The calculation of the electronic structure of zirconium dioxide in cubic and tetragonal phases

doi:10.1016/0921-4526(93)90033-3

Physica B: Condensed Matter

Volume 192, Issue 3, November 1993, Pages 284-290

https://doi.org/10.1016/0921-4526(93)90033-3 Get rights and content

Abstract

A self-consistent calculation of the electronic structure of zirconium dioxide in cubic and tetragonal phases has been performed by the linear muffin-tin orbital method in the atomic sphere approximation (LMTO-ASA). The band structure, total and partial densities of states, partial charges and optical conductivity in the constant-matrix-element approximation have been calculated. The variation of electronic characteristics as a function of the displacement of the oxygen atoms in the tetragonal phase has been analyzed. The effect of oxygen vacancies and of yttrium or magnesium substitutional impurities on the electronic structure and optical properties of cubic zirconium dioxide has also been studied.

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As revealed by the chemical composition of the films, the optical gap lowering could be attributed to the presence of defects in such a large amount of oxygen vacancies. Such defects can lead to optical gaps values of ∼ 3 eV [14,15], close to the ones obtained for the present films. Another origin of the gap red shift may be also due to the presence of a hydrous layer.
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Besides the zirconia phase and crystalline parameter changes induced by carbon addition, the electronic properties to the films were significantly modified: a drastical optical gap lowering was observed along an increased electronic dielectric constant and refractive index. The invariance of the film elasticity modulus and the similarity of the optical transition lifetime values with those of pure amorphous carbon films indicate an immiscibility of the ceramic and carbon components of the film structure.
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Theoretical calculations of the interaction between neighboring oxygen ions for selected clusters were performed by the density functional method (DFT/B3LYP) in order to investigate the stable effect of single and mixed doped c-ZrO₂. The Mulliken charge population numbers of oxygen ions for undoped, cation-doped, anion-doped and co-doped c-ZrO₂ were discussed. Theoretical results indicate that the stable ability of doped c-ZrO₂ could be described as the Coulomb repulsive force between neighboring oxygen ions (f_c), which agrees well with the experimental data. Moreover, the effect of third phase cation and/or anion-doped zirconia complex materials was successfully expounded by this method, especially on the conductivity decrease of the 8YSZ system with increasing SiC content.
A stabilization mechanism of zirconia based on oxygen vacancies only
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Above the bandgap, it is possible to identify the crystal field splitting of the zirconium d bands. In the undistorted case (left panel), the arrow points to a sharp peak within the bandgap, also predicted by other calculations [30,31]. The corresponding partial DOS shows that this peak corresponds to the NN Zr d bands with symmetry E.
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The calculation of the electronic structure of zirconium dioxide in cubic and tetragonal phases

Abstract

J. Nucl. Mater.

Acta Metall.

J. Phys. Chem. Sol.

Physica B

Z. Krystallogr.

Acta Cryst.

Acta Cryst.

J. Am. Ceram. Soc.

Acta Crystallogr.

Science

Acta Cryst.

J. Phys. C