Interdependent Intermetallic Compound Growth in an Electroless Ni-P/Sn-3.5Ag Reaction Couple

The interfacial microstructure of electroless Ni-P/Sn-3.5Ag solder joints was investigated after reflow and high-temperature solid-state aging to understand its interdependent growth mechanism and related kinetics of intermetallic compounds (IMCs) at the interface. The reflow and aging results showed that mainly three IMC layers, Ni₃Sn₄, Ni₂SnP, and Ni₃P, formed during the soldering reaction. It was found that the Ni₃Sn₄ and Ni₃P layers grow predominantly as long as the electroless Ni-P layer is present; however, once the Ni-P layer is fully consumed, the Ni₂SnP layer grows rapidly at the expense of the Ni₃P layer. A transition in the Ni₃Sn₄ morphology from needle and chunky shape to scallop shape was observed after the solid-state aging of reflowed samples. The kinetics data obtained from the growth of compound layers in the aged samples revealed that initially the growth of the Ni₂SnP layer is controlled by diffusion, and subsequently by the rate of reaction after the Ni-P metallization is fully consumed. It was found that complete transformation of the electroless Ni-P layer into a Ni₃P layer results in the rapid growth of the Ni₂SnP layer due to the dominating reaction of Sn with Ni₃P. The apparent activation energies for the growth of Ni₃Sn₄, Ni₂SnP, and Ni₃P compound layers were found to be 98.9 kJ/mol, 42.2 kJ/mol, and 94.3 kJ/mol, respectively.     

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.     

Characterization of Interfacial Reaction Layers Formed Between Sn-3.5Ag Solder and Electroless Ni-Immersion Au-Plated Cu Substrates

The interfacial reaction between a eutectic Sn-3.5wt.%Ag solder and an electroless nickel–immersion gold-plated Cu substrate during reflow was examined by transmission electron microscopy (TEM). During the initial reflowing, the amorphous, electroless Ni (P)-plated layer crystallized into two P-rich Ni layers: a Ni₁₂P₅ + Ni₃P mixed upper layer and a Ni₃P lower layer. No ternary Ni-Sn-P layer was observed in the initial stage. After subsequent reflow for 60 s, a ternary Ni₂SnP layer (containing a small amount of the Ni₃P phase) was formed between the Ni₃Sn₄ and P-rich Ni layers (Ni₃P + Ni₁₂P₅ + Ni).     

Effect of Interfacial Reaction on the Tensile Strength of Sn-3.5Ag/Ni-P and Sn-37Pb/Ni-P Solder Joints

This work investigates the effect of interfacial reaction on the mechanical strength of two types of solder joints, Sn-3.5Ag/Ni-P and Sn-37Pb/Ni-P. The tensile strength and fracture behavior of the joints under different thermal aging conditions have been studied. It is observed that the tensile strength decreases with increasing aging temperature and duration. Associated with the tensile strength decrease is the transition of failure modes from within the bulk solder in the as-soldered condition toward failures at the interface between the solder and the intermetallic compounds (IMCs). For the same aging treatment, the strength of the Sn-3.5Ag/Ni-P joint degrades faster than that of Sn-37Pb/Ni-P. The difference between the two types of joints can be explained by the difference in their interfacial reaction and growth kinetics. An empirical relation is established between the solder joint strength and the Ni₃Sn₄ intermetallic compound thickness.     

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.     

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.     

Metallurgical reaction of the Sn-3.5Ag solder and Sn-37Pb solder with Ni/Cu under-bump metallization in a flip-chip package

Several international legislations recently banned the use of Pb because of environmental concerns. The eutectic Sn-Ag solder is one of the promising candidates to replace the conventional Sn-Pb solder primarily because of its excellent mechanical properties. In this study, interfacial reaction of the eutectic Sn-Ag and Sn-Pb solders with Ni/Cu under-bump metallization (UBM) was investigated with a joint assembly of solder/Ni/Cu/Ti/Si₃N₄/Si multilayer structures. After reflows, only one (Ni,Cu)₃Sn₄ intermetallic compound (IMC) with faceted and particlelike grain feature was found between the solder and Ni. The thickness and grain size of the IMC increased with reflow times. Another (Cu,Ni)₆Sn₅ IMC with a rod-type grain formed on (Ni,Cu)₃Sn₄ in the interface between the Sn-Pb solder and the Ni/Cu UBM after more than three reflow times. The thickness of the (Ni,Cu)₃Sn₄ layer formed in the Sn-Pb system remained almost identical despite the numbers of reflow; however, the amounts of (Cu,Ni)₆Sn₅ IMC increased with reflow times. Correlations between the IMC morphologies, Cu diffusion behavior, and IMC transformation in these two solder systems will be investigated with respect to the microstructural evolution between the solders and the Ni/Cu UBM. The morphologies and grain-size distributions of the (Ni,Cu)₃Sn₄ IMC formed in the initial stage of reflow are crucial for the subsequent phase transformation of the other IMC.     

The Melting Characteristics and Interfacial Reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu Joints During Reflow Soldering

In this work, the melting characteristics and interfacial reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu (Sn/SAC305-paste/Cu) structure joints were studied using differential scanning calorimetry, in order to gain a deeper and broader understanding of the interfacial behavior and metallurgical combination among the substrate (under-bump metallization), solder ball and solder paste in a board-level ball grid array (BGA) assembly process, which is often seen as a mixed assembly using solder balls and solder pastes. Results show that at the SAC305 melting temperature of 217°C, neither the SAC305-paste nor the Sn-ball coalesce, while an interfacial reaction occurs between the SAC305-paste and Cu. A slight increase in reflow temperature (from 217°C to 218°C) results in the coalescence of the SAC305-paste with the Sn-ball. The Sn-ball exhibits premelting behavior at reflow temperatures below its melting temperature, and the premelting direction is from the bottom to the top of the Sn-ball. Remarkably, at 227°C, which is nearly 5°C lower than the melting point of pure Sn, the Sn-ball melts completely, resulting from two eutectic reactions, i.e., the reaction between Sn and Cu and that between Sn and Ag. Furthermore, a large amount of bulk Cu₆Sn₅ phase forms in the solder due to the quick dissolution of Cu substrate when the reflow temperature is increased to 245°C. In addition, the growth of the interfacial Cu₆Sn₅ layer at the SAC305-paste/Cu interface is controlled mainly by grain boundary diffusion, while the growth of the interfacial Cu₃Sn layer is controlled mainly by bulk diffusion.     

Effects of Zn-Containing Flux on Sn-3.5Ag Soldering with an Electroless Ni-P/Au Surface Finish: Microstructure and Wettability

The microstructure resulting from Sn-3.5Ag soldering on an electroless Ni-P/Au pad using flux containing Zn(II) stearate was investigated. The content of zinc compound in the flux was 0 wt.% (Z-0), 20 wt.% (Z-20) or 50 wt.% (Z-50). A study of the interfacial microstructure revealed that both Z-20 and Z-50 fluxes yielded a thinner P-rich layer at the interface than did the Z-0 flux. In addition, compared with the bulky Ni–Sn intermetallics of the Z-0 joint interface, refined interfacial intermetallic compounds (IMCs) were observed when using Zn-containing fluxes, Z-20 and Z-50. Based on qualitative analyses of both Z-20 and Z-50 joint interfaces, it was presumed that their intermetallic layers would consist of Ni, Zn, and Sn. Additionally, the Ni content in the IMC layer of the Z-50 joint was lower than that of the Z-20 joint. Electron probe microanalysis (EPMA) of the initial Z-50 joint interface revealed Zn in the interfacial reaction layer, suggesting that Zn participated in the reaction between solder and the surface finish at an early stage of soldering. Consequently, the supply of Zn from the flux diminished Ni diffusion into the molten solder during heating. This effect may have caused a thin P-rich layer to form at the joint interface.     

Effect of phosphorus content on Cu/Ni-P/Sn-3.5Ag solder joint strength after multiple reflows

Electroless Ni-P layers with three different P contents (6.1 wt.%, 8.8 wt.%, and 12.3wt.%) were deposited on copper (Cu) substrates. Multilayered samples of Sn-3.5Ag/Ni-P/Cu stack were prepared and subjected to multiple reflows at 250°C. A tensile test was performed to investigate the effect of P content on the solder joint strength. The low P samples exhibited the highest joint strength after multiple reflows, while the strength of medium and high P samples decreased more rapidly. From interfacial analysis, the Ni₃Sn₄ intermetallic compound (IMC) formed at the interface of low P sample was found to be more stable, while the one of medium and high P samples spalled into the molten solder. The IMC spallation sped up the consumption of electroless Ni-P, leading to the large formation of Cu-Sn IMCs. Fractographic and microstructural analyses showed that the degradation in solder joint strength was due to the formation of layers of voids and growth of Cu-Sn IMCs between the solder and the Cu substrate.     

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.     

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.     

Effect of Bi on the Interfacial Reaction between Sn-3.7Ag-xBi Solders and Cu

It was reported in previous studies that the addition of Bi could improve the wettability and reduce the melting temperature of Sn-Ag solders. This work investigates the effect of Bi on the interfacial reaction between Sn-Ag-xBi solders and the Cu substrate reflowed at 250°C for different times and thermally aged at 150°C for different durations. Five types of Sn-Ag-based solders, Sn-3.7Ag-xBi (x = 0 wt.% to 4 wt.%), were used in this study. The microstructure of the interfacial Cu-Sn intermetallic compound (IMC) layers between the solders and the Cu substrate was studied, and the thickness of the Cu-Sn IMCs in different solder/Cu systems has been measured. It was found that the thickness of the Cu-Sn IMC layer decreased with increasing amount of Bi in both the reflow and thermally aged condition. The effect of Bi addition on the interfacial reaction between the solder and the Cu substrate was discussed based on the experimental results.     

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.     

Shear deformation in Sn-3.5Ag and Sn-3.6Ag-1.0Cu solder joints subjected to asymmetric four-point bend tests

The shear deformation behavior of two lead-free solder compositions, Sn-3.5Ag (wt.%) and Sn-3.6Ag-1.0Cu (wt.%), both on copper substrates, was studied using an asymmetric four point bend technique. Four test joints were obtained from one master specimen of each composition, and each joint was subject to progressive loading, up to the maximum shear strength of the joint. One unstressed bar from each composition was retained as a reference. Each sample was metallo-graphically plished and lightly etched, and examined in a field emission scanning electron microscope (SEM) before shearing. Sheared joints were then re-examined in the SEM with no additional surface treatment. Compared with the traditional ring and plug method, the asymmetric four-point bend (AFPB) technique subjects the joints to a condition of pure shear, while providing an opportunity for unambiguous observation of microstructural features before and after shearing, without an intervening mechanical sectioning step. Shear banding in the Sn-rich matrix and crack nucleation in the vicinity of the intermetallic interface were observed at low displacements in the binary alloy. Evidence of non-homogeneous plastic flow in the matrix was seen at higher shear loading. No evidence of brittle fracture was observed in the Sn-3.6Ag-1.0 Cu alloy, with elastic deformation at low stress levels giving rise to plastic deformation at higher loading values. Results show that the AFPB technique is a viable approach to the study of shear loading on solder joints.     

The effect of substrate surface roughness on the fracture toughness of Cu/96.5Sn-3.5Ag solder joints

The effects of substrate surface roughness, joint thickness, time above liquidus, and testing temperature on the chevron notch fracture toughness of Cu/96.5Sn-3.5Ag solder joints are investigated. Of these four variables,only the surface roughness of the copper surfaces to be soldered has a significant effect. A minimum fracture toughness is obtained when the average surface roughness, R_a, is between 0.2 and 1.0 μm. This encompasses the surface roughnesses produced by many cold forming operations. Decreasing the roughness to 0.04 μm increases the fracture toughness from 4.7 to 11.0 MPa√m, an improvement of 135%. Increasing the roughness to 2.0 μm increases the fracture toughness to 8.8 MPa√m, an improvement of 80%. We attribute these effects to the increased growth stresses that develop in the brittle intermetallic layer when the size scale of individual intermetallic particles is comparable to the size of the roughness features of the substrate. Two models that describe how these growth stresses might develop are provided.     

Mechanical and Electrical Properties of Cu/Sn-3.5Ag/Cu Ball Grid Array (BGA) Solder Joints after Multiple Reflows

The microstructural evolution, die shear strength, and electrical resistivity of Cu/Sn-3.5Ag (wt.%)/Cu ball grid array (BGA) solder joints were investigated after 1 to 10 reflows using scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron probe microanalysis (EPMA), bonding testing, and a four-point probe station. A Cu₆Sn₅ intermetallic compound (IMC) was formed at both the upper and lower interfaces after one reflow. The IMC thickness increased at the lower interface with increasing reflow number, whereas the IMC morphology and thickness remained virtually unchanged at the upper interface, irrespective of the reflow number. The amount of Cu₆Sn₅ IMC contained in the solder ball increased with increasing reflow number. These microstructural evolutions with increasing reflow number strongly affected the mechanical and electrical properties of the solder joint.     

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.