. The Ni in Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. At the plastic substrate side, three interfacial products, (Cu_1−y,Ni_y)₆Sn₅, (Ni_1−x,Cu_x)₃Sn₄, and a P-rich layer, were observed between the solder and the EN layer in both Sn-Ag-Cu joints. The interfacial reaction near the chip side could be related to the Cu concentration in the solder joint. In addition, evolution of the diffusion path near the chip side in Sn-Ag-Cu joints during aging is also discussed herein.     

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.     

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.     

Dissolution and Interfacial Reactions of (Cu,Ni)6Sn5 Intermetallic Compound in Molten Sn-Cu-Ni Solders

(Cu,Ni)₆Sn₅ is an important intermetallic compound (IMC) in lead-free Sn-Ag-Cu solder joints on Ni substrate. The formation, growth, and microstructural evolution of (Cu,Ni)₆Sn₅ are closely correlated with the concentrations of Cu and Ni in the solder. This study reports the interfacial behaviors of (Cu,Ni)₆Sn₅ IMC (Sn-31 at.%Cu-24 at.%Ni) with various Sn-Cu, Sn-Ni, and Sn-Cu-Ni solders at 250°C. The (Cu,Ni)₆Sn₅ substrate remained intact for Sn-0.7 wt.%Cu solder. When the Cu concentration was decreased to 0.3 wt.%, (Cu,Ni)₆Sn₅ significantly dissolved into the molten solder. Moreover, (Cu,Ni)₆Sn₅ dissolution and (Ni,Cu)₃Sn₄ formation occurred simultaneously for the Sn-0.1 wt.%Ni solder. In Sn-0.5 wt.%Cu-0.2 wt.%Ni solder, many tiny (Cu,Ni)₆Sn₅ particulates were formed and dispersed in the solder matrix, while in Sn-0.3 wt.%Cu-0.2 wt.%Ni a lot of (Ni,Cu)₃Sn₄ grains were produced. Based on the local equilibrium hypothesis, these results are further discussed based on the liquid–(Cu, Ni)₆Sn₅–(Ni,Cu)₃Sn₄ tie-triangle, and the liquid apex is suggested to be very close to Sn-0.4 wt.%Cu-0.2 wt.%Ni.     

elemental redistribution and interfacial reaction mechanism for the flip chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump with Al/Ni(V)/Cu under-Bump metallization during aging

In flip chip technology, Al/Ni(V)/Cu under-bump metallization (UBM) is currently applicable for Pb-free solder, and Sn−Ag−Cu solder is a promising candidate to replace the conventional Sn−Pb solder. In this study, Sn-3.0Ag-(0.5 or 1.5)Cu solder bumps with Al/Ni(V)/Cu UBM after assembly and aging at 150°C were employed to investigate the elemental redistribution, and reaction mechanism between solders and UBMs. During assembly, the Cu layer in the Sn-3.0Ag-0.5Cu joint was completely dissolved into solders, while Ni(V) layer was dissolved and reacted with solders to form (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). The (Cu_1−y,Ni_y)₆Sn₅ IMC gradually grew with the rate constant of 4.63 × 10⁻⁸ cm/sec^0.5 before 500 h aging had passed. After 500 h aging, the (Cu_1−y,Ni_y)₆Sn₅ IMC dissolved with aging time. In contrast, for the Sn-3.0Ag-1.5Cu joint, only fractions of Cu layer were dissolved during assembly, and the remaining Cu layer reacted with solders to form Cu₆Sn₅ IMC. It was revealed that Ni in the Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. During the period of 2,000 h aging, the growth rate constant of (Cu_1−y,Ni_y)₆Sn₅ IMC was down to 1.74 × 10⁻⁸ cm/sec^0.5 in, the Sn-3.0Ag-1.5Cu joints. On the basis of metallurgical interaction, IMC morphology evolution, growth behavior of IMC, and Sn−Ag−Cu ternary isotherm, the interfacial reaction mechanism between Sn-3.0Ag-(0.5 or 1.5)Cu solder bump and Al/Ni(V)/Cu UBM was discussed and proposed.     

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 Reactions of Si Die Attachment with Zn-Sn and Au-20Sn High Temperature Lead-Free Solders on Cu Substrates

The interfacial reaction of Si die attachment with a high temperature lead-free solder of Zn-xSn (x = 20 wt.%, 30 wt.% and 40 wt.%) was investigated, and the currently used high temperature lead-free solder of Au-20Sn was compared. A sound die attachment to a Cu substrate can be achieved with Zn-Sn solder. No intermetallic compound (IMC) phase was observed in the solder layer, and only primary α-Zn and Sn-Zn eutectic phases were observed. At the interface with the Si die, with a metallization of Au/Ag/Ni, an AgAuZn₂, IMC layer was formed along the interface, and the Ni coating layer did not react with the solder. At the interface with the Cu substrate, CuZn₅ and Cu₅Zn₈ IMC layers were confirmed, and their thicknesses can be controlled by soldering conditions. During multiple reflows, the growth of these IMC layers was observed, but no additional voids or cracks were observed. For more reliable die attachment, a titanium nitride (TiN) coating layer was applied to suppress the formation of Cu-Zn IMCs. The Si die attached joint on the TiN-coated Cu was quite stable during the multiple reflows, and no visible IMC phase was confirmed in the interfacial microstructure.     

Effects of Co Addition on Bulk Properties of Sn-3.5Ag Solder and Interfacial Reactions with Ni-P UBM

The effects of Co addition on the undercooling, microstructure, and microhardness of Sn-3.5Ag solder (all in wt.% unless specified otherwise) and interfacial reactions with Ni-P under bump metallurgy (UBM) are investigated when the Co content varies from 0.01 wt.% to 0.7 wt.%. When more than 0.02 wt.% Co was added to Sn-3.5Ag solder, the undercooling of the Sn-3.5Ag solder was significantly reduced and the microstructures coarsened with the increased eutectic region. In addition, the hardness value increased as the Co content in Sn-3.5Ag increased. In the interfacial reactions with Ni-P UBM, a spalling phenomenon of intermetallic compounds (IMCs) during reflow was prevented in the Sn-3.5Ag-xCo (x ≥ 0.02 wt.%). However, when more than 0.05 wt.% Co was added to Sn-3.5Ag, the IMC morphology changed from a bulky shape to a plate-like shape. The bulky IMCs were Ni₃Sn₄ and the plate-like IMCs were Sn-Ni-Co ternary compounds. The main issues discussed include the relations between the morphological changes and the IMC phases, the effects of Co addition on the prevention of IMC spalling, and the optimum level of Co addition.     

Interfacial reactions and shear strengths between Sn-Ag-based Pb-free solder balls and Au/EN/Cu metallization

The morphological and compositional evolutions of intermetallic compounds (IMCs) formed at three Pb-free solder/electroless Ni-P interface were investigated with respect to the solder compositions and reflow times. The three Pb-free solder alloys were Sn3.5Ag, Sn3.5Ag0.75Cu, and Sn3Ag6Bi2In (in wt.%). After reflow reaction, three distinctive layers, Ni₃Sn₄ (or Ni-Cu-Sn for Sn3.5Ag0.75Cu solder), NiSnP, and Ni₃P, were formed on the electroless Ni-P layer in all the solder alloys. For the Sn3.5Ag0.75Cu solder, with increasing reflow time, the interfacial intermetallics switched from (Cu,Ni)₆Sn₅ to (Cu,Ni)₆Sn₅+(Ni,Cu)₃Sn₄, and then to (Ni,Cu)₃Sn₄ IMCs. The degree of IMC spalling for the Sn3.5Ag0.75Cu solder joint was more than that of other solders. In the cases of the Sn3.5Ag and Sn3Ag6Bi2In solder joints, the growth rate of the Ni₃P layer was similar because these two type solder joints had a similar interfacial reaction. On the other hand, for the Sn3.5Ag0.75Cu solder, the thickness of the Ni₃P and Ni-Sn-P layers depended on the degree of IMC spalling. Also, the shear strength showed various characteristics depending on the solder alloys and reflow times. The fractures mainly occurred at the interfaces of Ni₃Sn₄/Ni-Sn-P and solder/Ni₃Sn₄.     

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 Ni concentration and Ni3Sn4 nanoparticles on morphology of Sn-Ag-Ni solders by mechanical alloying

The mechanical alloying (MA) process was employed as an alternative method to produce the lead-free solder pastes of Sn-3.5Ag-xNi (x=0.1, 0.5, 1.0, 1.5, and 2.0) in this study. When the Ni concentration was low (x=0.1, 0.5), MA particles agglomerated to a flat ingot with particle sizes >100 μm. For higher Ni concentration (x=1.0, 1.5, and 2.0), MA particles turned into fragments with particle sizes <100 μm. The particle size of the solders appeared to be dependent on the Ni concentration. To reduce the particle size of SnAgNi alloys with low Ni concentration, Ni₃Sn₄ nanoparticles were doped into Sn and Ag powders to derive a Ni₃Sn₄-doped solder. For the Ni₃Sn₄-doped solder, the particle size was smaller than that doped by the pure Ni. The distinction of milling mechanism between Ni₃Sn₄-doped solder and the pure Ni-doped solder by MA process was probed and discussed. In addition, differential scanning calorimetry (DSC) results ensured its feasibility in applying the solder material in the reflow process. Wettability tests between solders and Cu substrate also revealed that the wetting angles for Ni₃Sn₄-doped solder with low Ni concentration (0.1 and 0.5 wt.%) were smaller than those for pure Ni-doped solder. The wetting angles on both Cu substrate and electroplated Ni metallization for SnAgNi solders were also comparable with commercial Sn-3.5Ag and Sn-3.0Ag-0.5Cu solders. Favorable wettability of the as-derived solder in this study was clearly demonstrated.