First principles calculations of interactions of ZrCl<sub>4</sub> precursors with the bare and hydroxylated ZrO<sub>2</sub> surfaces

I. M. Iskandarova; A. A. Knizhnik; A. A. Bagatur'yants; B. V. Potapkin; A. A. Korkin

doi:10.1117/12.558786

28 May 2004 First principles calculations of interactions of ZrCl₄ precursors with the bare and hydroxylated ZrO₂ surfaces

I. M. Iskandarova, A. A. Knizhnik, A. A. Bagatur'yants, B. V. Potapkin, A. A. Korkin

Author Affiliations +

Proceedings Volume 5401, Micro- and Nanoelectronics 2003; (2004) https://doi.org/10.1117/12.558786
Event: Micro- and Nanoelectronics 2003, 2003, Zvenigorod, Russian Federation

Abstract

First-principles calculations have been performed to determine the structures and relative energies of different zirconium chloride groups chemisorbed on the tetragonal ZrO₂(001) surface and to study the effects of the surface coverage with metal chloride groups and the degree of hydroxylation on the adsorption energies of metal precursors. It is shown that the molecular and dissociative adsorption energies of the ZrCl₄ precursor on the bare t-ZrO₂(001) surface are too small to hold ZrCl₄ molecules on the surface during an atomic layer deposition (ALD) cycle at temperatures higher than 300°C. On the contrary, it has been found that molecular adsorption on the fully hydroxylated zirconia surface leads to the formation of a stable adsorbed complex. This strong adsorption of ZrCl₄ molecules can lead to a decrease in the film growth rate of the ALD process at lower temperatures (<200°C). The energies of interaction between adsorbed ZrCl₄ groups at a 50% surface coverage has been found to be relatively small, which explains the maximum film growth rate observed in the ZrCl₄:H₂O ALD process. Moreover, we found that the adsorbed ZrCl₄ precursors after hydrolysis give rise to very stable hydroxyl groups, which can be responsible for film growth at high temperatures (up to 900°C).

Citation Download Citation

I. M. Iskandarova, A. A. Knizhnik, A. A. Bagatur'yants, B. V. Potapkin, and A. A. Korkin "First principles calculations of interactions of ZrCl₄ precursors with the bare and hydroxylated ZrO₂ surfaces", Proc. SPIE 5401, Micro- and Nanoelectronics 2003, (28 May 2004); https://doi.org/10.1117/12.558786

ACCESS THE FULL ARTICLE

INSTITUTIONAL
Select your institution to access the SPIE Digital Library.

SELECT YOUR INSTITUTION

PERSONAL
Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.

PERSONAL SIGN IN

No SPIE Account? Create one

PURCHASE THIS CONTENT

SUBSCRIBE TO DIGITAL LIBRARY

50 downloads per 1-year subscription

Members: $195

Non-members: $335 ADD TO CART

25 downloads per 1 - year subscription

Members: $145

Non-members: $250 ADD TO CART

PURCHASE SINGLE ARTICLE

Includes PDF, HTML & Video, when available