The reliability study of selected Sn–Zn based lead-free solders on Au/Ni–P/Cu substrate

Since both Ag and In are important melting point depressants in Sn–Zn based solders, a series Sn–Zn based solders with various amounts of Ag and In additions was studied in the experiment. The melting behavior of solder alloys, wetting characteristics, coefficients of thermal expansion, microstructural evolution and long-term reliability of the selected Sn–Zn based solder on Au/Ni–P metallized copper substrate were examined. Based on the experimental result, there is little change in the melting range of Sn–Zn based solder alloys by minor addition of Ag. On the contrary, the melting point of Sn–Zn based alloys can be effectively decreased by In additions. However, the difference between solidus and liquidus temperature is broadened as the increment of In into Sn–Zn based solders. 76Sn–9Zn–15In has the lowest liquidus temperature among all alloys, and it can effectively bond the Au/Ni–P metallized copper substrate. The microstructure of 76Sn–9Zn–15In alloy soldered at 200 °C for 20 min is primarily comprised of Sn–In γ phase and needle-like ZnO₂. Since there is no flux usage during soldering, zinc oxide cannot be avoided even the process performed under 2×10⁻² mbar vacuum environment. It is also noted that there is no interfacial reaction layer between 76Sn–9Zn–15In and Au/Ni–P metallized copper substrate after soldering. However, there is a reaction layer between 76Sn–9Zn–15In and substrate as the soldered specimen aged at 90 °C for 168 h. Its chemical composition is close to Zn-rich γ phase (NiZn₃) alloyed with minor Sn, In, Cu and P. For the specimen further aged at 90 °C for 336 h, there are cracks along the interface between solder alloy and electroless Ni–P layer. The oxidation of the interfacial Zn-rich γ phase plays an important role in deterioration of the bonding between 76Sn–9Zn–15In and Au/Ni–P metallized copper substrate.