ACS Publications. Most Trusted. Most Cited. Most Read
Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2021, 60, 18, 14190-14201
    Article

    Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides
    Click to copy article linkArticle link copied!

    • Xin Wang
      Xin Wang
      Department of Materials Science and Engineering and Joint Institute of Advanced Materials, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by Xin Wang
    • Bo Jiang
      Bo Jiang
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Bo Jiang
    • Yuanpeng Zhang
      Yuanpeng Zhang
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Yuanpeng Zhang
      Orcidhttps://orcid.org/0000-0003-4224-3361
    • Young-Il Kim
      Young-Il Kim
      Department of Chemistry, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic of Korea
      More by Young-Il Kim
      Orcidhttps://orcid.org/0000-0003-2755-9587
    • Katharine Page*
      Katharine Page
      Department of Materials Science and Engineering and Joint Institute of Advanced Materials, University of Tennessee, Knoxville, Tennessee 37996, United States
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Shull Wollan Center, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *Email: [email protected]
      More by Katharine Page
      Orcidhttps://orcid.org/0000-0002-9071-3383
    Other Access OptionsSupporting Information (1)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 18, 14190–14201
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.1c01594
    Published September 2, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Partial anion substitution in transition metal oxides provides rich opportunities to control and tune physical and chemical properties, for example, combining the merits of oxides and nitrides. In addition, the possibility of resulting anion sublattice order provides a means to target polar and chiral structures based on a wide array of accessible structural archetypes by design. Here, we investigate the local structures of a family of perovskite tantalum oxynitrides—ATaO2N (A = Ba, Sr, and Ca)—using a combination of experimental and theoretical approaches including neutron total scattering, density functional theory (DFT), and ab initio molecular dynamics (AIMD) simulations. We present the first experimental study of chemical short-range order (CSRO) in CaTaO2N, confirming local cis N ordering of the anion sub-lattice. Our systematic exploration of a local structure across the A cation size series (from the larger Ba to the smaller Ca) reveals a perovskite motif increasingly distorted with respect to long-range average structures. DFT and AIMD simulations support the observed trends. Overall, structures with cis ordering of the nitrogen anions in each TaO4N2 octahedron are favored over those with trans ordering. With diminishing A cation size, local cis ordering and Ta off-centering play decreasing roles in overall lattice stability, overshadowed by the stabilizing effects of octahedral tilting. The influence of these factors on local dipole formation and frustrated dipole ordering are discussed.

    Copyright © 2021 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c01594.

    • Influence of cation size on the local atomic structure and electronic properties of Ta perovskite oxynitrides: AC impedance of ATaO2N; details and results of alternate Rietveld analyses; numbers of refined atomic coordinate parameters involved in the local structure model fits; PDF sensitivity test results; “Large-box” PDF models and refinements; DFT results; and crystallographic powder data and refinement details (PDF).

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 11 publications.

    1. Shinichi Kikkawa. Nanocrystallization in Metal Nitrides and Oxynitrides. Chemistry of Materials 2024, 36 (19) , 9167-9172. https://doi.org/10.1021/acs.chemmater.4c01749
    2. Yuji Masubuchi, Kyohei Koyama, Akira Hosono, Mikio Higuchi, Masaki Takesada, Kazuki Shitara, Hiroki Moriwake, Shinichi Kikkawa. Average Cubic BaTaO2N Crystal Structure Formed by 50 nm Size Domains with Polar Nanoregions Consisting of cis-TaO4N2 Octahedral Chains. Chemistry of Materials 2024, 36 (15) , 7504-7513. https://doi.org/10.1021/acs.chemmater.4c01474
    3. Carolyne Chepkemboi, Kyle Jorgensen, Janell Sato, Geneva Laurita. Strategies and Considerations for Least-Squares Analysis of Total Scattering Data. ACS Omega 2022, 7 (17) , 14402-14411. https://doi.org/10.1021/acsomega.2c01285
    4. Faezeh Pakravesh, Mohammad Izadyar. Theoretical insights into the electronic and optical properties of lithium-based perovskite for solar cell applications. Journal of Photochemistry and Photobiology A: Chemistry 2024, 453 , 115602. https://doi.org/10.1016/j.jphotochem.2024.115602
    5. Mirabbos Hojamberdiev, Ronald Vargas, Fuxiang Zhang, Katsuya Teshima, Martin Lerch. Perovskite BaTaO 2 N: From Materials Synthesis to Solar Water Splitting. Advanced Science 2023, 10 (33) https://doi.org/10.1002/advs.202305179
    6. Marcos R. Imer, Leopoldo Suescun, Federico A. Rabuffetti. A small-box approach to the local crystal structure of Y3NbO7. Journal of Solid State Chemistry 2023, 325 , 124147. https://doi.org/10.1016/j.jssc.2023.124147
    7. Zhi Deng, Diancheng Chen, Mingyang Ou, Yuanpeng Zhang, Jia Xu, Dixing Ni, Zhaoran Ji, Jiantao Han, Yang Sun, Shuai Li, Chuying Ouyang, Zhaoxiang Wang. Cation Disordered Anti‐Perovskite Cathode Materials with Enhanced Lithium Diffusion and Suppressed Phase Transition. Advanced Energy Materials 2023, 13 (28) https://doi.org/10.1002/aenm.202300695
    8. Faezeh Pakravesh, Mohammad Izadyar. Theoretical Insights into the Electronic and Optical Properties of Lithium-Based Perovskite for Solar Cell Applications. 2023https://doi.org/10.2139/ssrn.4612011
    9. Young-Il Kim, Maxim Avdeev. Synthesis, structural distortion, and magnetic property of complex perovskites AMn0.2M0.8O2.6N0.4 (A = Sr, Ba; M = Nb, Ta). Journal of Solid State Chemistry 2022, 316 , 123636. https://doi.org/10.1016/j.jssc.2022.123636
    10. Xiaoming Xu, Wenjing Wang, Yuanming Zhang, Yong Chen, Huiting Huang, Tao Fang, Yang Li, Zhaosheng Li, Zhigang Zou. Centimeter-scale perovskite SrTaO2N single crystals with enhanced photoelectrochemical performance. Science Bulletin 2022, 67 (14) , 1458-1466. https://doi.org/10.1016/j.scib.2022.06.005
    11. Young-Il Kim, Maxim Avdeev. Synthesis, Structural Distortion, and Magnetic Property of Complex Perovskites Amn0.2m0.8o2.6n0.4 (a = Sr, Ba; M = Nb, Ta). SSRN Electronic Journal 2022, 31 https://doi.org/10.2139/ssrn.4157151
    12. Young-Il Kim, Maxim Avdeev. Synthesis, Structural Distortion, and Magnetic Property of Complex Perovskites Amn0.2m0.8o2.6n0.4 (a = Sr, Ba; M = Nb, Ta). SSRN Electronic Journal 2022, 31 https://doi.org/10.2139/ssrn.4197065
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 18, 14190–14201
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.1c01594
    Published September 2, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Article Views

    1097

    Altmetric

    -

    Citations

    11
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.