Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices
Abstract
Creating new functionality in materials containing transition metals is predicated on the ability to control the associated charge states. For a given transition metal, there is an upper limit on valence that is not exceeded under normal conditions. Here, it is demonstrated that this limit of 3+ for Ni and Fe can be exceeded via synthesis of (SrNiO3)(m)/(LaFeO3)(n)superlattices by tuningnandm. The Goldschmidt tolerance constraints are lifted, and SrNi(4+)O(3)with holes on adjacent O anions is stabilized as a perovskite at the single-unit-cell level (m = 1). Holdingm = 1, spectroscopy reveals that then = 1 superlattice contains Ni(3+)and Fe4+, whereas Ni(4+)and Fe(3+)are observed in then = 5 superlattice. It is revealed that the B-site cation valences can be tuned by controlling the magnitude of the FeO(6)octahedral rotations, which, in turn, determine the energy balance between Ni3+/Fe(4+)and Ni4+/Fe3+, thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. This approach can be extended to other systems for synthesizing novel, metastable layered structures with new functionalities.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1763017
- Alternate Identifier(s):
- OSTI ID: 1779076; OSTI ID: 1804235
- Report Number(s):
- PNNL-SA-152538
Journal ID: ISSN 0935-9648
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357; 10122
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 45; Journal ID: ISSN 0935-9648
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; charge transfer; octahedral rotation; Ni4+; Fe4+; superlattices
Citation Formats
Wang, Le, Yang, Zhenzhong, Bowden, Mark E., Freeland, John W., Sushko, Petr V., Spurgeon, Steven R., Matthews, Bethany E., Samarakoon, Widitha S., Zhou, Hua, Feng, Zhenxing, Engelhard, Mark H., Du, Yingge, and Chambers, Scott A. Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices. United States: N. p., 2020.
Web. doi:10.1002/adma.202005003.
Wang, Le, Yang, Zhenzhong, Bowden, Mark E., Freeland, John W., Sushko, Petr V., Spurgeon, Steven R., Matthews, Bethany E., Samarakoon, Widitha S., Zhou, Hua, Feng, Zhenxing, Engelhard, Mark H., Du, Yingge, & Chambers, Scott A. Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices. United States. https://doi.org/10.1002/adma.202005003
Wang, Le, Yang, Zhenzhong, Bowden, Mark E., Freeland, John W., Sushko, Petr V., Spurgeon, Steven R., Matthews, Bethany E., Samarakoon, Widitha S., Zhou, Hua, Feng, Zhenxing, Engelhard, Mark H., Du, Yingge, and Chambers, Scott A. Fri .
"Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices". United States. https://doi.org/10.1002/adma.202005003. https://www.osti.gov/servlets/purl/1763017.
@article{osti_1763017,
title = {Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices},
author = {Wang, Le and Yang, Zhenzhong and Bowden, Mark E. and Freeland, John W. and Sushko, Petr V. and Spurgeon, Steven R. and Matthews, Bethany E. and Samarakoon, Widitha S. and Zhou, Hua and Feng, Zhenxing and Engelhard, Mark H. and Du, Yingge and Chambers, Scott A.},
abstractNote = {Creating new functionality in materials containing transition metals is predicated on the ability to control the associated charge states. For a given transition metal, there is an upper limit on valence that is not exceeded under normal conditions. Here, it is demonstrated that this limit of 3+ for Ni and Fe can be exceeded via synthesis of (SrNiO3)(m)/(LaFeO3)(n)superlattices by tuningnandm. The Goldschmidt tolerance constraints are lifted, and SrNi(4+)O(3)with holes on adjacent O anions is stabilized as a perovskite at the single-unit-cell level (m = 1). Holdingm = 1, spectroscopy reveals that then = 1 superlattice contains Ni(3+)and Fe4+, whereas Ni(4+)and Fe(3+)are observed in then = 5 superlattice. It is revealed that the B-site cation valences can be tuned by controlling the magnitude of the FeO(6)octahedral rotations, which, in turn, determine the energy balance between Ni3+/Fe(4+)and Ni4+/Fe3+, thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. This approach can be extended to other systems for synthesizing novel, metastable layered structures with new functionalities.},
doi = {10.1002/adma.202005003},
journal = {Advanced Materials},
number = 45,
volume = 32,
place = {United States},
year = {Fri Oct 02 00:00:00 EDT 2020},
month = {Fri Oct 02 00:00:00 EDT 2020}
}
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