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Title: Nature of the structural symmetries associated with hybrid improper ferroelectricity in C a 3 X 2 O 7 ( X = Mn and Ti )

Abstract

In hybrid improper ferroelectric systems, polarization arises from the onset of successive nonpolar lattice modes. In this work, measurements and modeling were performed to determine the spatial symmetries of the phases involved in the transitions to these modes. Structural and optical measurements reveal that the tilt and rotation distortions of the MnO6 or TiO6 polyhedra relative to the high symmetry phases driving ferroelectricity in the hybrid improper Ca3X2O7 system (X = Mn and Ti) condense at different temperatures. The tilt angle vanishes abruptly at T-T similar to 400 K for Ca3Mn2O7 (and continuously for X = Ti) and the rotation mode amplitude is suppressed at much higher temperatures T-R similar to 1060 K. Moreover, Raman measurements in Ca3Mn2O7 under isotropic pressure reveal that the polyhedral tilts can be suppressed by very low pressures (between 1.4 and 2.3 GPa) indicating their softness. These results indicate that the Ca3Mn2O7 system provides a platform for strain engineering of ferroelectric properties in film-based systems with substrate-induced strain.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [5];  [6];  [6];  [6];  [7]
  1. New Jersey Inst. of Technology, Newark, NJ (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Univ. of Illinois, Chicago, IL (United States)
  5. UChicago, LLC., Argonne, IL (United States)
  6. Rutgers Univ., Piscataway, NJ (United States)
  7. New Jersey Inst. of Technology, Newark, NJ (United States); Rutgers Univ., Piscataway, NJ (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1550794
Alternate Identifier(s):
OSTI ID: 1546312; OSTI ID: 1560054
Report Number(s):
BNL-211931-2019-JAAM
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
SC0012704; GF02-07ER46382; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 99; Journal Issue: 22; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Liu, S., Zhang, H., Ghose, S., Balasubramanian, M., Liu, Zhenxian, Wang, S. G., Chen, Y. -S., Gao, B., Kim, Jaewook, Cheong, S. -W., and Tyson, T. A. Nature of the structural symmetries associated with hybrid improper ferroelectricity in Ca3X2O7(X=Mnand Ti). United States: N. p., 2019. Web. doi:10.1103/PhysRevB.99.224105.
Liu, S., Zhang, H., Ghose, S., Balasubramanian, M., Liu, Zhenxian, Wang, S. G., Chen, Y. -S., Gao, B., Kim, Jaewook, Cheong, S. -W., & Tyson, T. A. Nature of the structural symmetries associated with hybrid improper ferroelectricity in Ca3X2O7(X=Mnand Ti). United States. doi:10.1103/PhysRevB.99.224105.
Liu, S., Zhang, H., Ghose, S., Balasubramanian, M., Liu, Zhenxian, Wang, S. G., Chen, Y. -S., Gao, B., Kim, Jaewook, Cheong, S. -W., and Tyson, T. A. Thu . "Nature of the structural symmetries associated with hybrid improper ferroelectricity in Ca3X2O7(X=Mnand Ti)". United States. doi:10.1103/PhysRevB.99.224105. https://www.osti.gov/servlets/purl/1550794.
@article{osti_1550794,
title = {Nature of the structural symmetries associated with hybrid improper ferroelectricity in Ca3X2O7(X=Mnand Ti)},
author = {Liu, S. and Zhang, H. and Ghose, S. and Balasubramanian, M. and Liu, Zhenxian and Wang, S. G. and Chen, Y. -S. and Gao, B. and Kim, Jaewook and Cheong, S. -W. and Tyson, T. A.},
abstractNote = {In hybrid improper ferroelectric systems, polarization arises from the onset of successive nonpolar lattice modes. In this work, measurements and modeling were performed to determine the spatial symmetries of the phases involved in the transitions to these modes. Structural and optical measurements reveal that the tilt and rotation distortions of the MnO6 or TiO6 polyhedra relative to the high symmetry phases driving ferroelectricity in the hybrid improper Ca3X2O7 system (X = Mn and Ti) condense at different temperatures. The tilt angle vanishes abruptly at T-T similar to 400 K for Ca3Mn2O7 (and continuously for X = Ti) and the rotation mode amplitude is suppressed at much higher temperatures T-R similar to 1060 K. Moreover, Raman measurements in Ca3Mn2O7 under isotropic pressure reveal that the polyhedral tilts can be suppressed by very low pressures (between 1.4 and 2.3 GPa) indicating their softness. These results indicate that the Ca3Mn2O7 system provides a platform for strain engineering of ferroelectric properties in film-based systems with substrate-induced strain.},
doi = {10.1103/PhysRevB.99.224105},
journal = {Physical Review B},
number = 22,
volume = 99,
place = {United States},
year = {2019},
month = {6}
}

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Works referenced in this record:

Advances in ab-initio theory of multiferroics: Materials and mechanisms: modelling and understanding
journal, July 2012


Physics of thin-film ferroelectric oxides
journal, October 2005


Theory of displacive phase transitions in minerals
journal, April 1997


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


Symmetry analysis for the Ruddlesden-Popper systems Ca 3 Mn 2 O 7 and Ca 3 Ti 2 O 7
journal, August 2011


Negative Thermal Expansion in Hybrid Improper Ferroelectric Ruddlesden-Popper Perovskites by Symmetry Trapping
journal, January 2015


Interrelation between domain structures and polarization switching in hybrid improper ferroelectric Ca 3 (Mn,Ti) 2 O 7
journal, May 2017

  • Gao, Bin; Huang, Fei-Ting; Wang, Yazhong
  • Applied Physics Letters, Vol. 110, Issue 22
  • DOI: 10.1063/1.4984841

Experimental demonstration of hybrid improper ferroelectricity and the presence of abundant charged walls in (Ca,Sr)3Ti2O7 crystals
journal, January 2015

  • Oh, Yoon Seok; Luo, Xuan; Huang, Fei-Ting
  • Nature Materials, Vol. 14, Issue 4
  • DOI: 10.1038/nmat4168

Soft tilt and rotational modes in the hybrid improper ferroelectric Ca 3 Mn 2 O 7
journal, March 2018


Soft antiphase tilt of oxygen octahedra in the hybrid improper multiferroic Ca 3 Mn 1.9 Ti 0.1 O 7
journal, January 2018


Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations
journal, September 2016


SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Structure validation in chemical crystallography
journal, January 2009

  • Spek, Anthony L.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
  • DOI: 10.1107/S090744490804362X

Ca 3 Mn 2 O 7
journal, December 2001

  • Guiblin, Nicolas; Grebille, Dominique; Leligny, Henri
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 58, Issue 1
  • DOI: 10.1107/S0108270101018492

Lattice dynamics of BaTiO 3 , PbTiO 3 , and PbZrO 3 : A comparative first-principles study
journal, July 1999


Compression curves of transition metals in the Mbar range: Experiments and projector augmented-wave calculations
journal, September 2008


Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions
journal, January 1986

  • Mao, H. K.; Xu, J.; Bell, P. M.
  • Journal of Geophysical Research, Vol. 91, Issue B5, p. 4673-4676
  • DOI: 10.1029/JB091iB05p04673

Pressure calibration of diamond anvil Raman gauge to 310GPa
journal, August 2006

  • Akahama, Yuichi; Kawamura, Haruki
  • Journal of Applied Physics, Vol. 100, Issue 4
  • DOI: 10.1063/1.2335683

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

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


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


First principles phonon calculations in materials science
journal, November 2015


Phonon-phonon interactions in transition metals
journal, September 2011


Local structure of multiferroic Tb Mn 2 O 5 : Evidence for an anomalous Tb-O distribution
journal, May 2007


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Extraction of the fine structure from x-ray absorption spectra
journal, December 2000


Local spin-coupled distortions in multiferroic hexagonal HoMnO 3
journal, February 2010


Local structural distortions in manganites probed by comparative x-ray-emission and x-ray-absorption near-edge measurements
journal, June 2001


Relativistic effects in the x-ray-absorption fine structure
journal, May 1994


Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems
journal, September 2015

  • Juhás, Pavol; Farrow, Christopher L.; Yang, Xiaohao
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 6, p. 562-568
  • DOI: 10.1107/S2053273315014473

    Works referencing / citing this record:

    First principles phonon calculations in materials science
    journal, November 2015


    Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions
    journal, January 1986

    • Mao, H. K.; Xu, J.; Bell, P. M.
    • Journal of Geophysical Research, Vol. 91, Issue B5, p. 4673-4676
    • DOI: 10.1029/jb091ib05p04673

    Experimental demonstration of hybrid improper ferroelectricity and the presence of abundant charged walls in (Ca,Sr)3Ti2O7 crystals
    journal, January 2015

    • Oh, Yoon Seok; Luo, Xuan; Huang, Fei-Ting
    • Nature Materials, Vol. 14, Issue 4
    • DOI: 10.1038/nmat4168

    Pressure calibration of diamond anvil Raman gauge to 310GPa
    journal, August 2006

    • Akahama, Yuichi; Kawamura, Haruki
    • Journal of Applied Physics, Vol. 100, Issue 4
    • DOI: 10.1063/1.2335683

    Interrelation between domain structures and polarization switching in hybrid improper ferroelectric Ca 3 (Mn,Ti) 2 O 7
    journal, May 2017

    • Gao, Bin; Huang, Fei-Ting; Wang, Yazhong
    • Applied Physics Letters, Vol. 110, Issue 22
    • DOI: 10.1063/1.4984841

    Extraction of the fine structure from x-ray absorption spectra
    journal, December 2000


    Relativistic effects in the x-ray-absorption fine structure
    journal, May 1994


    Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
    journal, August 1995


    Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
    journal, January 1998

    • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
    • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
    • DOI: 10.1103/physrevb.57.1505

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


    Lattice dynamics of BaTiO 3 , PbTiO 3 , and PbZrO 3 : A comparative first-principles study
    journal, July 1999


    Local structural distortions in manganites probed by comparative x-ray-emission and x-ray-absorption near-edge measurements
    journal, June 2001


    Local structure of multiferroic Tb Mn 2 O 5 : Evidence for an anomalous Tb-O distribution
    journal, May 2007


    Compression curves of transition metals in the Mbar range: Experiments and projector augmented-wave calculations
    journal, September 2008


    Local spin-coupled distortions in multiferroic hexagonal HoMnO 3
    journal, February 2010


    Symmetry analysis for the Ruddlesden-Popper systems Ca 3 Mn 2 O 7 and Ca 3 Ti 2 O 7
    journal, August 2011


    Phonon-phonon interactions in transition metals
    journal, September 2011


    Soft antiphase tilt of oxygen octahedra in the hybrid improper multiferroic Ca 3 Mn 1.9 Ti 0.1 O 7
    journal, January 2018


    Soft tilt and rotational modes in the hybrid improper ferroelectric Ca 3 Mn 2 O 7
    journal, March 2018


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


    Negative Thermal Expansion in Hybrid Improper Ferroelectric Ruddlesden-Popper Perovskites by Symmetry Trapping
    journal, January 2015


    Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations
    journal, September 2016


    Physics of thin-film ferroelectric oxides
    journal, October 2005


    OLEX2 : a complete structure solution, refinement and analysis program
    journal, January 2009

    • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
    • Journal of Applied Crystallography, Vol. 42, Issue 2
    • DOI: 10.1107/s0021889808042726

    Ca 3 Mn 2 O 7
    journal, December 2001

    • Guiblin, Nicolas; Grebille, Dominique; Leligny, Henri
    • Acta Crystallographica Section C Crystal Structure Communications, Vol. 58, Issue 1
    • DOI: 10.1107/s0108270101018492

    Structure validation in chemical crystallography
    journal, January 2009

    • Spek, Anthony L.
    • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
    • DOI: 10.1107/s090744490804362x

    ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
    journal, June 2005


    SHELXT – Integrated space-group and crystal-structure determination
    journal, January 2015

    • Sheldrick, George M.
    • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
    • DOI: 10.1107/s2053273314026370

    Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems
    journal, September 2015

    • Juhás, Pavol; Farrow, Christopher L.; Yang, Xiaohao
    • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 6, p. 562-568
    • DOI: 10.1107/s2053273315014473

    Advances in ab-initio theory of multiferroics: Materials and mechanisms: modelling and understanding
    journal, July 2012


    Theory of displacive phase transitions in minerals
    journal, April 1997


    Interplay of spin, lattice, vibration, and charge degrees of freedom: Magneto‐dielectricity in Ca 3 Mn 2 O 7
    journal, January 2020

    • Sahlot, Pooja; Sharma, Gaurav; Sathe, Vasant
    • Journal of the American Ceramic Society, Vol. 103, Issue 5
    • DOI: 10.1111/jace.17013