Hole‐Trapping‐Induced Stabilization of Ni 4 + in SrNiO 3 /LaFeO 3 Superlattices

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...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Advanced materials (Weinheim) 2020-11, Vol.32 (45)
Hauptverfasser: Wang, Le, Yang, Zhenzhong, Bowden, Mark E., Freeland, John W., Sushko, Peter V., Spurgeon, Steven R., Matthews, Bethany, Samarakoon, Widitha S., Zhou, Hua, Feng, Zhenxing, Engelhard, Mark H., Du, Yingge, Chambers, Scott A.
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung: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 (SrNiO 3 ) m /(LaFeO 3 ) n superlattices by tuning n and m . 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). Holding m  = 1, spectroscopy reveals that the n  = 1 superlattice contains Ni 3+ and Fe 4+ , whereas Ni 4+ and Fe 3+ are observed in the n  = 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 Ni 3+ /Fe 4+ and Ni 4+ /Fe 3+ , 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.
ISSN:0935-9648
1521-4095
DOI:10.1002/adma.202005003