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Title: Carrier localization in perovskite nickelates from oxygen vacancies

Abstract

Point defects, such as oxygen vacancies, control the physical properties of complex oxides, relevant in active areas of research from superconductivity to resistive memory to catalysis. In most oxide semiconductors, electrons that are associated with oxygen vacancies occupy the conduction band, leading to an increase in the electrical conductivity. Here we demonstrate, in contrast, that in the correlated-electron perovskite rare-earth nickelates, R NiO 3 ( R is a rare-earth element such as Sm or Nd), electrons associated with oxygen vacancies strongly localize, leading to a dramatic decrease in the electrical conductivity by several orders of magnitude. This unusual behavior is found to stem from the combination of crystal field splitting and filling-controlled Mott–Hubbard electron–electron correlations in the Ni 3 d orbitals. Furthermore, we show the distribution of oxygen vacancies in NdNiO 3 can be controlled via an electric field, leading to analog resistance switching behavior. This study demonstrates the potential of nickelates as testbeds to better understand emergent physics in oxide heterostructures as well as candidate systems in the emerging fields of artificial intelligence.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1570476
Alternate Identifier(s):
OSTI ID: 1599062
Grant/Contract Number:  
AC02-06CH11357; N00014-17-1-2770; FA9550-16-1-0159; 1609898; W911NF-16-1-0042; DMR-0703406; 1751739; SC0008630; DMR-1610139; 1553251; FA9559-16-1-0172
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 44; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; charge localization; nickelates; oxygen deficiency; perovskite

Citation Formats

Kotiuga, Michele, Zhang, Zhen, Li, Jiarui, Rodolakis, Fanny, Zhou, Hua, Sutarto, Ronny, He, Feizhou, Wang, Qi, Sun, Yifei, Wang, Ying, Aghamiri, Neda Alsadat, Hancock, Steven Bennett, Rokhinson, Leonid P., Landau, David P., Abate, Yohannes, Freeland, John W., Comin, Riccardo, Ramanathan, Shriram, and Rabe, Karin M. Carrier localization in perovskite nickelates from oxygen vacancies. United States: N. p., 2019. Web. doi:10.1073/pnas.1910490116.
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Kotiuga, Michele, Zhang, Zhen, Li, Jiarui, Rodolakis, Fanny, Zhou, Hua, Sutarto, Ronny, He, Feizhou, Wang, Qi, Sun, Yifei, Wang, Ying, Aghamiri, Neda Alsadat, Hancock, Steven Bennett, Rokhinson, Leonid P., Landau, David P., Abate, Yohannes, Freeland, John W., Comin, Riccardo, Ramanathan, Shriram, & Rabe, Karin M. Carrier localization in perovskite nickelates from oxygen vacancies. United States. https://doi.org/10.1073/pnas.1910490116
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Kotiuga, Michele, Zhang, Zhen, Li, Jiarui, Rodolakis, Fanny, Zhou, Hua, Sutarto, Ronny, He, Feizhou, Wang, Qi, Sun, Yifei, Wang, Ying, Aghamiri, Neda Alsadat, Hancock, Steven Bennett, Rokhinson, Leonid P., Landau, David P., Abate, Yohannes, Freeland, John W., Comin, Riccardo, Ramanathan, Shriram, and Rabe, Karin M. Mon . "Carrier localization in perovskite nickelates from oxygen vacancies". United States. https://doi.org/10.1073/pnas.1910490116.
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@article{osti_1570476,
title = {Carrier localization in perovskite nickelates from oxygen vacancies},
author = {Kotiuga, Michele and Zhang, Zhen and Li, Jiarui and Rodolakis, Fanny and Zhou, Hua and Sutarto, Ronny and He, Feizhou and Wang, Qi and Sun, Yifei and Wang, Ying and Aghamiri, Neda Alsadat and Hancock, Steven Bennett and Rokhinson, Leonid P. and Landau, David P. and Abate, Yohannes and Freeland, John W. and Comin, Riccardo and Ramanathan, Shriram and Rabe, Karin M.},
abstractNote = {Point defects, such as oxygen vacancies, control the physical properties of complex oxides, relevant in active areas of research from superconductivity to resistive memory to catalysis. In most oxide semiconductors, electrons that are associated with oxygen vacancies occupy the conduction band, leading to an increase in the electrical conductivity. Here we demonstrate, in contrast, that in the correlated-electron perovskite rare-earth nickelates, R NiO 3 ( R is a rare-earth element such as Sm or Nd), electrons associated with oxygen vacancies strongly localize, leading to a dramatic decrease in the electrical conductivity by several orders of magnitude. This unusual behavior is found to stem from the combination of crystal field splitting and filling-controlled Mott–Hubbard electron–electron correlations in the Ni 3 d orbitals. Furthermore, we show the distribution of oxygen vacancies in NdNiO 3 can be controlled via an electric field, leading to analog resistance switching behavior. This study demonstrates the potential of nickelates as testbeds to better understand emergent physics in oxide heterostructures as well as candidate systems in the emerging fields of artificial intelligence.},
doi = {10.1073/pnas.1910490116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 44,
volume = 116,
place = {United States},
year = {2019},
month = {10}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1910490116
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Cited by: 6 works
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Figures / Tables:

Fig. 1 Fig. 1: Schematic of charge localization mechanism in oxygen deficient SmNiO3-δ (SNO3-δ). (A) Oxygen vacancy formation in SNO changes the local symmetry from octahedral to tetragonal, square planar, and square pyramid, as well as introduces charge (i.e. electrons) into the material. (B) The electrons accompanying the oxygen vacancies localize onmore » nearby Ni and reduce its valence state to Ni2+, where the strong on-site Coulomb interaction of electrons as well as crystal field splitting of the Ni 3d orbitals synergistically leads to carrier localization and opening of bandgap.« less
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