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.     

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.     

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

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

Intermetallic Reactions in Sn-0.4Co-0.7Cu Solder BGA Packages with an ENIG Surface Finish

As-cast Sn-0.4Co-0.7Cu solder contains both (Cu_0.98Co_0.02)₆Sn₅ and (Co_0.85Cu_0.15) Sn₃ intermetallic phases in the matrix. After reflowing, the Au thin film in the electroless Ni/immersion Au (ENIG) surface-finished Sn-0.4Co-0.7Cu solder ball grid array (BGA) packages dissolved rapidly into the solder matrix to form AuSn₄ intermetallics, and a thin layer of (Cu_0.57Ni_0.35Au_0.08)₆Sn₅ intermetallic compound appeared at the solder/pad interface, growing very slowly during aging at 100°C. Increasing the aging temperature to 150°C caused the formation of a new intermetallic layer, (Ni_0.79Cu_0.21)₃Sn₄, at the (Cu_0.57Ni_0.35Au_0.08)₆Sn₅/Ni interface. The reflowed Sn-0.4Co-0.7Cu BGA packages have a ball shear strength of 6.8 N, which decreases to about 5.7 N and 5.5 N after aging at 100°C and 150°C, respectively. The reflowed and aged solder joints fractured across the solder balls with ductile characteristics in ball shear tests.     

Intermetallic reactions in a Sn-20In-2.8Ag solder ball-grid-array package with Au/Ni/Cu pads

The intermetallic compounds formed during the reflow and aging of Sn-20In-2.8Ag ball-grid-array (BGA) packages are investigated. After reflow, a large number of cubic-shaped AuIn₂ intermetallics accompanied by Ag₂In precipitates appear in the solder matrix, while a Ni(Sn_0.72Ni_0.28)₂ intermetallic layer is formed at the solder/pad interface. With further aging at 100°C, many voids can be observed in the solder matrix and at the solder/pad interface. The continuous distribution of voids at the interface of specimens after prolonged aging at 100°C causes their bonding strength to decrease from 5.03 N (as reflowed) to about 3.50 N. Aging at 150°C induces many column-shaped (Cu_0.74Ni_0.26)₆(Sn_0.92In_0.08)₅ intermetallic compounds to grow rapidly and expand from the solder/pad interface into the solder matrix. The high microhardness of these intermetallic columns causes the bonding strength of the Sn-20In-2.8Ag BGA solder joints to increase to 5.68 N after aging at 150°C for 500 h.     

Interfacial microstructure of Pb-free and Pb-Sn solder balls in the ball-grid array package

Ball-grid array (BGA) samples were aged at 155°C up to 45 days. The formation and the growth of the intermetallic phases at the solder joints were investigated. The alloy compositions of solder balls included Sn-3.5Ag-0.7Cu, Sn-1.0Ag-0.7Cu, and 63Sn-37Pb. The solder-ball pads were a copper substrate with an Au/Ni surface finish. Microstructural analysis was carried out by electron microprobe. The results show that a ternary phase, (Au,Ni)Sn₄, formed with Ni₃Sn₄ in the 63Sn-37Pb solder alloy and that a quaternary intermetallic phase, (Au,Ni)₂Cu₃Sn₅, formed in the Sn-Ag-Cu solder alloys. The formation mechanism of intermetallic phases was associated with the driving force for Au and Cu atoms to migrate toward the interface during aging.     

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.     

Additive Effect of Kirkendall Void Formation in Sn-3.5Ag Solder Joints on Common Substrates

The Sn-3.5Ag and Sn-3.5Ag-0.2Co-0.1Ni lead-free solders were investigated on common electronics substrates, namely, organic solderability preservative (OSP) and electroless Ni/immersion Au (ENIG) surface finishes. The formation of Kirkendall voids at the interfacial region during isothermal solid aging was explored. For the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joint, the Kirkendall voids were present after isothermal solid-state aging at higher temperature (e.g., 150°C); however, the size of voids did not change remarkably with prolonged aging time due to the depressed Cu₃Sn layer growth. For ENIG surface finishes, the 0.2Co-0.1Ni additions seemed to enhance the longitudinal groove-shaped voids at the Ni₃P layer; however, void formation at the solder/Ni₃Sn₄ interface was effectively reduced. This might be attributed to the reduced Sn activity in the solder matrix and the suppressed Ni-P-Sn layer formation.     

Morphology and growth kinetics of intermetallic compounds in solid-state interfacial reaction of electroless Ni-P with Sn-based lead-free solders

A comparative study of solid/solid interfacial reactions of electroless Ni-P (15 at.% P) with lead-free solders, Sn-0.7Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn, was carried out by performing thermal aging at 150°C up to 1000 h. For pure Sn and Sn-3.5Ag solder, three distinctive layers, Ni₃Sn₄, SnNiP, and Ni₃P, were observed in between the solder and electroless Ni-P; while for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders, two distinctive layers, (CuNi)₆Sn₅ and Ni₃P, were observed. The differences in morphology and growth kinetics of the intermetallic compounds (IMCs) at the interfaces between electroless Ni-P and lead-free solders were investigated, as well as the growth kinetics of the P-enriched layers underneath the interfacial IMC layers. With increasing aging time, the coarsening of interfacial Ni₃Sn₄ IMC grains for pure Sn and Sn-3.5Ag solder was significantly greater than that of the interfacial (CuNi)₆Sn₅ IMC grains for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders. Furthermore, the Ni content in interfacial (CuNi)₆Sn₅ phase slightly increased during aging. A small addition of Cu (0.7 wt.%) resulted in differences in the type, morphology, and growth kinetics of interfacial IMCs. By comparing the metallurgical aspects and growth kinetics of the interfacial IMCs and the underneath P-enriched layers, the role of initial Cu and Ag in lead-free solders is better understood.     

The nanoindentation characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> intermetallic compounds in the solder bump

In general, formation and growth of intermetallic compounds (IMCs) play a major role in the reliability of the solder joint in electronics packaging and assembly. The formation of Cu-Sn or Ni-Sn IMCs have been observed at the interface of Sn-rich solders reacted with Cu or Ni substrates. In this study, a nanoindentation technique was employed to investigate nanohardness and reduced elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ IMCs in the solder joints. The Sn-3.5Ag and Sn-37Pb solder pastes were placed on a Cu/Ti/Si substrate and Ni foil then annealed at 240°C to fabricate solder joints. In Sn-3.5Ag joints, the magnitude of the hardness of the IMCs was in the order Ni₃Sn₄>Cu₆Sn₅>Cu₃Sn, and the elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ were 125 GPa, 136 GPa, and 142 GPa, respectively. In addition, the elastic modulus of the Cu₆Sn₅ IMC in the Sn-37Pb joint was similar to that for the bulk Cu₆Sn₅ specimen but less than that in the Sn-3.5Ag joint. This might be attributed to the strengthening effect of the dissolved Ag atoms in the Cu₆Sn₅ IMC to enhance the elastic modulus in the Sn-3.5Ag/Cu joint.     

Intermetallic reactions in Sn-8Zn-20In solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflow process of Sn-8Zn-20In solder joints in the ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the Au and Ag thin films react with liquid solder to form γ₃-AuZn₄/γ-Au₇Zn₁₈ and ε-AgZn₆ intermetallics, respectively. The γ₃/γ intermetallic layer is prone to floating away from the solder/Ni interface, and the appearance of any interfacial intermetallics cannot be observed in the Au/Ni surface finished Sn-8Zn-20In packages during further aging treatments at 75°C and 115°C. In contrast, ε-CuZn₅/γ-Cu₅Zn₈ intermetallics are formed at the aged Sn-8Zn-20In/Cu interface of the immersion Ag BGA packages. Bonding strengths of 3.8N and 4.0N are found in the reflowed Sn-8Zn-20In solder joints with Au/Ni/Cu and Ag/Cu pads, respectively. Aging at 75°C and 115°C gives slight increases of ball shear strength for both cases.     

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.     

Influence of Cu addition to interface microstructure between Sn-Ag solder and Au/Ni-6P plating

The formation and growth of intermetallics at the interface between Sn-Ag-(Cu) alloy balls and Au/Ni-6P plating were experimentally examined as a function of soldering period. Joint strengths were also evaluated by a ball pull test. For the joint with Sn-3.5Ag, the primary reaction product of Ni₃Sn₄ exhibits growth and shrinkage in thickness repeatedly with a passage of reaction time up to 30 min, while the Ni₃SnP reaction layer monotonously increases its thickness without fluctuation. In the cases of the joints with Cu bearing solder, Sn-3Ag-0.5Cu and Sn-3.5Ag-0.8Cu, a single η-(Cu,Ni)₆Sn₅ interface layer grows by fast Cu segregation from liquid solder to the interface layer on soldering. For all the soldered joints, a P-rich layer appears at the surface region of a Ni-6P plating layer by Ni depletion to form those intermetallic compounds at interfaces. The growth rate of a P-rich layer for Sn-3.5Ag is faster by about 4–8 times than those of the Sn-Ag-Cu. The presence of Cu in solder enhances the formation of the Cu₆Sn₅ intermetallic layer at the interface resulting in prevention of Ni diffusion to liquid solder. For all the soldered joints, coarsened reaction interfaces decrease the joint strengths.     

Intermetallic compounds formed during the reflow and aging of Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder ball grid array packages

After reflow of Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder balls on Au/Ni surface finishes in ball grid array (BGA) packages, scallop-shaped intermetallic compounds (Cu_0.70Ni_0.28Au_0.02)₆Sn₅ (IM1a) and (Cu_0.76Ni_0.24)₆(Sn_0.86In_0.14)₅ (IM1b), respectively, appear at the interfaces. Aging at 100°C and 150°C for Sn-3.8Ag-0.7Cu results in the formation of a new intermetallic phase (Cu_0.70Ni_0.14Au_0.16)₆Sn₅ (IM2a) ahead of the former IM1a intermetallics. The growth of the newly appeared intermetallic compound, IM2a, is governed by a parabolic relation with an increase in aging time, with a slight diminution of the former IM1a intermetallics. After prolonged aging at 150°C, the IM2a intermetallics partially spall off and float into the solder matrix. Throughout the aging of Sn-20In-2Ag-.5Cu solder joints at 75°C and 115°C, partial spalling of the IM1b interfacial intermetallics induces a very slow increase in thickness. During aging at 115°C for 700 h through 1,000 h, the spalled IM1b intermetallics in the solder matrix migrate back to the interfaces and join with the IM1b interfacial intermetallics to react with the Ni layers of the Au/Ni surface finishes, resulting in the formation and rapid growth of a new (Ni_0.85Cu_0.15)(Sn_0.71In_0.29)₂ intermetallic layer (IM2b). From ball shear tests, the strengths of the Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder joints after reflow are ascertained to be 10.4 N and 5.4 N, respectively, which drop to lower values after aging. An erratum to this article is available at .     

Interdiffusion analysis of the soldering reactions in Sn-3.5Ag/Cu couples

Extensive microstructural and kinetic studies on the formation and growth of the intermetallics of Sn-rich solder/Cu couples have been reported. However, experimental data on the interdiffusion mechanisms during soldering reactions are limited and in conflict. The interdiffusion processes for soldering of Sn-3.5Ag alloy/Cu couples were investigated by using the Cr-evaporated surface as a reference line. At the beginning of soldering, Cu was observed to outdiffuse to the molten Sn−3.5Ag alloy until saturation, and the Sn−Ag solder dissolved with Cu collapsed below the reference line. As a result, the scallop-shaped Cu₆Sn₅ intermetallic compound was formed at the newly-formed Sn−Ag−Cu solder/Cu interface below the original Cu surface. When the soldered joint was reflowed at the lower temperature to suppress the Cu dissolution, the Cu₆Sn₅/Cu interface moved into the Cu substrate. Therefore, Sn is the dominant diffusing species for the intermetallic formation during the soldering process, although the extensive Cu dissolution occurs at the early stage of soldering.     

Growth of an intermetallic compound layer with Sn-3.5Ag-5Bi on Cu and Ni-P/Cu during aging treatment

Growth kinetics of intermetallic compound (IMC) layers formed between the Sn-3.5Ag-5Bi solder and the Cu and electroless Ni-P substrates were investigated at temperatures ranging from 70°C to 200°C for 0–60 days. With the solder joints between the Sn-Ag-Bi solder and Cu substrates, the IMC layer consisted of two phases: the Cu₆Sn₅ (η phase) adjacent to the solder and the Cu₃Sn (ε phase) adjacent to the Cu substrate. In the case of the electroless Ni-P substrate, the IMC formed at the interface was mainly Ni₃Sn₄, and a P-rich Ni (Ni₃P) layer was also observed as a by-product of the Ni-Sn reaction, which was between the Ni₃Sn₄ IMC and the electroless Ni-P deposit layer. With all the intermetallic layers, time exponent (n) was approximately 0.5, suggesting a diffusion-controlled mechanism over the temperature range studied. The interface between electroless Ni-P and Ni₃P was planar, and the time exponent for the Ni₃P layer growth was also 0.5. The Ni₃P layer thickness reached about 2.5 μm after 60 days of aging at 170°C. The activation energies for the growth of the total Cu-Sn compound layer (Cu₆Sn₅ + Cu₃Sn) and the Ni₃Sn₄ IMC were 88.6 kJ/mol and 52.85 kJ/mol, respectively.     

A comparative study of the kinetics of interfacial reaction between eutectic solders and Cu/Ni/Pd metallization

A comparative study of the kinetics of interfacial reaction between the eutectic solders (Sn-3.5Ag, Sn-57Bi, and Sn-38Pb) and electroplated Ni/Pd on Cu substrate (Cu/Ni/NiPd/Ni/Pd) was performed. The interfacial microstructure was characterized by imaging and energy dispersive x-ray analysis in scanning electron microscope (SEM). For a Pd-layer thickness of less than 75 nm, the presence or the absence of Pd-bearing intermetallic was found to be dependent on the reaction temperature. In the case of Sn-3.5Ag solder, we did not observe any Pd-bearing intermetallic after reaction even at 230°C. In the case of Sn-57Bi solder the PdSn₄ intermetallic was observed after reaction at 150°C and 180°C, while in the case of Sn-38Pb solder the PdSn₄ intermetallic was observed after reaction only at 200°C. The PdSn₄ grains were always dispersed in the bulk solder within about 10 μm from the solder/substrate interface. At higher reaction temperatures, there was no Pd-bearing intermetallic due to increased solubility in the liquid solder. The presence or absence of Pd-bearing intermetallic was correlated with the diffusion path in the calculated Pd-Sn-X (X=Ag, Bi, Pb) isothermal sections. In the presence of unconsumed Ni, only Ni₃Sn₄ intermetallic was observed at the solder-substrate interface by SEM. The presence of Ni₃Sn₄ intermetallic was consistent with the expected diffusion path based on the calculated Ni-Sn-X (X=Ag, Bi, Pb) isothermal sections. Selective etching of solders revealed that Ni₃Sn₄ had a faceted scallop morphology. Both the radial growth and the thickening kinetics of Ni₃Sn₄ intermetallic were studied. In the thickness regime of 0.14 μm to 1.2 μm, the growth kinetics always yielded a time exponent n >3 for liquid-state reaction. The temporal law for coarsening also yielded time exponent m >3. The apparent activation energies for thickening were: 16936J/mol for the Sn-3.5Ag solder, 17804 J/mol for the Sn-57Bi solder, and 25749 J/mol for the Sn-38Pb solder during liquid-state reaction. The corresponding activation energies for coarsening were very similar. However, an apparent activation energy of 37599 J/mol was obtained for the growth of Ni₃Sn₄ intermetallic layer during solid-state aging of the Sn-57Bi/substrate diffusion couples. The kinetic parameters associated with thickening and radial growth were discussed in terms of current theories.     

Interfacial reactions between a Pb-Free solder and die backside metallizations

The interfacial reactions between Sn-3.0 Ag-0.7 Cu solder and backside metallizations on two semiconductor devices, field-effect transistors (FET) and diode, are studied. The metallizations on both devices were vacuum evaporated Ti/Ni/Ag. The intermetallic compounds (IMC) formed near the diode/solder and FET/solder joints during reflow, and the interdiffusion processes during solid state aging are characterized by the quantitative energy dispersive x-ray analysis and the x-ray mapping technique in a scanning electron microscope. Two different intermetallic compounds are found near the diode/solder interface. Both are in the form of particles, not a continuous layer, and are referred to as IMC-I and IMC-II. IMC-I corresponds to Ni₃Sn₄, with Cu atoms residing on the Ni sublattice. It is uncertain whether IMC-II is Cu₆Sn₅ or a Cu-Ni-Sn ternary phase. Near the as-reflowed FET/solder interface, both isolated scallops and a skeleton-like layer of Ni₃Sn₄ are observed. The primary microstructural dynamics during solid-state aging are the coarsening of IMCs and the reactions involving the Ni-and Ti-layer with Sn and Au. While the reaction with the Ni-layer yields only Ni₃Sn₄ intermetallic, the reaction involving the Ti-layer suggests the formation of Ti-Sn and Au-Sn-Ti intermetallics. The latter is due to the diffusion of Au from the substrate side to the die side. It is postulated that the kinetics of the Au-Sn-Ti layer is primarily governed by the diffusion of Au through the Ni₃Sn₄ layer by a grain boundary mechanism.     

Mechanisms for interfacial reactions between liquid Sn-3.5Ag solders and cu substrates

Intermetallic compounds formed during the soldering reactions between Sn-3.5Ag and Cu at temperatures ranging from 250°C to 375°C are investigated. The results indicate that scallop-shaped η-Cu₆(Sn_0.933 Ag_0.007)₅ intermetallics grow from the Sn-3.5Ag/Cu interface toward the solder matrix accompanied by Cu dissolution. Following prolonged or higher temperature reactions, ɛ-Cu₃ (Sn_0.996 Ag_0.004) intermetallic layers appear behind the Cu₆(Sn_0.933 Ag_0.007)₅ scallops. The growth of these interfacial intermetallics is governed by a kinetic relation: ΔX=tⁿ, where the n values for η and ɛ intermetallics are 0.75 and 0.96, respectively. The mechanisms for such nonparabolic growth of interfacial intermetallics during the liquid/solid reactions between Sn-3.5Ag solders and Cu substrates are probed.