Diffusion Soldering of Pb-Doped GeTe Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

Directly coating a GeTe(Pb) thermoelectric device with a Ni barrier layer and an Ag reaction layer and then diffusion soldering with a Cu electrode coated with Ag and Sn leads to breakage at the GeTe(Pb)/Ni interface and low bonding strengths of about 6 MPa. An improved process, precoating with 1 μm Sn film and heating at 250°C for 3 min before electroplating with Ni and Ag layers, results in satisfactory bonding strengths ranging from 12.6 MPa to 19.1 MPa. The precoated Sn film leads to the formation of a (Ni,Ge)₃Sn₄ layer between the GeTe(Pb) thermoelectric material and Ni barrier layer, reducing the thermal stress at the GeTe(Pb)/Ni interface.     

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.     

Ag/Ni Metallization Bilayer: A Functional Layer for Highly Efficient Polycrystalline SnSe Thermoelectric Modules

The structural and electrical characteristics of Ag/Ni bilayer metallization on polycrystalline thermoelectric SnSe were investigated. Two difficulties with thermoelectric SnSe metallization were identified for Ag and Ni single layers: Sn diffusion into the Ag metallization layer and unexpected cracks in the Ni metallization layer. The proposed Ag/Ni bilayer was prepared by hot-pressing, demonstrating successful metallization on the SnSe surface without interfacial cracks or elemental penetration into the metallization layer. Structural analysis revealed that the Ni layer reacts with SnSe, forming several crystalline phases during metallization that are beneficial for reducing contact resistance. Detailed investigation of the Ni/SnSe interface layer confirms columnar Ni-Sn intermetallic phases [(Ni₃Sn and Ni₃Sn₂) and Ni_5.63SnSe₂] that suppress Sn diffusion into the Ag layer. Electrical specific-contact resistivity (5.32 × 10^?4 Ω cm²) of the Ag/Ni bilayer requires further modification for development of high-efficiency polycrystalline SnSe thermoelectric modules.     

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.     

Electromigration Behaviors and Effects of Addition Elements on the Formation of a Bi-rich Layer in Sn58Bi-Based Solders

This study investigates the electromigration (EM) behaviors and effects of the addition elements on the formation of a Bi-rich layer in Sn58Bi-based solders including Sn58Bi (SB), Sn58Bi0.5Ag (SBA) and Sn58Bi0.5Ag0.1Cu0.07Ni0.01Ge (SBACNG) solders. The EM tests were conducted at a relatively high temperature of 373 K and at a current density of 30 kA/cm². Although the dominant diffusing atom was Bi, hillocks were formed from Sn more easily than from Bi. The electrical resistance increased in the solder during the current stressing, and the dominant factor was attributed to the formation of a Bi-rich layer. SBACNG solder showed the highest resistance to the formation of a Bi-rich layer, followed by SBA, and then SB solder. The possible addition elements enhancing the resistance of SBACNG solder are Ag, Ni and Ge. The effects of the addition elements are summarized as follows: (1) Ag distributes in the Sn phase as Ag₃Sn intermetallic compounds (IMCs) that enhance the mechanical strength of Sn; (2) Ni distribution in Bi as Ni-Bi IMCs stabilizes Bi and suppresses its migration; and (3) Ge may distribute in Bi, stabilizing Bi, or Ge exists at the phase boundaries as a precipitate that inhibits Bi migration.     

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.     

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.     

A Study on the Breakdown Mechanism of an Electroless-Plated Ni(P) Diffusion Barrier for Cu/Sn/Cu 3D Interconnect Bonding Structures

This study examined the thermal stability of an electroless-plated Ni(P) barrier layer inserted between Sn and Cu in the bonding structure of Cu/Sn/Cu for three-dimensional (3D) interconnect applications. A combination of transmission electron microscopy (TEM) and scanning electron microscopy allowed us to fully characterize the bonding morphology of the Cu/Ni(P)/Sn/Ni(P)/Cu joints bonded at various temperatures. The barrier suppressed Cu and Sn interdiffusion very effectively up to 300°C; however, an interfacial reaction between Ni(P) and Sn led to gradual decomposition into Ni₃P and Ni₃Sn₄. Upon 350°C bonding, the interfacial reaction brought about complete disintegration of the barrier in local areas, which allowed unhindered interdiffusion between Cu and Sn.     

Solid-State Reactions between Cu(Ni) Alloys and Sn

Solid-state interfacial reactions between Sn and Cu(Ni) alloys have been investigated at the temperature of 125°C. The following results were obtained. Firstly, the addition of 0.1 at.% Ni to Cu decreased the total thickness of the intermetallic compound (IMC) layer to about half of that observed in the␣binary Cu/Sn diffusion couple; the Ni addition decreased especially the thickness of Cu₃Sn. Secondly, the addition of 1 to 2.5 at.% Ni to Cu further decreased the thickness of Cu₃Sn, increased that of Cu₆Sn₅ (compared to that in the binary Cu/Sn couple) and produced significant amount of voids at the Cu/Cu₃Sn interface. Thirdly, the addition of 5 at.% Ni to Cu increased the total thickness of the IMC layer to about two times that observed in the binary Cu/Sn diffusion couple and made the Cu₃Sn disappear. Fourthly, in contrast to the previous case, the addition of 10 at.% Ni to Cu decreased the total IMC (Cu₆Sn₅) thickness again close to that of the Cu/Sn couple. With this Ni content no voids were detected. The results are rationalized with the help of␣the thermodynamics of the Sn-Cu-Ni system as well as with kinetic considerations.     

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.     

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.     

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.     

Cross-Interaction between Ni and Cu across Sn Layers with Different Thickness

The Ni/solder/Cu material sequence is one of the most common material sequences in the solder joints of electronic packages. In this study, the Ni/Sn/Cu ternary diffusion couples were used to investigate the solder volume effect on the cross-interaction between Ni and Cu. Experimentally, a pure Sn layer with the thickness of 100–400 μm was electroplated over Cu foils. A pure Ni layer (20 μm) was then deposited over the as-deposited Sn surface. The diffusion couples were aged at 160°C for different periods of time. With this technique, the diffusion couples were assembled without experiencing any high temperature process, such as reflow, which would have accelerated the interaction and caused difficulties in analysis. This study revealed that the cross-interaction could occur in as short as 30 min. A detailed atomic flux analysis showed that the Cu flux through the Sn layer was about 25–40 times higher than the Ni flux. Moreover, it was found that (Cu_1−x Ni _x )₆Sn₅ on the Ni side reduced the consumption rate of the Ni layer, and the cross-interaction also reduced the Cu₃Sn thickness on the Cu side.     

Low Temperature Bonding of Alumina/Alumina and Alumina/Copper in Air Using Sn3.5Ag4Ti(Ce,Ga) Filler

Sn3.5Ag4Ti(Ce,Ga) active filler was used for joining alumina with alumina and alumina with copper at 250°C in air. The joining process was done without flux and without the need for pre-metallization of alumina or a protective atmosphere. After mechanical activation of the bonding surfaces of alumina and copper, the filler showed good wetting on both alumina and copper and led to a strong bond between alumina and copper. Through tensile testing, a bonding strength of 23.7 MPa was found in the alumina/copper joint region. The shear strengths for alumina/alumina, copper/copper and alumina/copper joints were 13.5, 14.3, and 10.2 MPa, respectively. The affinity of cerium for oxygen protects titanium from oxidation, giving rise to the reaction of titanium with alumina at such a low temperature. Electron probe microanalyzer (EPMA) elemental mapping revealed that titanium segregates effectively at the alumina/solder interfaces. After aging tests at 200°C and 150°C, a double layer of Cu₃Sn and Cu₆Sn₅ intermetallic compound was formed at the solder/copper interfaces. With an increase of aging periods, the amount of brittle compound in the joints increased and resulted in decreases in the shear strengths of the alumina/copper joints.     

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.     

Interfacial Reactions in Sn-Ag/Co Couples

Sn-Ag alloys are important solders, and Co and Co alloys are investigated as barrier layers. Interfacial reactions in Sn-Ag/Co couples were examined in this study for Ag contents of 1.0 wt.%, 2.0 wt.%, and 3.5 wt.% and reaction temperatures of 250°C, 200°C, and 150°C. Only CoSn₃ formed in Sn-Ag/Co couples reacted at 250°C, but both CoSn₃ and Ag₃Sn formed in couples reacted at 200°C and 150°C. The reaction layer was 100 μm thick in Sn-3.5 wt.%Ag/Co couples reacted at 200°C for 110 h. The reaction rates were lower if Ag was added, but remained very fast compared with those for Ni and Ni-based substrates.     

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.     

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 Sn/Ni-7Wt.%V interfacial reactions

Ni-7wt.%V(8at.%V) is an important under bump metallization material, and Sn is the primary element in most solders. This study examines the Sn/Ni-8at.%V interfacial reactions at 160°C, 200°C, 250°C, 300°C, 325°C, 350°C, and 400°C. Unlike the interfacial reactions in the Sn/Ni couples, a ternary T phase and the binary Ni₃Sn₄ phase are formed at 160°C. The vanadium solubility in the Ni₃Sn₄ phase is only 0.2 at.%, while the T phase contains 13.9at.%V. Similar results are found in the couples at 200°C, and the reaction paths are Sn/Ni₃Sn₄/T/Ni-V. The reaction paths are liquid/T/Ni₃Sn₄/Ni-V at 250°C and 300°C and are liquid/Ni₃Sn₄/Ni-V at 350°C and 400°C. Because the reaction products and the reaction rates in the Sn/Ni-8at.%V and Sn/Ni couples are different, reliabilities of the electronic products with the Ni-8at.%V barrier layer should not be assessed based only on the results of the Sn/Ni couples.     

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.