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Hole‐Trapping‐Induced Stabilization of Ni 4 + in SrNiO 3 /LaFeO 3 Superlattices
Author(s) -
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.
Publication year - 2020
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.202005003
Subject(s) - superlattice , materials science , transition metal , valence (chemistry) , metastability , octahedron , perovskite (structure) , trapping , condensed matter physics , valence band , crystallography , band gap , crystal structure , optoelectronics , physics , catalysis , chemistry , biochemistry , quantum mechanics , ecology , biology
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.