Growth and characterization of CVD Ru and amorphous Ru-P alloy films for liner application in Cu interconnect
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Copper interconnect requires liner materials that function as a diffusion barrier, a seed layer for electroplating, and an adhesion promoting layer. Ruthenium has been considered as a promising liner material, however it has been reported that Ru itself is not an effective Cu diffusion barrier due to its microstructure, which is polycrystalline with columnar grains. The screening study of Ru precursors revealed that all Ru films were polycrystalline with columnar structure, and, due to its strong 3D growth mode, a conformal and ultrathin Ru film was difficult to form, especially on high aspect ratio features. The microstructure of Ru films can be modified by incorporating P. Amorphous Ru(P) films are formed by chemical vapor deposition at 575 K using a single source precursor, cis-RuH₂(P(CH₃)₃)₄, or dual sources, Ru₃(CO)₁₂ and P(CH₃)₃ or P(C6H5)₃ The films contain Ru and P, which are in zero-valent states, and C as an impurity. Phosphorus dominantly affects the film microstructure, and incorporating > 13% P resulted in amorphous Ru(P) films. Metastable Ru(P) remains amorphous after annealing at 675 K for 3 hr, and starts recrystallization at ~775 K. The density of states analysis of the amorphous Ru(P) alloy illustrates metallic character of the films, and hybridization between Ru 4d and P 3p orbitals, which contributes to stabilizing the amorphous structure. Co-dosing P(CH)₃ with Ru₃(CO)₁₂ improves film step coverage, and the most conformal Ru(P) film is obtained with cis-RuH2(P(CH₃)₃)₄; a fully continuous 5 nm Ru(P) film is formed within 1 µm deep, 8:1 aspect ratio trenches. First principles density functional theory calculations illustrate degraded Cu/Ru adhesion by the presence of P at the interface, however, due to the strong Ru-Cu bonds, amorphous Ru(P) forms a stronger interface with Cu than Ta and TaN do. Cu diffusion studies at 575 K suggests improved barrier property of amorphous Ru(P) films over polycrystalline PVD Ru.