Area-selective Ru ALD by amorphous carbon modification using H plasma: from atomistic modeling to full wafer process integration.

Selective deposition of various materials on pre-defined areas on the substrate is of crucial importance nowadays for microelectronic technology. Carbon-based layers, such as self-assembled monolayers and polymerized fluorocarbon etch residues are often used as passivation layers in order to inhibit the deposition of the required material. In our previous paper, we reported on selective ALD of Ru enabled by H2 plasma passivation of amorphous carbon (a-C) as the non-growth surface and simultaneous activation of a SiCN growth surface. In the present work, we demonstrate a-C modification by H radicals in the absence of H ions in a downstream plasma chamber. The H radical treatment significantly improves the ALD selectivity with respect to the standard H2 plasma treatment by reducing the number of unwanted hydroxyl groups on the a-C surface and providing strong chemical modification of the a-C via surface hydrogenation. In addition, the H radical treatment results in the zero-damage of the a-C film and, therefore, it does not change the pattern profile or the aspect ratio. The experimental data and the investigation of the interaction mechanism between H2 plasma and the a-C surface were supported by molecular dynamic modeling, where effects of the a-C modification by H ions and H radicals were decoupled. The chemical modification of the a-C surface by H radicals results in 10 nm Ru being deposited on Si-based dielectric substrates, while no Ru can be detected by high-resolution RBS on a-C. The H radical surface treatment was also tested on patterned structures with 45 nm half-pitch a-C lines on the SiCN surface.