Crystal Engineering of Bi2WO6 to Polar Aurivillius-Phase Oxyhalides

Kazuki Morita; Ji Sang Park; Sunghyun Kim; Kenji Yasuoka; Aron Walsh

doi:10.1021/acs.jpcc.9b09806

Crystal Engineering of Bi₂WO₆ to Polar Aurivillius-Phase Oxyhalides

Kazuki Morita, Ji Sang Park, Sunghyun Kim, Kenji Yasuoka, Aron Walsh

Department of Physics

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The Aurivillius phases of complex bismuth oxides have attracted considerable attention because of their lattice polarization (ferroelectricity) and photocatalytic activity. We report a first-principles exploration of Bi₂WO₆ and the crystal engineering through replacing W⁶⁺ by pentavalent (Nb⁵⁺ and Ta⁵⁺) and tetravalent (Ti⁴⁺ and Sn⁴⁺) ions, with charge neutrality maintained by the formation of a mixed anion oxyhalide sublattice. We find that Bi₂SnO₄F₂ is thermodynamically unstable, in contrast to Bi₂TaO₅F, Bi₂NbO₅F, and Bi₂TiO₄F₂. The electric dipoles introduced by chemical substitutions in the parent compound are found to suppress the spontaneous polarization from 61.55 μC/cm² to below 15.50 μC/cm². Analysis of the trends in electronic structure, surface structure, and ionization potentials is reported. This family of materials can be further extended with control of layer thicknesses and choice of compensating halide species.

Original language	English
Pages (from-to)	29155-29161
Number of pages	7
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	48
DOIs	https://doi.org/10.1021/acs.jpcc.9b09806
State	Published - 5 Dec 2019

Bibliographical note

Funding Information:
This research has been partially supported by Keio University Research Grant for Young Researcher’s Program, Yoshida Scholarship Foundation, Japan Student Services Organization, and Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London. Part of computation in this work has been done using the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo. Some of the calculations were also carried out in the UK national Archer HPC facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202).

Publisher Copyright:
© 2019 American Chemical Society.

Access to Document

10.1021/acs.jpcc.9b09806

Cite this

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title = "Crystal Engineering of Bi2WO6 to Polar Aurivillius-Phase Oxyhalides",

abstract = "The Aurivillius phases of complex bismuth oxides have attracted considerable attention because of their lattice polarization (ferroelectricity) and photocatalytic activity. We report a first-principles exploration of Bi2WO6 and the crystal engineering through replacing W6+ by pentavalent (Nb5+ and Ta5+) and tetravalent (Ti4+ and Sn4+) ions, with charge neutrality maintained by the formation of a mixed anion oxyhalide sublattice. We find that Bi2SnO4F2 is thermodynamically unstable, in contrast to Bi2TaO5F, Bi2NbO5F, and Bi2TiO4F2. The electric dipoles introduced by chemical substitutions in the parent compound are found to suppress the spontaneous polarization from 61.55 μC/cm2 to below 15.50 μC/cm2. Analysis of the trends in electronic structure, surface structure, and ionization potentials is reported. This family of materials can be further extended with control of layer thicknesses and choice of compensating halide species.",

author = "Kazuki Morita and Park, {Ji Sang} and Sunghyun Kim and Kenji Yasuoka and Aron Walsh",

note = "Funding Information: This research has been partially supported by Keio University Research Grant for Young Researcher{\textquoteright}s Program, Yoshida Scholarship Foundation, Japan Student Services Organization, and Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London. Part of computation in this work has been done using the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo. Some of the calculations were also carried out in the UK national Archer HPC facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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AU - Walsh, Aron

N1 - Funding Information: This research has been partially supported by Keio University Research Grant for Young Researcher’s Program, Yoshida Scholarship Foundation, Japan Student Services Organization, and Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London. Part of computation in this work has been done using the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo. Some of the calculations were also carried out in the UK national Archer HPC facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). Publisher Copyright: © 2019 American Chemical Society.

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N2 - The Aurivillius phases of complex bismuth oxides have attracted considerable attention because of their lattice polarization (ferroelectricity) and photocatalytic activity. We report a first-principles exploration of Bi2WO6 and the crystal engineering through replacing W6+ by pentavalent (Nb5+ and Ta5+) and tetravalent (Ti4+ and Sn4+) ions, with charge neutrality maintained by the formation of a mixed anion oxyhalide sublattice. We find that Bi2SnO4F2 is thermodynamically unstable, in contrast to Bi2TaO5F, Bi2NbO5F, and Bi2TiO4F2. The electric dipoles introduced by chemical substitutions in the parent compound are found to suppress the spontaneous polarization from 61.55 μC/cm2 to below 15.50 μC/cm2. Analysis of the trends in electronic structure, surface structure, and ionization potentials is reported. This family of materials can be further extended with control of layer thicknesses and choice of compensating halide species.

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