Mass transport mechanism of Cu species at the metal/dielectric interfaces with a graphene barrier

Abstract

The interface between the metal and dielectric is an indispensable part in various electronic devices. The migration of metallic species into the dielectric can adversely affect the reliability of the insulating dielectric and can also form a functional solid-state electrolyte device. In this work, we insert graphene between Cu and SiO2 as a barrier layer and investigate the mass transport mechanism of Cu species through the graphene barrier using density functional theory calculations, second-ion mass spectroscopy (SIMS), capacitance-voltage measurement, and cyclic voltammetry. Our theoretical calculations suggest that the major migration path for Cu species to penetrate through the multiple-layered graphene is the overlapped defects larger than 0.25 nm2. The depth-profile SIMS characterizations indicate that the "critical" thickness of the graphene barrier for completely blocking the Cu migration is 5 times smaller than that of the conventional TaN barrier. Capacitance-voltage and cyclic voltammetry measurement reveal that the electrochemical reactions at the Cu/SiO2 interface become a rate-limiting factor during the bias-temperature stressing process with the use of a graphene barrier. These studies provide a distinct roadmap for designing controllable mass transport in solid-state electrolyte devices with the use of a graphene barrier.