Area-Selective Atomic Layer Deposition of Ru Using Carbonyl-Based Precursor and Oxygen Co-Reactant: Understanding...

Area selective deposition (ASD) is a promising IC fabrication technique to address misalignment issues arising in a top-down litho-etch patterning approach. ASD can enable resist tone inversion and bottom-up metallization, such as via prefill. It is achieved by promoting selective growth in the growth area (GA) while passivating the non-growth area (NGA). Nevertheless, preventing undesired particles and defect growth on the NGA is still a hurdle. This work shows the selectivity of Ru films by passivating the Si oxide NGA with self-assembled monolayers (SAMs) and small molecule inhibitors (SMIs). Ru films are deposited on the TiN GA using a metal-organic precursor tricarbonyl (trimethylenemethane) ruthenium (Ru TMM(CO)₃) and O₂ as a co-reactant by atomic layer deposition (ALD). This produces smooth Ru films (<0.1 nm RMS roughness) with a growth per cycle (GPC) of 1.6 Å/cycle. Minimizing the oxygen co-reactant dose is necessary to improve the ASD process selectivity due to the limited stability of the organic molecule and high reactivity of the ALD precursor, still allowing a Ru GPC of 0.95 Å/cycle. This work sheds light on Ru defect generation mechanisms on passivated areas from the detailed analysis of particle growth, coverage, and density as a function of ALD cycles. Finally, an optimized ASD of Ru is demonstrated on TiN/SiO₂ 3D patterned structures using dimethyl amino trimethyl silane (DMA-TMS) as SMI.