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Title: New Mechanism for Ferroelectricity in the Perovskite Ca 2–x Mn x Ti 2 O 6 Synthesized by Spark Plasma Sintering

Abstract

Perovskite oxides hosting ferroelectricity are particularly important materials for modern technologies. The ferroelectric transition in the well-known oxides BaTiO3 and PbTiO3 is realized by softening of a vibration mode in the cubic perovskite structure. For most perovskite oxides, octahedral-site tilting systems are developed to accommodate the bonding mismatch due to a geometric tolerance factor t = (A–O)/[√2(B–O)] < 1. In the absence of cations having lone-pair electrons, e.g., Bi3+ and Pb2+, all simple and complex A-site and B-site ordered perovskite oxides with a t < 1 show a variety of tilting systems, and none of them become ferroelectric. The ferroelectric CaMnTi2O6 oxide is, up to now, the only one that breaks this rule. It exhibits a columnar A-site ordering with a pronounced octahedral-site tilting and yet becomes ferroelectric at Tc ≈ 650 K. Most importantly, the ferroelectricity at T < Tc is caused by an order–disorder transition instead of a displacive transition; this character may be useful to overcome the critical thickness problem experienced in all proper ferroelectrics. Application of this new ferroelectric material can greatly simplify the structure of microelectronic devices. However, CaMnTi2O6 is a high-pressure phase obtained at 7 GPa and 1200 °C, which limits its application. Heremore » we report a new method to synthesize a gram-level sample of ferroelectric Ca2–xMnxTi2O6, having the same crystal structure as CaMnTi2O6 and a similarly high Curie temperature. The new finding paves the way for the mass production of this important ferroelectric oxide. In conclusion, we have used neutron powder diffraction to identify the origin of the peculiar ferroelectric transition in this double perovskite and to reveal the interplay between magnetic ordering and the ferroelectric displacement at low temperatures.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [7];  [2]; ORCiD logo [8]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Texas, Austin, TX (United States). Material Science and Engineering Program, Mechanical Engineering
  2. Univ. of Texas, Austin, TX (United States). Dept. of Physics
  3. Tokyo Univ. of Science, Chiba (Japan). Dept. of Pure and Applied Chemistry, Faculty of Science and Technology
  4. Gakushuin Univ., Tokyo (Japan). Dept. of Chemistry, Faculty of Science
  5. Spanish National Research Council (CSIC), Madrid (Spain). Inst. of Materials Science of Madrid
  6. Inst. Laue-Langevin (ILL),Grenoble (France)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  8. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461940
Grant/Contract Number:  
AC05-00OR22725; F-1066; F-1841; F-1038
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 6; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Zongyao, Cho, Yujin, Li, Xiang, Li, Xinyu, Aimi, Akihisa, Inaguma, Yoshiyuki, Alonso, Jose A., Fernandez-Diaz, Maria T., Yan, Jiaqiang, Downer, Michael C., Henkelman, Graeme, Goodenough, John B., and Zhou, Jianshi. New Mechanism for Ferroelectricity in the Perovskite Ca 2–x Mn x Ti 2 O 6 Synthesized by Spark Plasma Sintering. United States: N. p., 2018. Web. doi:10.1021/jacs.7b11219.
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Li, Zongyao, Cho, Yujin, Li, Xiang, Li, Xinyu, Aimi, Akihisa, Inaguma, Yoshiyuki, Alonso, Jose A., Fernandez-Diaz, Maria T., Yan, Jiaqiang, Downer, Michael C., Henkelman, Graeme, Goodenough, John B., & Zhou, Jianshi. New Mechanism for Ferroelectricity in the Perovskite Ca 2–x Mn x Ti 2 O 6 Synthesized by Spark Plasma Sintering. United States. https://doi.org/10.1021/jacs.7b11219
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Li, Zongyao, Cho, Yujin, Li, Xiang, Li, Xinyu, Aimi, Akihisa, Inaguma, Yoshiyuki, Alonso, Jose A., Fernandez-Diaz, Maria T., Yan, Jiaqiang, Downer, Michael C., Henkelman, Graeme, Goodenough, John B., and Zhou, Jianshi. Mon . "New Mechanism for Ferroelectricity in the Perovskite Ca 2–x Mn x Ti 2 O 6 Synthesized by Spark Plasma Sintering". United States. https://doi.org/10.1021/jacs.7b11219. https://www.osti.gov/servlets/purl/1461940.
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@article{osti_1461940,
title = {New Mechanism for Ferroelectricity in the Perovskite Ca 2–x Mn x Ti 2 O 6 Synthesized by Spark Plasma Sintering},
author = {Li, Zongyao and Cho, Yujin and Li, Xiang and Li, Xinyu and Aimi, Akihisa and Inaguma, Yoshiyuki and Alonso, Jose A. and Fernandez-Diaz, Maria T. and Yan, Jiaqiang and Downer, Michael C. and Henkelman, Graeme and Goodenough, John B. and Zhou, Jianshi},
abstractNote = {Perovskite oxides hosting ferroelectricity are particularly important materials for modern technologies. The ferroelectric transition in the well-known oxides BaTiO3 and PbTiO3 is realized by softening of a vibration mode in the cubic perovskite structure. For most perovskite oxides, octahedral-site tilting systems are developed to accommodate the bonding mismatch due to a geometric tolerance factor t = (A–O)/[√2(B–O)] < 1. In the absence of cations having lone-pair electrons, e.g., Bi3+ and Pb2+, all simple and complex A-site and B-site ordered perovskite oxides with a t < 1 show a variety of tilting systems, and none of them become ferroelectric. The ferroelectric CaMnTi2O6 oxide is, up to now, the only one that breaks this rule. It exhibits a columnar A-site ordering with a pronounced octahedral-site tilting and yet becomes ferroelectric at Tc ≈ 650 K. Most importantly, the ferroelectricity at T < Tc is caused by an order–disorder transition instead of a displacive transition; this character may be useful to overcome the critical thickness problem experienced in all proper ferroelectrics. Application of this new ferroelectric material can greatly simplify the structure of microelectronic devices. However, CaMnTi2O6 is a high-pressure phase obtained at 7 GPa and 1200 °C, which limits its application. Here we report a new method to synthesize a gram-level sample of ferroelectric Ca2–xMnxTi2O6, having the same crystal structure as CaMnTi2O6 and a similarly high Curie temperature. The new finding paves the way for the mass production of this important ferroelectric oxide. In conclusion, we have used neutron powder diffraction to identify the origin of the peculiar ferroelectric transition in this double perovskite and to reveal the interplay between magnetic ordering and the ferroelectric displacement at low temperatures.},
doi = {10.1021/jacs.7b11219},
journal = {Journal of the American Chemical Society},
number = 6,
volume = 140,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2018},
month = {Mon Jan 15 00:00:00 EST 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.7b11219
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Cited by: 23 works
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Figures / Tables:

Fig. 1 Fig. 1: The structural models of (a) non-polar and (b) polar CaMnTi2O6. Like the simple perovskite, the framework of double perovskite structure consists of corner-shared TiO6 octahedra. The columnar ordering means that the A-site Ca are ordered in columns along the c axis, which are surrounded by the Mn columns.more » The space group of the non-polardouble perovskite allows that Mn2+ at the coplanar sites shift out of the plane and the shifting direction is random between the Mn sites. The polar double perovskite structure is different from the non-polar one by (i) all Mn2+ at coplanar sites are ordered with the same shifting direction along the c axis, as can be observed in the structural mode (b); (ii) Ti4+ cations shift from the center of the octahedral sites and the Ti-O bond length splitting is enhanced dramatically; (iii) Mn2+ cations at tetrahedral-sites also shift from center of the tetrahedra, but the shifting direction is temperature dependent. Arrows in (b) indicate the direction of atomic displacement.« less
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Works referenced in this record:

Isotope Effect on the Ferroelectric Phase Transitions in BaTiO 3, SrTiO 3 and PbTiO 3
journal, January 2003

Theory of ferroelectric phase transition in SrTiO 3 induced by isotope replacement
journal, January 2004

Why Are There so Few Magnetic Ferroelectrics?
journal, July 2000

  • Hill, Nicola A.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 29
  • DOI: 10.1021/jp000114x

Why Are There So Few Perovskite Ferroelectrics?
journal, May 2013

  • Benedek, Nicole A.; Fennie, Craig J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 26
  • DOI: 10.1021/jp402046t

A -site-driven ferroelectricity in strained ferromagnetic La 2 NiMnO 6 thin films
journal, April 2015

Polar metals by geometric design
journal, April 2016

A-site cation ordering in AA′BB′O6 perovskites
journal, April 2006

Cation ordering in perovskites
journal, January 2010

  • King, Graham; Woodward, Patrick M.
  • Journal of Materials Chemistry, Vol. 20, Issue 28
  • DOI: 10.1039/b926757c

A-Site-Ordered Perovskites with Intriguing Physical Properties
journal, October 2008

Synthesis and Characterization of New AA ′ B WO 6 Perovskites Exhibiting Simultaneous Ordering of A -Site and B -Site Cations
journal, December 2007

  • King, Graham; Thimmaiah, Srinivasa; Dwivedi, Akansha
  • Chemistry of Materials, Vol. 19, Issue 26
  • DOI: 10.1021/cm0716708

Large ferroelectric polarization in the new double perovskite NaLaMnWO6 induced by non-polar instabilities
journal, January 2011

  • Fukushima, T.; Stroppa, A.; Picozzi, S.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 26
  • DOI: 10.1039/c1cp20626e

High-Pressure Synthesis and Crystal Structure of CaFeTi2O6, a New Perovskite Structure Type
journal, January 1995

  • Leinenweber, Kurt; Parise, John
  • Journal of Solid State Chemistry, Vol. 114, Issue 1
  • DOI: 10.1006/jssc.1995.1040

Hybrid Improper Ferroelectricity: A Mechanism for Controllable Polarization-Magnetization Coupling
journal, March 2011

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993

Projector augmented-wave method
journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

New Ferrimagnetic Oxide CaCu 3 Cr 2 Sb 2 O 12 :  High-Pressure Synthesis, Structure, and Magnetic Properties
journal, June 2005

  • Byeon, Song-Ho; Lee, Seoung-Soo; Parise, John B.
  • Chemistry of Materials, Vol. 17, Issue 13
  • DOI: 10.1021/cm050397b

New Perovskite Oxide CaCu 3 Cr 2 Ru 2 O 12 :  Comparison with Structural, Magnetic, and Transport Properties of the CaCu 3 B 2 B‘ 2 O 12 Perovskite Family
journal, August 2006

  • Byeon, Song-Ho; Lee, Seoung-Soo; Parise, John B.
  • Chemistry of Materials, Vol. 18, Issue 16
  • DOI: 10.1021/cm060835u

High-Pressure Synthesis and Characterization of Perovskites with Simultaneous Ordering of Both the A- and B-Site Cations, CaCu 3 Ga 2 M 2 O 12 (M = Sb, Ta)
journal, October 2003

  • Byeon, Song-Ho; Lufaso, Michael W.; Parise, John B.
  • Chemistry of Materials, Vol. 15, Issue 20
  • DOI: 10.1021/cm034318c

High-Pressure Synthesis of Metallic Perovskite Ruthenate CaCu 3 Ga 2 Ru 2 O 12
journal, September 2004

  • Byeon, Song-Ho; Lee, Seoung-Soo; Parise, John B.
  • Chemistry of Materials, Vol. 16, Issue 19
  • DOI: 10.1021/cm049265t

Frustration relieved ferrimagnetism in novel A- and B-site-ordered quadruple perovskite
journal, January 2013

  • Chen, Wei-tin; Mizumaki, Masaichiro; Saito, Takashi
  • Dalton Transactions, Vol. 42, Issue 28
  • DOI: 10.1039/c3dt50489a

New Routes to Synthesizing an Ordered Perovskite CaCu 3 Fe 2 Sb 2 O 12 and Its Magnetic Structure by Neutron Powder Diffraction
journal, April 2014

  • Larregola, Sebastian A.; Zhou, Jianshi; Alonso, Jose A.
  • Inorganic Chemistry, Vol. 53, Issue 9
  • DOI: 10.1021/ic500458m

New Technique for Measuring Ferroelectric and Antiferroelectric Hysteresis Loops
journal, June 2008

  • Fukunaga, Mamoru; Noda, Yukio
  • Journal of the Physical Society of Japan, Vol. 77, Issue 6
  • DOI: 10.1143/JPSJ.77.064706

Origin of ferroelectricity in perovskite oxides
journal, July 1992

Polarization that Holds Steady
journal, March 2014

Rise of A-site columnar-ordered A 2 A′A′′B 4 O 12 quadruple perovskites with intrinsic triple order
journal, January 2018

A -Site Ordered Double Perovskite CaMnTi 2 O 6 as a Multifunctional Piezoelectric and Ferroelectric–Photovoltaic Material
journal, September 2017

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    Works referencing / citing this record:

    Spin freezing into a disordered state in CaFeT i 2 O 6 synthesized under high pressure
    journal, August 2018

    Magnetic transitions in exotic perovskites stabilized by chemical and physical pressure
    journal, January 2020

    • Ma, Yalin; Molokeev, Maxim S.; Zhu, Chuanhui
    • Journal of Materials Chemistry C, Vol. 8, Issue 15
    • DOI: 10.1039/c9tc06976c
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      Figures / Tables found in this record:

      Fig. 1 (p. 14)figure
      Fig. 2 (p. 15)figure
      Fig. 3 (p. 16)figure
      Fig. 4 (p. 17)figure
      Fig. 5 (p. 18)figure
      Fig. 6 (p. 19)figure
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