Fluorocarbon based atomic layer etching of Si{sub 3}N{sub 4} and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4}
Angstrom-level plasma etching precision is required for semiconductor manufacturing of sub-10 nm critical dimension features. Atomic layer etching (ALE), achieved by a series of self-limited cycles, can precisely control etching depths by limiting the amount of chemical reactant available at the surface. Recently, SiO{sub 2} ALE has been achieved by deposition of a thin (several Angstroms) reactive fluorocarbon (FC) layer on the material surface using controlled FC precursor flow and subsequent low energy Ar{sup +} ion bombardment in a cyclic fashion. Low energy ion bombardment is used to remove the FC layer along with a limited amount of SiO{sub 2} from the surface. In the present article, the authors describe controlled etching of Si{sub 3}N{sub 4} and SiO{sub 2} layers of one to several Angstroms using this cyclic ALE approach. Si{sub 3}N{sub 4} etching and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4} were studied and evaluated with regard to the dependence on maximum ion energy, etching step length (ESL), FC surface coverage, and precursor selection. Surface chemistries of Si{sub 3}N{sub 4} were investigated by x-ray photoelectron spectroscopy (XPS) after vacuum transfer at each stage of the ALE process. Since Si{sub 3}N{sub 4} has a lower physical sputtering energy threshold than SiO{sub 2}, Si{sub 3}N{sub 4} physical sputtering can take place after removal of chemical etchant at the end of each cycle for relatively high ion energies. Si{sub 3}N{sub 4} to SiO{sub 2} ALE etching selectivity was observed for these FC depleted conditions. By optimization of the ALE process parameters, e.g., low ion energies, short ESLs, and/or high FC film deposition per cycle, highly selective SiO{sub 2} to Si{sub 3}N{sub 4} etching can be achieved for FC accumulation conditions, where FC can be selectively accumulated on Si{sub 3}N{sub 4} surfaces. This highly selective etching is explained by a lower carbon consumption of Si{sub 3}N{sub 4} as compared to SiO{sub 2}. The comparison of C{sub 4}F{sub 8} and CHF{sub 3} only showed a difference in etching selectivity for FC depleted conditions. For FC accumulation conditions, precursor chemistry has a weak impact on etching selectivity. Surface chemistry analysis shows that surface fluorination and FC reduction take place during a single ALE cycle for FC depleted conditions. A fluorine rich carbon layer was observed on the Si{sub 3}N{sub 4} surface after ALE processes for which FC accumulation takes place. The angle resolved-XPS thickness calculations confirmed the results of the ellipsometry measurements in all cases.