Phase equilibria and the related properties of Sn-Ag-Cu based Pb-free solder alloys

We have recently developed a thermodynamic database for micro-soldering alloys which consists of the elements Pb, Bi, Sn, Sb, Cu, Ag, Zn, and In. In this paper, the phase equilibria and the related thermodynamic properties of the Sn-Ag-Cu base alloys are presented using this database, alloy systems being one of the promising candidates for Pb-free solders. The isothermal section diagrams of the Sn-Ag-Cu ternary system were experimentally determined by SEM-EDS, x-ray diffraction and metallographic techniques. Based on the present results as well as the previous data on phase boundaries and thermochemical properties, thermodynamic assessment of this system was carried out. The isothermal and vertical section diagrams, liquidus surface, mass fractions of the phase constitution, etc., were calculated. The predictions of surface energy and viscosity were also investigated. Moreover, a non-equilibrium solidification process using the Scheil model was simulated and compared with the equilibrium solidification behavior in some Sn-Ag-Cu base alloys. Calculated results based on the Scheil model were incorporated into a three-dimensional solidification simulation and the prediction of practical solidification procedures was performed.     

Apple iMac MA199LL台式电脑拆解分析

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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.     

Wetting characteristics of Pb-free solder alloys and PWB finishes

For a successful transition to Pb-free manufacturing in electronics assembly, it is critical to understand the behavior of Pb-free solders (in bulk and paste form) and their interaction with the Pb-free printed wiring board (PWB) finishes. This paper presents the results obtained from solder paste spread tests and wetting balance experiments with several Pb-free solder alloys and Pb-free PWB finishes. The solder alloys studied were Sn3.4Ag4.8Bi, Sn4.0Ag0.5Cu, Sn3.5Ag and Sn0.7Cu. Eutectic Sn37Pb was used as a reference. The PWB surface finishes were Sn, NiAu, Ag and OSP. Wetting balance experiments were conducted in air while the spread tests were performed in air and nitrogen to understand the effect of reflow atmosphere on the spreading. Surface analysis techniques such as Nomarski phase contrast microscopy, Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the as-received PWB finishes. Sequential electrochemical reduction analysis (SERA) was also performed on the as-received PWB test coupons and on the Sn test coupons after multiple reflow cycles. The effect of multiple reflow cycles on the wetting performance, spreading and the surface composition of the PWB finishes was studied.     

Zn-Al-Mg-Ga alloys as Pb-free solder for die-attaching use

Zn-based alloys have been investigated to replace Pb-5%Sn solder for die-attaching use. We have found that a Zn-4%Al-3%Mg-3%Ga alloy has a 309°C solidus and a 347°C liquidus. A die-attaching test was done with preforms of this alloy, Ag-plated lead-frames, and Au-plated dummy dies. Good die-attaching with a small amount of voids can be achieved at 320°C or higher. In subsequent reliability tests, no failure was observed until 1000 cycles between −65°C and 150°C or until 1000 h at 85°C and 85% humidity. Although the poor workability and poor ability of stress relaxation at room temperature of this alloy may somewhat limit its application areas, this solder is the first Pb-free solder for die-attaching use to our knowledge.     

Phase equilibria and solidification properties of Sn-Cu-Ni alloys

Ternary Sn-Cu-Ni alloys were prepared and annealed at 240°C. The annealed alloys were metallographically examined and the equilibrium phases formed were identified on the basis of compositional determinations and x-ray diffraction (XRD) analysis. The isothermal section of the ternary Sn-Cu-Ni system at 240°C was proposed on the basis of experimental results of this study and related information on phase equilibrium available in the literature. The binary compounds, Cu₆Sn₅, Ni₃Sn₂, and Ni₃Sn₄, have very extensive ternary solubility. Continuous solid solutions form between Cu and Ni as well as between Cu₃Sn and Ni₃Sn. In addition to the isothermal section, the liquidus projection of the Sn-Cu-Ni system was determined based on results from the existing literature. Interfacial reactions between Sn-Cu alloys and Ni substrate and the primary solidification phases of various Sn-Cu-Ni alloys were also examined in this study.     

Phase equilibria of Sn-In based micro-soldering alloys

The phase equilibria of Sn-In-X (X=Ag, Bi, Sb, Zn), the most basic information necessary for the development of Pb-free micro-soldering alloys, were studied using the CALPHAD method. Thermodynamic analyses for describing the Gibbs energies of the constituent phases were made by optimizing the obtained data on the experimental phase diagrams, and such data in the literature, including data on thermochemical properties. The present results combined with the thermodynamic database which was recently developed by our group [I. Ohnuma et al., J. Electron. Mater. 28, 1164 (1999)] provide various information on phase equilibria such as liquidus and solidus surfaces, isothermal and vertical section diagrams, mole fractions of the phase constitutions, etc., and thermodynamic properties such as activity, heat of mixing, surface energy, viscosity, etc., in multi-component soldering alloy systems including the elements of Pb, Bi, Sn, Sb, Cu, Ag, Zn, and In. Typical examples for the phase diagrams and thermodynamic properties of Sn-In-X ternary systems are shown. The application of the database to the alloy design for Pb-free solders is also presented.     

Microstructure and mechanical properties of Pb-free solder alloys for low-cost electronic assembly: A review

Lead-free solders, including Sn-58Bi, Sn-52In, and Sn-3.5Ag, are potential replacements for Sn-37Pb solder in low-cost electronic assembly. This paper reviews the literature on the microstructure and mechanical properties of these alloys. Because of the processing and testing conditions, many of the data are not predictive for electronic assembly applications. However, eutectic Sn-Bi seems to have properties approaching those of eutectic Sn-Pb under most conditions, while eutectic Sn-In seems far inferior in most respects. Eutectic Sn-Ag has many promising characteristics, but its relatively high melting temperature may preclude its use for this type of application.     

Effects of Cu contents in Pb-free solder alloys on interfacial reactions and bump reliability of Pb-free solder bumps on electroless Ni-P under-bump metallurgy

Using the screen-printed solder-bumping technique on the electroless plated Ni-P under-bump metallurgy (UBM) is potentially a good method because of cost effectiveness. As SnAgCu Pb-free solders become popular, demands for understanding of interfacial reactions between electroless Ni-P UBMs and Cu-containing Pb-free solder bumps are increasing. It was found that typical Ni-Sn reactions between the electroless Ni-P UBM and Sn-based solders were substantially changed by adding small amounts of Cu in Sn-based Pb-free solder alloys. In Cu-containing solder bumps, the (Cu,Ni)₆Sn₅ phase formed during initial reflow, followed by (Ni,Cu)₃Sn₄ phase formation during further reflow and aging. The Sn3.5Ag solder bumps showed a much faster electroless Ni-P UBM consumption rate than Cu-containing solder bumps: Sn4.0Ag0.5Cu and Sn0.7Cu. The initial formation of the (Cu,Ni)₆Sn₅ phase in SnAgCu and SnCu solders significantly reduced the consumption of the Ni-P UBM. The more Cu-containing solder showed slower consumption rate of the Ni-P UBM than the less Cu-containing solder below 300°C heat treatments. The growth rate of the (Cu,Ni)₆Sn₅ intermetallic compound (IMC) should be determined by substitution of Ni atoms into the Cu sublattice in the solid (Cu,Ni)₆Sn₅ IMC. The Cu contents in solder alloys only affected the total amount of the (Cu,Ni)₆Sn₅ IMC. More Cu-containing solders were recommended to reduce consumption of the Ni-based UBM. In addition, bump shear strength and failure analysis were performed using bump shear test.     

Residual-mechanical behavior of thermomechanically fatigued Sn-Ag based solder joints

Thermomechanical fatigue (TMF) due to the mismatch in coefficients of thermal expansion between solder and substrate gradually degrades the mechanical properties of electronic solder joints during service. This study investigated the role of TMF on the residual-mechanical behavior of solder joints made with eutectic Sn-Ag solder and Sn-Ag solder with Cu or Ni additions. The TMF tests were carried out between −15°C and +150°C with a ramp rate of 25°C/min for the heating segment and 7°C/min for the cooling segment. The hold times were 20 min at the high extreme and 300 min at the low extreme. Residual shear strength was found to drop significantly during the first 250 TMF cycles, although it did remain relatively constant between 250 and 1000 cycles. Alloying elements were found to affect the residual creep strength of solder joints after TMF.     

A thermodynamic study of phase equilibria in the Au-Sb-Sn solder system

To design and develop high-temperature solder alloys, the thermodynamic calculations of phase equilibria have been performed on the binary Au-Sb and ternary Au-Sb-Sn systems over the entire composition range. The Gibbs free energy of individual phases has been approximated using a subregular-solution model, and the thermodynamic parameters for each phase have been evaluated using available experimental information on phase boundaries and other related thermodynamic properties. The calculated phase diagrams and thermodynamic quantities of the Au-Sb binary system show good agreement with experimental data, and the liquidus projection and the vertical sections in the Au-Sb-Sn ternary system are well reproduced using assessed thermodynamic parameters derived in this work.     

Phase equilibria studies of Sn-Ag-Cu eutectic solder using differential cooling of Sn-3.8Ag-0.7Cu alloys

This paper is a study of the phase equilibria of the Sn-3.8Ag-0.7Cu alloy investigated by a differential cooling method. The difficulty in assessing phase equilibria of the Sn-Ag-Cu (SAC) system because of the insufficient resolution of conventional characterization techniques is solved by inducing preferential growth of a solid phase in a melt by holding the alloy at the solid-liquid phase-equilibrium field. Application of the technique to Sn-3.8Ag-0.7Cu with varying holding temperatures yielded results that the alloy is slightly off eutectic composition. The phase-formation sequence of the alloy during solidification was found to be Ag₃Sn, β-Sn, and finally the ternary eutectic microstructure.     

Microstructural characterization of damage in thermomechanically fatigued Sn-Ag based solder joints

Sn-Ag based solder joints of 100-μm thickness were thermomechanically fatigued between −15°C and +150°C with a ramp rate of 25°C/min for the heating segment and 7°C/min for the cooling segment. The hold times were 20 min at high temperature extreme and 300 min at the low temperature extreme. Surface damage accumulation predominantly consisted of shear banding, surface relief due to Sn-grain extrusion, grain boundary sliding, and grain decohesion usually near the solder/substrate interface. Small alloy additions were found to affect the extent of this surface damage accumulation.     

Sn-Ag基无铅焊料应变率效应的研究

随着人们环保意识的增强,在世界范围内开展了对无铅焊料的研究和开发。利用分离式Hopkinson压杆实验技术研究了Sn-Ag系无铅焊料在不同应变率下的动态压缩性能。实验表明Sn-Ag系无铅焊料有的明显应变率效应:与静载荷作用下的情况相比,冲击载荷作用下的屈服和流动应力有显著的提高;与锡铅焊料相比,其动态力学性能有明显的优势。     

Mechanical properties of intermetallic compounds associated with Pb-free solder joints using nanoindentation

Mechanical properties of intermetallic compound (IMC) phases in Pb-free solder joints were obtained using nanoindentation testing (NIT). The elastic modulus and hardness were determined for IMC phases associated with insitu FeSn particle reinforced and mechanically added, Cu particle-reinforced, composite solder joints. The IMC layers that formed around Cu particle reinforcement and at the Cu substrate/solder matrix interface were probed with NIT. Moduli and hardness values obtained by NIT revealed were noticeably higher for Cu-rich Cu₃Sn than those of Cu₆Sn₅. The Ag₃Sn platelets that formed during reflow were also examined for eutectic Sn-Ag solder column joints. The indentation modulus of Ag₃Sn platelets was significantly lower than that of FeSn, SnCuNi, and CuSn IMCs. Indentation creep properties were assessed in localized microstructure regions of the as-cast, eutectic Sn-Ag solder. The stress exponent, n, associated with secondary creep differed widely depending on the microstructure feature probed by the indenter tip.     

Partitioned viscoplastic-constitutive properties of the Pb-free Sn3.9Ag0.6Cu solder

The partitioned viscoplastic-constitutive properties of the Sn3.9Ag0.6Cu Pb-free alloy are presented and compared with baseline data from the eutectic Sn63Pb37 solder. Steady-state creep models are obtained from creep and monotonic tests at three different temperatures for both solders. Based on steady-state creep results and creep-test data, a transient creep model is developed for both Pb-free and Sb37Pb solders. A one-dimensional (1-D), incremental analytic model of the test setup is developed to simulate constant-load creep and monotonic and isothermal cyclic-mechanical tests performed over various temperatures and strain rates and stresses using a thermome-chanical-microscale (TMM) test system developed by the authors. By fitting simulation results to monotonic testing data, plastic models are also achieved. The comparison between the two solders shows that Sn3.9Ag0.6Cu has much better creep resistance than Sn37Pb at low and medium stresses. The obtained, partitioned viscoplastic-constitutive properties of the Sn3.9Ag0.6Cu Pb-free alloy can be used in commercial finite-element model software.     

Microstructure evolution of eutectic Sn-Ag solder joints

Laser and infrared reflow soldering methods were used to make Sn-Ag eutectic solder joints for surface-mount components on printed wiring boards. The microstructures of the joints were evaluated and related to process parameters. Aging tests were conducted on these joints for times up to 300 days and at temperature up to 190°C. The evolution of microstructure during aging was examined. The results showed that Sn-Ag solder microstructure is unstable at high temperature, and microstructural evolution can cause solder joint failure. Cu-Sn intermetallics in the solder and at copper-solder interfaces played an important role in both the microstructure evolution and failure of solder joints. Void and crack formation in the aged joints was also observed.     

Thermomechanical fatigue behavior of Sn-Ag solder joints

Microstructural studies of thermomechanically fatigued actual electronic components consisting of metallized alumina substrate and tinned copper lead, soldered with Sn-Ag or 95.5Ag/4Ag/0.5Cu solder were carried out with an optical microscope and environmental scanning electron microscope (ESEM). Damage characterization was made on samples that underwent 250 and 1000 thermal shock cycles between −40°C and 125°C, with a 20 min hold time at each extreme. Surface roughening and grain boundary cracking were evident even in samples thermally cycled for 250 times. The cracks were found to originate on the free surface of the solder joint. With increased thermal cycles these cracks grew by grain boundary decohesion. The crack that will affect the integrity of the solder joint was found to originate from the free surface of the solder very near the alumina substrate and progress towards and continue along the solder region adjacent to the Ag₃Sn intermetallic layer formed with the metallized alumina substrate. Re-examination of these thermally fatigued samples that were stored at room temperature after ten months revealed the effects of significant residual stress due to such thermal cycles. Such observations include enhanced surface relief effects delineating the grain boundaries and crack growth in regions inside the joint.     

Zn-Al based alloys as Pb-free solders for die attach

The present study examines the potential of Zn-Al based alloys for replacing Pb-containing solders used in the die-attaching process. Four alloys (Zn-6wt.%Al, Zn-6wt.%Al-1wt.%Ga, Zn-3wt.%Al-3wt.%Mg, and Zn-4wt.%Al-3wt.%Ga-3wt.%Mg) were cast and characterized in terms of microstructure and mechanical behavior. Based on the criteria of thermodynamics (phase diagram extrapolations) and mechanical behavior (flow curves), it was possible to select the Zn-Al-Ga alloy as best meeting the requirements concerning melting range necessary for die attach and mechanical properties. A wire with 0.76-mm thickness was produced successfully by extrusion. However, the alloy, in the form of wires, is subject to substantial embrittlement after extruding to a degree that further handling becomes impossible. The reason for the embrittlement was investigated using x-ray techniques (x-ray diffraction and x-ray photo spectroscopy (XPS)) and transmission electron microscopy. The temperature dependence of the Ga solubility in the hexagonal close-packed (hcp) Zn-rich phase in combination with the affinity of Ga to the surface of the Al-rich and Zn-rich phases is held responsible for the embrittlement. A remedy for the embrittlement could be a reduction of the solubility at high temperatures in the Zn-rich phase. This will be attempted by adding small fractions of further alloying elements in future work.