Benzethonium chloride as a tungsten corrosion inhibitor in neutral and alkaline media for the post-chemical mechanical planarization application

Ranjith Punathil Meethal; Palwasha Jalalzai; Muskan; Sumit Kumar; Jerome Peter; Andreas Klipp; Tae-Gon Kim; Jin-Goo Park

doi:10.1016/j.jcis.2023.04.012

Benzethonium chloride as a tungsten corrosion inhibitor in neutral and alkaline media for the post-chemical mechanical planarization application

J Colloid Interface Sci. 2023 Aug:643:465-479. doi: 10.1016/j.jcis.2023.04.012. Epub 2023 Apr 14.

Authors

Ranjith Punathil Meethal¹, Palwasha Jalalzai¹, Muskan¹, Sumit Kumar¹, Jerome Peter¹, Andreas Klipp², Tae-Gon Kim³, Jin-Goo Park⁴

Affiliations

¹ Department of Materials Science and Chemical Engineering, Hanyang University, Ansan 15588, Republic of Korea.
² BASF SE, Ludwigshafen 67056, Germany.
³ Department of Smart Convergence Engineering, Hanyang University, Ansan 15588, Republic of Korea. Electronic address: tgon@hanyang.ac.kr.
⁴ Department of Materials Science and Chemical Engineering, Hanyang University, Ansan 15588, Republic of Korea. Electronic address: jgpark@hanyang.ac.kr.

PMID: 37088050
DOI: 10.1016/j.jcis.2023.04.012

Abstract

The cleaning solution for the post-chemical mechanical planarization (post-CMP) process of tungsten in neutral-alkaline media requires corrosion inhibitors as an additive, especially for advanced devices where the device node size shrinks below 10 nm. In the present study, the corrosion inhibition performance of benzethonium chloride (BTC) is evaluated in neutral-alkaline conditions. The electrochemical impedance spectroscopy (EIS) analysis showed ∼ 90 % of corrosion inhibition efficiency with an optimum concentration of 0.01 wt% BTC at both pH 7 and 11. Langmuir adsorption isotherm, frontier molecular orbital theory, molecular simulation, contact angle, precipitation study, and X-ray photoelectron spectroscopy analysis were performed to identify the inhibition mechanism of the BTC molecule on the W surface. Based on the proposed mechanism, the electrostatic attraction between the positively charged N atom in the BTC molecule and the negatively charged W surface initiates the adsorption of the molecule. The high dipole moment and large molecular size enhance the physical adsorption of the molecule to the surface. In addition to this, the adsorption isotherm analysis shows that possible chemical interaction with a moderate value of Gibbs free energy change of adsorption exists between the W and BTC molecule. The excellent corrosion inhibition efficiency of BTC on W is confirmed by the frontier molecular orbital theory and molecular dynamic simulation analysis.

Keywords: Corrosion inhibitors; EIS; Frontier molecular orbital theory; Langmuir adsorption; Molecular simulation; Tungsten post-CMP.