Reaction Mechanism and Selectivity Control of Si Compound ALE Based on Plasma Modification and F‑Radical Exposure

In this work, atomic layer etching (ALE) of Si compounds using H2 or N2 plasma modification followed by fluorine radical exposure is discussed. It is shown that the H2 plasma modification process promotes the selective etching of SiN, SiC, and SiCO versus SiO2. The N2 plasma modification, on the other hand, enables the selective etching of SiC and SiCO versus SiN and SiO2. The origin of the etching selectivity between different Si compounds is investigated using a combination of in situ SE and FTIR supported by several ex situ analysis techniques. It is shown that the formation of a hydrogen-rich layer after plasma modification is essential to enable the ALE process. The hydrogen-rich layer can be formed due to ion and radicals of the modification plasma (H2 plasma modification) or be a result of the reconfiguration of hydrogen that is already present in the film (N2 plasma modification). The obtained insights are expected to further enhance the etching selectivity of Si compound ALE processes. Furthermore, it is anticipated that the process can be extended to many other compound materials such as Ti and Hf, as well as enable selective etching between their oxides, carbides, and nitrides.