In search of new lead-free electronic solders

Tin-lead solder has been widely used in the electronics industry for many years. However, increasing environmental pressures, together with some technological issues, have now prompted great interest in finding a viable nonleaded substitute. This paper first summarizes some of the background issues, specifically availability, cost, and toxicity. It then outlines some of the work undertaken by Cookson Group plc on behalf of Alpha-Fry in searching for alloys with a narrow melting range between 135 and 183°C.     

Creep phenomena in lead-free solders

A critical review of data on microstructure and creep process activation energy values for a number of lead-free solder alloys like Sn-Ag; Sn-Bi; Sn-In was conducted. The review revealed a scatter in experimental data, which could not be explained by the dislocation creep mechanism only, even after the published data was corrected for Young’s modulus temperature dependence. An analysis of the data implies that possible origin of such a scatter is nucleation, accumulation and further growth of such internal defects as pores and microcracks during creep. It is shown that these processes may affect the measured steady-state creep rates, and may be one of the major reasons for the observed scatter in experimental data, and, therefore, must be taken into consideration in lead-free solder alloys’ creep studies.     

Investigation of multi-component lead-free solders

Binary phase diagrams of interest for lead-free solder development have been entered into the THERMO-CALC data base. These may be used directly to calculate multi-component phase relations vs temperature provided there are no ternary or higher order interactions. Such occur in the Sn-Ag-Zn system and are being evaluated. Contact angles of a number of solder-flux combinations on copper were directly measured in spreading tests. With a rosin-isopropyl alcohol flux, the contact angles of binary eutectic solders were in degrees: Sn-Bi at 166°C, 40; Sn-Zn at 225°C, 60; Sn-Ag at 250°C, 45. These angles were little affected by a number of 1% ternary additions to the solder. The contact angles were 20 degrees or less when SnCl₂ was used as a flux. The SnCl₂ reacts with Cu to form Cu₃Sn. The most likely successful approach to obtain satisfactory wetting with lead-free solders appears to be development of a satisfactory flux.     

无铅焊料Sn-Zn-In系列合金的研究

对熔化起始温度和终止温度作线性回归进行合金设计,并对其焊料合金进行了熔点、抗剪切强度及微观组织等研究分析。结果表明:当w(In)(质量分数)为3%~5%,w(Zn)为5%~9%时,焊料的熔化温度在170~200℃,接近于焊料Sn-37Pb的熔化温度183℃;焊料与Cu焊合后形成γ-Cu5Zn8化合物;Sn-Zn-In系焊料的抗剪切强度与焊料Sn-37Pb的剪切强度33.73 MPa相当。     

Resonant vibration behavior of lead-free solders

This study investigated the resonant vibration-fatigue characteristics of some potential lead-free solders, including Sn-Zn, Sn-Ag Sn-Cu, and Sn-Bi alloys. Results show that, under a fixed vibration force, the damping capacity and vibration-fracture resistance of Sn-Cu and Sn-Ag eutectic alloys with an off-eutectic structure are higher than Sn-Pb and are also higher than Sn-Bi and Sn-Zn. This is closely related to the vibration-deformed structure and crack-propagation morphology associated with the microstructural features of the materials. Also, the striated deformation in the Sn-rich phase can be regarded as an effective mechanism in absorbing vibration energy. Moreover, microstructural modification of the Sn-Zn eutectic alloy can be achieved through Ag addition, and thus, the damping capacity and vibration-fracture resistance can be significantly improved.     

纳米颗粒增强无铅复合焊料的研究现状

熔化温度、润湿性及长期使用过程中的可靠性决定了无铅焊料的应用范围.通过添加适量纳米颗粒可显著提高无铅焊料的性能,特别是添加适量纳米Ag颗粒后SnCu焊料蠕变断裂寿命是未添加时的13倍.介绍了添加纳米颗粒对无铅焊料的物理化学性能的影响;探讨了纳米颗粒增强无铅复合焊料微观结构和力学性能;展望了纳米颗粒增强手段对焊料应用的前...     

Development of nano-composite lead-free electronic solders

Inert, hybrid inorganic/organic, nano-structured chemicals can be incorporated into low melting metallic materials, such as lead-free electronic solders, to achieve desired levels of service performance. The nano-structured materials technology of polyhedral oligomeric silsesquioxanes (POSS), with appropriate organic groups, can produce suitable means to promote bonding between nano-reinforcements and the metallic matrix. The microstructures of lead-free solder reinforced with surface-active POSS tri-silanols were evaluated using scanning electron microscopy (SEM). Wettability of POSS-containing lead-free solders to copper substrate was also examined. Steady-state deformation of solder joints made of eutectic Sn-Ag solder containing varying weight fractions of POSS of different chemical moieties were evaluated at different temperatures (25°C, 100°C, and 150°C) using a rheometric solids analyzer (RSA-III). Mechanical properties such as shear stress versus simple shear-strain relationships, peak shear stress as a function of rate of simple shear strain, and testing temperature for such nano-composite solders are reported. The service reliability of joints made with these newly formulated nano-composite solders was evaluated using a realistic thermomechanical fatigue (TMF) test profile. Evolution of microstructures and residual mechanical property after different extents of TMF cycles were evaluated and compared with joints made of standard, unreinforced eutectic Sn-Ag solder.     

Reliability investigation and interfacial reaction of ball-grid-array packages using the lead-free Sn-Cu solder

The interfacial reactions between two Sn-Cu (Sn-0.7Cu and Sn-3Cu, wt.%) ball-grid-array (BGA) solders and the Au/Ni/Cu substrate by solid-state isothermal aging were examined at temperatures between 70°C and 170°C for 0 to 100 days. For the Sn-0.7Cu solder, a (Cu,Ni)₆Sn₅ layer was observed in the samples aged at 70–150°C. After isothermal aging at 170°C for 50 days, the solder/Ni interface exhibited a duplex structure of (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄. For the Sn-3Cu solder, only the (Cu,Ni)₆Sn₅ layer was formed in all aged samples. Compared to these two Sn-Cu solders, the Cu content in the (Cu,Ni)₆Sn₅ layer formed at the interface increased with the Cu concentration in the Sn-xCu solders. And, the shear strength was measured to evaluate the effect of the interfacial reactions on the mechanical reliability as a function of aging conditions. The shear strength significantly decreased after aging for 1 day and then remained nearly unchanged by further prolonged aging. In all the samples, the fracture always occurred in the bulk solder. Also, we studied the electrical property of Cu/Sn-3Cu/Cu BGA packages with the number of reflows. The electrical resistivity increased with the number of reflows because of an increase of intermetallic compound (IMC) thickness.     

Reactions of lead-free solders with CuNi metallizations

We have done experimental research on the dissolution rate and intermetallic growth on Cu, Ni, and CuNi-alloy substrates as a function of time and Cu/Ni ratio of the substrate. Reactions that occur when CuNi metallizations are soldered with lead-free solders were investigated. The experiments were performed using Sn-3.5Ag and Sn-3.8Ag-0.7Cu solders and different CuNi alloys. To determine the rate of dissolution of the substrate material into the solder, CuNi foils of different concentrations were immersed in Sn-3.5Ag and Sn-3.8Ag-0.7Cu solder baths for soldering times ranging from 15 sec to 5 min at 250°C. In addition, reflows of solder balls were made on top of bulk substrates to study the reaction when there is a practically infinite amount of CuNi available compared to the amount of solder. Thin film experiments were also done, where Ni containing under bump metallizations (UBMs) were fabricated and reflowed with eutectic SnAg solder balls. The nickel slows down the dissolution of the UBM into the solder and the formation of intermetallics during reflow compared to Cu metallizations. The solder/UBM interfaces were analyzed with SEM to find out how Ni concentration affects the reaction, and how much Ni is needed to obtain a sufficiently slow reaction rate.     

Kinetics of AuSn4 migration in lead-free solders

The relatively fast diffusion of Au atoms in eutectic PbSn matrix is considered one of the contributing factors to the Au embrittlement problem. In this study, we further investigated the Au embrittlement problem in high-Sn solders. Experimentally, Sn3.5Ag (wt.%) spheres with 500-μm diameter were soldered over the Au/Ni soldering pads. It was found that some of the AuSn₄ needles that formed after reflow inside the solder migrated back to the solder/pad interface during thermal aging. However, the migration kinetics in high-Sn solders was slower compared to that in eutectic PbSn. The difference in migration kinetics of AuSn₄ in eutectic PbSn and SnAg was ascribed to the difference in the magnitudes of the Au flux and the Ni flux. In eutectic PbSn, the Au flux was much greater than that of the Ni flux, and the Au and Ni flux were in the same order of magnitude in eutectic SnAg. The relative magnitude of the Au and Ni flux changed in eutectic PbSn and SnAg because the homologous temperatures of PbSn and SnAg were different.     

A review of lead-free solders for electronics applications

Ever since RoHS was implemented in 2006, Sn3.0Ag0.5Cu (SAC305) has been the primary lead-free solder for attaching electronic devices to printed circuit boards (PCBs). However, due to the 3.0 wt% Silver (Ag) in SAC305, companies have been looking at less expensive solder alternatives, especially for use in inexpensive products that have short operating lives and are used in mild application conditions. This paper reviews new lead-free solder alternatives and the trends in the industry, including SnCu-based solders, SnAgCu solders with Ag content < 1.0 wt%, SnAg solders, and no-Ag low-temperature solders (e.g., SnBi-based solders). The analysis is conducted for reflow, wave, and rework conditions and for packaged and flip-chip devices.     

Creep rupture of lead-free Sn-3.5Ag-Cu solders

Creep-rupture properties of lead-free Sn-3.5Ag-based alloys with varying amount of Cu were investigated using rolled and heat-treated dog-bone-shaped specimens. Nominal compositions of added copper were 0 wt.%, 0.5 wt.%, 0.75 wt.%, 1.0 wt.%, and 1.5 wt.%. During creep tests, the matrix hardness dropped significantly, and the minimum strain rates ( ) were lowest for the 0.75Cu specimens. The stress exponents (n) of were usually around 4, with the exception of the 0.5Cu and 0.75Cu alloys, which showed somewhat higher values of n. Fractographic analyses revealed typical creep rupture by the nucleation and growth of cavities in the matrix except the 1.5Cu specimens, which showed cavity nucleation at brittle Cu₆Sn₅ particles.     

The creep of lead-free solders at elevated temperatures

Full implementation of the new generation of lead-free solders requires a detailed knowledge and understanding of their mechanical behavior. This paper reports an investigation of the creep behavior of three lead-free alloys: Sn-0.5 Cu, Sn-3.5 Ag, and Sn-3.8Ag-0.7Cu, at 75°C, and compares their response to that of Sn-37Pb at the same temperature. In terms of stress and time to rupture, the Sn-0.5Cu alloy behaves similarly to the eutectic Sn-Pb over the range of rupture lives considered (up to 1000 h). The silver-containing alloys exhibit much greater creep resistance, typically a hundred fold and a thousand fold for the binary and tenanary, respectively. These alloys are less ductile but their creep strains to failure are generally above ten percent. Their minimum creep rates are at least 100 times slower. When testing at the same homologous temperature (0.76), the silver-containing alloys retain the substantial superiority. The relationship between applied steady-state (or minimum) creep rate behavior is best described by a power law equation, although the steady state domain generally occupies less than 30 percent of life. The microstructural changes induced by creep are briefly described and used to explain some of the creep characteristics of the alloys.     

Mechanical characterization of Sn–Ag-based lead-free solders

Recently, preventing environmental pollutions, lead-free (Pb-free) solders are about to replace tin–lead (Sn–Pb) eutectic solders. However, the mechanical properties of Pb-free solders have not been clarified. Hence, the following study was conducted; first, a rate-dependent plasticity was characterized to represent the inelastic deformation behavior for Sn–Ag-based lead-free solders. The material parameters in a constitutive model were determined in a direct method combining both rate-dependent and rate-independent plastic strains. The constitutive model unifies both rate-dependent creep behavior and rate-independent plastic behavior occurring concurrently at the same time in the solders. Secondly, the strength of solders with a variety of plating materials was studied. Intermetallic compounds (IMC) between solder and electrical pads are formed during reflow process and gradually grow in service. By using the Cu-plates on which Cu or Ni or Ni/Au plating was deposited, the specimens of solder joints were fabricated with Sn–Ag-based lead-free solders. After aging the specimens in an isothermal chamber, tensile tests were performed. From scanning electron microscope (SEM) microscope observation and EDX microprobe analysis, the growth and components of the IMC layer were also examined. Based on the experimental tests, the relations between solder joint strength and the aging period were discussed. Furthermore, the validation of fracture strength of solder joints resulting from the tensile tests was verified with package-mounted board level reliability tests.     

Fatigue crack-growth behavior of Sn-Ag-Cu and Sn-Ag-Cu-Bi lead-free solders

Fatigue crack-growth behavior and mechanical properties of Sn-3Ag-0.5Cu, Sn-3Ag-0.5Cu-1Bi, and Sn-3Ag-0.5Cu-3Bi solders have been investigated at room temperature (20°C). The tensile strength and hardness of the solders increased with increasing Bi content. However, the yield strengths of Sn-3Ag-0.5Cu-1Bi and Sn-3Ag-0.5Cu-3Bi solders were nearly similar, but the 3Bi solder exhibited the lowest ductility. Fatigue crack-growth behavior of the solders was dominantly cycle dependent in the range of stress ratios from 0.1–0.7 at a frequency of 10 Hz, except for the Sn-3Ag-0.5Cu solder tested at a stress ratio of 0.7. Mixed intergranular/transgranular crack propagation was observed for the Sn-3Ag-0.5Cu solder tested at the stress ratio of 0.7, indicating the importance of creep in crack growth. The Sn-3Ag-0.5Cu-1Bi and Sn-3Ag-0.5Cu-3Bi solders had higher resistance to time-dependent crack growth, resulting from the strengthening effect of the Bi constituent. It appears that the addition of Bi above a certain concentration is harmful to the mechanical properties of Sn-3Ag-0.5Cu.     

Intermetallic phase detection in lead-free solders using synchrotron x-ray diffraction

The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.     

电子组装用高温无铅钎料的研究进展

分析了国内外电子组装用高温无铅钎料的研究现状。指出目前常用的高温钎料仍然是高Pb焊料或80Au-20Sn钎料,导致焊料含Pb而污染环境,或者含质量分数为80%的Au而使焊料成本奇高。指明了Bi-Ag系钎料具有潜力替代高Pb焊料或80Au-20Sn钎料。未来的研究将在成分设计及可靠性等方面进行探索,以最终找到既经济又可替代传统高铅钎料的高温无铅钎料。     

Failure mechanism of lead-free solder joints in flip chip packages

The failure mechanisms of SnAgCu solder on Al/Ni(V)/Cu thin-film, underbump metallurgy (UBM) were investigated after multiple reflows and high-temperature storage using a ball shear test, fracture-surface analysis, and cross-sectional microstructure examination. The results were also compared with those of eutectic SnPb solder. The Al/Ni (V)/Cu thin-film UBM was found to be robust enough to resist multiple reflows and thermal aging at conditions used for normal production purposes in both SnAgCu and eutectic SnPb systems. It was found that, in the SnAgCu system, the failure mode changed with the number of reflows, relating to the consumption of the thin-film UBM because of the severe interfacial reaction between the solder and the UBM layer. After high-temperature storage, the solder joints failed inside the solder ball in a ductile manner in both SnAgCu and SnPb systems. Very fine Ag₃Sn particles were formed during multiple reflows in the SnAgCu system. They were found to be able to strengthen the bulk solder. The dispersion-strengthening effect of Ag₃Sn was lost after a short period of thermal aging, caused by the rapid coarsening of these fine particles.     

Reliability evaluation of ultra-thin CSP using new flip-chip bonding technology––double-sided CSP and single-sided CSP

A high-density packaging technology has been developed that uses new flip-chip bonding technology with a thin IC and a thin substrate. Numerical analysis with the finite element method as well experiments clearly showed that deflection of the IC and reliability were affected by the IC thickness. Consequently, reliability could be improved by reducing IC thickness. The dependency of the life in single-sided chip-size packages (CSPs) could be expressed using a normal stress value in thickness, which is computed by the IC thickness and substrate type and thickness. The dependency of the life in double-sided CSPs could be expressed using a shear stress value in the vertical cross section, which is computed in IC thickness and substrate type and thickness, respectively.Moreover, a double-sided flip-chip approach solved the problem of warpage. A high-capacity memory card of 512 MB was put to practical use by applying these results. This increased the Si density by four times over that of a conventional CSP.     

Evaluation of Cu-bumps with lead-free solders for flip-chip package applications

Low cost electroplated Cu-bump with environmental friendly Sn solder was developed for flip-chip applications. The seed layer used was Ti/WN_x/Ti/Cu where WN_x was used as the Cu diffusion barrier and Ti was used to enhance the adhesion between bump and the chip pad. Thick negative photoresist (THB JSR-151N) with a high aspect ratio of 2.4 was used for electroplating of copper bump and Sn solder. The Sn solder cap was reflowed at 225° for 6 min at N₂ atmosphere. No wetting phenomenon was observed for the Sn solder as evaluated by energy-dispersed spectroscopy (EDS). The Cu-bump with Ti/WN_x/Ti/Cu seed layer not only have higher shear force than the Cu-bump with Ti/Cu seed layer but also has higher resistance to fatigue failure than the Au, SnCu, SnAg bumps.