We have proposed a novel bonding process using silver nanoparticles, which can be alternative to lead-rich high melting point solders. The bonding mechanism of silver metallo-organic nanoparticles to bulk materials (gold and copper) is discussed based on the observations of the bonded interface using Transmission Electron Microscope (TEM). At the interface of sintered silver and bulk gold, the crystal orientation of silver corresponded to that of gold. It is thought that the epitaxial layer of silver formed through silver nanoparticles being oriented in the direction of the gold crystal. At the interface of sintered silver and bulk copper, no epitaxial layer of silver on the copper crystal formed. Though the appearance of the crystal structure of silver/copper interface is different from that of the silver/gold interface, copper as well as gold are coherent with silver, and have been successfully bonded using the silver nanoparticles.
The evolution of the transient liquid-phase sintered (TLPS) Cu–Sn skeleton microstructure during thermal aging was evaluated to clarify the thermal reliability for die-attach applications. The Cu–Sn skeleton microstructure, which consists of Cu particles connected with Cu–Sn intermetallic compounds partially filled with polyimide resin, was obtained by the pressure-less TLP sintering process at 250 °C for 1 min using a novel Cu-solder-resin composite as a bonding material in a nitrogen atmosphere. Experimental results indicate that the TLPS joints were mainly composed of Cu, Cu6Sn5, and Cu3Sn in the as-bonded state, where submicron voids were observed at the interface between Cu3Sn and Cu particles. After thermal aging at 150, 175, and 200 °C for 1000 h, the Cu6Sn5 phase fully transformed into Cu3Sn except at the chip-side interface, where the number of the submicron voids appeared to increase. The averaged shear strengths were found to be 22.1 (reference), 22.8 (+3%), 24.0 (+9%), and 19.0 MPa (−14%) for the as-bonded state and specimens aged at 150, 175, and 200 °C for 1000 h, respectively. The TLPS joints maintained a shear strength over 19 MPa after thermal aging at 200 °C for 1000 h because of both the positive and negative impacts of the thermal aging, which include the transformation of Cu6Sn5 into Cu3Sn and the formation of submicron voids at the interface, respectively. These results indicate an excellent thermal reliability of the TLPS Cu–Sn skeleton microstructure.
Molecular dynamics (MD) simulation was applied to the sintering behavior of silver nanoparticles on a gold substrate in order to elucidate the sintering mechanism of the nanoparticles on the substrate. The simulation revealed that silver atoms from 1 and 2 nm nanoparticles migrated freely because of their larger surface energy and then epitaxially reoriented to the gold substrate so as to reduce grain boundary energy. The silver nanoparticles were more spread out on the (011) gold substrate than on the (001) substrate, indicating that substrates with larger surface energy induce greater spreading rates. Consideration of the competition of neck growth and epitaxial growth in sintering of nanoparticles revealed that reduction of surface energy is the predominant driving force in the initiation of sintering of silver nanoparticles, and that the reduction of grain boundary energy is subsequently consequential.
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