The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

Morrow, Ryan; McGuire, Michael A.; Yan, Jiaqiang; Woodward, Patrick M.

doi:10.1021/acs.inorgchem.7b02282

Title: The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O ₆ (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

Journal Article · Fri Feb 23 00:00:00 EST 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b02282· OSTI ID:1427710

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The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Department of Materials Science and Engineering

In this work, six LaABB'O₆ (A = Ca, Sr; B = Co, Ni; B' = Ru, Os) double perovskites were synthesized, several for the first time, and their crystal structures and magnetic behavior were characterized with neutron powder diffraction and direct-current and alternating-current magnetometry. All six compounds crystallize with P2₁/n space group symmetry, resulting from a^–a^–c⁺ octahedral tilting and complete rock salt ordering of transition-metal ions. Despite the electronic configurations of the transition-metal ions, either d⁸–d³ or d⁷–d³, not one of the six compounds shows ferromagnetism as predicted by the Goodenough–Kanamori rules. LaSrNiOsO₆, LaSrNiRuO₆, and LaCaNiRuO₆ display long-range antiferromagnetic order, while LaCaNiOsO₆, LaCaCoOsO₆, and LaSrCoOsO₆ exhibit spin-glass behavior. These compounds are compared to the previously studied LaCaCoRuO₆ and LaSrCoRuO₆, both of which order antiferromagnetically. Lastly, the observed variations in magnetic properties can be attributed largely to the response of competing superexchange pathways due to changes in B–O–B' bond angles, differences in the radial extent of the 4d (B' = Ru) and 5d (B' = Os) orbitals, and filling of the t_2g orbitals of the 3d ion.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1427710

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 6; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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References (45)

Cation ordering in perovskites King, Graham; Woodward, Patrick M. Journal of Materials Chemistry, Vol. 20, Issue 28 https://doi.org/10.1039/b926757c	journal	January 2010
A2B′B″O6 perovskites: A review Vasala, Sami; Karppinen, Maarit Progress in Solid State Chemistry, Vol. 43, Issue 1-2 https://doi.org/10.1016/j.progsolidstchem.2014.08.001	journal	May 2015
Room-temperature magnetoresistance in an oxide material with an ordered double-perovskite structure Kobayashi, K. -I.; Kimura, T.; Sawada, H. Nature, Vol. 395, Issue 6703 https://doi.org/10.1038/27167	journal	October 1998
Multiferroic thin film of Bi2NiMnO6 with ordered double-perovskite structure Sakai, Maiko; Masuno, Atsunobu; Kan, Daisuke Applied Physics Letters, Vol. 90, Issue 7 https://doi.org/10.1063/1.2539575	journal	February 2007
Erratum: ${Sr}_{2} Cr Os O_{6}$ : End point of a spin-polarized metal-insulator transition by $5 d$ band filling [Phys. Rev. B 75 , 020404(R) (2007)] Krockenberger, Y.; Mogare, K.; Reehuis, M. Physical Review B, Vol. 75, Issue 17 https://doi.org/10.1103/PhysRevB.75.179901	journal	May 2007
The effect of chemical pressure on the structure and properties of A2CrOsO6 (A=Sr, Ca) ferrimagnetic double perovskite Morrow, Ryan; Soliz, Jennifer R.; Hauser, Adam J. Journal of Solid State Chemistry, Vol. 238 https://doi.org/10.1016/j.jssc.2016.02.025	journal	June 2016
Metallic ordered double-perovskite Sr2CrReO6 with maximal Curie temperature of 635 K Kato, H.; Okuda, T.; Okimoto, Y. Applied Physics Letters, Vol. 81, Issue 2 https://doi.org/10.1063/1.1493646	journal	July 2002
Theory of the Role of Covalence in the Perovskite-Type Manganites $[La, M (II)] Mn O_{3}$ Goodenough, John B. Physical Review, Vol. 100, Issue 2 https://doi.org/10.1103/PhysRev.100.564	journal	October 1955
Superexchange interaction and symmetry properties of electron orbitals Kanamori, Junjiro Journal of Physics and Chemistry of Solids, Vol. 10, Issue 2-3 https://doi.org/10.1016/0022-3697(59)90061-7	journal	July 1959
Magnetic structures of fcc systems with nearest-neighbor and next-nearest-neighbor exchange interactions Seehra, Mohindar S.; Giebultowicz, T. M. Physical Review B, Vol. 38, Issue 16 https://doi.org/10.1103/PhysRevB.38.11898	journal	December 1988
Matrix elements of four-quark operators relevant to life time difference $\Delta \Gamma _{B_s}$ from QCD sum rules Huang, C. -S.; Zhang, Ailin; Zhu, S. -L. The European Physical Journal C, Vol. 21, Issue 2 https://doi.org/10.1007/s100520100724	journal	June 2001
The crystal structures and magnetic properties of Ba2LaRuO6 and Ca2LaRuO6 Battle, P. D.; Goodenough, J. B.; Price, R. Journal of Solid State Chemistry, Vol. 46, Issue 2 https://doi.org/10.1016/0022-4596(83)90147-0	journal	February 1983
Spin-orbit coupling controlled ground state in ${Sr}_{2} {ScOsO}_{6}$ Taylor, A. E.; Morrow, R.; Fishman, R. S. Physical Review B, Vol. 93, Issue 22 https://doi.org/10.1103/PhysRevB.93.220408	journal	June 2016
Spin-orbit coupling control of anisotropy, ground state and frustration in 5d2 Sr2MgOsO6 Morrow, Ryan; Taylor, Alice E.; Singh, D. J. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep32462	journal	August 2016
Magnetic order and electronic structure of the $5 d^{3}$ double perovskite ${Sr}_{2} {ScOsO}_{6}$ Taylor, A. E.; Morrow, R.; Singh, D. J. Physical Review B, Vol. 91, Issue 10 https://doi.org/10.1103/PhysRevB.91.100406	journal	March 2015
Structure and Magnetic Properties of Sr ₂ CoWO ₆ : An Ordered Double Perovskite Containing Co ²⁺ (HS) with Unquenched Orbital Magnetic Moment Viola, M. C.; Martínez-Lope, M. J.; Alonso, J. A. Chemistry of Materials, Vol. 15, Issue 8 https://doi.org/10.1021/cm0208455	journal	April 2003
Synthesis, Crystal and Magnetic Structure of the Double Perovskites A2NiMoO6 (A = Sr, Ba): A Neutron Diffraction Study Martínez-Lope, María J.; Alonso, José A.; Casais, María T. European Journal of Inorganic Chemistry, Vol. 2003, Issue 15 https://doi.org/10.1002/ejic.200300063	journal	August 2003
Oxygen stoichiometry, ferromagnetism, and transport properties of ${La}_{2 - x} {NiMnO}_{6 + δ}$ Dass, R. I.; Yan, J. -Q.; Goodenough, J. B. Physical Review B, Vol. 68, Issue 6 https://doi.org/10.1103/PhysRevB.68.064415	journal	August 2003
Magnetocapacitance and Magnetoresistance Near Room Temperature in a Ferromagnetic Semiconductor: La2NiMnO6 Rogado, N. S.; Li, J.; Sleight, A. W. Advanced Materials, Vol. 17, Issue 18 https://doi.org/10.1002/adma.200500737	journal	September 2005
Designed Ferromagnetic, Ferroelectric Bi ₂ NiMnO ₆ Azuma, Masaki; Takata, Kazuhide; Saito, Takashi Journal of the American Chemical Society, Vol. 127, Issue 24 https://doi.org/10.1021/ja0512576	journal	June 2005
Composition-controlled metal-insulator transitions and minimum metallic conductivity in the oxide systems LaNi1−xMxO3 (M = Cr, Mn, Fe, or Co) Ganguly, P.; Vasanthacharya, N. Y.; Rao, C. N. R. Journal of Solid State Chemistry, Vol. 54, Issue 3 https://doi.org/10.1016/0022-4596(84)90171-3	journal	October 1984
Magnetism in Ca ₂ CoOsO ₆ and Ca ₂ NiOsO ₆ : Unraveling the Mystery of Superexchange Interactions between 3d and 5d Ions Morrow, Ryan; Samanta, Kartik; Saha Dasgupta, Tanusri Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.6b00254	journal	May 2016
Lattice Instability and Competing Spin Structures in the Double Perovskite Insulator ${Sr}_{2} {FeOsO}_{6}$ Paul, Avijit Kumar; Reehuis, Manfred; Ksenofontov, Vadim Physical Review Letters, Vol. 111, Issue 16 https://doi.org/10.1103/PhysRevLett.111.167205	journal	October 2013
Independent Ordering of Two Interpenetrating Magnetic Sublattices in the Double Perovskite Sr ₂ CoOsO ₆ Morrow, Ryan; Mishra, Rohan; Restrepo, Oscar D. Journal of the American Chemical Society, Vol. 135, Issue 50 https://doi.org/10.1021/ja407342w	journal	December 2013
Lattice-Site-Specific Spin Dynamics in Double Perovskite ${Sr}_{2} {CoOsO}_{6}$ Yan, Binghai; Paul, Avijit Kumar; Kanungo, Sudipta Physical Review Letters, Vol. 112, Issue 14 https://doi.org/10.1103/PhysRevLett.112.147202	journal	April 2014
Probing the Links between Structure and Magnetism in Sr _{2– x} Ca _x FeOsO ₆ Double Perovskites Morrow, Ryan; Freeland, John W.; Woodward, Patrick M. Inorganic Chemistry, Vol. 53, Issue 15 https://doi.org/10.1021/ic5006715	journal	July 2014
High-Temperature Ferrimagnetism Driven by Lattice Distortion in Double Perovskite Ca ₂ FeOsO ₆ Feng, Hai L.; Arai, Masao; Matsushita, Yoshitaka Journal of the American Chemical Society, Vol. 136, Issue 9 https://doi.org/10.1021/ja411713q	journal	February 2014
Effects of chemical pressure on the magnetic ground states of the osmate double perovskites $SrCaCoOs O_{6}$ and $C a_{2} CoOs O_{6}$ Morrow, Ryan; Yan, Jiaqiang; McGuire, Michael A. Physical Review B, Vol. 92, Issue 9 https://doi.org/10.1103/PhysRevB.92.094435	journal	September 2015
Structural, Magnetic, and Transport Properties of (La ₁₊ _x Sr _1- _x )CoRuO ₆ Double Perovskites Bos, Jan-Willem G.; Attfield, J. Paul Chemistry of Materials, Vol. 16, Issue 9 https://doi.org/10.1021/cm0497733	journal	May 2004
Control of antisite disorder, magnetism, and asymmetric doping effects in (La1+xCa1-x)CoRuO6 double perovskites Bos, Jan-Willem; Attfield, J. Physical Review B, Vol. 69, Issue 9 https://doi.org/10.1103/PhysRevB.69.094434	journal	March 2004
Powgen: A third-generation highresolution high-throughput powder diffraction instrument at the Spallation Neutron Source Huq, A.; Hodges, J. P.; Gourdon, O. European Powder Diffraction Conference; August 2010, Darmstadt, Germany https://doi.org/10.1524/9783486991321-024	book	December 2011
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
A new protocol for the determination of magnetic structures using simulated annealing and representational analysis (SARAh) Wills, A. S. Physica B: Condensed Matter, Vol. 276-278 https://doi.org/10.1016/S0921-4526(99)01722-6	journal	March 2000
Structure determination of A ₂ M ³⁺ TaO ₆ and A ₂ M ³⁺ NbO ₆ ordered perovskites: octahedral tilting and pseudosymmetry Barnes, Paris W.; Lufaso, Michael W.; Woodward, Patrick M. Acta Crystallographica Section B Structural Science, Vol. 62, Issue 3 https://doi.org/10.1107/S0108768106002448	journal	May 2006
Structure prediction of ordered and disordered multiple octahedral cation perovskites using SPuDS Lufaso, Michael W.; Barnes, Paris W.; Woodward, Patrick M. Acta Crystallographica Section B Structural Science, Vol. 62, Issue 3 https://doi.org/10.1107/S010876810600262X	journal	May 2006
Bond-valence parameters for solids Brese, N. E.; O'Keeffe, M. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2 https://doi.org/10.1107/S0108768190011041	journal	April 1991
Synthesis, Structure, and Magnetic Properties of Sr₂NiOsO₆ and Ca₂NiOsO₆: Two New Osmium-Containing Double Perovskites Macquart, René; Kim, Seung-Joo; Gemmill, William R. Inorganic Chemistry, Vol. 44, Issue 26 https://doi.org/10.1021/ic051045+	journal	November 2005
Magnetic properties of the $S = \frac{3}{2}$ geometrically frustrated double perovskites ${La}_{2} {LiRuO}_{6}$ and ${Ba}_{2} {YRuO}_{6}$ Aharen, Tomoko; Greedan, John E.; Ning, Fanlong Physical Review B, Vol. 80, Issue 13 https://doi.org/10.1103/PhysRevB.80.134423	journal	October 2009
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Die Gesetze der Krystallochemie Goldschmidt, V. M. Die Naturwissenschaften, Vol. 14, Issue 21 https://doi.org/10.1007/BF01507527	journal	May 1926
Synthesis, Crystal Structure, and Properties of the Ordered Double Perovskite Sr ₂ CoOsO ₆ : Ordered Double Perovskite Sr Kumar Paul, Avijit; Reehuis, Manfred; Felser, Claudia Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 14 https://doi.org/10.1002/zaac.201300429	journal	September 2013
Synthesis, crystal structures, and magnetic properties of double perovskites SrLaNiOsO6 and BaLaNiOsO6 Feng, Hai L.; Schnelle, Walter; Tjeng, Liu Hao Solid State Communications, Vol. 243 https://doi.org/10.1016/j.ssc.2016.06.008	journal	October 2016
$B a_{2} NiOs O_{6}$ : A Dirac-Mott insulator with ferromagnetism near 100 K Feng, Hai L.; Calder, Stuart; Ghimire, Madhav Prasad Physical Review B, Vol. 94, Issue 23 https://doi.org/10.1103/PhysRevB.94.235158	journal	December 2016
Synthesis, structure, and magnetic properties of novel B-site ordered double perovskites, SrLaMReO ₆ (M = Mg, Mn, Co and Ni) Thompson, Corey M.; Chi, Lisheng; Hayes, John R. Dalton Transactions, Vol. 44, Issue 23 https://doi.org/10.1039/C4DT03821E	journal	January 2015
‘A’ cation control of perovskite properties Attfield, J. P. Crystal Engineering, Vol. 5, Issue 3-4 https://doi.org/10.1016/S1463-0184(02)00054-0	journal	September 2002

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Title: The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

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