A Novel Method for the Metallization of 3D Silicon Induced by Metastable Copper Nanoparticles.

The development of efficient copper deposition processes in high-aspect-ratio silicon structures is still a key technological issue for the microelectronic industry. We describe here a new process for the deposition of copper thin films in three-dimensional (3D) structures induced by the decomposition of a copper amidinate precursor in solution under a moderate H2 pressure. The reduction of a metal precursor under soft conditions (3 bar, 110 °C) affords the preparation of a high-purity, conformal metallic layer. We unveil a novel deposition mechanism driven by colloidal copper nanoparticles (NPs) in solution that behave as a reservoir of metastable metallic NPs that eventually condense as a solid film on all immersed surfaces. The film growth process is characterized by time-resolved analyses of the NPs in the colloidal state (nuclear magnetic resonance NMR and UV-vis spectra) and of the NPs and metallic layer on substrates (transmission electron microscopy TEM, and scanning electron microscopy SEM). Major deposition stages of this process are proposed and the conformal metallization of 3D silicon substrates is successfully achieved. This method is transposable to other metallic layers such as silver or nickel.