Dynamics of Plasma Atomic Layer Etching: Molecular Dynamics Simulations and Optical Emission Spectroscopy

Atomic layer etching is intrinsically dynamic as it involves sequential and repeated exposures of a surface to be etched with different species at different energies. The composition and structure of the near surface region changes in both time and depth. Full understanding of this process requires resolving both temporal and spatial variations. In this work, we consider silicon (Si) atomic layer etching (ALE) by alternating exposure to chlorine gas (Cl2) and argon ions (Ar⁺). Molecular dynamics (MD) simulations are compared to experimental measurements with the aim of better understanding the dynamics of ALE and to test the simulation procedure. MD predictions of etch per cycle and species leaving the surface during the Ar⁺ step are compared to experimental measurements. Optical emission measured just above the surface being etched can be related to etch products and can therefore be directly compared to simulation predictions. The simulations capture the measured initial product distribution leaving the surface and match the measured etch per cycle reasonably well. Simulations demonstrate the importance of ion-induced surface damage and mixing into a layer below the surface, the depth of which depends mainly on ion energy. But the experiments also suggest there is more Cl mixed into the layer than the MD procedure predicts. The implications of these observations are discussed.