Local cation ordering in compositionally complex Ruddlesden-Popper n = 1 oxides

Bo Jiang; Krishna Chaitanya Pitike; De Ye Lin; Stephen C. Purdy; Xin Wang; Yafan Zhao; Yuanpeng Zhang; Peter Metz; Antonio Macias; Harry M. Meyer; Albina Y. Borisevich; Jiaqiang Yan; Valentino R. Cooper; Craig A. Bridges; Katharine Page

doi:10.1063/5.0144766

Local cation ordering in compositionally complex Ruddlesden-Popper n = 1 oxides

Bo Jiang, Krishna Chaitanya Pitike, De Ye Lin, Stephen C. Purdy, Xin Wang, Yafan Zhao, Yuanpeng Zhang, Peter Metz, Antonio Macias, Harry M. Meyer, Albina Y. Borisevich, Jiaqiang Yan, Valentino R. Cooper, Craig A. Bridges, Katharine Page

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Abstract

The Ruddlesden-Popper (RP) layered perovskite structure is of great interest due to its inherent tunability, and the emergence and growth of the compositionally complex oxide (CCO) concept endows the RP family with further possibilities. Here, a comprehensive assessment of thermodynamic stabilization, local order/disorder, and lattice distortion was performed in the first two reported examples of lanthanum-deficient La_n+1B_nO_3n+1 (n = 1, B = Mg, Co, Ni, Cu, Zn) obtained via various processing conditions. Chemical short-range order (CSRO) at the B-site and the controllable excess interstitial oxygen (δ) in RP-CCOs are uncovered by neutron pair distribution function analysis. Reverse Monte Carlo analysis of the data, Metropolis Monte Carlo simulations, and extended x-ray absorption fine structure analysis implies a modest degree of magnetic element segregation on the local scale. Further, ab initio molecular dynamics simulations results obtained from special quasirandom structure disagree with experimentally observed CSRO but confirm Jahn-Teller distortion of CuO₆ octahedra. These findings highlight potential opportunities to control local order/disorder and excess interstitial oxygen in layered RP-CCOs and demonstrate a high degree of freedom for tailoring application-specific properties. They also suggest a need for expansion of theoretical and data modeling approaches in order to meet the innate challenges of CCO and related high-entropy phases.

Original language	English
Article number	051104
Journal	APL Materials
Volume	11
Issue number	5
DOIs	https://doi.org/10.1063/5.0144766
State	Published - May 1 2023

Funding

The authors acknowledge the support provided for material compositions evaluation, synthesis, and initial theory by the Laboratory Directed Research and Development (LDRD) Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. DOE. Work by V.R.C. and C.A.B. after 2020 was funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Work by K.P. after 2021 was funded by a National Science Foundation CAREER Award, Division of Materials Research, Solid State Chemistry Program. This research used the NOMAD beamline at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The computing resources were made available through the VirtuES project as well as the Compute and Data Environment for Science (CADES) at Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. We thank Charl J. Jafta for his valuable contributions to discussions.

Funders	Funder number
V.R.C.
National Science Foundation
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Argonne National Laboratory	DE-AC05-00OR22725, DE-AC02-06CH11357
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Division of Materials Sciences and Engineering

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title = "Local cation ordering in compositionally complex Ruddlesden-Popper n = 1 oxides",

abstract = "The Ruddlesden-Popper (RP) layered perovskite structure is of great interest due to its inherent tunability, and the emergence and growth of the compositionally complex oxide (CCO) concept endows the RP family with further possibilities. Here, a comprehensive assessment of thermodynamic stabilization, local order/disorder, and lattice distortion was performed in the first two reported examples of lanthanum-deficient Lan+1BnO3n+1 (n = 1, B = Mg, Co, Ni, Cu, Zn) obtained via various processing conditions. Chemical short-range order (CSRO) at the B-site and the controllable excess interstitial oxygen (δ) in RP-CCOs are uncovered by neutron pair distribution function analysis. Reverse Monte Carlo analysis of the data, Metropolis Monte Carlo simulations, and extended x-ray absorption fine structure analysis implies a modest degree of magnetic element segregation on the local scale. Further, ab initio molecular dynamics simulations results obtained from special quasirandom structure disagree with experimentally observed CSRO but confirm Jahn-Teller distortion of CuO6 octahedra. These findings highlight potential opportunities to control local order/disorder and excess interstitial oxygen in layered RP-CCOs and demonstrate a high degree of freedom for tailoring application-specific properties. They also suggest a need for expansion of theoretical and data modeling approaches in order to meet the innate challenges of CCO and related high-entropy phases.",

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AU - Jiang, Bo

AU - Pitike, Krishna Chaitanya

AU - Lin, De Ye

AU - Purdy, Stephen C.

AU - Wang, Xin

AU - Zhao, Yafan

AU - Zhang, Yuanpeng

AU - Metz, Peter

AU - Macias, Antonio

AU - Meyer, Harry M.

AU - Borisevich, Albina Y.

AU - Yan, Jiaqiang

AU - Cooper, Valentino R.

AU - Bridges, Craig A.

AU - Page, Katharine

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AB - The Ruddlesden-Popper (RP) layered perovskite structure is of great interest due to its inherent tunability, and the emergence and growth of the compositionally complex oxide (CCO) concept endows the RP family with further possibilities. Here, a comprehensive assessment of thermodynamic stabilization, local order/disorder, and lattice distortion was performed in the first two reported examples of lanthanum-deficient Lan+1BnO3n+1 (n = 1, B = Mg, Co, Ni, Cu, Zn) obtained via various processing conditions. Chemical short-range order (CSRO) at the B-site and the controllable excess interstitial oxygen (δ) in RP-CCOs are uncovered by neutron pair distribution function analysis. Reverse Monte Carlo analysis of the data, Metropolis Monte Carlo simulations, and extended x-ray absorption fine structure analysis implies a modest degree of magnetic element segregation on the local scale. Further, ab initio molecular dynamics simulations results obtained from special quasirandom structure disagree with experimentally observed CSRO but confirm Jahn-Teller distortion of CuO6 octahedra. These findings highlight potential opportunities to control local order/disorder and excess interstitial oxygen in layered RP-CCOs and demonstrate a high degree of freedom for tailoring application-specific properties. They also suggest a need for expansion of theoretical and data modeling approaches in order to meet the innate challenges of CCO and related high-entropy phases.

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Local cation ordering in compositionally complex Ruddlesden-Popper n = 1 oxides

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