Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O2, H2, or N2O: The Role of Ruthenium Etching

Qin, Xiangdong; Zaera, Francisco

doi:10.1021/acs.jpcc.2c04266

Title: Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O₂, H₂, or N₂O: The Role of Ruthenium Etching

Journal Article · 22 July 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.2c04266 · OSTI ID:1903633

Qin, Xiangdong ^[1];

^[2]

Univ. of California, Riverside, CA (United States); University of California
Univ. of California, Riverside, CA (United States)

In this work, the evolution of the surface during the steps that comprise the atomic layer deposition (ALD) of ruthenium films on a nickel substrate using tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) (Ru(tmhd)₃) and molecular oxygen was characterized using a combination of X-ray photoelectron (XPS) and reflection–absorption infrared (RAIRS) spectroscopies. The uptake of the Ru metalorganic precursor was determined to be activated, involving the average loss of two out of the three ligands (and the retention of the third, in molecular form, at the surface–vacuum interface), and self-limited, as required in ALD. The reaction of the resulting layer from that first half of the ALD cycle with O₂ proved to be more complex: in addition to the desired removal of the carbon-containing material, the Ni substrate becomes oxidized, and some Ru is etched away in the form of the volatile RuO₄ gas. By testing different combinations of exposures and temperatures it was determined that Ru film growth was possible, but tuning and optimizing the ALD or atomic layer etching (ALE) process conditions for maximum film growth or removal rate per cycle proved difficult. Replacing O₂ with H₂ was shown not to be viable either, as such an agent can reduce the nickel oxide formed after O₂ treatments (in fact, Ru(tmhd)₃ can do this as well) but not remove the carbonaceous material deposited on the surface by the Ru precursor. The use of N₂O, on the other hand, showed much promise, being capable of removing most of the surface carbon without affecting the Ru film or the Ni substrate.

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Research Organization:: Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0001839

OSTI ID:: 1903633

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 30 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O2, H2, or N2O: The Role of Ruthenium Etching

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Title: Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O₂, H₂, or N₂O: The Role of Ruthenium Etching