首页|Correlated perovskite nickelates with valence variable rare-earth compositions
Correlated perovskite nickelates with valence variable rare-earth compositions
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While the metal to insulator transition(MIT)of d-band correlated perovskite nickelates(RENiO3)are widely adjustable via their rare-earth composition,the roles of potential valence variabilities associated with the rare-earth elements were rarely concerned.Herein,we demonstrate the material synthesis and MIT properties of RENiO3 containing valence variable rare-earth compositions,such as Ce,Pr,Sm,Eu and Tb.The metastable perovskite structure of SmNiO3 and EuNiO3 with a rare-earth valence states variable towards+2 can be effectively synthesized under high oxygen pressures as it is necessary to reduce their formation free energies.This is in contrast to Ce and Tb,in which situations the variable rare-earth valence state towards+4 reduces their ionic radius and prohibits their occupation or co-occupation of the rare-earth site within the perovskite structured RENiO3.Nevertheless,PrNiO3 with MIT properties can be effectively synthesized at lower oxygen pressures,owing to the higher stability to form a fully occupied 6s orbit associated Pr3+compared to the half-filled one related to Pr4+.The present work provides guidance for regulating the MIT properties of RENiO3.
Metal to insulator transitionMetastable perovskitesRare-earth nickelatesOxides
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