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

Jihong Yim; Eero Haimi; Miia Mäntymäki; Ville Kärkäs; René Bes; Aitor Arandia Gutierrez; Kristoffer Meinander; Philipp Brüner; Thomas Grehl; Lars Gell; Tiia Viinikainen; Karoliina Honkala; Simo Huotari; Reetta Karinen; Matti Putkonen; Riikka L. Puurunen

doi:10.1021/acs.chemmater.3c00668

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

Jihong Yim, Eero Haimi, Miia Mäntymäki, Ville Kärkäs, René Bes, Aitor Arandia Gutierrez, Kristoffer Meinander, Philipp Brüner, Thomas Grehl, Lars Gell, Tiia Viinikainen, Karoliina Honkala, Simo Huotari, Reetta Karinen, Matti Putkonen, Riikka L. Puurunen^*

^*Tämän työn vastaava kirjoittaja

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

2 Sitaatiot (Scopus)

62 Lataukset (Pure)

Abstrakti

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.

Alkuperäiskieli	Englanti
Sivut	7915-7930
Sivumäärä	16
Julkaisu	Chemistry of Materials
Vuosikerta	35
Numero	19
Varhainen verkossa julkaisun päivämäärä	29 syysk. 2023
DOI - pysyväislinkit	https://doi.org/10.1021/acs.chemmater.3c00668
Tila	Julkaistu - 10 lokak. 2023
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Pääsy asiakirjaan

10.1021/acs.chemmater.3c00668Lisenssi: CC BY

CHEM_Yim_et_al_Atomic_Layer_2023_Chemistry_of_MaterialsFinal published version, 4,2 MBLisenssi: CC BY

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Linkki julkaisuun Scopuksessa

ALDI: Reactive flow in porous media: modelling and experiments in atomic layer deposition context
Puurunen, R. (Vastuullinen tutkija), Revitzer, H. (Projektin jäsen), Viinikainen, T. (Projektin jäsen), Gonsalves, C. (Projektin jäsen), Velasco Calsina, J. (Projektin jäsen), Yim, J. (Projektin jäsen), Miikkulainen, V. (Projektin jäsen), Ossama, M. (Projektin jäsen), Andsten, S. (Projektin jäsen) & Larkiala, S. (Projektin jäsen)
01/09/2020 → 31/08/2024
Projekti: Academy of Finland: Other research funding
Renable Carbon Cycle - Uusiutuva hiilikierto: Hiilidioksidin muuntaminen polttoaineiksi räätälöytyjen heterogeenisten katalyyttien avulla
Puurunen, R. (Vastuullinen tutkija), Arandia Gutierrez, A. (Projektin jäsen), Viinikainen, T. (Projektin jäsen), Revitzer, H. (Projektin jäsen), Sajid, A. (Projektin jäsen), Chahal, A. (Projektin jäsen), Yim, J. (Projektin jäsen), Karinen, R. (Projektin jäsen), Haimi, E. (Projektin jäsen), Velasco Calsina, J. (Projektin jäsen), Kattelus, J. (Projektin jäsen), Gonsalves, C. (Projektin jäsen) & Kumar Singh, A. (Projektin jäsen)
01/01/2020 → 31/12/2023
Projekti: Academy of Finland: Other research funding

Raaka-aineiden tutkimusinfrastruktuuri
Karppinen, M. (Manager)
Kemian tekniikan korkeakoulu
Laitteistot/tilat: Facility

Siteeraa tätä

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, 35(19), 7915-7930. https://doi.org/10.1021/acs.chemmater.3c00668

@article{8d09f9fcd21145c1b93111ec0f574d5c,

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

abstract = "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.",

author = "Jihong Yim and Eero Haimi and Miia M{\"a}ntym{\"a}ki and Ville K{\"a}rk{\"a}s and Ren{\'e} Bes and {Arandia Gutierrez}, Aitor and Kristoffer Meinander and Philipp Br{\"u}ner and Thomas Grehl and Lars Gell and Tiia Viinikainen and Karoliina Honkala and Simo Huotari and Reetta Karinen and Matti Putkonen and Puurunen, {Riikka L.}",

note = "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{\textquoteright}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: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

year = "2023",

month = oct,

day = "10",

doi = "10.1021/acs.chemmater.3c00668",

language = "English",

volume = "35",

pages = "7915--7930",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "19",

}

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, RL 2023, 'Atomic Layer Deposition of Zinc Oxide on Mesoporous Zirconia Using Zinc(II) Acetylacetonate and Air', Chemistry of Materials, Vuosikerta 35, Nro 19, Sivut 7915-7930. https://doi.org/10.1021/acs.chemmater.3c00668

TY - JOUR

T1 - Atomic Layer Deposition of Zinc Oxide on Mesoporous Zirconia Using Zinc(II) Acetylacetonate and Air

AU - Yim, Jihong

AU - Haimi, Eero

AU - Mäntymäki, Miia

AU - Kärkäs, Ville

AU - Bes, René

AU - Arandia Gutierrez, Aitor

AU - Meinander, Kristoffer

AU - Brüner, Philipp

AU - Grehl, Thomas

AU - Gell, Lars

AU - Viinikainen, Tiia

AU - Honkala, Karoliina

AU - Huotari, Simo

AU - Karinen, Reetta

AU - Putkonen, Matti

AU - Puurunen, Riikka L.

N1 - 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.

PY - 2023/10/10

Y1 - 2023/10/10

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85175093658&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.3c00668

DO - 10.1021/acs.chemmater.3c00668

M3 - Article

AN - SCOPUS:85175093658

SN - 0897-4756

VL - 35

SP - 7915

EP - 7930

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 19

ER -

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

Abstrakti

Pääsy asiakirjaan

Muut tiedostot ja linkit

Sormenjälki

Projektit

ALDI: Reactive flow in porous media: modelling and experiments in atomic layer deposition context

Renable Carbon Cycle - Uusiutuva hiilikierto: Hiilidioksidin muuntaminen polttoaineiksi räätälöytyjen heterogeenisten katalyyttien avulla

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Raaka-aineiden tutkimusinfrastruktuuri

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