Influence of cerium oxide (CeO₂) nanoparticles on the microstructure and hardness of tin–silver–copper (Sn–Ag–Cu) solders on silver (Ag) surface-finished copper (Cu) substrates

Nano-sized, non-reacting, non-coarsening CeO₂ particles with a density close to that of solder alloy were incorporated into Sn–3.0 wt%Ag–0.5 wt%Cu solder paste. The interfacial microstructure and hardness of Ag surface-finished Cu substrates were investigated, as a function of reaction time, at various temperatures. After the initial reaction, an island-shaped Cu₆Sn₅ intermetallic compound (IMC) layer was clearly observed at the interfaces of the Sn–Ag–Cu based solders/immersion Ag plated Cu substrates. However, after a prolonged reaction, a very thin, firmly adhering Cu₃Sn IMC layer was observed between the Cu₆Sn₅ IMC layer and the substrates. Rod-like Ag₃Sn IMC particles were also clearly observed at the interfaces. At the interfaces of the Sn–Ag–Cu based solder-Ag/Ni metallized Cu substrates, a (Cu, Ni)–Sn IMC layer was found. Rod-like Ag₃Sn and needle-shaped Cu₆Sn₅ IMC particles were also observed on the top surface of the (Cu, Ni)–Sn IMC layer. As the temperature and reaction time increased, so did the thickness of the IMC layers. In the solder ball region of both systems, a fine microstructure of Ag₃Sn, Cu₆Sn₅ IMC particles appeared in the β-Sn matrix. However, the growth behavior of the IMC layers of composite solder doped with CeO₂ nanoparticles was inhibited, due to an accumulation of surface-active CeO₂ nanoparticles at the grain boundary or in the IMC layers. In addition, the composite solder joint doped with CeO₂ nanoparticles had a higher hardness value than the plain Sn–Ag–Cu solder joints, due to a well-controlled fine microstructure and uniformly distributed CeO₂ nanoparticles. After 5 min of reaction on immersion Ag-plated Cu substrates at 250 °C, the micro-hardness values of the plain Sn–Ag–Cu solder joint and the composite solder joints containing 1 wt% of CeO₂ nanoparticles were approximately 16.6 and 18.6 Hv, respectively. However after 30 min of reaction, the hardness values were approximately 14.4 and 16.6 Hv, while the micro-hardness values of the plain Sn–Ag–Cu solder joints and the composite solder joints on Ag/Ni metallized Cu substrates after 5 min of reaction at 250 °C were approximately 15.9 and 17.4 Hv, respectively. After 30 min of reaction, values of approximately 14.4 and 15.5 Hv were recorded.