With continued advances in microelectronics, it is anticipated that next-generation microelectronic assemblies will require a reduction of the flip-chip solder bump pitch to 100 μm or less from the current industrial practice of 130 μm to 150 μm. With this reduction in pitch size, and thus in bump height and diameter, the interaction between die pad metallurgy and substrate pad metallurgy becomes more critical due to the shorter diffusion path and greater stress. Existing literature has not addressed such metallurgical interaction in actual fine-pitch flip-chip assemblies. This work studies intermetallic growth and kinetics in fine-pitch lead-free solder bumps through thermal aging of flip-chip assemblies. Based on this study, it is seen that Ni from the die pad diffuses to the substrate pad region and Cu from the substrate pad diffuses to the die pad region, thus the resulting intermetallic compounds at the die and substrate pad regions are influenced by the other pad as well. Such cross-pad interaction is much stronger in fine-pitch solder bumps with smaller standoff height. It is seen that the die pad region contains Ni3P and (Cu,Ni)6Sn5 after thermal aging, while the substrate pad region contains Cu3Sn and (Cu,Ni)6Sn5. By digitally measuring the thickness of the interfacial phases, the kinetics parameters and the activation energy were calculated for the growth of (Cu,Ni)6Sn5 on the substrate side. The Cu diffusion coefficient through the intermetallic compound (IMC) layer was found to be 0.03370 μm2/h, 0.1423 μm2/h, and 0.4463 μm2/h at 100°C, 125°C, and 150°C, respectively, and the apparent activation energy for the growth of compound layers was 67.89 kJ/mol.