Solder reaction-assisted crystallization of electroless Ni–P under bump metallization in the Si/SiO2/Al/Ni–P/63Sn–37Pb multilayer structure was analyzed using transmission electron microscopy, scanning electron microscopy, energy dispersive x-ray, and electron probe microanalyzer. The electroless Ni–P had an amorphous structure and a composition of Ni85P15 in the as-plated condition. Upon reflow, the electroless Ni–P transformed to Ni3Sn4 and Ni3P. The crystallization of electroless Ni–P to Ni3P was induced by the depletion of Ni from electroless Ni–P to form Ni3Sn4. The interface between electroless Ni–P and Ni3P layer was planar. From the Ni3P thickness-time relationship, the kinetics of crystallization was found to be diffusion controlled. Conservation of P occurs between electroless Ni–P and Ni3P, meaning that little or no P diffuses into the molten solder. Combining the growth rates of Ni3Sn4 and Ni3P, the consumption rate of electroless Ni–P was determined. Based upon microstructural and diffusion results, a grain-boundary diffusion of the Ni or an interstitial diffusion of the P in the Ni3P layer was proposed.

Editor's Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/ Frear-0106.html A variety of lead-free solder alloys were studied for use as flip-chip interconnects including , and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder microstructure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag 3 Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni 3 Sn 4 formed and on copper, Cu 6 Sn 5 Cu 3 Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu.

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The morphology of interfacial reaction products between four lead-free solder alloys on electroless Ni–P was characterized. The four Pb-free solders were 99.3Sn0.7Cu, 95.5Sn3.8Ag0.7Cu, 96.5Sn3.5Ag, and 96Sn2Ag2Bi (in wt%) alloys. After reflow, the interfacial intermetallics in the first two solders that contain Cu (99.3Sn0.7Cu and 95.5Sn3.8Ag0.7Cu) had good adhesion with electroless Ni–P. However, the 96.5Sn3.5Ag and 96Sn2Ag2Bi alloys formed interfacial intermetallics with a needle shaped morphology that spalled off the surface of electroless Ni–P. This difference is attributed to the role of Cu in the solders (which modified the chemical potential of the interfacial intermetallics), the volume change that occurs during intermetallic formation, and the interfacial properties of the compound. In solid state aging experiments, the consumption of electroless Ni–P by intermetallic growth was not significant (approximately 1 μm) and all the intermetallics had good adhesion to the electroless Ni–P. The electroless Ni–P exhibited some damage at the outer edge of the bond pad due to stress imposed during solid state aging. Large Ag3Sn and Cu6Sn5 intermetallics were observed in the bulk of the solders (except for SnAgBi solder), and these intermetallics are discussed in terms of soldering reaction at the interface and phase equilibrium.

The use of soft solders, particularly those containing lead, dates back nearly 5,000 years. Solders similar to the materials used to seal the aqueducts of ancient Rome are now an important building block in the manufacture of high-speed computer assemblies. This history attests to the technological versatility of soft solders and, in particular, the solder alloys that contain lead. However, the health effects of prolonged exposure to lead have also been documented; measures to limit human exposure-at the work place and indirectly through the environment-are being considered. The successful introduction of lead-free solders into future electronic products will rely heavily upon their solderability, which can be evaluated by test procedures such as the meniscometerjwetting balance technique and the capillary flow test.