In Situ Monitoring of Etching Characteristic and Surface Reactions in Atomic Layer Etching of SiN Using Cyclic CF₄/H₂ and H₂ Plasmas

Cyclic atomic layer etching (ALE) of SiN with high selectivity to SiO₂, utilizing a hydrofluorocarbon deposition followed by exposure to hydrogen plasma, is presented. The surface reaction mechanism and etching behavior were investigated with in situ attenuated total reflectance Fourier transformation infrared spectroscopy (ATR-FTIR) and spectroscopic ellipsometry. In the deposition step, the hydrofluorocarbon film was deposited on top of the SiN films using the CF₄/H₂ plasmas with varying H₂ contents (33 to 85%). Subsequently, the surface-modified SiN film was exposed to a hydrogen plasma for etching. The self-limiting SiN etching was observed, where the etch depth solely depended on the F concentration of the deposited hydrofluorocarbon layer once its thickness exceeded a critical value. A high selectivity of approximately 8.6 for SiN over SiO₂ was achieved. The in situ ATR-FTIR spectra revealed that during the deposition step, besides the formation of the C-H peak associated with hydrofluorocarbon deposition, the appearance of the N-H₄ absorbance band indicated the formation of an ammonium fluorosilicate layer on top of SiN. In the subsequent H₂ plasma etching step, both the surface modification layer and the pre-deposited hydrofluorocarbon layer were removed. The removal of the surface-modified layer and hydrofluorocarbon layer was associated with the etch rate during H₂ plasma exposure. These findings indicate the importance of the formation and removal of the surface modification layer for achieving ALE of SiN. The dissociation of the hydrofluorocarbon layer by the H₂ plasma released reactants that interacted with SiN, leading to the formation of a new surface modification layer. The etching process significantly slowed down once the hydrofluorocarbon deposition and surface modification layer were completely removed.