Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond

Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases

Suguru Yoshida, Hirofumi Akamatsu, Ryosuke Tsuji, Olivier Hernandez, Haricharan Padmanabhan, Arnab Sen Gupta, Alexandra S. Gibbs, Ko Mibu, Shunsuke Murai, James M. Rondinelli, Venkatraman Gopalan, Katsuhisa Tanaka, Koji Fujita

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approaches blending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature (TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1-xCax)3Sn2O7 (x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 hybrid improper ferroelectrics, indicating that the TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergent group-theoretical and first-principles design approach.

Original languageEnglish (US)
Pages (from-to)15690-15700
Number of pages11
JournalJournal of the American Chemical Society
Volume140
Issue number46
DOIs
StatePublished - Nov 21 2018

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Ferroelectricity
Transition Temperature
Superconducting transition temperature
Ferroelectric materials
Cations
Guidelines
Temperature
Crystal chemistry
Group theory
Crystal symmetry
Curie temperature
Ground state
Positive ions
Polarization

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Yoshida, Suguru ; Akamatsu, Hirofumi ; Tsuji, Ryosuke ; Hernandez, Olivier ; Padmanabhan, Haricharan ; Sen Gupta, Arnab ; Gibbs, Alexandra S. ; Mibu, Ko ; Murai, Shunsuke ; Rondinelli, James M. ; Gopalan, Venkatraman ; Tanaka, Katsuhisa ; Fujita, Koji. / Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond : Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 46. pp. 15690-15700.
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abstract = "Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approaches blending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature (TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1-xCax)3Sn2O7 (x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 hybrid improper ferroelectrics, indicating that the TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergent group-theoretical and first-principles design approach.",
author = "Suguru Yoshida and Hirofumi Akamatsu and Ryosuke Tsuji and Olivier Hernandez and Haricharan Padmanabhan and {Sen Gupta}, Arnab and Gibbs, {Alexandra S.} and Ko Mibu and Shunsuke Murai and Rondinelli, {James M.} and Venkatraman Gopalan and Katsuhisa Tanaka and Koji Fujita",
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Yoshida, S, Akamatsu, H, Tsuji, R, Hernandez, O, Padmanabhan, H, Sen Gupta, A, Gibbs, AS, Mibu, K, Murai, S, Rondinelli, JM, Gopalan, V, Tanaka, K & Fujita, K 2018, 'Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond: Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases', Journal of the American Chemical Society, vol. 140, no. 46, pp. 15690-15700. https://doi.org/10.1021/jacs.8b07998

Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond : Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases. / Yoshida, Suguru; Akamatsu, Hirofumi; Tsuji, Ryosuke; Hernandez, Olivier; Padmanabhan, Haricharan; Sen Gupta, Arnab; Gibbs, Alexandra S.; Mibu, Ko; Murai, Shunsuke; Rondinelli, James M.; Gopalan, Venkatraman; Tanaka, Katsuhisa; Fujita, Koji.

In: Journal of the American Chemical Society, Vol. 140, No. 46, 21.11.2018, p. 15690-15700.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond

T2 - Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases

AU - Yoshida, Suguru

AU - Akamatsu, Hirofumi

AU - Tsuji, Ryosuke

AU - Hernandez, Olivier

AU - Padmanabhan, Haricharan

AU - Sen Gupta, Arnab

AU - Gibbs, Alexandra S.

AU - Mibu, Ko

AU - Murai, Shunsuke

AU - Rondinelli, James M.

AU - Gopalan, Venkatraman

AU - Tanaka, Katsuhisa

AU - Fujita, Koji

PY - 2018/11/21

Y1 - 2018/11/21

N2 - Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approaches blending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature (TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1-xCax)3Sn2O7 (x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 hybrid improper ferroelectrics, indicating that the TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergent group-theoretical and first-principles design approach.

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