Atomic Layer Deposition of Nanometer-Sized CeO2 Layers in Ordered Mesoporous ZrO2 Films and Their Impact on the Ionic/Electronic Conductivity

  • Pascal Cop
    Pascal Cop
    Physikalisch-Chemisches Institut, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    More by Pascal Cop
  • Erdogan Celik
    Erdogan Celik
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
  • Kevin Hess
    Kevin Hess
    Physikalisch-Chemisches Institut, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    More by Kevin Hess
  • Yannik Moryson
    Yannik Moryson
    Physikalisch-Chemisches Institut, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
  • Philip Klement
    Philip Klement
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    Institute of Experimental Physics I, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
  • Matthias T. Elm*
    Matthias T. Elm
    Physikalisch-Chemisches Institut, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    Institute of Experimental Physics I, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    *Email: [email protected]
  • , and 
  • Bernd M. Smarsly*
    Bernd M. Smarsly
    Physikalisch-Chemisches Institut, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany
    Center for Materials Research, Justus-Liebig University, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany
    *Email: [email protected]
Cite this: ACS Appl. Nano Mater. 2020, 3, 11, 10757–10766
Publication Date (Web):November 5, 2020
https://doi.org/10.1021/acsanm.0c02060
Copyright © 2020 American Chemical Society
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Abstract

The physicochemical properties of thin metal oxide layers strongly depend on the layer thickness and thus differ significantly from their bulk counterpart. In this work, we present the growth of defined thin layers of CeO2 within mesostructured ZrO2 thin films using atomic layer deposition (ALD). The prepared films consist of a cubic ordered arrangement of 15 nm spherical mesopores induced by the used diblock copolymer poly(isobutylene)-block-poly(ethylene oxide) (PIB50-b-PEO45), which allows studying the growth process and the successful coating of the interior pore surfaces via the combination of scanning electron microscopy (SEM), time-of-flight mass spectrometry (ToF-SIMS), and laser ellipsometry. These methods prove the CeO2 layer growth and impregnation of the pores up to 100 ALD cycles, at which the interconnecting channels between the mesopore layers are filled completely impeding further transport of the gaseous CeO2 precursors. X-ray photoelectron spectroscopy (XPS) and diffractometry (XRD) measurements point out the increased amount of Ce3+ after a low number of ALD cycles and show the presence of cubic CeO2 with increasing amount of ALD cycles, respectively. Impedance spectroscopic investigation further proves the formation of a continuous CeO2 path through the entire porous network of the insulating ZrO2 film and shows a strong influence of the layer thickness on the conductivity. All in all, our work presents the preparation of novel hybrid CeO2/ZrO2 model systems, which enable us to tailor their physicochemical properties by changing the thickness of the active oxide layer, and promises improvements for their use as catalysts in oxidation reactions such as the HCl oxidation reaction or as a three-way catalytic converter in automotives.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsanm.0c02060.

  • Laser ellipsometric studies of the CeO2-coated silicon wafer, SEM and ToF-SIMS analyses of the CeO2-coated ZrO2 films dependent on different dwell times, ToF-SIMS depth profiles of all the coated mesoporous ZrO2 films, XPS measurements—Ce 3d spectra with fittings—of the CeO2-coated films, and Arrhenius plots of the total conductivity and the corresponding fits for the uncoated ZrO2 film, after 25, 75, and 150 ALD cycles (PDF)

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Cited By


This article is cited by 4 publications.

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  2. Erdogan Celik, Yanjiao Ma, Torsten Brezesinski, Matthias T. Elm. Ordered mesoporous metal oxides for electrochemical applications: correlation between structure, electrical properties and device performance. Physical Chemistry Chemical Physics 2021, 23 (18) , 10706-10735. https://doi.org/10.1039/D1CP00834J
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  4. Rajendra S. Negi, Sean P. Culver, Miguel Wiche, Shamail Ahmed, Kerstin Volz, Matthias T. Elm. Optimized atomic layer deposition of homogeneous, conductive Al 2 O 3 coatings for high-nickel NCM containing ready-to-use electrodes. Physical Chemistry Chemical Physics 2021, 23 (11) , 6725-6737. https://doi.org/10.1039/D0CP06422J