The Effects of Dopants on the Aging Behavior of Lead Free Solders

Author(s):  
Zijie Cai ◽  
Jeffrey C. Suhling ◽  
Pradeep Lall ◽  
Michael J. Bozack

The microstructure, mechanical response, and failure behavior of lead free solder joints in electronic assemblies are constantly evolving when exposed to isothermal aging and/or thermal cycling environments. Over the past several years, we have demonstrated that the observed material behavior variations of Sn-Ag-Cu (SAC) lead free solders during room temperature aging (25 C) and elevated temperature aging (50, 75, 100, 125, and 150 C) were unexpectedly large and universally detrimental to reliability. The measured stress-strain data demonstrated large reductions in stiffness, yield stress, ultimate strength, and strain to failure (up to 50%) during the first 6 months after reflow solidification. In addition, even more dramatic evolution was observed in the creep response of aged solders, where up to 100X increases were found in the steady state (secondary) creep strain rate (creep compliance) of lead free solders that were simply aged at room temperature. For elevated temperature aging at 125 C, the creep strain rate was observed to change even more dramatically (up to 10,000X increase). There is much interest in the industry on establishing optimal SAC-based lead free solder alloys that minimize aging effects and thus enhance thermal cycling and elevated temperature reliability. During the past year, we have extended our previous studies to include several doped SAC alloys (SAC-X) where the standard SAC alloys have been modified with small percentages of one or two additional elements (X). Materials under consideration include SAC0307-X, Sn-.7Cu-X, SAC305-X, SAC3595-X and SAC3810-X. Using dopants (e.g. Bi, In, Ni, La, Mg, Mn, Ce, Co, Ti, etc.) has become widespread to enhance shock/drop reliability, and we have extended this approach to examine the ability of dopants reduce the effects of aging and extend thermal cycling reliability. In the current paper, we concentrate on showing results for SACX™, which has the composition Sn-0.3Ag-0.7Cu-X with X = 0.1Bi. We have performed aging under 5 different conditions including room temperature (25 C), and four elevated temperatures (50, 75, 100 and 125). We have also extended the duration of aging considered in our experiments to up to 12 months of aging on selected alloys. Variations of the mechanical and creep properties (elastic modulus, yield stress, ultimate strength, creep compliance, etc.) have been observed. We have correlated the aging results for the doped SAX-X alloy with our prior data for the “standard” lead free alloys SACN05 (SAC105, SAC205, SAC305, SAC405). The doped SAC-X alloy shows improvements (reductions) in the aging-induced degradation in stiffness, strength, and creep rate when compared to SAC105, even though it has lower silver content. In addition, the doped SAC-X alloy has been observed to reach a stabilized microstructure more rapidly when aged. Mathematical models for the observed aging variations have been established so that the variation of the stress-strain and creep properties can be predicted as a function of aging time and aging temperature.

Author(s):  
Hongtao Ma ◽  
Jeffrey C. Suhling ◽  
Yifei Zhang ◽  
Pradeep Lall ◽  
Michael J. Bozack

The microstructure, mechanical response, and failure behavior of lead free solder joints in electronic assemblies are constantly evolving when exposed to isothermal aging and/or thermal cycling environments. In our prior work on aging effects (Ma, et al., ECTC 2006), we demonstrated that the observed material behavior variations of SAC405 and SAC305 lead free solders during room temperature aging (25 °C) were unexpectedly large and universally detrimental to reliability. Such effects for lead free solder materials are much more dramatic at the higher aging temperatures (e.g. 100–150 °C) typical of the harsh environments present in high performance computing and in automotive, aerospace, and defense applications. However, there has been little work in the literature, and the work that has been done has concentrated on the degradation of solder ball shear strength (e.g. Dage Shear Tester). Current finite element models for solder joint reliability during thermal cycling accelerated life testing are based on traditional solder constitutive and failure models that do not evolve with material aging. Thus, there will be significant errors in the calculations with the new lead free SAC alloys that illustrate dramatic aging phenomena. In the current work, we have explored the effects of elevated temperature isothermal aging on the mechanical behavior and reliability of lead free solders. The effects of aging on mechanical behavior have been examined by performing stress-strain and creep tests on SAC405 and SAC305 samples that were aged for various durations (0–6 months) at several elevated temperatures (80, 100, 125, and 150 °C). Analogous tests were performed with 63Sn-37Pb eutectic solder samples for comparison purposes. Variations of the temperature dependent mechanical properties (elastic modulus, yield stress, ultimate strength, creep compliance, etc.) were observed and modeled as a function of aging time and temperature. In this paper, we have concentrated our efforts on presenting the results for samples aged at 125 °C. In addition, the new elevated temperature aging data were correlated with our room temperature results from last year’s investigation. The results obtained in this work have demonstrated the significant effects of elevated temperature exposure on solder joints. As expected, the mechanical properties evolved at a higher rate and experienced larger changes during elevated temperature aging (compared to room temperature aging). After approximately 200 hours of aging, the lead free solder joint material properties were observed to degrade at a nearly constant rate. We have developed a mathematical model to predict the variation of the properties with aging time and aging temperature. Our data for the evolution of the creep response of solders with elevated temperature aging show that the creep behavior of lead free and tin-lead solders experience a “crossover point” where lead free solders begin to creep at higher rates than standard 63Sn-37Pb solder for the same stress level. Such an effect is not observed for solder joints aged at room temperature, where SAC alloys always creep at lower rates than Sn-Pb solder.


Author(s):  
Yifei Zhang ◽  
Zijie Cai ◽  
Jeffrey C. Suhling ◽  
Pradeep Lall

The microstructure, mechanical response, and failure behavior of lead free solder joints in electronic assemblies are constantly evolving when exposed to isothermal aging and/or thermal cycling environments. In our prior work on aging effects, we have demonstrated that the observed material behavior variations of Sn-Ag-Cu (SAC) lead free solders during room temperature aging (25°C) and elevated temperature aging (125°C) were unexpectedly large and universally detrimental to reliability. Such effects for lead free solder materials are especially important for the harsh applications environments present in high performance computing and in automotive, aerospace, and defense applications. However, there has been little work in the literature, and the work that has been done has concentrated on the degradation of solder ball shear strength (e.g. Dage Shear Tester). Current finite element models for solder joint reliability during thermal cycling accelerated life testing are based on traditional solder constitutive and failure models that do not evolve with material aging. Thus, there will be significant errors in the calculations with the new lead free SAC alloys that illustrate dramatic aging phenomena. In the current work, we have extended our previous studies to include a full test matrix of aging temperatures and solder alloys. The effects of aging on mechanical behavior have been examined by performing stress-strain and creep tests on four different SAC alloys (SAC105, SAC205, SAC305, SAC405) that were aged for various durations (0–6 months) at room temperature (25°C), and several elevated temperatures (50, 75, 100, and 125°C). Analogous tests were performed with 63Sn-37Pb eutectic solder samples for comparison purposes. Variations of the mechanical and creep properties (elastic modulus, yield stress, ultimate strength, creep compliance, etc.) were observed and modeled as a function of aging time and aging temperature. In this paper, we report on the creep results. The chosen selection of SAC alloys has allowed us to explore the effects of silver content on aging behavior (we have examined SACN05 with N = 1%, 2%, 3%, and 4% silver; with all alloys containing 0.5% copper). In order to reduce the aging induced degradation of the material behavior of the SAC alloys, we are testing several doped SAC alloys in our ongoing work. These materials include SAC0307-X, SAC105-X, and SAC305-X; where the standard SAC alloys have been modified by the addition of small percentages of one or more additional elements (X). Using dopants (e.g. Bi, In, Ni, La, Mg, Mn, Ce, Co, Ti, etc.) has become widespread to enhance shock/drop reliability, and we have extended this approach to examine the ability of dopants to reduce the effects of aging and extend thermal cycling reliability.


Author(s):  
Hongtao Ma ◽  
Jeffrey C. Suhling ◽  
Pradeep Lall ◽  
Michael J. Bozack

Solder materials demonstrate evolving microstructure and mechanical behavior that changes significantly with environmental exposures such as isothermal aging and thermal cycling. These aging effects are greatly exacerbated at higher temperatures typical of thermal cycling qualification tests for harsh environment electronic packaging. In the current study, mechanical measurements of thermal aging effects and material behavior evolution of lead free solders have been performed. Extreme care has been taken so that the fabricated solder uniaxial test specimens accurately reflect the solder materials present in actual lead free solder joints. A novel specimen preparation procedure has been developed where the solder uniaxial test specimens are formed in high precision rectangular cross-section glass tubes using a vacuum suction process. The tubes are then sent through a SMT reflow to re-melt the solder in the tubes and subject them to any desired temperature profile (i.e. same as actual solder joints). Using specimens fabricated with the developed procedure, isothermal aging effects and viscoplastic material behavior evolution have been characterized for 95.5Sn4.0Ag-0.5Cu (SAC405) and 96.5Sn-3.0Ag-0.5Cu (SAC305) lead free solders, which are commonly used as the solder ball alloy in lead free BGAs and other components. Analogous tests were performed with 63Sn-37Pb eutectic solder samples for comparison purposes. In our total experimental program, samples have been solidified with both reflowed and water quenching temperature profiles, and isothermal aging has been performed at room temperature (25 °C) and elevated temperatures (100 °C, 125 °C and 150 °C). In this paper, we have concentrated on reporting the results of the room temperature aging experiments. Variations of the temperature dependent mechanical properties (elastic modulus, yield stress, ultimate strength, creep compliance, etc.) were observed and modeled as a function of room temperature aging time. Microstructural changes during. room temperature aging have also been recorded for the solder alloys and correlated with the observed mechanical behavior changes.


Author(s):  
Munshi Basit ◽  
Mohammad Motalab ◽  
Jeffrey C. Suhling ◽  
John L. Evans ◽  
Pradeep Lall

The microstructure, mechanical response, and failure behavior of lead free solder joints in electronic assemblies are constantly evolving when exposed to isothermal aging and/or thermal cycling environments. In our prior work on aging effects, we have demonstrated that the observed material behavior degradations of Sn-Ag-Cu (SAC) lead free solders during room temperature aging (25 C) and elevated temperature aging (50, 75, 100, 125, and 150 C) were unexpectedly large. The measured stress-strain data demonstrated large reductions in stiffness, yield stress, ultimate strength, and strain to failure (up to 50%) during the first 6 months after reflow solidification. In this study, we have used both accelerated life testing and finite element modeling to explore how prior isothermal aging affects the overall reliability of PBGA packages subjected to thermal cycling. In the experimental work, an extensive test matrix of thermal cycling reliability testing has been performed using a test vehicle incorporating several sizes (5, 10, 15, 19 mm) of BGA daisy chain components with 0.4 and 0.8 mm solder joint pitches (SAC305). PCB test boards with 3 different surface finishes (ImAg, ENIG and ENEPIG) were utilized. In this paper, we concentrate on the reporting the results for a PBGA component with 15 mm body size. Before thermal cycling began, the assembled test boards were divided up into test groups that were subjected to several sets of aging conditions (preconditioning) including 0, 6, and 12 months aging at T = 125 °C. After aging, the assemblies were subjected to thermal cycling (−40 to +125 °C) until failure occurred. The Weibull data failure plots have demonstrated that the thermal cycling reliabilities of pre-aged assemblies were significantly less than those of non-aged assemblies. A three-dimensional finite element model of the tested 15 mm PBGA packages was also developed. The cross-sectional details of the solder ball and the internal structure of the BGA were examined by scanning electron microscopy (SEM) to capture the real geometry of the package. Simulations of thermal cycling from −40 to 125 C were performed. To include the effects of aging in the calculations, we have used a revised set of Anand viscoplastic stress-strain relations for the SAC305 Pb-free solder material that includes material parameters that evolve with the thermal history of the solder material. The accumulated plastic work (energy density dissipation) was used is the failure variable; and the Darveaux approach to predict crack initiation and crack growth was applied with aging dependent parameters to estimate the fatigue lives of the studied packages. We have obtained good correlation between our new reliability modeling procedure that includes aging and the measured solder joint reliability data. As expected from our prior studies on degradation of SAC material properties with aging, the reliability reductions were more severe for higher aging temperature and longer aging times.


Author(s):  
Biao Yuan ◽  
Zhimin Liang ◽  
Zongyuan Yang ◽  
Fei Shen ◽  
Da Xu ◽  
...  

AbstractSn–Sb lead-free solders are considered to substitute the tin–lead solders due to their great mechanical properties. At room temperature, the mechanical properties of Ni/Au/Sn–5Sb/Au/Ni and Ni/Au/Sn–5Sb–0.3Ag–0.05Cu/Au/Ni linear solder joints were investigated by nanoindentation experiments at different loads. The results showed that the Sn–Sb intermetallic compound (IMC) was distributed in the β-Sn matrix in Ni/Au/Sn–5Sb/Au/Ni solder joints. Co-addition of Cu and Ag resulted in the formation of the rod-shaped Cu6Sn5 and the fine granular Ag3Sn IMCs. At the same load and loading/unloading rate, the indentation depth and residual indentation morphologies of Ni/Au/Sn–5Sb–0.3Ag–0.05Cu/Au/Ni solder joints were smaller than those of Ni/Au/Sn–5Sb/Au/Ni solder joints. The hardness of the two kinds of solder joints decreased with the increase in load, while the Young’s modulus was independent of load. In addition, compared to the Ni/Au/Sn–5Sb/Au/Ni solder joints, the hardness, Young’s modulus and stress exponents of Ni/Au/Sn–5Sb–0.3Ag–0.05Cu/Au/Ni solder joints achieved an improvement due to the co-addition of Ag and Cu.


Author(s):  
Zijie Cai ◽  
Jeffrey C. Suhling ◽  
Pradeep Lall ◽  
Michael J. Bozack

The microstructure, mechanical response, and failure behavior of lead free solder joints in electronic assemblies are constantly evolving when exposed to isothermal aging and/or thermal cycling environments. In our prior work on aging effects, we have demonstrated that large degradations occur in the material properties (stiffness and strength) and creep behavior of Sn-Ag-Cu (SAC) lead free solders during aging. These effects are universally detrimental to reliability and are exacerbated as the aging temperature and aging time increases. Conversely, changes due to aging are relatively small in conventional Sn-Pb solders. In our current work, we are exploring several doped SAC+X alloys in an attempt to reduce the aging induced degradation of the material behavior of SAC solders. The doped materials are lead free SAC solders that have been modified by the addition of small percentages of one or more additional elements (X). Using dopants (e.g. Bi, In, Ni, La, Mg, Mn, Ce, Co, Ti, Zn, etc.) has become widespread to enhance shock/drop reliability, wetting, and other properties; and we have extended this approach to examine the ability of dopants to reduce the effects of aging and extend thermal cycling reliability. In this paper, we concentrate on presenting the results for SAC+X (X = Zn, Co, Ni). The enhancement of aging resistance for the doped lead free solders was explored. Comparisons were made to the responses of non-doped SAC lead free solder alloys. The effects of aging on mechanical behavior have been examined by performing stress-strain and creep tests on solder samples that were aged for various durations (0–6 months) at elevated temperature (100 °C). Variations of the mechanical and creep properties (elastic modulus, yield stress, ultimate strength, creep compliance, etc.) were observed and modeled as a function of aging time and aging temperature. Our findings show that the doped SAC+X alloys illustrate reduced degradations with aging for all of the aging temperatures considered. Also, the stress-strain and creep mechanical properties of doped solders are better than those of reference solders after short durations of aging. After long term aging, doped solder alloys were found to have more stable behaviors than those of the standard SAC alloys. A parallel microstructure study has shown that less degradation and coarsening of the phases occurs in doped solder materials relative to non-doped solders after severe aging.


Author(s):  
S. M. Kamrul Hasan ◽  
Abdullah Fahim ◽  
Jeffrey C. Suhling ◽  
Pradeep Lall

Abstract In the electronic assembly arena, lead is being targeted due to the concern regarding environmental pollutants. So, the lead-free solder and its reliability are getting highlighted. During qualification testing or actual use lead-free solders in electronic assemblies, they are often subjected to thermal cycling. In the lead-free solder material, microstructural evolution and material property degradation occurs due to the thermal aging phenomena during dwell periods at the high temperature extreme of thermal cycling. In addition, during ramping between low and high temperature extreme, lead-free solders can experience additional aging phenomena. In our prior work, we have compared material properties (stiffness and strength) degradation of lead-free solder materials in isothermal aging and five different thermal cycling exposures. Changes in material properties were higher for all the thermal cycling exposures compared to the aging. In addition, microstructural evolution and material property degradation were exacerbated as the ramp rate decreased in the thermal cycling. In this study, the creep behavior evolutions occurring in SAC305 lead free solder subjected to isothermal aging and slow thermal cycling exposures have been investigated. Uniaxial test specimens were prepared by reflowing solder in rectangular cross-section glass tubes with a controlled temperature profile. Afterwards, the reflowed samples were exposed to either isothermal aging at 125 °C, or to thermal cycling from −40 to +125 °C, under a stress-free condition (no load) for various durations in an environmental chamber. A slow thermal cycling profile, e.g. 150 minutes cycle with 45 minutes ramps and 30 minutes dwells, was chosen for this study as it was found in our previous work that it caused the most detrimental effects on the mechanical behavior evolution. The thermally exposed samples were isothermally aged for 0, 1, 2, and 5 days; or were thermally cycled for 0, 48, 96, and 240 slow thermal cycles, which had the same aging times at the high temperature extreme of T = 125 °C. After aging or cycling, creep testing was performed at room temperature on the thermally exposed samples at three different stress levels (10, 12, 15 MPa). The evolutions of the secondary creep strain rate were obtained as a function of the stress level, as well as the net aging time at the high temperature extreme, and then compared. Results showed that secondary creep strain rate increased dramatically with equivalent aging time, and that the degradation effects were larger for slow thermal cycling than for pure aging. For example, the creep rate increased by 3.0–3.4X for 5 days of pure aging at T = 125 °C; while they increased by 10.9–13.1X for 240 thermal cycles, when there had been 5 days of equivalent aging at the T = 125 °C high temperature extreme.


2018 ◽  
Vol 140 (3) ◽  
Author(s):  
Sinan Su ◽  
Nianjun Fu ◽  
Francy John Akkara ◽  
Sa'd Hamasha

Solder joints in electronic assemblies are subjected to mechanical and thermal cycling. These cyclic loadings lead to the fatigue failure of solder joints involving damage accumulation, crack initiation, crack propagation, and failure. Aging leads to significant changes on the microstructure and mechanical behavior of solder joints. While the effect of thermal aging on solder behavior has been examined, no prior studies have focused on the effect of long-term room temperature aging (25 °C) on the solder failure and fatigue behavior. In this paper, the effects of long-term room temperature aging on the fatigue behavior of five common lead-free solder alloys, i.e., SAC305, SAC105, SAC-Ni, SAC-X-Plus, and Innolot, have been investigated. Several individual lead-free solder joints on printed circuited boards with two aging conditions (no aging and 4 years of aging) have been prepared and subjected to shear cyclic stress–strain loadings until the complete failure. Fatigue life was recorded for each solder alloy. From the stress–strain hysteresis loop, inelastic work and plastic strain ranges were measured and empirically modeled with the fatigue life. The results indicated that 4 years of room temperature aging significantly decreases the fatigue life of the solder joints. Also, inelastic work per cycle and plastic strain range are increased after 4 years of room temperature aging. The fatigue life degradation for the solder alloys with doped elements (Ni, Bi, Sb) was relatively less compared to the traditional SAC105 and SAC305.


2015 ◽  
Vol 10 (1) ◽  
pp. 2641-2648
Author(s):  
Rizk Mostafa Shalaby ◽  
Mohamed Munther ◽  
Abu-Bakr Al-Bidawi ◽  
Mustafa Kamal

The greatest advantage of Sn-Zn eutectic is its low melting point (198 oC) which is close to the melting point. of Sn-Pb eutectic solder (183 oC), as well as its low price per mass unit compared with Sn-Ag and Sn-Ag-Cu solders. In this paper, the effect of 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 wt. % Al as ternary additions on melting temperature, microstructure, microhardness and mechanical properties of the Sn-9Zn lead-free solders were investigated. It is shown that the alloying additions of Al at 4 wt. % to the Sn-Zn binary system lead to lower of the melting point to 195.72 ˚C.  From x-ray diffraction analysis, an aluminium phase, designated α-Al is detected for 4 and 5 wt. % Al compositions. The formation of an aluminium phase causes a pronounced increase in the electrical resistivity and microhardness. The ternary Sn-9Zn-2 wt.%Al exhibits micro hardness superior to Sn-9Zn binary alloy. The better Vickers hardness and melting points of the ternary alloy is attributed to solid solution effect, grain size refinement and precipitation of Al and Zn in the Sn matrix.  The Sn-9%Zn-4%Al alloy is a lead-free solder designed for possible drop-in replacement of Pb-Sn solders.  


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