Practically all microelectronic assemblies in use today utilize Pb–Sn solders for interconnection. With the advent of chip scale packaging technologies, the usage of solder connections has increased. The most widely used Pb–Sn solder has the eutectic composition. Emerging environmental regulations worldwide, most notably in Europe and Japan, have targeted the elimination of Pb usage in electronic assemblies, due to the inherent toxicity of Pb. This has made the search for suitable “Pb-free” solders an important issue for microelectronics assembly. Approximately 70 Pb-free solder alloy compositions have been proposed thus far. There is a general lack of engineering information, and there is also significant disparity in the information available on these alloys. The issues involved can be divided into two broad categories: manufacturing and reliability/performance. A major factor affecting alloy selection is the melting point of the alloy, since this will have a major impact on the other polymeric materials used in microelectronic assembly and encapsulation. Other important manufacturing issues are cost, availability, and wetting characteristics. Reliability related properties include mechanical strength, fatigue resistance, coefficient of thermal expansion and intermetallic compound formation. The data available in the open literature have been reviewed and are summarized in this paper. Where data were not available, such as for corrosion and oxidation resistance, chemical thermodynamics was used to develop this information. While a formal alloy selection decision analysis methodology has not been developed, less formal approaches indicate that Sn-rich alloys will be the Pb-free solder alloys of choice, with three to four alloys being identified for each of the different applications. Research on this topic continues at the present time at a vigorous pace, in view of the imminence of the issue.

Lead-free Solders in Microelectronics

Lead-free soldering has emerged as one of the key technologies for assembling in environmental-conscious electronics. Among several candidate alloys, the Sn–Ag–Cu alloy family is believed to be the first choice with the combination of other alloys such as Sn–Zn–Bi, Sn–Cu and Sn–Bi–Ag. Phase diagrams of lead-free alloy systems have been intensively examined by using careful thermal and microstructural analysis combined with the thermodynamic calculation such as the CLAPHAD method. The Cu6Sn5/Cu3Sn layers are formed at most lead-free solder alloy/Cu interfaces, while Cu–Zn compound layers are formed in the Sn–Zn/Cu system. Growth kinetics of intermetallic layers both in solid-state and in soldering are also discussed. Creep and fatigue phenomena are also reviewed. In many aspects of lead-free soldering, much more work is required to establish a sound scientific basis to promote their applications.

Advances in lead-free electronics soldering

A review : On the development of low melting temperature Pb-free solders

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Database for Solder Properties with Emphasis on New Lead-free Solders

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: (Δep/2D)· Nfα, where Δep is plastic strain range, Nf 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 characteristics of Sn-3.5Ag-x (X=Bi, Cu, Zn and In) solder alloys

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.

Investigation of multi-component lead-free solders

The liquidus surface and invariant reactions involving the liquid phase are calculated to determine the solidification behavior of Bi-Sb-Sn alloys. Only two U-type invariant reactions Liq. + Sb2Sn3 = SbSn + (Sn) at 517.9Kand Liq. + SbSn = (Sn) + (Sb) at 411.8K are found. Thermodynamic calculation does not predict the presence of a ternary eutectic reaction in this system. The calculated solidification behavior of ternary alloys are found to be consistent with the experimental data as determined by differential scanning calorimetry. An isothermal section of the Bi-Sb-Sn system at 398K is also established. The equilibrium composition of the solid phases are determined by analytical electron microscopy. In contrast to an earlier report, the Bi-content in the SbSn phase is found to be about 5 wt.%.

M. E. Loomans

Papers

Investigation of multi-component lead-free solders

An investigation of phase equilibria of the Bi-Sb-Sn system