Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

Abstract

Low-k SiONC thin films with excellent thermal stabilities were deposited using plasma-assisted molecular layer deposition (PA-MLD) with a tetraisocyanatesilane (Si(NCO)4) precursor, N2 plasma, and phloroglucinol (C6H3(OH)3). By adjusting the order of the N2 plasma exposure steps within the PA-MLD process, we successfully developed a deposition technique that allows accurate control of thickness at the Ångström level via self-limiting reactions. The thicknesses of the thin films were measured through spectroscopic ellipsometry (SE). By tuning the N2 plasma power, we facilitated the formation of –NH2 sites for phloroglucinol adsorption, achieving a growth per cycle of 0.18 Å cycle−1 with 300 W of N2 plasma power. Consequently, the thickness of the films increased linearly with each additional cycle. Moreover, the organic linkers within the film formed stable bonds through surface reactions, resulting in a negligible decrease in thickness of approximately −11% even upon exposure to a high annealing temperature of 600 °C. This observation was confirmed by SE, distinguishing the as-prepared film from previously reported low-k films that fail to maintain their thickness under similar conditions. X-ray photoelectron spectroscopy (XPS) and current–voltage (I–V) and capacitance–voltage (C–V) measurement were conducted to evaluate the composition, insulating properties, and dielectric constant according to the deposition and annealing conditions. XPS results revealed that as the plasma power increased from 200 to 300 W, the C/Si ratio increased from 0.37 to 0.67, decreasing the dielectric constant from 3.46 to 3.12. Furthermore, there was no significant difference in the composition before and after annealing, and the hysteresis decreased from 0.58 to 0.19 V owing to defect healing, while maintaining the leakage current density, breakdown field, and dielectric constant. The low dielectric constant, accurate thickness control, and excellent thermal stability of this MLD SiONC thin film enable its application as an interlayer dielectric in back-end-of-line process.