In Situ Infrared Absorption Study of Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride

Despite the success of plasma-enhanced atomic layer deposition (PEALD) in depositing quality silicon nitride films, a fundamental understanding of the growth mechanism has been difficult to obtain because of lack of in situ characterization to probe the surface reactions noninvasively and the complexity of reactions induced/enhanced by the plasma. These challenges have hindered the direct observation of intermediate species formed during the reactions. We address this challenge by examining the interaction of Ar plasma using atomically flat, monohydride-terminated Si(111) as a well-defined model surface and focusing on the initial PEALD with aminosilanes. In situ infrared and X-ray photoelectron spectroscopy reveals that an Ar plasma induces desorption of H atoms from H-Si(111) surfaces, leaving Si dangling bonds, and that the reaction of di-sec-butylaminosilane (DSBAS) with Ar plasma-treated surfaces requires the presence of both active sites (Si dangling bonds) and Si-H; there is no reaction on fully H-terminated or activated surfaces. By contrast, high-quality hydrofluoric acid-etched Si₃N₄ surfaces readily react with DSBAS, resulting in the formation of O-SiH₃. However, the presence of back-bonded oxygen in O-SiH₃ inhibits H desorption by Ar or N₂ plasma, presumably because of stabilization of H against ion-induced desorption. Consequently, there is no reaction of adsorbed aminosilanes even after extensive Ar or N₂ plasma treatments; a thermal process is necessary to partially remove H, thereby promoting the formation of active sites. These observations are consistent with a mechanism requiring the presence of both undercoordinated nitrogen and/or dangling bonds and unreacted surface hydrogen. Because active sites are involved, the PEALD process is found to be sensitive to the duration of the plasma exposure treatment and the purge time, during which passivation of these sites can occur.