Title Mechanisms of Oxidation of NdNiO3-delta Thermochromic Thin Films Synthesized by a Two-Step Method in Soft Conditions
Authors Boileau, A. , Capon, F. , Laffez, P. , Barrat, S. , ENDRINO ARMENTEROS, JOSÉ LUIS, Escobar Galindo, R. , Horwat, D. , Pierson, J. F.
External publication Si
Means JOURNAL OF PHYSICAL CHEMISTRY C
Scope Article
Nature Científica
JCR Quartile 1
SJR Quartile 1
JCR Impact 4.772
SJR Impact 2.032
Web https://www.scopus.com/inward/record.uri?eid=2-s2.0-84897875555&doi=10.1021%2fjp4111597&partnerID=40&md5=53e44b2af539321238643e81b3e0242b
Publication date 20/03/2014
ISI 000333381300036
Scopus Id 2-s2.0-84897875555
DOI 10.1021/jp4111597
Abstract Considering it is somewhat difficult to crystallize thermochromic nickelates through a soft process, a major challenge in NdNiO3 crystallization is the stabilization of the Ni3+ oxidation state against Ni2+. The aim of the present work was to understand why a soft annealing is sufficient while an oxygen high pressure (200 bar) is usually considered as required. Thin films of 300 nm have been deposited by reactive magnetron sputtering at room temperature and working pressure of 0.5, 4, and 7 Pa. The oxygen content of as-deposited and annealed films was estimated by Rutherford backscattering spectrometry, whereas the nickel oxidation state evolution was followed by X-ray photoelectron spectroscopy. The measurements showed that the Ni3+ state is reached after deposition whatever the deposition pressure but that an oxygen loss occurs during air annealing with a magnitude depending on the deposition pressure. X-ray diffraction measurements, four-point probe electrical measurements, and infrared optical properties vs temperature were consistent with these results. Thin films deposited at 0.5 Pa and annealed in air at 820 K lead to an orthorhombic structure which becomes rhombohedral when the deposition pressure reaches 7 Pa. The oxygen was also evidenced by the loss causes a deterioration of the electrical resistivity, which thermochromic behavior measured using Fourier transform infrared spectroscopy.
Keywords Deposition pressures; Electrical measurement; Infrared optical properties; Orthorhombic structures; Reactive magnetron sputtering; Rutherford back-scattering spectrometry; Thermochromic behavior; X-ray diffraction measurements; Fourier transform infrared spectroscopy; Nickel; Oxygen; Photoelectrons; Rutherford backscattering spectroscopy; Thin films; X ray diffraction; X ray photoelectron spectroscopy; Deposition
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