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<p>Introducing oxygen deficiencies into metallic oxides dramatically improves their functional properties. We produced periodic oxygen-defective ZrO<sub>2−<i>x</i></sub> films via a stepwise oxidation process involving annealing Zr metal foil in air and under a controlled oxygen partial pressure. Transmission electron microscopy (TEM) and high-angle annular dark-field scanning TEM revealed that the <i>c</i>-axis of the unit cell of monoclinic ZrO<sub>2</sub> structure contracted upon introduction of oxygen vacancies. The <i>β</i> angle of the monoclinic structure also changed to 90.5°. The ordering of oxygen deficiencies related to the &lt; 111 &gt; fluorite direction on the (<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43578_2025_1641_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="25" /> </InlineMediaObject> <EquationSource Format="TEX">\(\overline{1} 01\)</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mover> <mn>1</mn> <mo>¯</mo> </mover> <mn>01</mn> </mrow> </math></EquationSource> </InlineEquation>)<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43578_2025_1641_Article_IEq2.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="34" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{P2_{1} /c}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow> <mi>P</mi> <msub> <mn>2</mn> <mn>1</mn> </msub> <mo stretchy="false">/</mo> <mi>c</mi> </mrow> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> plane led to a periodic structure with a spacing of some nanometers. This work is the first report visualizing the ordering of oxygen vacancies in the monoclinic ZrO<sub>2−<i>x</i></sub> structure. Our process can be used to control the content and ordering of oxygen deficiencies through the selection of appropriate oxidation conditions, thereby improving the functional properties of ZrO<sub>2−<i>x</i></sub> films.</p> Graphical abstract <p>(a) Bright-field conventional transmission electron microscopy image from the surface to depth of a few micrometers in the cross-section of sample A. (b) Higher-magnification image near the surface in (a). (c) Selected-area electron diffraction pattern for grain C in (b). High-angle annular dark-field scanning transmission electron microscopy image taken along (d) the [101]<InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43578_2025_1641_Article_IEq2.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="34" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{P2_{1} /c}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow> <mi>P</mi> <msub> <mn>2</mn> <mn>1</mn> </msub> <mo stretchy="false">/</mo> <mi>c</mi> </mrow> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> and (e) the [010]<InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43578_2025_1641_Article_IEq2.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="34" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{P2_{1} /c}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow> <mi>P</mi> <msub> <mn>2</mn> <mn>1</mn> </msub> <mo stretchy="false">/</mo> <mi>c</mi> </mrow> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> zone axis of the monoclinic ZrO<sub>2</sub> structure, respectively. Atomic arrangements and lattice spacing of the [010]<InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43578_2025_1641_Article_IEq2.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="34" /> </InlineMediaObject> <EquationSource Format="TEX">\(_{{P2_{1} /c}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow> <mi>P</mi> <msub> <mn>2</mn> <mn>1</mn> </msub> <mo stretchy="false">/</mo> <mi>c</mi> </mrow> <mrow /> </mmultiscripts> </math></EquationSource> </InlineEquation> direction of the monoclinic ZrO<sub>2</sub> structure with <i>β</i> angles; (f) <i>β</i> = 99.1°and (g) <i>β</i> = 90.5°, respectively.</p> <p></p>

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Unveiling the periodic structure in oxygen-defective ZrO2−x films produced by stepwise oxidation of metallic Zr foil

  • 期刊论文

  • 发表日期：

    2025年7月3日

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  • Mitsuhiro Matsuda,
  • Kaori Kusuda,
  • Kenji Shida,
  • Hiroshi Akamine,
  • Masatoshi Mitsuhara,
  • Motohide Matsuda,
  • Yasushi Nakajima

摘要

Introducing oxygen deficiencies into metallic oxides dramatically improves their functional properties. We produced periodic oxygen-defective ZrO2−x films via a stepwise oxidation process involving annealing Zr metal foil in air and under a controlled oxygen partial pressure. Transmission electron microscopy (TEM) and high-angle annular dark-field scanning TEM revealed that the c-axis of the unit cell of monoclinic ZrO2 structure contracted upon introduction of oxygen vacancies. The β angle of the monoclinic structure also changed to 90.5°. The ordering of oxygen deficiencies related to the < 111 > fluorite direction on the ( \(\overline{1} 01\) 1 ¯ 01 ) \(_{{P2_{1} /c}}\) P 2 1 / c plane led to a periodic structure with a spacing of some nanometers. This work is the first report visualizing the ordering of oxygen vacancies in the monoclinic ZrO2−x structure. Our process can be used to control the content and ordering of oxygen deficiencies through the selection of appropriate oxidation conditions, thereby improving the functional properties of ZrO2−x films.

Graphical abstract

(a) Bright-field conventional transmission electron microscopy image from the surface to depth of a few micrometers in the cross-section of sample A. (b) Higher-magnification image near the surface in (a). (c) Selected-area electron diffraction pattern for grain C in (b). High-angle annular dark-field scanning transmission electron microscopy image taken along (d) the [101] \(_{{P2_{1} /c}}\) P 2 1 / c and (e) the [010] \(_{{P2_{1} /c}}\) P 2 1 / c zone axis of the monoclinic ZrO2 structure, respectively. Atomic arrangements and lattice spacing of the [010] \(_{{P2_{1} /c}}\) P 2 1 / c direction of the monoclinic ZrO2 structure with β angles; (f) β = 99.1°and (g) β = 90.5°, respectively.