Mechanical fatigue characteristics of Sn-3.5Ag-X (X=Bi, Cu, Zn and In) solder alloys

In our previous study, the fatigue life of Sn-3.5Ag-Bi alloy was found to be dominated by the fracture ductility of the alloy and to obey a modified Coffin-Manson’s law: (Δε_p/2D)· N _f ^α , where Δε_p is plastic strain range, N_f is fatigue life, and α and=C are nondimensional constants. In this study, copper, zinc, and indium are selected as the third element, and the effect of these elements on the isothermal fatigue properties of Sn-3.5%Ag alloy has been investigated. The relationship between fatigue life and crack propagation rate estimated from load drop curve during fatigue test is also discussed. The addition of copper, indium, and zinc up to 2% slightly decreases the fatigue life of Sn-3.5Ag alloy due to the loss of ductility, while the life still remains higher than that of tin-lead eutectic alloy. The modified Coffin-Manson’s equation can also be applied to ternary Sn-3.5Ag-X. It is found that both ductility and fatigue life are significantly responsible for the load drop rate of the alloy, which reflects the extent of crack propagation. The fatigue life of Sn-3.5Ag-X alloy is therefore dominated not by the kinds and amount of third element but by the ductility of each alloy.     

Mechanical fatigue of thin copper foil

The electrodeposited and the rolled 12 to 35 μm thick copper foils are subjected to the bending/unbending strain-controlled flex fatigue over a wide range of strain amplitudes. The fatigue life is associated with an increase in electrical resistance of the specimen beyond a preassigned threshold. For each foil type, in the rolled or as-deposited as well as in the (recrystallization-like) annealed conditions, the inverse Coffin-Manson (C-M) relationship between strain amplitude (Δε/2) and fatigue life (N_f) is established in the high Δε/2 (low N_f) and the low Δε/2 (high N_f) regimes. The N_f, Δε/2, and C-M slopes (c,b) are utilized to calculate the cyclic strain hardening (n′) and fatigue ductility (D_f) parameters. It is shown that for a given foil thickness, an universal relationship exists between D_f and the strength (σ) normalized fatigue life (N_f/σ). The propagation of fatigue crack through the foil thickness and across the sample width is related to the unique fine grain structure for each foil type: pancaked grains for the rolled foil and equiaxed grains for the electrodeposited foil. The fatal failure corresponds to convergence of the through-thickness and the across-the-width fatigue cracks. The variations in (i) electrical resistance, (ii) mid-thickness microhardness and grain structure and (iii) dislocation configurations with fatigue are monitored. Except for a small but significant fatigue induced softening (or hardening), no convincing evidence of strain localization (and the associated dislocation configurations generally observed for the bulk samples) has been found.     

Energy-Based Micromechanics Analysis on Fatigue Crack Propagation Behavior in Sn-Ag Eutectic Solder

Sn-Ag-eutectic-based solders are replacing Sn-Pb eutectic solders in the electronics industry. The current paper extends the recently developed approach based on phase transformation theory, micromechanics, and fracture mechanics to treat fatigue crack nucleation and propagation for steels and alloys to predict fatigue crack propagation in solder alloys. To verify the proposed method, fatigue experiments were conducted on Sn-3.5Ag solder alloys. Finite element analysis is performed to predict the stress intensity factor range ΔK and the required energy U to increase the crack by a unit area. Unified creep-plasticity theory and a cohesive zone model are incorporated to predict the creep and hysteresis effects on fatigue crack propagation in solder and the interfacial behavior between the solder alloy and the intermetallic layer, respectively. With U determined numerically, the predicted fatigue crack propagation rate using phase transformation theory is compared with experimental data for Sn-3.5Ag and Sn-37Pb eutectic solders. Reasonable agreement between theoretical predictions and experimental results is obtained.     

Density measurement of Sn-40Pb,Sn-57Bi,and Sn-9Zn by indirect Archimedean method

By the indirect Archimedean method, the density and the density-temperature relationship of the Sn-40Pb eutectic alloy and two Pb-free solders, Sn-57Bi and Sn-9Zn eutectic alloys, were measured from room temperature to about 250°C. The results showed that the density-temperature dependence for each alloy in both solid and melting states can be fitted linearly as ρ_S(Sn-40Pb)=8.51−8.94×10⁻⁴(T−25°C), ρ_L(Sn-40Pb)=8.15−13.8×10⁻⁴(T−T_m); ρ_S(Sn-57Bi)=8.54−5.86 × 10⁻⁴(T−25°C), ρ_L(Sn-57Bi)=8.51−10.9×10⁻⁴(T−T_m); and ρ_s(Sn-9Zn)=7.22−7.78×10⁻⁴(T−25°C), ρ_L(Sn-9Zn)=6.89−5.88×10 ⁻⁴(T−T_m), where the density unit was g/cm³. At the melting point, density of the melt of these solders is 8.15 g/cm³, 8.51 g/cm³, and 6.89 g/cm³, respectively. The density decreased 2.6% for Sn-40Pb eutectic alloy during melting, and 2.7% for Sn-9Zn eutectic alloy, but increased 0.5% for Sn-57Bi eutectic alloy. The excess molar volume for these alloys after mixing at their melting point is 0.03 cm³/mol for Sn-40Pb, 0.09 cm³/mol for Sn-57Bi, and 0.21 cm³/mol for Sn-9Zn.     

Low-cycle fatigue behavior of Sn-Ag, Sn-Ag-Cu, and Sn-Ag-Cu-Bi lead-free solders

Low-cycle fatigue (LCF) tests on as-cast Sn-3.5Ag, Sn-3Ag-0.5Cu, Sn-3Ag-0.5Cu-1Bi, and Sn-3Ag-0.5Cu-3Bi solders was carried out using a noncontact strain-controlled system at 20°C with a constant frequency of 0.1 Hz. The addition of Cu does not significantly affect the fatigue life of eutectic Sn-Ag solder. However, the fatigue life was significantly reduced with the addition of Bi. The LCF behavior of all solders followed the Coffin-Manson relationship. The fatigue life of the present solders is dominated by the fracture ductility and can be described by the ductility-modified Coffin-Manson’s relationship. Steps at the boundaries of dendrite phases were the initiation sites for microcracks for Sn-3.5Ag, Sn-3Ag-0.5Cu, and Sn-3Ag-0.5Cu-1Bi solders, while for Sn-3Ag-0.5Cu-3Bi solder, cracks initiated along both the dendrite boundaries and subgrain boundaries in the dendrite phases. The linking of these cracks and the propagation of cracks inside the specimen occurred both transgranularly through eutectic phases and intergranularly along dendrite boundaries or subgrain boundaries.     

Creep Behavior of Lead-Free Sn-Ag-Cu + Ni-Ge Solder Alloys

We developed a new lead-free solder alloy, an Sn-Ag-Cu base to which a small amount of Ni and Ge is added, to improve the mechanical properties of solder alloys. We examined creep deformation in bulk and through-hole (TH)␣form for two lead-free solder alloys, Sn-3.5Ag-0.5Cu-Ni-Ge and Sn-3.0Ag-0.5Cu, at elevated temperatures, finding that the creep rupture life of the Sn-3.5Ag-0.5Cu-Ni-Ge solder alloy was over three times better than that of the Sn-3.0Ag-0.5Cu solder at 398 K. Adding Ni to the solder appears to make microstructural development finer and more uniform. The Ni added to the solder readily combined with Cu to form stable intermetallic compounds of (Cu, Ni)₆Sn₅ capable of improving the creep behavior of solder alloys. Moreover, microstructural characterization based on transmission electron microscopy analyses observing creep behavior in detail showed that such particles in the Sn-3.5Ag-0.5Cu-Ni-Ge solder alloy prevent dislocation and movement.     

Improved mechanical properties in new,Pb-free solder alloys

The mechanical properties of solders benefit from uniform dispersion of fine precipitates and small effective grain sizes. Metallurgical methods of attaining such a beneficial microstructure have been investigated in two new, near-eutectic, Pb-free solder alloys systems—Sn-Zn-In (m.p. ∼188°C) and Sn-Ag-Zn (m.p.∼217°C). It has been found that small alloying additions of Ag dramatically improve the mechanical properties of the ternary Sn-8Zn-5In alloy. The improvement is attributed to the elimination of the coarse and nonuniform distribution of plate-like dendrites and refining the effective grain size in the solidified microstructure. Also, small amounts of Cu dramatically improve the ductility in the ternary Sn-3.5Ag-lZn alloy. The quaternary Sn-3.5Ag-lZn-0.5Cu has better mechanical properties than the binary Sn-3.5Ag alloy because it has a uniform fine dispersion of precipitates and a small effective grain size. The combination of high mechanical strength and high ductility is likely to yield improved fatigue resistance properties in the interconnection of electronic components.     

The thermal property of lead-free Sn-8.55Zn-1Ag-XAl solder alloys and their wetting interaction with Cu

The wetting behaviors between the quaternary Sn-8.55Zn-1Ag-XAl solder alloys and Cu have been investigated with the wetting balance method. The Al contents, x, of the quaternary solder alloys investigated were 0.01–0.45 wt.%. The results of differential scanning calorimeter (DSC) analysis indicate that the solders exhibit a solid-liquid coexisting range of about 7–10°C. The solidus temperature of the quaternary Sn-8.55Zn-1Ag-XAl solder alloys is about 198.2°C, while the liquidus temperatures are 205–207°C. The experimental results showed that the wettability of the Sn-8.55Zn-1Ag-XAl solder alloys is improved by the addition of Al. The mean maximum wetting force of the solders with Cu is within 0.75–1.18 mN and the mean wetting time is around 1.0–1.1 sec, better than the ∼1.3 sec of eutectic Sn-9Zn and Sn-8.55Zn-1Ag solder alloys. The addition of Al also depresses the formation of ε-Ag-Zn compounds at the interface between Sn-8.55Zn-1Ag-XAl solders and copper.     

Alloying effects in near-eutectic Sn-Ag-Cu solder alloys for improved microstructural stability

This study included a comparison of the baseline Sn-3.5Ag eutectic to one near-eutectic ternary alloy, Sn-3.6 Ag-1.0Cu and two quaternary alloys, Sn-3.6Ag-1.0Cu-0.15Co and Sn-3.6Ag-1.0 Cu-0.45 Co, to increase understanding of the beneficial effects of Co on Sn-Ag-Cu solder joints cooled at 1–3 C/sec, typical of reflow practice. The results indicated that joint microstructure refinement is due to Co-enhanced nucleation of the Cu₆Sn₅ phase in the solder matrix, as suggested by Auger elemental mapping and calorimetric measurements. The Co also reduced intermetallic interface faceting and improved the ability of the solder joint samples to maintain their shear strength after aging for 72 hr at 150 C. The baseline Sn-3.5Ag joints exhibited significantly reduced strength and coarser microstructures.     

Low-cycle fatigue behavior and mechanisms of a lead-free solder 96.5Sn/3.5Ag

Low-cycle fatigue tests of as-cast Sn-Ag eutectic solder (96.5Sn/3.5Ag) were performed using a noncontact strain controlled system at 20°C. The fatigue behavior followed the Coffin-Manson equation with a fatigue-ductility exponent of 0.76. Without local deformation and stress concentration at contact points between the extensometer and the specimen surface in strain-controlled fatigue tests, crack initiation and propagation behavior was observed on the specimen surface using a replication technique. After failure, the longitudinal cross sections were also examined using scanning electron microscopy (SEM). Microcracks initiated from steps at the boundary between the Sn-dendrite and the Sn-Ag eutectic structure and cavities along the boundaries especially around the Ag₃Sn particles. Stage II crack propagated in mixed manner with intergranular cracks along the Sn-dendrite boundaries and transgranular cracks through the Sn-dendrites and the Sn-Ag eutectic structure. Propagation of stage II cracks could be expressed by the relation of da_c/dN = 4.7 × 10⁻¹¹[ΔJ]^1.5, where a_c is the average crack length and ΔJ is the J-integral range. After fatigue tests, small grains were observed in Sn-dendrites near the fracture surface.     

Effect of Polyethylene Glycol Additives on Pulse Electroplating of SnAg Solder

Eutectic Sn-3.5wt.%Ag alloy is one of the most promising lead-free solders in low temperature processes for wafer bumping. Near eutectic composition of deposited alloy films could be readily acquired by pulse electroplating with a proper combination of active ingredients including K₄P₂O₇, KI, Sn₂P₂O₇, and AgI, as well as polyethylene glycol (PEG), with molecular weights of 200, 600, 2,000, and 4,000, as an inhibitive agent. Pulse electroplating was carried out with current in alternating polarity to conduct electroplating and electropolishing sequentially. As a result, alloy films with grains of less than 1 μm and uniform surface morphology can be obtained. The addition of PEG was necessary for the stabilization of the plating baths to promote a wider process window for the desirable eutectic composition. Electrochemical characterization established that PEG with molecular weight of 4,000 exhibited the strongest inhibition behavior. In contrast, PEG with molecular weight of 200 demonstrated the least interference. Energy dispersive X-ray and differential scanning calorimeter data confirmed the formation of eutectic alloy as a function of deposition current density. X-ray diffraction results indicated that a biphasic structures of β-Sn and ε-Ag₃Sn was present in the as-deposited film.     

Developing a lead-free solder alloy Sn-Bi-Ag-Cu by mechanical alloying

A new lead free alloy, Sn-6Bi-2Ag-0.5Cu, has been developed by mechanical alloying and has great potential as a lead-free solder system. Initial trials on the manufacture of solder joints with this alloy revealed that a high quality bond with copper could be formed. Its melting range of 193.87°C to 209.88°C is slightly higher than that of eutectic tin-lead solder. Examination of the microstructure of the as-soldered joints revealed that it mainly consists of small bismuth (1 μm to 2 μm) and Ag₃Sn (1 μm) particles finely dispersed in a nearly pure tin matrix with a small amount of η-Cu₆Sn₅ particles. The Cu-Sn intermetallic compound (IMC) layer formed at solder-copper interface is the η-Cu₆Sn₅ phase with grain size of 2 μm. The shear strength of the solder joint is higher than that of Sn-37Pb or Sn-3.5Ag. Under shear loading, fracture occurred at IMC layer-solder interface as well as in the bulk of solder.     

Low-cycle fatigue characteristics of Sn-based solder joints

Low-cycle, lap-shear fatigue behavior of Sn-based, Pb-free solder alloys, Sn-3.5Ag, Sn-3.5Ag-Cu, Sn-3.5Ag-Bi, and Sn-0.7Cu, were studied at room temperature using specimens with printed circuit board (PCB)/solder/PCB structure under total displacement of ±10 μm, 12 μm, 15 μm, and 20 μm. The fatigue lives of various solder joint materials, defined as 50% load drop, were correlated with the fracture paths and analyzed using the Coffin-Manson relation, Morrow’s plastic-energy dissipation model, and Solomon’s load-drop parameter. The Sn-3.5Ag, Sn-0.7Cu eutectics, and Sn-3.5Ag-Cu ternary alloys showed the same level of fatigue resistance, while Bi-containing alloys showed substantially worse fatigue properties. Cross-sectional fractography revealed cracks initiated at the solder wedge near the solder mask and subsequently propagated into the solder matrix in the former group of alloys, in contrast with the crack propagation along the solder/under bump metallurgy (UBM) interfaces in the Sn-3.5Ag-Bi alloys. Inferior fatigue resistance of Bi-containing alloys was ascribed to high matrix hardness, high stiffness, possible Bi segregation to the interface, and high residual stress in the interfacial area.     

The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si₃N₄/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni_1−x,Cu_x)₃Sn₄ intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni_1−x,Cu_x)₃Sn₄ IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu_1−y,Ni_y)₆Sn₅ IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu_1−y,Ni_y)₆Sn₅ IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 10¹⁶−10¹⁷ atoms/cm²sec in both the eutectic Sn-Ag and Sn-Pb systems.     

Intermetallic growth kinetics for Sn-Ag, Sn-Cu, and Sn-Ag-Cu lead-free solders on Cu, Ni, and Fe-42Ni substrates

Soldering with the lead-free tin-base alloys requires substantially higher temperatures (∼235–250°C) than those (213–223°C) required for the current tin-lead solders, and the rates for intermetallic compound (IMC) growth and substrate dissolution are known to be significantly greater for these alloys. In this study, the IMC growth kinetics for Sn-3.7Ag, Sn-0.7Cu, and Sn-3.8Ag-0.7Cu solders on Cu substrates and for Sn-3.8Ag-0.7Cu solder with three different substrates (Cu, Ni, and Fe-42Ni) are investigated. For all three solders on Cu, a thick scalloped layer of η phase (Cu₆Sn₅) and a thin layer of ε phase (Cu₃Sn) were observed to form, with the growth of the layers being fastest for the Sn-3.8Ag-0.7Cu alloy and slowest for the Sn-3.7Ag alloy. For the Sn-3.8Ag-0.7Cu solder on Ni, only a relatively uniform thick layer of η phase (Cu,Ni)₆Sn₅ growing faster than that on the Cu substrate was found to form. IMC growth in both cases appears to be controlled by grain-boundary diffusion through the IMC layer. For the Fe-42Ni substrate with the Sn-3.8Ag-0.7Cu, only a very thin layer of (Fe,Ni)Sn₂ was observed to develop.     

Overview of fatigue performance of Cu processed by severe plastic deformation

This study investigates discrepancies regarding cyclic softening of Cu processed by severe plastic deformation (SPD). All samples softened if the microhardnesses before and after fatiguing are compared. However, the effect decreases if the strain amplitude is small, Δε_p <1 × 10⁻³). Samples with equiaxed subgrains were more resistant to softening and thermal recovery. All samples had “persistent” shear bands except those tested at the highest amplitudes, Δε_p >1 × 10⁻². Cu processed by SPD exhibits an enhanced fatigue life at low amplitudes. However, low thermal stability, potential for softening, and poor low-cycle properties discredit this advantage.     

Effect of thermal cycles on the mechanical strength of quad flat pack leads/Sn-3.5Ag-X (X=Bi and Cu) solder joints

Quad Flat Pack (QFP) Leads/Sn-3.5Ag-X (X=Bi and Cu) joint was thermally cycled between 243 K and 403 K or 273 K and 373 K, and both metallographic examination and mechanical pull test were performed to evaluate thermal fatigue damage of the joint. The addition of bismuth drastically degrades the thermal fatigue resistance of Sn-3.5Ag solder. On the other hand, the pull strength of Sn-3.5Ag-Cu solder joints slightly decreased with increasing number of thermal cycles, though it still remains higher in comparison to that for conventional Sn-37Pb or bismuth containing solder joint. The behavior observed here reflects the isothermal fatigue properties of bulk solder, because thermal fatigue crack initiates at the surface of solder fillet and propagates within the fillet in an early stage of fatigue damage. Furthermore, the lead phases lying at the interface between lead-frame and bismuth containing solder joint may promote the crack propagation at the interface, resulting in the extremely low thermal fatigue resistance of the joint.     

Effect of Ag and Cu Concentrations on the Creep Behavior of Sn-Based Solders

The creep behavior of Sn-1Ag-0.5Cu, Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu ball grid array (BGA) solder balls and 99.99% pure polycrystalline bulk Sn was studied using impression creep and related to the microstructure. Sn-Ag-Cu solders generally consist of primary dendrites/grains of β-Sn, and a eutectic microconstituent comprising fine Ag₃Sn and Cu₆Sn₅ particles in β phase. With increasing concentrations of Ag and Cu in the alloy, the proportion of the eutectic microconstituent in relation to the primary β phase increases. In pure Sn and Sn-1Ag-0.5Cu, the β grains form the continuous matrix, whereas in Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu, the eutectic microconstituent forms a continuous network around the β grains, which form isolated islands within the eutectic. The steady-state creep behavior of the alloys was dominated by the response of the continuous microstructural constituent (β-Sn or solid solution β for pure Sn and Sn-1Ag-0.5Cu, and the eutectic microconstituent for Sn-2.5Ag-0.5Cu and Sn-4Ag-0.5Cu). In general, the steady-state creep rate decreased with increasing alloy content, and in particular, the volume fraction of Ag₃Sn and Cu₆Sn₅ precipitates. The rate-limiting creep mechanism in all the materials investigated here was core diffusion controlled dislocation climb. However, subtle changes in the stress exponent n and activation energy Q were observed. Pure Sn shows n = 5, Q = 42 kJ/mol, Sn-1Ag-0.5Cu shows n = 5, Q = 61 kJ/mol, whereas both Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu show n = 6 and Q = 61 kJ/mol. Rationalizations for the observed changes of n and Q are provided, based on the influence of the microstructure and the solute concentrations.     

Interfacial Reactions of Sn-8wt.%Zn-3wt.%Bi Solder with Cu,Ag, and Ni Substrates

Sn-Zn-Bi alloys are promising Pb-free solders. Interfacial reactions between the Sn-8wt.%Zn-3wt.%Bi (Sn-13.80at.%Zn-1.62at.%Bi) alloy and the Cu, Ag, and Ni substrates are examined. Two different kinds of substrates, the bulk plate and the electroplating layer, are used, and the reactions are carried out at 250°C and 220°C. Although the Zn content is only 13.8 at.%, two Zn-Cu compounds, γ-Cu₅Zn₈ and ε-CuZn₅ phases, are formed in the Sn-13.80at.%Zn-1.62at.%Bi/Cu couples. The ε-CuZn₅ phase is scallop shaped, and the γ-Cu₅Zn₈ phase is planar. In the Sn-13.80at.%Zn-1.62at.%Bi/Ag couples, three Zn-Ag compounds are observed, and they are ε-AgZn₃, γ-Ag₅Zn₈, and ζ-AgZn phases. In the Sn-13.80at.%Zn-1.62at.%Bi/Ni couples, a Zn-Ni compound, γ-Ni₅Zn₂₁ phase, is formed. Similar results are found in the couples prepared with an electroplating layer: the reaction phases are the same, but the growth rates are different.     

Nucleation Control and Thermal Aging Resistance of Near-Eutectic Sn-Ag-Cu-X Solder Joints by Alloy Design

Elemental (X) additions to Sn-3.5Ag-0.95Cu (SAC3595) solder were developed with minimal (<0.25 wt.%) concentration to avoid pro-eutectic Ag₃Sn blades by reducing undercooling (ΔT) and to eliminate thermal-aging-induced embrittlement. Calorimetry and microstructure results on simple Cu/Cu joints identified 0.21Zn, 0.10Mn, and 0.05Al as sufficient to reduce undercooling below that for SAC3595 and to eliminate Ag₃Sn blades. A 211°C melting onset for the X = Mn alloys also suggested the discovery of a new quaternary eutectic. Shear testing and microstructure analysis of larger joints showed that 0.05Al and 0.21Zn additions resulted in reduced as-soldered strength (30 MPa), like Sn-0.95Cu, but all joints showed ductile failure at about 30 MPa after 1000 h at 150°C.