Lead-free antiferroelectric

XCaZrO3-(1 - X)NaNbO3 system (0 ≤ x ≤ 0.10)

Hiroyuki Shimizu, Hanzheng Guo, Sebastian E. Reyes-Lillo, Youichi Mizuno, Karin M. Rabe, Clive A. Randall

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

This study demonstrates that antiferroelectricity can be stabilized in NaNbO3 (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr4+ and Ca2+ ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na1-xCax)(Nb1-xZrx)O3 (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO3 substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤ x ≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE虠FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.

Original languageEnglish
Pages (from-to)10763-10772
Number of pages10
JournalDalton Transactions
Volume44
Issue number23
DOIs
Publication statusPublished - 21 Jun 2015

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Substitution reactions
Ferroelectric materials
Polarization
Antiferroelectricity
Crystal chemistry
Transmission electron microscopy
Hysteresis loops
Solid solutions
Phase transitions
Ions
X ray diffraction
sodium niobate
Lead
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Shimizu, Hiroyuki ; Guo, Hanzheng ; Reyes-Lillo, Sebastian E. ; Mizuno, Youichi ; Rabe, Karin M. ; Randall, Clive A. / Lead-free antiferroelectric : XCaZrO3-(1 - X)NaNbO3 system (0 ≤ x ≤ 0.10). In: Dalton Transactions. 2015 ; Vol. 44, No. 23. pp. 10763-10772.
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abstract = "This study demonstrates that antiferroelectricity can be stabilized in NaNbO3 (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr4+ and Ca2+ ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na1-xCax)(Nb1-xZrx)O3 (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO3 substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤ x ≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE虠FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.",
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Shimizu, H, Guo, H, Reyes-Lillo, SE, Mizuno, Y, Rabe, KM & Randall, CA 2015, 'Lead-free antiferroelectric: XCaZrO3-(1 - X)NaNbO3 system (0 ≤ x ≤ 0.10)', Dalton Transactions, vol. 44, no. 23, pp. 10763-10772. https://doi.org/10.1039/c4dt03919j

Lead-free antiferroelectric : XCaZrO3-(1 - X)NaNbO3 system (0 ≤ x ≤ 0.10). / Shimizu, Hiroyuki; Guo, Hanzheng; Reyes-Lillo, Sebastian E.; Mizuno, Youichi; Rabe, Karin M.; Randall, Clive A.

In: Dalton Transactions, Vol. 44, No. 23, 21.06.2015, p. 10763-10772.

Research output: Contribution to journalArticle

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T2 - XCaZrO3-(1 - X)NaNbO3 system (0 ≤ x ≤ 0.10)

AU - Shimizu, Hiroyuki

AU - Guo, Hanzheng

AU - Reyes-Lillo, Sebastian E.

AU - Mizuno, Youichi

AU - Rabe, Karin M.

AU - Randall, Clive A.

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N2 - This study demonstrates that antiferroelectricity can be stabilized in NaNbO3 (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr4+ and Ca2+ ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na1-xCax)(Nb1-xZrx)O3 (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO3 substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤ x ≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE虠FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.

AB - This study demonstrates that antiferroelectricity can be stabilized in NaNbO3 (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr4+ and Ca2+ ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na1-xCax)(Nb1-xZrx)O3 (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO3 substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤ x ≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE虠FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.

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