skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis, structure, and properties of the layered perovskite La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]

Abstract

Single-phase samples of La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]] with [sigma] = 0, 0.08, and 0.65 were prepared and characterized by powder X-ray diffraction, TGA, electrical resistivity, and magnetic susceptibility. The crystal symmetry of the as-prepared ([sigma] = 0.08) and oxygenated ([sigma] = 0.00) samples is orthorhombic (space group Fmmm). Oxidation of the as-prepared La[sub 3]Ni[sub 2]O[sub 6.92] sample to La[sub 3]Ni[sub 2]O[sub 7.00] shows little change in the unit-cell parameters. Reduction of La[sub 3]Ni[sub 2]O[sub 6.92] to La[sub 3]Ni[sub 2]O[sub 6.35] results in a structural phase transition from orthorhombic to tetragonal symmetry, a dramatic decrease in the c cell parameter, and significant increase in the a and b cell parameters. These data are consistent with loss of oxygen from the apical octahedral sites connecting two perovskite layers in La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]. The electrical transport properties change with decreasing oxygen content from metallic for La[sub 3]Ni[sub 2]O[sub 7.00] to semiconducting for La[sub 3]Ni[sub 2]O[sub 6.92] and La[sub 3]Ni[sub 2]O[sub 6.35]. The fully reduced sample, La[sub 3]Ni[sub 2]O[sub 6.35], shows a linear dependence of ln [rho] versus T[sup [minus]1/4] in the temperature range 90-140 K, suggesting a variable-range hopping mechanism. A nearly temperature-independent magnetic susceptibility is observed in the temperature range 100-300more » K for the [sigma] = 0 and 0.08 samples. The relatively high values and the temperature dependence of the magnetic susceptibility indicate a Stoner enhanced Pauli paramagnetism for [sigma] = 0 and evidence for a weak ferromagnetism in the [sigma] = 0.65 sample. The electrical and magnetic properties of La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]] are discussed in terms of the mixed-valent character of nickel and vacancy-induced localization effects.« less

Authors:
; ;  [1]
  1. State Univ. of New Jersey, Piscataway, NJ (United States) Univ. of Texas, Austin, TX (United States)
Publication Date:
OSTI Identifier:
5114849
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry; (United States)
Additional Journal Information:
Journal Volume: 108:2; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; LANTHANUM OXIDES; CRYSTAL STRUCTURE; PHYSICAL PROPERTIES; NICKEL OXIDES; ELECTRIC CONDUCTIVITY; LATTICE PARAMETERS; ORTHORHOMBIC LATTICES; PEROVSKITES; PHASE TRANSFORMATIONS; SEMICONDUCTOR MATERIALS; STOICHIOMETRY; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0065-0273 K; TEMPERATURE RANGE 0273-0400 K; TETRAGONAL LATTICES; THERMAL GRAVIMETRIC ANALYSIS; CHALCOGENIDES; CHEMICAL ANALYSIS; CRYSTAL LATTICES; ELECTRICAL PROPERTIES; GRAVIMETRIC ANALYSIS; LANTHANUM COMPOUNDS; MATERIALS; NICKEL COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; QUANTITATIVE CHEMICAL ANALYSIS; RARE EARTH COMPOUNDS; TEMPERATURE RANGE; THERMAL ANALYSIS; TRANSITION ELEMENT COMPOUNDS; 360202* - Ceramics, Cermets, & Refractories- Structure & Phase Studies; 360204 - Ceramics, Cermets, & Refractories- Physical Properties

Citation Formats

Zhang, Z, Greenblatt, M, and Goodenough, J B. Synthesis, structure, and properties of the layered perovskite La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]. United States: N. p., 1994. Web. doi:10.1006/jssc.1994.1059.
Zhang, Z, Greenblatt, M, & Goodenough, J B. Synthesis, structure, and properties of the layered perovskite La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]. United States. https://doi.org/10.1006/jssc.1994.1059
Zhang, Z, Greenblatt, M, and Goodenough, J B. Tue . "Synthesis, structure, and properties of the layered perovskite La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]". United States. https://doi.org/10.1006/jssc.1994.1059.
@article{osti_5114849,
title = {Synthesis, structure, and properties of the layered perovskite La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]},
author = {Zhang, Z and Greenblatt, M and Goodenough, J B},
abstractNote = {Single-phase samples of La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]] with [sigma] = 0, 0.08, and 0.65 were prepared and characterized by powder X-ray diffraction, TGA, electrical resistivity, and magnetic susceptibility. The crystal symmetry of the as-prepared ([sigma] = 0.08) and oxygenated ([sigma] = 0.00) samples is orthorhombic (space group Fmmm). Oxidation of the as-prepared La[sub 3]Ni[sub 2]O[sub 6.92] sample to La[sub 3]Ni[sub 2]O[sub 7.00] shows little change in the unit-cell parameters. Reduction of La[sub 3]Ni[sub 2]O[sub 6.92] to La[sub 3]Ni[sub 2]O[sub 6.35] results in a structural phase transition from orthorhombic to tetragonal symmetry, a dramatic decrease in the c cell parameter, and significant increase in the a and b cell parameters. These data are consistent with loss of oxygen from the apical octahedral sites connecting two perovskite layers in La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]]. The electrical transport properties change with decreasing oxygen content from metallic for La[sub 3]Ni[sub 2]O[sub 7.00] to semiconducting for La[sub 3]Ni[sub 2]O[sub 6.92] and La[sub 3]Ni[sub 2]O[sub 6.35]. The fully reduced sample, La[sub 3]Ni[sub 2]O[sub 6.35], shows a linear dependence of ln [rho] versus T[sup [minus]1/4] in the temperature range 90-140 K, suggesting a variable-range hopping mechanism. A nearly temperature-independent magnetic susceptibility is observed in the temperature range 100-300 K for the [sigma] = 0 and 0.08 samples. The relatively high values and the temperature dependence of the magnetic susceptibility indicate a Stoner enhanced Pauli paramagnetism for [sigma] = 0 and evidence for a weak ferromagnetism in the [sigma] = 0.65 sample. The electrical and magnetic properties of La[sub 3]Ni[sub 2]O[sub 7[minus][sigma]] are discussed in terms of the mixed-valent character of nickel and vacancy-induced localization effects.},
doi = {10.1006/jssc.1994.1059},
url = {https://www.osti.gov/biblio/5114849}, journal = {Journal of Solid State Chemistry; (United States)},
issn = {0022-4596},
number = ,
volume = 108:2,
place = {United States},
year = {1994},
month = {2}
}