AgIn2/Ag2In transformations in an In-49Sn/Ag soldered joint under thermal aging

The interfacial reaction between liquid In-49Sn solders and Ag substrates results in the formation of a thicker Ag₂In intermetallic compound accompanied with the development of a thin AgIn₂ layer. Through further aging of the In-49Sn/Ag soldered specimens at various temperatures ranging from room to 100°C, solid/solid trnasitions between Ag₂In and AgIn₂ intermetallic compounds can be observed. When the temperature drops below 75°C, Ag₂In will react with the In-49Sn solder to form the dominant AgIn₂ phase. Conversely, AgIn₂ is consumed at a higher temperature (e.g., 100°C) when reacting with the Ag substrate to create a now dominant Ag₂In phase. Lastly, the different mechanical, electrical, magnetic, and corrosion behaviors of both intermetallic compounds are respectively made known through direct measurements of the material properties of the individual Ag₂In and AgIn₂ bulk samples.     

Solid Liquid Interdiffusion Bonding of (Pb,Sn)Te Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

A (Pb, Sn)Te thermoelectric element plated with a Ni barrier layer and a Ag reaction layer has been joined with a Cu electrode coated with Ag and Sn thin films using a solid–liquid interdiffusion bonding method. This method allows the interfacial reaction between Ag and Sn such that Ag₃Sn intermetallic compounds form at low temperature and are stable at high temperature. In this study, the bonding strength was about 6.6 MPa, and the specimens fractured along the interface between the (Pb, Sn)Te thermoelectric element and the Ni barrier layer. Pre-electroplating a film of Sn with a thickness of about 1 μm on the thermoelectric element and pre-heating at 250°C for 3 min ensures the adhesion between the thermoelectric material and the Ni barrier layer. The bonding strength is thus increased to a maximal value of 12.2 MPa, and most of the fractures occur inside the thermoelectric material. During the bonding process, not only the Ag₃Sn intermetallics but also Cu₆Sn₅ forms at the Ag₃Sn/Cu interface, which transforms into Cu₃Sn with increases in the bonding temperature or bonding time.     

Interfacial Microstructure Evolution Between Sn-Zn Solders and Ag Substrate During Solid-State Annealing

In this study, solid-state interfacial reactions between Ag and Sn-Zn alloys with varying Zn content (0.1 wt.% to 9 wt.%) were investigated at 170°C. The reaction couples were prepared by electroplating Ag on the Sn-Zn alloy to avoid dissolution of Ag into the molten solder during soldering. The Zn content greatly influenced the reaction products and the interfacial microstructures. When the Zn content was less than 4 wt.%, Ag₃Sn and AgZn layers were simultaneously formed. Notably, Zn could actively diffuse through the Ag₃Sn layer and react with Ag to form the AgZn phase. With the proceeding reaction, small α-Ag particulates were produced within the AgZn phase. With 9 wt.% Zn, the dominant reactions formed Ag₅Zn₈ and AgZn layers. The interfacial microstructure evolved significantly with reaction time. Interface instability due to Zn depletion in the solder resulted in massive spalling of the Ag₅Zn₈ layer. The Ag₃Sn phase was then produced next to the AgZn layer. Moreover, another reaction couple, Sn-9 wt.%Zn/Sn(15 μm)/Ag, was prepared, in which fast interdiffusion between Zn and Ag across the Sn layer was demonstrated due to the strong chemical affinity of Zn.     

Intermetallic reactions in Sn-3.5Ag solder ball grid array packages with Ag/Cu and Au/Ni/Cu pads

During the reflow process of Sn-3.5Ag solder ball grid array (BGA) packages with Ag/Cu and Au/Ni/Cu pads, Ag and Au thin films dissolve rapidly into the liquid solder, and the Cu and Ni layers react with the Sn-3.5Ag solder to form Cu₆Sn₅ and Ni₃Sn₄ intermetallic compounds at the solder/pad interfaces, respectively. The Cu₆Sn₅ intermetallic compounds also appear as clusters in the solder matrix of Ag surface-finished packages accompanied by Ag₃Sn dispersions. In the solder matrix of Au/Ni surface-finished specimens, Ag₃Sn and AuSn₄ intermetallics can be observed, and their coarsening coincides progressively with the aging process. The interfacial Cu₆Sn₅ and Ni₃Sn₄ intermetallic layers grow by a diffusion-controlled mechanism after aging at 100 and 150°C. Ball shear strengths of the reflowed Sn-3.5Ag packages with both surface finishes are similar, displaying the same degradation tendencies as a result of the aging effect.     

The effect of Ag content on the formation of Ag3Sn plates in Sn-Ag-Cu lead-free solder

The formation of Ag₃Sn plates in the Sn-Ag-Cu lead-free solder joints for two different Ag content solder balls was investigated in wafer level chip scale packages (WLCSPs). After an appropriate surface mount technology reflow process on a printed circuit board, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging, or 1,000 cycles thermal cycling test (TCT). Sequentially, the cross-sectional analysis was scrutinized using a scanning electron microscope/energy dispersive spectrometer (SEM/EDX) to observe the metallurgical evolution of the amount of the Ag₃Sn plates at the interface and the solder bulk itself. Pull and shear tests were also performed on samples. It was found that the interfacial intermetallic compound (IMC) thickness, the overall IMC area, and the numbers of Ag₃Sn plates increase with increasing HTS and TCT cycles. The amount of large Ag₃Sn plates found in the Sn-4.0Ag-0.5 Cu solder balls is much greater than that found in the Sn-2.6Ag-0.5Cu solder balls; however, no significant difference was found in the joint strength between two different Ag content solder joints.     

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.     

Intermetallic reactions in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes

The intermetallic compounds (IMCs) formed during the reflow and aging of Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes were investigated. After reflow, the thickness of (Cu, Ni, Au)₆Sn₅ interfacial IMCs in Sn3Ag0.5Cu0.06Ni0.01Ge was similar to that in the Sn3Ag0.5Cu specimen. The interiors of the solder balls in both packages contained Ag₃Sn precipitates and brick-shaped AuSn₄ IMCs. After aging at 150°C, the growth thickness of the interfacial (Ni, Cu, Au)₃Sn₄ intermetallic layers and the consumption of the Ni surface-finished layer on Cu the pads in Sn3Ag0.5Cu0.06Ni0.01Ge solder joints were both slightly less than those in Sn3Ag0.5Cu. In addition, a coarsening phenomenon for AuSn₄ IMCs could be observed in the solder matrix of Sn3Ag0.5Cu, yet this phenomenon did not occur in the case of Sn3Ag0.5Cu0.06Ni0.01Ge. Ball shear tests revealed that the reflowed Sn3Ag0.5Cu0.06Ni0.01Ge packages possessed bonding strengths similar to those of the Sn3Ag0.5Cu. However, aging treatment caused the ball shear strength in the Sn3Ag0.5Cu packages to degrade more than that in the Sn3Ag0.5Cu0.06Ni0.01Ge packages.     

Intermetallic Compound Formation and Evolution in Solid-State Sn/Immersion-Ag/Cu Trilayer Interfacial Reactions on a Flexible Polymer Board

Immersion Ag is a promising candidate Pb-free surface finish on printed circuit boards (PCBs). For flexible PCB and optoelectronic packaging, solid-state bonding rather than reflow is commonly used to join the chips to the PCB with Sn-based solders, after which the immersion Ag layer remains at the joint interface and participates in the interfacial reactions at the solder joints. Solder joint samples composed of a Sn/Ag/Cu trilayer on flexible PCBs were prepared to study the interfacial reactions at 150°C and 200°C. Three phases, Ag₃Sn, Cu₆Sn₅, and Cu₃Sn, were sequentially formed at the interface. Remarkable change of the morphology of the Ag₃Sn phase was observed during thermal aging. The thickness of the immersion Ag layer was found to have significant effects on the growth rates of the Cu₆Sn₅ and Cu₃Sn phases and the void formation in the Cu₃Sn phase.     

Electric current effects on Sn/Ag interfacial reactions

The effect of electric current on the Sn/Ag interfacial reaction was studied at 140°C and 200°C, by examining the growth of phase (ε-Ag₃Sn) in the Sn/Ag reaction couples with a constant current density. Only at 140°C was the growth of phase affected by the passage of electric current. The growth rate was enhanced when diffusion of Sn and electron flow were in the same direction, and retarded when they were in the opposite direction. It was found that the diffusion coefficient of Sn through Ag₃Sn was 3.37 μm²/h and the apparent effective charge for Sn in Ag₃Sn was −90, at 140°C.     

A Study on the Physical Properties and Interfacial Reactions with Cu Substrate of Rapidly Solidified Sn-3.5Ag Lead-Free Solder

A rapidly solidified Sn-3.5Ag eutectic alloy produced by the melt-spinning technique was used as a sample in this research to investigate the microstructure, thermal properties, solder wettability, and inhibitory effect of Ag₃Sn on Cu₆Sn₅ intermetallic compound (IMC). In addition, an as-cast Sn-3.5Ag solder was prepared as a reference. Rapidly solidified and as-cast Sn-3.5Ag alloys of the same size were soldered at 250°C for 1 s to observe their instant melting characteristics and for 3 s with different cooling methods to study the inhibitory effect of Ag₃Sn on Cu₆Sn₅ IMC. Experimental techniques such as scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectrometry were used to observe and analyze the results of the study. It was found that rapidly solidified Sn-3.5Ag solder has more uniform microstructure, better wettability, and higher melting rate as compared with the as-cast material; Ag₃Sn nanoparticles that formed in the rapidly solidified Sn-3.5Ag solder inhibited the growth of Cu₆Sn₅ IMC during aging significantly much strongly than in the as-cast material because their number in the rapidly solidified Sn-3.5Ag solder was greater than in the as-cast material with the same soldering process before aging. Among the various alternative lead-free solders, this study focused on comparison between rapidly solidified and as-cast solder alloys, with the former being observed to have better properties.     

Intermetallics Evolution in Sn-3.5Ag Based Lead-Free Solder Matrix on an OSP Cu Finish

The 0.2Co + 0.1Ni dual additives were used to dope a Sn-3.5Ag solder matrix to modify the alloy microstructure and the solder joint on an organic solderability preservative (OSP) Cu pad. The refined microstructure of the Sn-3.5Ag-0.2Co-0.1Ni solder alloy or the reduced β-Sn size was attributed to the depressed undercooling achieved by the Co-Ni addition. After soldering on the OSP Cu pad, a large Ag₃Sn plate was formed at the Sn-3.5Ag/OSP solder joint, whereas it was absent at the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joints. With isothermal aging at 150°C, large Ag₃Sn plates formed at the Sn-3.5Ag/OSP solder joint were still observed. A coarsened and dispersed Ag₃Sn phase was found in the solder joints with Co-Ni additions as well. Compared to Cu₆Sn₅, the (Co,Ni)Sn₂ intermetallic compound showed much lower microhardness values. However, (Co,Ni)Sn₂ hardness was comparable to that of the Ag₃Sn phase. Pull strength testing of Sn-3.5Ag-0.2Co-0.1Ni/OSP revealed slightly lower values than for Sn-3.5Ag/OSP during aging. Such results are thought be due to the phase transformation of (Co,Ni)Sn₂ to (Cu,Co,Ni)₆Sn₅.     

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.     

Microstructures in solder joints between Sn95.5Ag4Cu0.5 solder and Ag/Pd thick film

A joint between Sn95.5Ag4Cu0.5 (mass%) solder and an Ag/Pd thick film was soldered by dipping at 260°C for 3–30 sec. Shrinkage voids and Sn grain growth were characterized as well as their transformation kinetics. Void shrinkage occurred in the zone near the top surface of the joint. Shrinkage was always accompanied by colonies of ternary/quaternary meta-eutectic that were the regions solidified last in the joint. The Sn grains accumulated into two bands across the joint during solidification: one was transverse through the thickness and the other was parallel to the solder pad.     

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.     

IMC Growth at the Interface of Sn–2.0Ag–2.5Zn Solder Joints with Cu,Ni, and Ni–W Substrates

Growth of intermetallic compounds (IMC) at the interface of Sn–2.0Ag–2.5Zn solder joints with Cu, Ni, and Ni–W substrates have been investigated. For the Cu substrate, a Cu₅Zn₈ IMC layer with Ag₃Sn particles on top was observed at the interface; this acted as a barrier layer preventing further growth of Cu–Sn IMC. For the Ni substrate, a thin Ni₃Sn₄ film was observed between the solder and the Ni layer; the thickness of the film increased slowly and steadily with aging. For the Ni–W substrate, a thin Ni₃Sn₄ film was observed between the solder and Ni–W layer. During the aging process a thin layer of the Ni–W substrate was transformed into a bright layer, and the thickness of bright layer increased with aging.     

Intermetallic formation in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with immersion Ag surface finish

The intermetallic compounds formed in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Ag/Cu pads are investigated. After reflow, scallop-shaped η-Cu₆Sn₅ and continuous planar η-(cu_0.9Ni_0.1)₆Sn₅ intermetallics appear at the interfaces of the Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder joints, respectively. In the case of the Sn3Ag0.5Cu specimens, an additional ε-Cu₃Sn intermetallic layer is formed at the interface between the η-Cu₆Sn₅ and Cu pads after aging at 150°C, while the same type of intermetallic formation is inhibited in the Sn3Ag0.5Cu0.06Ni0.01Ge packages. In addition, the coarsening of Ag₃Sn precipitates also abates in the solder matrix of the Sn3Ag0.5Cu0.06Ni0.01Ge packages, which results in a slightly higher ball shear strength for the specimens.     

Intermetallic compounds formed during the reflow of In-49Sn solder ball-grid array packages

The intermetallic compounds formed at the interfaces between In-49Sn solder balls and Au/Ni/Cu pads during the reflow of In-49Sn solder, ball-grid array (BGA) packages are investigated. Various temperature profiles with peak temperatures ranging from 140°C to 220°C and melting times ranging from 45 sec to 170 sec are plotted for the reflow processes. At peak temperatures below 170°C, a continuous double layer of intermetallics can be observed, showing a composition of Au(In,Ni)₂/Au(In,Ni). Through selective etching of the In-49Sn solders, the intermetallic layer is made up of irregular coarse grains. In contrast, a number of cubic-shaped AuIn₂ intermetallic compounds appear at the interfaces and migrate toward the upper domes of In-49Sn solder balls after reflow at peak temperatures above 200°C for longer melting times. The upward floating of the AuIn₂ cubes can be explained by a thermomigration effect caused by the temperature gradient present in the liquid solder ball. The intermetallic compounds formed under various reflow conditions in this study exhibit different types of morphology, yet the ball shear strengths of the solder joints in the In-49Sn BGA packages remain unaffected.     

Effects of Au and Pd Additions on Joint Strength, Electrical Resistivity, and Ion-Migration Tolerance in Low-Temperature Sintering Bonding Using Ag2O Paste

A new bonding process using an Ag₂O paste consisting of Ag₂O particles mixed with a triethylene glycol reducing agent has been proposed as an alternative joining approach for microsoldering in electronics assembly, which currently uses Pb-rich, high-temperature solders. Ag nanoparticles were formed at approximately 130°C to 160°C through a reduction process, sintered to one another immediately, and bonded to a metal substrate. An Au-coated Cu specimen was successfully bonded using the Ag₂O paste. The resulting joint exhibited superior strength compared with joints fabricated using conventional Pb-rich solders. To improve ion-migration tolerance, the Ag₂O paste was mixed with Au and Pd microparticles to form sintered Ag-Au and Ag-Pd layers, respectively. The additions of Au and Pd improved the ion-migration tolerance of the joint. Regarding the mechanical properties of the joints, addition of secondary Au and Pd both resulted in decreased joint strength. To match the joint strength of conventional Pb-10Sn solder, the mixing ratios of Au and Pd were estimated to be limited to 16?vol.% and 7?vol.%, respectively. The electrical resistivities of the sintered layers consisting of 16?vol.% Au and 7?vol.% Pd were lower than that of Pb-10Sn solder. Thus, the additive fractions of Au and Pd to the Ag₂O paste should be less than 16?vol.% and 7?vol.%, respectively, to avoid compromising the mechanical and electrical properties of the sintered layer relative to those of contemporary Pb-10Sn solder. Following the addition of Au and Pd to the paste, the ion-migration tolerances of the sintered layers were approximately 3 and 2 times higher than that of pure Ag, respectively. Thus, the addition of Au was found to improve the ion-migration tolerance of the sintered Ag layer more effectively and with less sacrifice of the mechanical and electrical properties of the sintered layer than the addition of Pd.     

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.     

Microstructure and shear strength evolution of Sn-Ag-Cu solder bumps during aging at different temperatures

Flip-chip devices with Sn-3.8Ag-0.7Cu solder on electroless Ni (EN) without immersion Au were studied after aging at different temperatures. The (Cu,Ni)₆Sn₅ intermetallics (IMCs) growth was volume diffusion controlled and Kirkendall voids were found in the Ni₃P layer even at the initial stage of high-temperature aging due to the faster diffusion of Ni in the Ni₃P layer via its column structure boundaries. The Ag₃Sn IMCs were distributed in the bulk solder, existing as plate- or lamella-like phases or as small particles around the β-Sn dendrites, and the (Cu,Ni)₆Sn₅ IMCs existed as facet-like phases. The plate- and lamella-like Ag₃Sn phases break up into small parts and these broken parts, together with small Ag₃Sn particles, coarsen into pebble-like phases during high-temperature aging. Shear tests showed that all the solder bumps fractured in the bulk solder. The shear strength of solder bumps decreases at the initial stage of aging at 150°C and 175°C, and the strength degradation during aging may be caused by the coarsening of small Ag₃Sn particles.