Thermal atomic layer etching of crystalline aluminum nitride using sequential, self-limiting hydrogen fluoride and Sn(acac)2 reactions and enhancement by H2 and Ar plasmas

Abstract

Thermal atomic layer etching (ALE) of crystalline aluminum nitride (AlN) films was demonstrated using sequential, self-limiting reactions with hydrogen fluoride (HF) and tin(II) acetylacetonate [Sn(acac)2] as the reactants. Film thicknesses were monitored versus number of ALE reaction cycles at 275 °C using in situ spectroscopic ellipsometry (SE). A low etch rate of ∼0.07 Å/cycle was measured during etching of the first 40 Å of the film. This small etch rate corresponded with the AlOxNy layer on the AlN film. The etch rate then increased to ∼0.36 Å/cycle for the pure AlN films. In situ SE experiments established the HF and Sn(acac)2 exposures that were necessary for self-limiting surface reactions. In the proposed reaction mechanism for thermal AlN ALE, HF fluorinates the AlN film and produces an AlF3 layer on the surface. The metal precursor, Sn(acac)2, then accepts fluorine from the AlF3 layer and transfers an acac ligand to the AlF3 layer in a ligand-exchange reaction. The possible volatile etch products are SnF(acac) and either Al(acac)3 or AlF(acac)2. Adding a H2 plasma exposure after each Sn(acac)2 exposure dramatically increased the AlN etch rate from 0.36 to 1.96 Å/cycle. This enhanced etch rate is believed to result from the ability of the H2 plasma to remove acac surface species that may limit the AlN etch rate. The active agent from the H2 plasma is either hydrogen radicals or radiation. Adding an Ar plasma exposure after each Sn(acac)2 exposure increased the AlN etch rate from 0.36 to 0.66 Å/cycle. This enhanced etch rate is attributed to either ions or radiation from the Ar plasma that may also lead to the desorption of acac surface species.