Inductive Effect Of Nd For Ni3+ Stabilization In Ndnio3 Synthesized By Reactive Dc Cosputtering

JOURNAL OF PHYSICAL CHEMISTRY C(2017)

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摘要
This work focus on the oxidation states of nickel in NdNiO3, Nd2NiO4, and NiOx thin films deposited by reactive magnetron sputtering. Thin films with a high Ni3+ content have been reached in the ternary oxides using a soft subsequent annealing in air. In order to understand the presence of Ni3+ oxidation state, the present work establishes a comparative study between the NiOx and Nd-Ni-O-x thin films deposited at room temperature in reactive conditions using different oxygen partial pressures. Crystallographic phases have been systematically identified by X-ray diffraction showing crystallized NiOx and amorphous thin films in the case of Ni and Nd cosputtering. The ionization state of Ni ions has been tracked by X-ray photoelectron spectroscopy. Analyses confirm the presence of Ni2+ in NiOx films whereas Ni3+ is systematically observed in Nd-Ni-O-x films highlighting the key role of Nd element during the deposition. The electron donor character of Nd3+ on Ni3+ via O 2p states-by an inductive effect is clearly evidenced. This effect is strengthened by a strong difference in electronegativity between the rare earth (Re) and the transition metal (M). This concept is enlarged and faced with other ReMO3 perovskites, and their thermodynamic stability is discussed.
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