Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides

Jiang, Bo; Bridges, Craig A.; Unocic, Raymond R.; Pitike, Krishna Chaitanya; Cooper, Valentino R.; Zhang, Yuanpeng; Lin, De-Ye; Page, Katharine

doi:10.1021/jacs.0c10739

Title: Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides

Journal Article · 22 December 2020 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.0c10739 · OSTI ID:1777738

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Institute of Applied Physics and Computational Mathematics, Beijing (China); CAEP Software Center for High Performance Numerical Simulation, Beijing (China)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

High-entropy oxides (HEOs) have attracted great interest in diverse fields because of their inherent opportunities to tailor and combine materials functionalities. The control of local order/disorder in the class is by extension a grand challenge toward realizing their vast potential. In this paper, we report the first examples of pyrochlore HEOs with five M-site cations, for Nd₂M₂O₇, in which the local structure has been investigated by neutron diffraction and pair distribution function (PDF) analysis. The average structure of the pyrochlores is found to be orthorhombic Imma, in agreement with radius-ratio rules governing the structural archetype. The computed PDFs from density functional theory relaxed special quasirandom structure models are compared with real space PDFs in this work to evaluate M-site order/disorder. Reverse Monte Carlo combined with ab initio molecular dynamics and Metropolis Monte Carlo simulations demonstrates that Nd₂(Ta_0.2Sc_0.2Sn_0.2Hf_0.2Zr_0.2)₂O₇ is synthesized with its M-site local to nanoscale order highly randomized/disordered, while Nd₂(Ti_0.2Nb_0.2Sn_0.2Hf_0.2Zr_0.2)₂O_7+x exhibits a strong distortion of the TiO₆ octahedron and small degree of Ti chemical short-range order (SRO) on the subnanometer scale. Calculations suggest that this may be intrinsic, energetically favored SRO rather than due to sample processing. These results offer an important demonstration that the engineered variation of participating ions in HEOs, even among those with very similar radii, provides richly diverse opportunities to control local order/disorder motifs—and therefore materials properties for future designs. This work also hints at the exquisite level of detail that may be needed in computational and experimental data analysis to guide structure–property tuning in the emerging HEO materials class.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS) and Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1777738

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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