Area-Selective Atomic Layer Deposition of TiN Using Trimethoxy(octadecyl)silane as a Passivation Layer

Area-selective deposition (ASD) offers tremendous advantages when compared with conventional patterning processes, such as the possibility of achieving three-dimensional features in a bottom-up additive fashion. Recently, ASD is gaining more and more attention from IC manufacturers and equipment and material suppliers. Through combination of self-assembled monolayer (SAM) surface passivation of the nongrowth substrate area and atomic layer deposition (ALD) on the growth area, ASD selective to the growth area can be achieved. With the purpose of screening SAM precursors to provide optimal passivation performance on SiO₂, various siloxane precursors with different terminal groups and alkyl chains were investigated. Additionally, the surface dependence and growth inhibition of TiN ALD on -NH₂, -CF₃, and -CH₃ terminations is investigated. We demonstrated the methyl termination of the SAM precursor combined with a C18 alkyl chain plays an important role in broadening the ALD selectivity window by suppressing precursor adsorption. Owing to the high surface coverage, excellent thermal stability and longer carbon chain length, an optimized trimethoxy(octadecyl)silane (TMODS) film deposited from liquid phase was able to provide a selectivity higher than 0.99 up to 20 nm ALD film deposited on hydroxyl-terminated Si oxide. The approach followed in this work can allow extending the ASD process window, and it is relevant for a wide variety of applications.