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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 BaTiO 3 and PbTiO 3 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., Bi 3+ and Pb 2+, 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 CaMnTi 2O 6 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 T c ≈ 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 andmore » 1200 °C, which limits its application. Here we report a new method to synthesize a gram-level sample of ferroelectric Ca 2–xMn xTi 2O 6, having the same crystal structure as CaMnTi 2O 6 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]
  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 Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1461940
Grant/Contract Number:  
AC05-00OR22725; F-1066; F-1841; F-1038
Resource Type:
Journal Article: 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.
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. doi:10.1021/jacs.7b11219.
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. doi:10.1021/jacs.7b11219. https://www.osti.gov/servlets/purl/1461940.
@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},
issn = {0002-7863},
number = 6,
volume = 140,
place = {United States},
year = {2018},
month = {1}
}

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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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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.