Nucleation and Growth of Cu-Al Intermetallics in Al-Modified Sn-Cu and Sn-Ag-Cu Lead-Free Solder Alloys

Abstract

Lead-free solder alloys Sn-Cu (SC) and Sn-Ag-Cu (SAC) are widely used by the microelectronics industry, but enhanced control of the microstructure is needed to improve solder performance. For such control, nucleation and stability of Cu-Al intermetallic compound (IMC) solidification catalysts were investigated by variation of the Cu (0.7–3.0 wt.%) and Al (0.0–0.4 wt.%) content of SC + Al and SAC + Al alloys, and of SAC + Al ball-grid array (BGA) solder joints. All of the Al-modified alloys produced Cu-Al IMC particles with different morphologies and phases (occasionally non-equilibrium phases). A trend of increasing Cu-Al IMC volume fraction with increasing Al content was established. Because of solidification of non-equilibrium phases in wire alloy structures, differential scanning calorimetry (DSC) experiments revealed delayed, non-equilibrium melting at high temperatures related to quenched-in Cu-Al phases; a final liquidus of 960–1200°C was recorded. During cooling from 1200°C, the DSC samples had the solidification behavior expected from thermodynamic equilibrium calculations. Solidification of the ternary alloys commenced with formation of ternary β and Cu-Al δ phases at 450–550°C; this was followed by β-Sn, and, finally, Cu6Sn5 and Cu-Al γ1. Because of the presence of the retained, high-temperature phases in the alloys, particle size and volume fraction of the room temperature Cu-Al IMC phases were observed to increase when the alloy casting temperature was reduced from 1200°C to 800°C, even though both temperatures are above the calculated liquidus temperature of the alloys. Preliminary electron backscatter diffraction results seemed to show Sn grain refinement in the SAC + Al BGA alloy.