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

doi:10.1021/jacs.7b11219

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 »« less

Authors:

Li, Zongyao ^[1]; Cho, Yujin ^[2]; Li, Xiang ^[1]; Li, Xinyu ^[1]; Aimi, Akihisa ^[3]; Inaguma, Yoshiyuki ^[4];

^[5]; Fernandez-Diaz, Maria T. ^[6];

^[7]; Downer, Michael C. ^[2];

^[8];

^[1];

^[1]

Univ. of Texas, Austin, TX (United States). Material Science and Engineering Program, Mechanical Engineering
Univ. of Texas, Austin, TX (United States). Dept. of Physics
Tokyo Univ. of Science, Chiba (Japan). Dept. of Pure and Applied Chemistry, Faculty of Science and Technology
Gakushuin Univ., Tokyo (Japan). Dept. of Chemistry, Faculty of Science
Spanish National Research Council (CSIC), Madrid (Spain). Inst. of Materials Science of Madrid
Inst. Laue-Langevin (ILL),Grenoble (France)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Univ. of Texas, Austin, TX (United States). Dept. of Chemistry

Publication Date:: 2018-01-15

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.

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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.  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., 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.

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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},

  issn         = {0002-7863},

  number       = 6,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {1}

}

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DOI: 10.1021/jacs.7b11219

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Cited by: 4 works

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Figures / Tables:

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 »

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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

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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