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Title: Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure

Abstract

We report the synthesis, structural investigation, and magnetic property studies of Sr1.31Co0.63Mn0.37O3 that adopts an incommensurate composite hexagonal perovskite-related structure. The crystal structure has been solved using a (3 + 1)-dimensional superspace approach from powder X-ray and neutron diffraction data (SSG Rm(00 )0s, a = 9.5548(1) Angstroms, c = 2.5599(1) Angstroms, q = 0.65581(4)c*, RB = 0.041, RP = 0.059). The structure consists of face-sharing chains of octahedra and trigonal prisms, wherein the trigonal prismatic sites are preferentially occupied by Co with some cation disorder. A combination of electron diffraction and high-resolution electron microscopic analysis has demonstrated that the compound possesses a complicated microstructure related to the formation of domains with slightly different lengths of the modulation vector. X-ray absorption near-edge spectroscopic (XAS) studies clearly indicate the presence of Mn in the 4+ and Co in the 3+ oxidation state. While the magnetic susceptibility data indicates the presence of antiferromagnetic correlations in the system, the calculation of effective paramagnetic moment ({mu}cal = 3.561 {mu}B), assuming the metal oxidation states as obtained from XAS and the cation distribution as obtained from neutron refinement, is in agreement with the value obtained experimentally ({mu}exp = 3.676 {mu}B).

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
959649
Report Number(s):
BNL-82635-2009-JA
Journal ID: ISSN 0897-4756; CMATEX; TRN: US201016%%793
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 19
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION; CATIONS; CHAINS; CRYSTAL STRUCTURE; DISTRIBUTION; ELECTRON DIFFRACTION; ELECTRONS; MAGNETIC PROPERTIES; MAGNETIC SUSCEPTIBILITY; MICROSTRUCTURE; MODULATION; NEUTRON DIFFRACTION; NEUTRONS; PEROVSKITE; PRISMS; RUTHERFORD BACKSCATTERING SPECTROSCOPY; SYNTHESIS; VALENCE; national synchrotron light source

Citation Formats

Mandal,T., Abakumov, A., Hadermann, J., Van Tendeloo, G., Croft, M., and Greenblatt, M. Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure. United States: N. p., 2007. Web. doi:10.1021/cm071840g.
Mandal,T., Abakumov, A., Hadermann, J., Van Tendeloo, G., Croft, M., & Greenblatt, M. Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure. United States. doi:10.1021/cm071840g.
Mandal,T., Abakumov, A., Hadermann, J., Van Tendeloo, G., Croft, M., and Greenblatt, M. Mon . "Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure". United States. doi:10.1021/cm071840g.
@article{osti_959649,
title = {Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure},
author = {Mandal,T. and Abakumov, A. and Hadermann, J. and Van Tendeloo, G. and Croft, M. and Greenblatt, M.},
abstractNote = {We report the synthesis, structural investigation, and magnetic property studies of Sr1.31Co0.63Mn0.37O3 that adopts an incommensurate composite hexagonal perovskite-related structure. The crystal structure has been solved using a (3 + 1)-dimensional superspace approach from powder X-ray and neutron diffraction data (SSG Rm(00 )0s, a = 9.5548(1) Angstroms, c = 2.5599(1) Angstroms, q = 0.65581(4)c*, RB = 0.041, RP = 0.059). The structure consists of face-sharing chains of octahedra and trigonal prisms, wherein the trigonal prismatic sites are preferentially occupied by Co with some cation disorder. A combination of electron diffraction and high-resolution electron microscopic analysis has demonstrated that the compound possesses a complicated microstructure related to the formation of domains with slightly different lengths of the modulation vector. X-ray absorption near-edge spectroscopic (XAS) studies clearly indicate the presence of Mn in the 4+ and Co in the 3+ oxidation state. While the magnetic susceptibility data indicates the presence of antiferromagnetic correlations in the system, the calculation of effective paramagnetic moment ({mu}cal = 3.561 {mu}B), assuming the metal oxidation states as obtained from XAS and the cation distribution as obtained from neutron refinement, is in agreement with the value obtained experimentally ({mu}exp = 3.676 {mu}B).},
doi = {10.1021/cm071840g},
journal = {Chemistry of Materials},
number = ,
volume = 19,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The authors report a new structure determination of the Sr{sub 1.2872}NiO{sub 3} incommensurate composite hexagonal perovskite compound. Three different refinement strategies are presented: (1) a 3D supercell approximation with a nonharmonic development of the atomic displacement factor, (2) an original (3+1)D incommensurate composite description with the use of crenel functions, and (3) a (3+1)D commensurate composite model. The three strategies are discussed and compared to previous refinements carried out for the hexagonal perovskites in a classical way or with the superspace group formalism. Out of the three methods, the incommensurate composite approach gives slightly better results with a final globalmore » R value of 2.89% for 635 independent reflections and only 60 parameters (R{bar 3}m(00{gamma})Os) superspace group. The use of crenel functions notably improves previously reported results. New structural features are evidenced for Sr{sub 1.2872}NiO{sub 3}: (1) an incommensurate character, (2) a splitting of the trigonal prismatic nickel atoms over 5 positions, (3) a definite stoichiometry which induces a perfect charge balance, and (4) a nonharmonic behavior of some Sr atoms. Those characteristics seem general to most hexagonal perovskite compounds and essential for correctly interpreting their interesting magnetic properties. Finally, a new generic formulation is proposed, which explains the various stoichiometries observed and suggests a new compound possibility.« less
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