Electronic State of Nickel in Barium Nickel Oxide, BaNiO<sub>3</sub>

Gottschall, Reiner; Schöllhorn, R.; Mühler, Martin; Jansen, N.; Walcher, D.; Gütlich, Philipp

doi:10.1021/ic9709279

Cited by 61 publications

(44 citation statements)

References 16 publications

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“…3 eV in an octahedral coordination as reported by Gottschall et al. 28 Figure 5d shows the relative areas of the Ni 2+ and Ni 3+ peaks: at low Nd/Ni ratio, the Ni 2+ content is the weakest, and it increases for higher Nd/Ni ratios. This implies that the cationic off-stoichiometry in samples D, B, A and E is due to Nd excess.…”

Section: Fig 3 Transport Characterization Of the Five Nno Thin Filmsupporting

confidence: 66%

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

et al. 2017

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Rare-earth nickelates are strongly correlated oxides displaying a metal-to-insulator transition at a temperature tunable by the rare-earth ionic radius. In PrNiO 3 and NdNiO 3 , the transition is very sharp and shows an hysteretic behavior akin to a first-order transition. Both the temperature at which the transition occurs and the associated resistivity change are extremely sensitive to doping and therefore to offstoichiometry issues that may arise during thin film growth. Here we report that strong deviations in the transport properties of NdNiO 3 films can arise in films grown consecutively under nominally identical conditions by pulsed laser deposition; some samples show a well-developed transition with a resistivity change of up to five orders of magnitude while others are metallic down to low temperatures. Through a detailed analysis of in-situ X-ray photoelectron spectroscopy data, we relate this behavior to large levels of cationic off-stoichoimetry that also translate in changes in the Ni valence and bandwidth. Finally, we demonstrate that this lack of reproducibility can be remarkably alleviated by using single-phase NdNiO 3 targets.

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Section: Fig 3 Transport Characterization Of the Five Nno Thin Filmsupporting

confidence: 66%

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

et al. 2017

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“…We note that a Ni close to a 4+ oxidation state was experimentally observed for some Ni compounds through 61 Ni Mössbauer spectroscopy. 48 These conclusions were ratified by considering larger clusters of Ni sites for the MLWFs optimization, as well as individual Ni's and/or optimizations in which the oxygen bands were not included.…”

Section: Disproportionation Signaturesmentioning

confidence: 97%

Complete phase diagram of rare-earth nickelates from first-principles

et al. 2017

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The structural, electronic and magnetic properties of AMO 3 perovskite oxides, where M is a 3d transition metal, are highly sensitive to the geometry of the bonds between the metal-d and oxygen-p ions (through octahedra rotations and distortions) and to their level of covalence. This is particularly true in rare-earth nickelates RNiO 3 that display a metal-insulator transition with complex spin orders tunable by the rare-earth size, and are on the border line between dominantly ionic (lighter elements) and covalent characters (heavier elements). Accordingly, computing their ground state is challenging and a complete theoretical description of their rich phase diagram is still missing. Here, using first-principles simulations, we successfully describe the electronic and magnetic experimental ground state of nickelates. We show that the insulating phase is characterized by a split of the electronic states of the two Ni sites (i.e., resembling low-spin 4+ and high-spin 2+) with a concomitant shift of the oxygen-2p orbitals toward the depleted Ni cations. Therefore, from the point of view of the charge, the two Ni sites appear nearly identical whereas they are in fact distinct. Performing such calculations for several nickelates, we built a theoretical phase diagram that reproduces all their key features, namely a systematic dependence of the metal-insulator transition with the rare-earth size and the crossover between a second to first order transition for R = Pr and Nd. Finally, our results hint at strategies to control the electronic and magnetic phases of perovskite oxides by fine tuning of the level of covalence.npj Quantum Materials (2017) 2:21 ; doi:10.1038/s41535-017-0024-9 INTRODUCTIONTransition metal oxides with an AMO 3 perovskite structure have attracted widespread interest over the last decades, both from academic and application points of view. This can be ascribed to their wide range of functionalities that originates from the interplay between lattice, electronic, and magnetic degrees of freedom.1 Among all perovskites, rare-earth nickelates R 3+ Ni 3+ O 3 (R = Lu-La, Y) might be considered as a prototypical case because they posses almost all possible degrees of freedom present in these materials. Nickelates were intensively studied during the nineties 2, 3 and have regained interest in the last few years due to their great potential for engineering novel electronic and magnetic states.

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“…Another small peak is located at the higher binding energy of 531.0 eV. This peak can be assigned to the active oxygen species on nickel oxides [21] or the impurity of adsorbed species. For the stored sample, the O 1s peak at high binding energy becomes dominating and the peak at low binding energy almost disappears.…”

Section: Determination Of Composition/structure Changesmentioning

confidence: 98%

Investigation and improvement on the storage property of LiNi0.8Co0.2O2 as a cathode material for lithium-ion batteries

Liu

Yang

Zhang

2006

Journal of Power Sources

199

187

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Electronic State of Nickel in Barium Nickel Oxide, BaNiO₃

Cited by 61 publications

References 16 publications

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

Complete phase diagram of rare-earth nickelates from first-principles

Investigation and improvement on the storage property of LiNi0.8Co0.2O2 as a cathode material for lithium-ion batteries

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Electronic State of Nickel in Barium Nickel Oxide, BaNiO3

Cited by 61 publications

References 16 publications

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

Complete phase diagram of rare-earth nickelates from first-principles

Investigation and improvement on the storage property of LiNi0.8Co0.2O2 as a cathode material for lithium-ion batteries

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Electronic State of Nickel in Barium Nickel Oxide, BaNiO₃