Comparative study of microstructures and properties of three valuable SnAgCuRE lead-free solder alloys

Lead-free solders with excellent material properties and low cost are essential for the electronics industry. It has been proved that mechanical properties of SnAgCu alloys can be remarkably improved with a minute addition of rare earth (RE) elements. For comparison and optimization, three valuable solder candidates, Sn3.8Ag0.7Cu0.05RE, Sn3Ag0.5Cu0.05RE, and Sn2.9Ag1.2Cu0.05RE, were chosen due to the excellent properties of their own SnAgCu basic alloys. Wetting properties, melting temperature, bulk tensile properties, and joint tensile and shear properties were investigated. In addition, the microstructures of solder joints were observed and the effects of microstructure on mechanical properties were analyzed. Experimental results indicated that the tensile and shear strengths of solder joints were decreased from Sn3.8Ag0.7Cu0.05RE, Sn2.9Ag1.2Cu0.05RE, to Sn3Ag0.5Cu0.05RE, in order. Such difference in mechanical properties could be attributed to the influence of slightly coarse or strong Cu₆Sn₅ scallops in the reaction layer as well as superior eutectic network and large volume percentage of large primary intermetallic compounds (IMCs) inside the solder joints. It is also suggested that the size and volume percentage of large primary IMCs inside the solder be controlled. In addition, serration morphology was observed at the edge of large primary and eutectic IMCs in the three solder joints, which could be related to the content of Ag, Cu, and RE. The serration morphology was proved to be beneficial to mechanical properties theoretically. Furthermore, the three alloys investigated possessed similar wetting properties, melting temperatures, and bulk tensile properties.     

Spreading Behavior and Evolution of IMCs During Reactive Wetting of SAC Solders on Smooth and Rough Copper Substrates

The effect of surface roughness of copper substrate on the reactive wetting of Sn-Ag-Cu solder alloys and morphology of intermetallic compounds (IMCs) was investigated. The spreading behavior of solder alloys on smooth and rough Cu substrates was categorized into capillary, diffusion/reaction, and contact angle stabilization zones. The increase in substrate surface roughness improved the wetting of solder alloys, being attributed to the presence of thick Cu₃Sn IMC at the interface. The morphology of IMCs transformed from long needle shaped to short protruded type with an increase in the substrate surface roughness for the Sn-0.3Ag-0.7Cu and Sn-3Ag-0.5Cu solder alloys. However, for the Sn-2.5Ag-0.5Cu solder alloy the needle-shaped IMCs transformed to the completely scallop type with increase in the substrate surface roughness. The effect of Ag content on wetting behavior was not significant.     

Mechanical Characterization of Lead-Free Sn-Ag-Cu Solder Joints by High-Temperature Nanoindentation

The reliability of Pb-free solder joints is controlled by their microstructural constituents. Therefore, knowledge of the solder microconstituents’ mechanical properties as a function of temperature is required. Sn-Ag-Cu lead-free solder alloy contains three phases: a Sn-rich phase, and the intermetallic compounds (IMCs) Cu₆Sn₅ and Ag₃Sn. Typically, the Sn-rich phase is surrounded by a eutectic mixture of β-Sn, Cu₆Sn₅, and Ag₃Sn. In this paper, we report on the Young’s modulus and hardness of the Cu₆Sn₅ and Cu₃Sn IMCs, the β-Sn phase, and the eutectic compound, as measured by nanoindentation at elevated temperatures. For both the β-Sn phase and the eutectic compound, the hardness and Young’s modulus exhibited strong temperature dependence. In the case of the intermetallics, this temperature dependence is observed for Cu₆Sn₅, but the mechanical properties of Cu₃Sn are more stable up to 200°C.     

Microstructure, thermal analysis and hardness of a Sn–Ag–Cu–1 wt% nano-TiO2 composite solder on flexible ball grid array substrates

Sn-Ag-Cu composite solders reinforced with nano-sized, nonreacting, noncoarsening 1 wt% TiO₂ particles were prepared by mechanically dispersing TiO₂ nano-particles into Sn-Ag-Cu solder powder and the interfacial morphology of the solder and flexible BGA substrates were characterized metallographically. At their interfaces, different types of scallop-shaped intermetallic compound layers such as Cu₆Sn₅ for a Ag metallized Cu pad and Sn-Cu-Ni for a Au/Ni and Ni metallized Cu pad, were found in plain Sn-Ag-Cu solder joints and solder joints containing 1 wt% TiO₂ nano-particles. In addition, the intermetallic compound layer thicknesses increased substantially with the number of reflow cycles. In the solder ball region, Ag₃Sn, Cu₆Sn₅ and AuSn₄ IMC particles were found to be uniformly distributed in the β-Sn matrix. However, after the addition of TiO₂ nano-particles, Ag₃Sn, AuSn₄ and Cu₆Sn₅ IMC particles appeared with a fine microstructure and retarded the growth rate of IMC layers at their interfaces. The Sn-Ag-Cu solder joints containing 1 wt% TiO₂ nano-particles consistently displayed a higher hardness than that of the plain Sn-Ag-Cu solder joints as a function of the number of reflow cycles due to the well-controlled fine microstructure and homogeneous distribution of TiO₂ nano-particles which gave a second phase dispersion strengthening mechanism.     

Microstructure characterization of SnAgCu solder bearing Ce for electronic packaging

The creep-rupture lives of Sn3.8Ag0.7Cu and Sn3.8Ag0.7Cu0.03Ce lead-free solder joints for electronic packaging were investigated, respectively. And the relationship between creep behavior and intermetallic compound (IMC: Ag₃Sn, Cu₆Sn₅, CeSn₃) particles in SnAgCu/SnAgCuCe solder joints has been obtained. Meanwhile, rare earth Ce concentration gradient and retardation effect of Ce on the IMC layer have been observed at the solder/Cu interface. Moreover, aging reaction of Sn and Cu, and the effect mechanism of rare earth Ce on two IMCs (Cu₆Sn₅ and Cu₃Sn) are reported.     

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.     

Electrical characteristics for Sn-Ag-Cu solder bump with Ti/Ni/Cu under-bump metallization after temperature cycling tests

Lead-free solder bumps have been widely used in current flip-chip technology (FCT) due to environmental issues. Solder joints after temperature cycling tests were employed to investigate the interfacial reaction between the Ti/Ni/Cu under-bump metallization and Sn-Ag-Cu solders. The interfacial morphology and quantitative analysis of the intermetallic compounds (IMCs) were obtained by electron probe microanalysis (EPMA) and field emission electron probe microanalysis (FE-EPMA). Various types of IMCs such as (Cu_1−x,Ag_x)₆Sn₅, (Cu_1−y,Ag_y)₃Sn, and (Ag_1−z,Cu_z)₃Sn were observed. In addition to conventional I–V measurements by a special sample preparation technique, a scanning electron microscope (SEM) internal probing system was introduced to evaluate the electrical characteristics in the IMCs after various test conditions. The electrical data would be correlated to microstructural evolution due to the interfacial reaction between the solder and under-bump metallurgy (UBM). This study demonstrated the successful employment of an internal nanoprobing approach, which would help further understanding of the electrical behavior within an IMC layer in the solder/UBM assembly.     

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.     

Interfacial Reactions and Joint Strengths of Sn-<Emphasis Type="Italic">x</Emphasis>Zn Solders with Immersion Ag UBM

The solder joint microstructures of immersion Ag with Sn-xZn (x = 0 wt.%, 1 wt.%, 5 wt.%, and 9 wt.%) solders were analyzed and correlated with their drop impact reliability. Addition of 1 wt.% Zn to Sn did not change the interface microstructure and was only marginally effective. In comparison, the addition of 5 wt.% or 9 wt.% Zn formed layers of AgZn₃/Ag₅Zn₈ at the solder joint interface, which increased drop reliability significantly. Under extensive aging, Ag-Zn intermetallic compounds (IMCs) transformed into Cu₅Zn₈ and Ag₃Sn, and the drop impact resistance at the solder joints deteriorated up to a point. The beneficial role of Zn on immersion Ag pads was ascribed to the formation of Ag-Zn IMC layers, which were fairly resistant to the drop impact, and to the suppression of the brittle Cu₆Sn₅ phase at the joint interface.     

Effect of volume in interfacial reaction between eutectic Sn-3.5% Ag-0.5% Cu solder and Cu metallization in microelectronic packaging

The Sn-3.5Ag-0.5Cu (wt.%) is the most promising replacement for the eutectic tin-lead solder alloy. Here, an investigation has been carried out to compare the interfacial reactions of the Cu pad of a ball grid array (BGA) substrate with molten eutectic Sn-3.5% Ag-0.5% Cu solder having different volumes. Two different sizes of BGA solder balls were used: 760-μm and 500-μm diameter. Scanning electron microscopy (SEM) was used to measure the consumed thickness of the Cu and also the thickness of the intermetallic compound (IMC). The soldering reaction was carried out at 230°C, 240°C, and 250°C for 1 min, 5 min, 10 min, and 20 min. The Cu consumption was much higher for the Sn-Ag-Cu solder with higher volume. On the other hand, the mean thickness of the intermetallics for solder with smaller volume was thicker than that of the bigger solder balls. The Cu₃Sn compound was also observed at the interface between the Cu₆Sn₅ IMCs and Cu substrate for longer reflow for the both solder balls. Larger Cu₆Sn₅ IMCs were observed in the bulk of the solder with bigger volume. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Reaction of Liquid Sn-Ag-Cu-Ce Solders with Solid Copper

Small amounts of the rare-earth element Ce were added to the Sn-rich lead-free eutectic solders Sn-3.5Ag-0.7Cu, Sn-0.7Cu, and Sn-3.5Ag to improve their properties. The microstructures of the solders without Ce and with different amounts (0.1 wt.%, 0.2 wt.%, and 0.5 wt.%) of Ce were compared. The microstructure of the solders became finer with increasing Ce content. Deviation from this rule was observed for the Sn-Ag-Cu solder with 0.2 wt.% Ce, and for the Sn-0.7Cu eutectic alloy, which showed the finest microstructure without Ce. The melting temperatures of the solders were not affected. The morphology of intermetallic compounds (IMC) formed at the interface between the liquid solders and a Cu substrate at temperatures about 40°C above the melting point of the solder for dipping times from 2 s to 256 s was studied for the basic solder and for solder with 0.5 wt.% Ce addition. The morphology of the Cu₆Sn₅ IMC layer developed at the interface between the solders and the substrate exhibited the typical scallop-type shape without significant difference between solders with and without Ce for the shortest dipping time. Addition of Ce decreased the thickness of the Cu₆Sn₅ IMC layer only at the Cu/Sn-Ag-Cu solder interface for the 2-s dipping. A different morphology of the IMC layer was observed for the 256-s dipping time: The layers were less continuous and exhibited a broken relief. Massive scallops were not observed. For longer dipping times, Cu₃Sn IMC layers located near the Cu substrate were also observed.     

Microstructural modifications and properties of Sn-Ag-Cu solder joints induced by alloying

Slow cooling (1–3°C/sec) of Sn-Ag-Cu and Sn-Ag-Cu-X (X = Fe, Co) solder-joint specimens, made by hand soldering, simulated reflow in a surface-mount assembly to achieve similar as-solidified joint microstructures for realistic shear-strength testing, using Sn-3.5Ag (wt.%) as a baseline. Consistent with predictions from a recent Sn-Ag-Cu ternary phase-diagram study, either Sn dendrites, Ag₃Sn primary phase, or Cu₆Sn₅ primary phase were formed during solidification of joint samples made from the selected near-eutectic Sn-Ag-Cu alloys. Minor substitution of Co for Cu in Sn-3.7Ag-0.9Cu refined the joint-matrix microstructure by an apparent catalysis effect on the Cu₆Sn₅ phase, whereas Fe substitution promoted extreme refinement of the Sn-dendritic phase. Ambient-temperature shear strength was reduced by Sn dendrites in the joint microstructure, especially coarse dendrites in solute poor Sn-Ag-Cu, e.g., Sn-3.0Ag-0.5Cu, while Sn-3.7Ag-0.9Cu with Co and Fe additions have increased shear strength. At elevated (150°C) temperature, no significant difference exists between the maximum shear-strength values of all of the alloys studied.     

Microstructural Evolution of Sn-Ag-Sb Solder with Indium Additions

The effects of 1 wt.%, 5 wt.%, and 10 wt.% additions of indium (In) on the microstructure and compound morphology of Sn-Ag-Sb lead-free solder joints␣were examined. The results showed that In prompts the formation of Ag₃(Sn,In), Ag₂(In,Sn), and InSb compounds within the solder matrix. As the amount of In was increased, the Sn atoms in the Ag₃Sn compound were gradually replaced by In atoms, prompting a transformation from Ag₃Sn to Ag₃(Sn,In) and finally to Ag₂(In,Sn). This transformation occurs more readily under high-temperature conditions. The Ag₂(In,Sn) compound formed in Sn-Ag-Sb-xIn/Cu solder joints was found to have either a leaf-like morphology or an antler-like morphology. Finally, with In additions greater than 5 wt.%, the Cu₆Sn₅ interfacial compounds in the solder/Cu joints transformed into Cu₆(Sn,In)₅.     

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.     

Interfacial Reaction of Sn and Cu-<Emphasis Type="Italic">x</Emphasis>Zn Substrates After Reflow and Thermal Aging

Zn additions to Cu under bump metallurgy (UBM) in solder joints were the subject of this study. An alternative design was implemented to fabricate pure Sn as the solder and Cu-xZn (x = 15 wt.% and 30 wt.%) as the UBM to form the reaction couple. As the Zn content increased from 15 wt.% to 30 wt.% in the Sn/Cu-Zn system, growth of both Cu₃Sn and Cu₆Sn₅ was suppressed. In addition, no Kirkendall voids were observed at the interface in either Sn/Cu-Zn couple during heat treatment. After 40-day aging, different multilayered phases of [Cu₆Sn₅/Cu₃Sn/Cu(Zn)] and [Cu₆Sn₅/Cu(Zn,Sn)/CuZn] formed at the interface of [Sn/Cu-15Zn] and [Sn/Cu-30Zn] couples, respectively. The growth mechanism of intermetallic compounds (IMCs) during aging is discussed on the basis of the composition variation in the joint assembly with the aid of electron-microscopic characterization and the Sn-Cu-Zn ternary phase diagram. According to these analyses of interfacial morphology and IMC formation in the Sn/Cu-Zn system, Cu-Zn is a potential UBM for retarding Cu pad consumption in solder joints.     

Drop impact reliability of Sn–1.0Ag–0.5Cu BGA interconnects with different mounting methods

The poor drop-shock resistance of near-eutectic Sn–Ag–Cu (SAC) solder interconnects drives the research and application low-Ag SAC solder alloys, especially for Sn–1.0Ag–0.5Cu (SAC105). In this work, by dynamic four-point bend testing, we investigate the drop impact reliability of SAC105 alloy ball grid array (BGA) interconnects with two different surface mounting methods: near-eutectic solder paste printing and flux dipping. The results indicate that the flux dipping method improves the interconnects failure strain by 44.7% over paste printing. Further mechanism studies show the fine interfacial intermetallic compounds (IMCs) at the printed circuit board side and a reduced Ag content inside solder bulk are the main beneficial factors overcoming other negative factors. The flux dipping SAC105 BGA solder joints possess fine Cu₆Sn₅ IMCs at the interface of solder/Cu pads, which increases the bonding strength between the solder/IMCs and the fracture resistance of the IMC grains themselves. Short soldering time of flux dipping joints above the solder alloy liquidus mitigates the growth of interfacial IMCs in size. In addition, a reduced Ag content in flux dipping joint bulk causes a low hardness and high compliance, thus increasing fracture resistance under higher-strain rate conditions.     

The growth of intermetallic compounds at Sn-Ag-Cu solder/Cu and Sn-Ag-Cu solder/Ni interfaces and the associated evolution of the solder microstructure

The evolution of intermetallics at and near SnAgCu/Cu and SnAgCu/Ni interfaces was examined, and compared to the behavior, near PbSn/metal and Sn/metal interfaces. Two different solder compositions were considered, Sn_93.6Ag_4.7Cu_1.7 and Sn_95.5Ag_3.5Cu_1.0 (Sn_91.8Ag_5.1 Cu_3.1 and Sn_94.35Ag_3.8Cu_1.85 in atomic percent). In both cases, phase formation and growth at interfaces with Cu were very similar to those commonly observed for eutectic SnPb solder. However, the evolution of intermetallics at SnAgCu/Ni interfaces proved much more complex. The presence of the Cu in the solder dramatically altered the phase selectivity at the solder/Ni interface and affected the growth kinetics of intermetallics. As long as sufficient Cu was available, it would combine with Ni and Sn to form (Cu,Ni)₆)Sn₅ which grew instead of the Ni₃Sn₄ usually observed in PbSn/Ni and Sn/Ni diffusion couples. This growing phase would, however, eventually consume essentially all of the available Cu in the solder. Because the mechanical properties of Sn-Ag-Cu alloys, depend upon the Cu content, this consumption can be expected to alter the mechanical properties of these Pb-free solderjoints. After depletion of the Cu from the solder, further annealing then gradually transformed the (Cu,Ni)₆Sn₅ phase into a (Ni,Cu)₃Sn₄ phase.     

Elevated temperature aging of solder joints based on Sn-Ag-Cu: Effects on joint microstructure and shear strength

The shear strength behavior and microstructural effects after aging for 100 h and 1,000 h at 150°C are reported for near-eutectic Sn-Ag-Cu (SAC) solder joints (joining to Cu) made from Sn-3.5Ag (wt.%) and a set of SAC alloys (including Co- and Fe-modified SAC alloys). All joints in the as-soldered and 100-h aged condition experienced shear failure in a ductile manner by either uniform shear of the solder matrix (in the strongest solders) or by a more localized shear of the solder matrix adjacent to the Cu₆Sn₅ interfacial layer, consistent with other observations. After 1,000 h of aging, a level of embrittlement of the Cu₃Sn/Cu interface can be detected in some solder joints made with all of the SAC alloys and with Sn-3.5Ag, which can lead to partial debonding during shear testing. However, only ductile failure was observed in all solder joints made from the Co- and Fe-modified SAC alloys after aging for 1,000 h. Thus, the strategy of modifying a strong (high Cu content) SAC solder alloy with a substitutional alloy addition for Cu seems to be effective for producing a solder joint that retains both strength and ductility for extended isothermal aging at high temperatures.     

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.