Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices

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.

doi:10.1002/adma.202005003

Hole-Trapping-Induced Stabilization of Ni⁴⁺ in SrNiO₃/LaFeO₃ Superlattices

Journal Article · Fri Oct 02 04:00:00 EDT 2020 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202005003· OSTI ID:1763017

^[1]; Yang, Zhenzhong ^[1]; Bowden, Mark E. ^[1]; Freeland, John W. ^[2]; ^[1]; ^[1]; Matthews, Bethany E. ^[1]; Samarakoon, Widitha S. ^[3]; Zhou, Hua ^[2]; Feng, Zhenxing ^[3]; ^[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)

Creating new functionality in materials containing transition metals is predicated on our ability to control the associated charge states. For a given metal, forming lower oxidation states is typically easier than generating higher values, and there is an upper limit on valence that is not exceeded under normal conditions. Here we demonstrate that we can exceed the normal upper limit of 3+ for Ni and Fe via synthesis of (SrNiO₃)m/(LaFeO₃)n superlattices by tuning n and m. The Goldschmidt tolerance constraints are lifted and SrNi⁴⁺O₃ with holes on adjacent O anions can be stabilized as a perovskite at the single unit cell level (m = 1). Spectroscopy reveals that the n = 1 superlattice contains Ni³⁺ and Fe⁴⁺, whereas Ni⁴⁺ and Fe³⁺ are observed in the n = 5 superlattice. Here, our results show that the B-site cation valences can be tuned by controlling the magnitude of the FeO6 octahedral rotations which in turn drive the energy balance between Ni³⁺/Fe⁴⁺ and Ni⁴⁺/Fe³⁺, thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. We suggest that this approach may be generally useful for synthesizing novel, metastable layered structures with new functionalities.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 1763017

Alternate ID(s):: OSTI ID: 1804235
OSTI ID: 1779076

Report Number(s):: PNNL-SA--152538

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 45 Vol. 32; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Hole-Trapping-Induced Stabilization of Ni4+ in SrNiO3/LaFeO3 Superlattices

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Hole-Trapping-Induced Stabilization of Ni⁴⁺ in SrNiO₃/LaFeO₃ Superlattices