Atomic Layer Deposition of Zinc Oxide on Mesoporous Zirconia Using Zinc(II) Acetylacetonate and Air

The self-terminating chemistry of atomic layer deposition (ALD) ideally enables the growth of homogeneously distributed materials on the atomic scale. This study investigates the ALD of zinc oxide (ZnO) on mesoporous zirconium oxide (ZrO2) using zinc acetylacetonate [Zn(acac)2] and synthetic air in a fixed-bed powder ALD reactor. A broad variety of methods, including thermogravimetry analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy, low-energy ion scattering, X-ray absorption near-edge structure, X-ray photoelectron spectroscopy, in-situ diffuse reflectance infrared Fourier transform spectroscopy-mass spectrometry, and density functional theory calculations, were used to analyze the reactant and the resulting samples. The factors affecting the zinc loading (wt %) on ZrO2 were investigated by varying the ALD reaction temperature (160-240 °C), the calcination temperature of zirconium oxide (400-1000 °C), and the ALD cycle number (up to three). The studied process showed self-terminating behavior with the areal number density of zinc of approximately two atoms per square nanometer per cycle. Zinc was distributed throughout ZrO2. After the Zn(acac)2 reaction, acac ligands were removed using synthetic air at 500 °C. In the following cycles, already-deposited ZnO acted as nuclei for further ZnO growth. This study demonstrates the potential of Zn(acac)2 as an ALD reactant and provides an initial understanding of ZnO growth via ALD on high surface area porous particles as an example for catalytic applications.

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Liliana Krotz and Walter Galotta are thanked for carbon content analysis. Hannu Revitzer is thanked for ICP-OES measurements. Joakim Kattelus is thanked for the standard deviation of ICP-OES measurements. Zahra Ahaliabadeh and Ville Miikkulainen are thanked for the design of the fixed bed reactor space for the F-120 reactor. This work made use of the Raw Materials Research Infrastructure and the ALD Center Finland Research Infrastructure. The University of Helsinki acknowledges the Center for X-ray Spectroscopy for providing experiment time and support with the HelXAS spectrometer under Proposal 2021-0011. The DFT calculations were made possible by computational resources provided by the CSC- IT Center for Science. The materials created in the Virtual Project on the History of ALD (VPHA) are acknowledged as a source of information on the early publications on ALD, including catalysis applications. Part of this work has been presented at the ALD 2022 conference, Ghent, Belgium, June 26–29, 2022. Funding Information: The work was financially supported by Prof. Puurunen’s starting grant at Aalto University and by the Academy of Finland (COOLCAT consortium, decision no. 329977 and 329978; ALDI consortium, decision no. 331082; Matter and Materials, decision no. 318913 and decision no. 295696). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

DOI

10.1021/acs.chemmater.3c00668

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Yim, J, Haimi, E, Mäntymäki, M, Kärkäs, V, Bes, R, Arandia Gutierrez, A, Meinander, K, Brüner, P, Grehl, T, Gell, L, Viinikainen, T, Honkala, K, Huotari, S, Karinen, R, Putkonen, M & Puurunen, R L 2023, ' Atomic Layer Deposition of Zinc Oxide on Mesoporous Zirconia Using Zinc(II) Acetylacetonate and Air ', Chemistry of Materials, vol. 35, no. 19, pp. 7915-7930 . https://doi.org/10.1021/acs.chemmater.3c00668

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https://urn.fi/URN:NBN:fi:aalto-202312117215

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[article-cris] Kemian tekniikan korkeakoulu / CHEM

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Atomic Layer Deposition of Zinc Oxide on Mesoporous Zirconia Using Zinc(II) Acetylacetonate and Air

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