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Title: High-pressure preparation, crystal structure, magnetic properties, and phase transitions in GdNiO{sub 3} and DyNiO{sub 3} perovskites

Abstract

Strongly distorted RNiO{sub 3}(R = Gd, Dy) perovskites, containing Ni{sup 3+}, have been prepared under high-pressure conditions: 90 MPa of O{sub 2} pressure (R = Gd) or 2 GPa of hydrostatic pressure in the presence of KClO{sub 4} (R = Dy). These materials have been characterized by X-ray diffraction, neutron powder diffraction (NPD) (for DyNiO{sub 3}), DSC, magnetic measurements, and specific heat measurements. In contrast with the next member of the series, HoNiO{sub 3}, which shows a subtle monoclinic distortion at room temperature, DyNiO{sub 3} exhibits orthorhombic symmetry, as shown by NPD data. A noticeable distortion is observed in NiO{sub 6} octahedra, at variance with the almost regular octahedra exhibited by the first members (R = La, Pr, Nd) of the series: it is interpreted as a manifestation of the Jahn-Teller character of the Ni{sup 3+} cation, enhanced in the RNiO{sub 3} perovskites with heavier rare earths, showing weaker, less covalent Ni-O bonds. DSC measurements show sharp endothermic peaks at 510.9 K (Gd) and 564.1 K (Dy) in the heating run, which have been assigned to the corresponding metal-insulator transitions of both charge-transfer perovskites, based on the analogous behavior observed for the precedent members of the RNiO{sub 3} series. Subtlemore » slope variations in the susceptibility vs T curves, highly dominated by the strong paramagnetic signal of Gd{sub 3+} and Dy{sup 3+}, indicate the onset of antiferromagnetic ordering of the Ni{sup 3+} sublattice, confirmed by specific heat measurements, below T{sub N} values of 185 and 154 K, respectively. Additionally, the Dy{sup 3+} sublattice becomes ordered below 8 K.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
CSIC, Madrid (ES)
OSTI Identifier:
20001169
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 11; Journal Issue: 9; Other Information: PBD: Sep 1999; Journal ID: ISSN 0897-4756
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; PEROVSKITES; NICKEL OXIDES; GADOLINIUM OXIDES; DYSPROSIUM OXIDES; CRYSTAL STRUCTURE; MAGNETIC PROPERTIES; CRYSTAL-PHASE TRANSFORMATIONS

Citation Formats

Alonso, J.A., Martinez-Lope, M.J., Casais, M.T., Martinez, J.L., Demazeau, G., Largeteau, A., Garcia-Munoz, J.L., Munoz, A., and Fernandez-Diaz, M.T. High-pressure preparation, crystal structure, magnetic properties, and phase transitions in GdNiO{sub 3} and DyNiO{sub 3} perovskites. United States: N. p., 1999. Web. doi:10.1021/cm991033k.
Alonso, J.A., Martinez-Lope, M.J., Casais, M.T., Martinez, J.L., Demazeau, G., Largeteau, A., Garcia-Munoz, J.L., Munoz, A., & Fernandez-Diaz, M.T. High-pressure preparation, crystal structure, magnetic properties, and phase transitions in GdNiO{sub 3} and DyNiO{sub 3} perovskites. United States. doi:10.1021/cm991033k.
Alonso, J.A., Martinez-Lope, M.J., Casais, M.T., Martinez, J.L., Demazeau, G., Largeteau, A., Garcia-Munoz, J.L., Munoz, A., and Fernandez-Diaz, M.T. Wed . "High-pressure preparation, crystal structure, magnetic properties, and phase transitions in GdNiO{sub 3} and DyNiO{sub 3} perovskites". United States. doi:10.1021/cm991033k.
@article{osti_20001169,
title = {High-pressure preparation, crystal structure, magnetic properties, and phase transitions in GdNiO{sub 3} and DyNiO{sub 3} perovskites},
author = {Alonso, J.A. and Martinez-Lope, M.J. and Casais, M.T. and Martinez, J.L. and Demazeau, G. and Largeteau, A. and Garcia-Munoz, J.L. and Munoz, A. and Fernandez-Diaz, M.T.},
abstractNote = {Strongly distorted RNiO{sub 3}(R = Gd, Dy) perovskites, containing Ni{sup 3+}, have been prepared under high-pressure conditions: 90 MPa of O{sub 2} pressure (R = Gd) or 2 GPa of hydrostatic pressure in the presence of KClO{sub 4} (R = Dy). These materials have been characterized by X-ray diffraction, neutron powder diffraction (NPD) (for DyNiO{sub 3}), DSC, magnetic measurements, and specific heat measurements. In contrast with the next member of the series, HoNiO{sub 3}, which shows a subtle monoclinic distortion at room temperature, DyNiO{sub 3} exhibits orthorhombic symmetry, as shown by NPD data. A noticeable distortion is observed in NiO{sub 6} octahedra, at variance with the almost regular octahedra exhibited by the first members (R = La, Pr, Nd) of the series: it is interpreted as a manifestation of the Jahn-Teller character of the Ni{sup 3+} cation, enhanced in the RNiO{sub 3} perovskites with heavier rare earths, showing weaker, less covalent Ni-O bonds. DSC measurements show sharp endothermic peaks at 510.9 K (Gd) and 564.1 K (Dy) in the heating run, which have been assigned to the corresponding metal-insulator transitions of both charge-transfer perovskites, based on the analogous behavior observed for the precedent members of the RNiO{sub 3} series. Subtle slope variations in the susceptibility vs T curves, highly dominated by the strong paramagnetic signal of Gd{sub 3+} and Dy{sup 3+}, indicate the onset of antiferromagnetic ordering of the Ni{sup 3+} sublattice, confirmed by specific heat measurements, below T{sub N} values of 185 and 154 K, respectively. Additionally, the Dy{sup 3+} sublattice becomes ordered below 8 K.},
doi = {10.1021/cm991033k},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 9,
volume = 11,
place = {United States},
year = {1999},
month = {9}
}