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Title: Thermal atomic layer etching of crystalline aluminum nitride using sequential, self-limiting hydrogen fluoride and Sn(acac){sub 2} reactions and enhancement by H{sub 2} and Ar plasmas

Journal Article · · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films
DOI:https://doi.org/10.1116/1.4959779· OSTI ID:22592847
; ;  [1]
  1. Department of Chemistry and Biochemistry, University of Colorado at Boulder, Colorado 80309 (United States)

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){sub 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 AlO{sub x}N{sub y} 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){sub 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 AlF{sub 3} layer on the surface. The metal precursor, Sn(acac){sub 2}, then accepts fluorine from the AlF{sub 3} layer and transfers an acac ligand to the AlF{sub 3} layer in a ligand-exchange reaction. The possible volatile etch products are SnF(acac) and either Al(acac){sub 3} or AlF(acac){sub 2}. Adding a H{sub 2} plasma exposure after each Sn(acac){sub 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 H{sub 2} plasma to remove acac surface species that may limit the AlN etch rate. The active agent from the H{sub 2} plasma is either hydrogen radicals or radiation. Adding an Ar plasma exposure after each Sn(acac){sub 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.

OSTI ID:
22592847
Journal Information:
Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films, Vol. 34, Issue 5; Other Information: (c) 2016 American Vacuum Society; Country of input: International Atomic Energy Agency (IAEA); ISSN 0734-2101
Country of Publication:
United States
Language:
English