Enhanced atomic layer etching of native aluminum oxide for ultraviolet optical applications

We report on the development and application of an atomic layer etching (ALE) procedure based on alternating exposures of trimethylaluminum and anhydrous hydrogen fluoride (HF) implemented to controllably etch aluminum oxide. Our ALE process utilizes the same chemistry previously demonstrated in the atomic layer deposition of aluminum fluoride thin films, and can therefore be exploited to remove the surface oxide from metallic aluminum and replace it with thin fluoride layers in order to improve the performance of ultraviolet aluminum mirrors. This ALE process is modified relative to existing methods through the use of a chamber conditioning film of lithium fluoride, which is shown to enhance the loss of fluorine surface species and results in conformal layer-by-layer etching of aluminum oxide films. Etch properties were explored over a temperature range of 225 to 300 {\deg}C with the Al2O3 etch rate increasing from 0.8 to 1.2 {\AA} per ALE cycle at a fixed HF exposure of 60 ms per cycle. The effective etch rate has a dependence on the total HF exposure, but the process is shown to be scalable to large area substrates with a post-etch uniformity of better than 2% demonstrated on 125 mm diameter wafers. The efficacy of the ALE process in reducing interfacial native aluminum oxide on evaporated aluminum mirrors is demonstrated with characterization by x-ray photoelectron spectroscopy and measurements of ultraviolet reflectance at wavelengths down to 120 nm.