Linking the Electrical Conductivity and Non-Stoichiometry of Thin Film Ce 1-x Zr x O 2-δ by a Resonant Nanobalance Approach

Materials (Basel). 2021 Feb 5;14(4):748. doi: 10.3390/ma14040748.


Bulk ceria-zirconia solid solutions (Ce1-xZrxO2-δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO2 in the range of 10-24-0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO2-ZrO2 as compared to CeO2-δ and ZrO2 were observed. A comparison of temperature- and pO2-dependences of the non-stoichiometry of thin films with literature data for bulk Ce1-xZrxO2-δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce0.8Zr0.2O2-δ, whereas Ce0.5Zr0.5O2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO2 of 10-14 bar. The defect interactions in Ce1-xZrxO2-δ are analyzed in the framework of defect models for ceria and zirconia.

Keywords: ceria-zirconia solid solutions; defect interactions; electrical conductivity; non-stoichiometry; redox reactions; reducing atmosphere; resonant nanobalance; thermogravimetry; thin films; three-way catalytic converters (TWC).