The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu6Sn5 grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu6Sn5 obeys a t1/3 law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed.

The growth behavior of intermetallic compounds (IMCs) at the liquid-solid interfaces in Cu/Sn/Cu interconnects during reflow at 250 °C and 280 °C on a hot plate was investigated. Being different from the symmetrical growth during isothermal aging, the interfacial IMCs showed clearly asymmetrical growth during reflow, i.e., the growth of Cu₆Sn₅ IMC at the cold end was significantly enhanced while that of Cu₃Sn IMC was hindered especially at the hot end. It was found that the temperature gradient had caused the mass migration of Cu atoms from the hot end toward the cold end, resulting in sufficient Cu atomic flux for interfacial reaction at the cold end while inadequate Cu atomic flux at the hot end. The growth mechanism was considered as reaction/thermomigration-controlled at the cold end and grain boundary diffusion/thermomigration-controlled at the hot end. A growth model was established to explain the growth kinetics of the Cu₆Sn₅ IMC at both cold and hot ends. The molar heat of transport of Cu atoms in molten Sn was calculated as + 11.12 kJ/mol at 250 °C and + 14.65 kJ/mol at 280 °C. The corresponding driving force of thermomigration in molten Sn was estimated as 4.82 × 10⁻¹⁹ N and 6.80 × 10⁻¹⁹ N.

The focus of this study is on the role of Cu content in the dissolution kinetics of Cu in high-Sn solders during the solid/liquid reaction accompanied by interfacial intermetallic compound formation. Small additions of Cu (0.7%, 1.5%) in high-Sn solders dramatically decrease the dissolution rate of Cu at low temperatures. Sn-3.5Ag, as expected, has a dissolution rate similar to that of pure Sn. The difference in dissolution rate of Cu in various molten solders is explained in terms of the solubility limit of Cu in molten solders based on the Cu-Sn phase diagram. The correlation between the metallurgical aspects of interfacial $\eta \left({\mathrm{Cu}}_6{\mathrm{Sn}}_5\right)$ phase formation and dissolution kinetics of Cu in molten solders leads to an understanding of the mechanism that controls the dissolution rate of Cu in molten solders.