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Title: Average and local structure of the Pb-free ferroelectric perovskites ( Sr , Sn ) TiO 3 and ( Ba , Ca , Sn ) TiO 3

Abstract

The characteristic structural off -centering of Pb2+ in oxides, associated with its 6s2 lone pair, allows it to play a dominant role in polar materials, and makes it a somewhat ubiquitous component of ferroelectrics. In this work, we examine the compounds Sr0.9Sn0.1TiO3 and Ba0.79Ca0.16Sn0.05TiO3 using neutron total scattering techniques with data acquired at di erent temperatures. In these compounds, previously reported as ferroelectrics, Sn2+ appears to display some of the characteristics of Pb2+. We compare the local and long-range structures of the Sn2+-substituted compositions to the unsubstituted parent compounds SrTiO3 and BaTiO3. Lastly, we find that even at these small substitution levels, the Sn2+ lone pairs drive the local ordering behavior, with the local structure of both compounds more similar to the structure of PbTiO3 rather than the parent compounds.

Authors:
 [1];  [2];  [3];  [4]
  1. Univ. of California, Santa Barbara, CA (United States). Materials Research Laboratory
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  3. Murata Manufacturing, Co., Ltd., Nagaokakyo, Kyoto (Japan)
  4. Univ. of California, Santa Barbara, CA (United States). Materials Department and Materials Research Laboratory
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1254476
Alternate Identifier(s):
OSTI ID: 1229913
Grant/Contract Number:  
DMR-1403862
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 92; Journal Issue: 21; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Laurita, Geneva, Page, Katharine, Suzuki, Shoichiro, and Seshadri, Ram. Average and local structure of the Pb-free ferroelectric perovskites (Sr,Sn)TiO3 and (Ba,Ca,Sn)TiO3. United States: N. p., 2015. Web. https://doi.org/10.1103/PhysRevB.92.214109.
Laurita, Geneva, Page, Katharine, Suzuki, Shoichiro, & Seshadri, Ram. Average and local structure of the Pb-free ferroelectric perovskites (Sr,Sn)TiO3 and (Ba,Ca,Sn)TiO3. United States. https://doi.org/10.1103/PhysRevB.92.214109
Laurita, Geneva, Page, Katharine, Suzuki, Shoichiro, and Seshadri, Ram. Wed . "Average and local structure of the Pb-free ferroelectric perovskites (Sr,Sn)TiO3 and (Ba,Ca,Sn)TiO3". United States. https://doi.org/10.1103/PhysRevB.92.214109. https://www.osti.gov/servlets/purl/1254476.
@article{osti_1254476,
title = {Average and local structure of the Pb-free ferroelectric perovskites (Sr,Sn)TiO3 and (Ba,Ca,Sn)TiO3},
author = {Laurita, Geneva and Page, Katharine and Suzuki, Shoichiro and Seshadri, Ram},
abstractNote = {The characteristic structural off -centering of Pb2+ in oxides, associated with its 6s2 lone pair, allows it to play a dominant role in polar materials, and makes it a somewhat ubiquitous component of ferroelectrics. In this work, we examine the compounds Sr0.9Sn0.1TiO3 and Ba0.79Ca0.16Sn0.05TiO3 using neutron total scattering techniques with data acquired at di erent temperatures. In these compounds, previously reported as ferroelectrics, Sn2+ appears to display some of the characteristics of Pb2+. We compare the local and long-range structures of the Sn2+-substituted compositions to the unsubstituted parent compounds SrTiO3 and BaTiO3. Lastly, we find that even at these small substitution levels, the Sn2+ lone pairs drive the local ordering behavior, with the local structure of both compounds more similar to the structure of PbTiO3 rather than the parent compounds.},
doi = {10.1103/PhysRevB.92.214109},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 21,
volume = 92,
place = {United States},
year = {2015},
month = {12}
}

Journal Article:

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Cited by: 6 works
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Works referenced in this record:

Substitution of Sn Ions in (Ba,Ca)TiO 3 Perovskites
journal, September 2012

  • Suzuki, Shoichiro; Iwaji, Naoki; Honda, Atsushi
  • Japanese Journal of Applied Physics, Vol. 51, Issue 9S1
  • DOI: 10.7567/JJAP.51.09LC08

Order-Disorder Phase Transitions
journal, January 2000


Effect of Sn 2+ Ion Substitution on Dielectric Properties of (Ba,Ca)TiO 3 Ferroelectric Ceramics
journal, September 2010

  • Suzuki, Shoichiro; Takeda, Toshikazu; Ando, Akira
  • Japanese Journal of Applied Physics, Vol. 49, Issue 9
  • DOI: 10.1143/jjap.49.09mc04

High Permittivity Crystalline Aggregates
journal, December 1945

  • Jackson, Willis; Reddish, W.
  • Nature, Vol. 156, Issue 3972
  • DOI: 10.1038/156717a0

The influence of A-cation disorder on the Curie temperature of ferroelectric ATiO3 perovskites
journal, January 1999

  • Sinclair, Derek C.; Paul Attfield, J.
  • Chemical Communications, Issue 16
  • DOI: 10.1039/a903680f

Non- d 0 Mn-driven ferroelectricity in antiferromagnetic BaMnO 3
journal, May 2009

  • Rondinelli, James M.; Eidelson, Aaron S.; Spaldin, Nicola A.
  • Physical Review B, Vol. 79, Issue 20
  • DOI: 10.1103/physrevb.79.205119

Anomalous Phase Diagram of Ferroelectric ( Ba , Ca ) TiO 3 Single Crystals with Giant Electromechanical Response
journal, June 2008


Ferroelectric phase transition in Sn2+ ions doped (Ba,Ca)TiO3 ceramics
journal, March 2010

  • Suzuki, Shoichiro; Takeda, Toshikazu; Ando, Akira
  • Applied Physics Letters, Vol. 96, Issue 13
  • DOI: 10.1063/1.3367733

SrTi O 3 : An intrinsic quantum paraelectric below 4 K
journal, April 1979


Local Structural Origins of the Distinct Electronic Properties of Nb-Substituted SrTiO 3 and BaTiO 3
journal, November 2008


The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • DOI: 10.1016/j.nimb.2012.05.037

Ferroelectric Ceramics: History and Technology
journal, April 1999


Raman Spectroscopic Study of Ferroelectric Sn-Doped SrTiO 3
journal, May 2014


XAFS Study of Local Structure Change in Perovskite Titanates
journal, January 2005


Entropically Stabilized Local Dipole Formation in Lead Chalcogenides
journal, December 2010


Optical detection of symmetry breaking on a nanoscale in SrTiO 3 :Ca
journal, November 1997


PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007


High-throughput screening of perovskite alloys for piezoelectric performance and thermodynamic stability
journal, April 2014


Effects of Lattice Constant and Sintering Atmosphere on Substitution of Sn 2+ Ions at Ba Site in (Ba,Ca)TiO 3 Perovskites: Experimental and Theoretical Studies
journal, September 2011

  • Suzuki, Shoichiro; Honda, Atsushi; Higai, Shin'ichi
  • Japanese Journal of Applied Physics, Vol. 50, Issue 9S2
  • DOI: 10.7567/jjap.50.09nc11

Origin of ferroelectricity in perovskite oxides
journal, July 1992


EXPGUI , a graphical user interface for GSAS
journal, April 2001


Origin of Composition Variation of Ferroelectric Phase Transition Temperature in (Ba,Ca)TiO 3 by Synchrotron Radiation Powder Diffraction
journal, September 2013

  • Moriyoshi, Chikako; Takeda, Shoichi; Magome, Eisuke
  • Japanese Journal of Applied Physics, Vol. 52, Issue 9S1
  • DOI: 10.7567/jjap.52.09kf02

Local-structure origins of the sustained Curie temperature in (Ba,Ca)TiO 3 ferroelectrics
journal, April 2013

  • Levin, Igor; Krayzman, Victor; Woicik, Joseph C.
  • Applied Physics Letters, Vol. 102, Issue 16
  • DOI: 10.1063/1.4802996

Substitution of Sn Ions in (Ba,Ca)TiO$_{3}$ Perovskites
journal, September 2012

  • Suzuki, Shoichiro; Iwaji, Naoki; Honda, Atsushi
  • Japanese Journal of Applied Physics, Vol. 51
  • DOI: 10.1143/jjap.51.09lc08

Lattice modes in ferroelectric perovskites. II. Pb 1 x Ba x Ti O 3 including BaTi O 3
journal, September 1974


Effects of Sn 2+ Ion Size on Sn Doped SrTiO 3
journal, September 2013

  • Suzuki, Shoichiro; Honda, Atsushi; Suzuki, Keigo
  • Japanese Journal of Applied Physics, Vol. 52, Issue 9S1
  • DOI: 10.7567/jjap.52.09kc04

Cluster and domain-state dynamics of ferroelectric Sr 1 x Ca x TiO 3 ( x =0.007)
journal, April 1995


Local off-centering symmetry breaking in the high-temperature regime of SnTe
journal, January 2014


Rietveld analysis of strontium titanate in the Müller state
journal, May 1996


Probing Local Dipoles and Ligand Structure in BaTiO 3 Nanoparticles
journal, August 2010

  • Page, Katharine; Proffen, Thomas; Niederberger, Markus
  • Chemistry of Materials, Vol. 22, Issue 15
  • DOI: 10.1021/cm100440p

First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb
journal, March 2003


Dielectric and X-Ray Studies of Ca x Ba 1 x Ti O 3 and Ca x Sr 1 x Ti O 3
journal, December 1961


Ferroelectricity of Sn-doped SrTiO 3 perovskites with tin at both A and B sites
journal, August 2012


VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


First-Principles Study of Lead-Free Piezoelectric SnTiO 3
journal, September 2008

  • Uratani, Yoshitaka; Shishidou, Tatsuya; Oguchi, Tamio
  • Japanese Journal of Applied Physics, Vol. 47, Issue 9
  • DOI: 10.1143/jjap.47.7735

Local structure and the phase transitions of BaTiO 3
journal, February 1998


First principles studies of SnTiO3 perovskite as potential environmentally benign ferroelectric material
journal, January 2009


Structures of the ferroelectric phases of barium titanate
journal, March 1993

  • Kwei, G. H.; Lawson, A. C.; Billinge, S. J. L.
  • The Journal of Physical Chemistry, Vol. 97, Issue 10
  • DOI: 10.1021/j100112a043

Total scattering and reverse Monte Carlo study of the 105 K displacive phase transition in strontium titanate
journal, January 2005

  • Hui, Qun; Tucker, Matthew G.; Dove, Martin T.
  • Journal of Physics: Condensed Matter, Vol. 17, Issue 5
  • DOI: 10.1088/0953-8984/17/5/012

Pair-distribution functions of ferroelectric perovskites: Direct observation of structural ground states
journal, February 1995


Non- d 0 Mn-driven ferroelectricity in antiferromagnetic BaMnO 3
journal, May 2009

  • Rondinelli, James M.; Eidelson, Aaron S.; Spaldin, Nicola A.
  • Physical Review B, Vol. 79, Issue 20
  • DOI: 10.1103/PhysRevB.79.205119

First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb
journal, March 2003


First-Principles Study of Lead-Free Piezoelectric SnTiO 3
journal, September 2008

  • Uratani, Yoshitaka; Shishidou, Tatsuya; Oguchi, Tamio
  • Japanese Journal of Applied Physics, Vol. 47, Issue 9
  • DOI: 10.1143/JJAP.47.7735

SrTi O 3 : An intrinsic quantum paraelectric below 4 K
journal, April 1979


Ferroelectricity of Sn-doped SrTiO 3 perovskites with tin at both A and B sites
journal, August 2012


Effects of Sn 2+ Ion Size on Sn Doped SrTiO 3
journal, September 2013

  • Suzuki, Shoichiro; Honda, Atsushi; Suzuki, Keigo
  • Japanese Journal of Applied Physics, Vol. 52, Issue 9S1
  • DOI: 10.7567/JJAP.52.09KC04

Lattice modes in ferroelectric perovskites. II. Pb 1 x Ba x Ti O 3 including BaTi O 3
journal, September 1974


Dielectric and X-Ray Studies of Ca x Ba 1 x Ti O 3 and Ca x Sr 1 x Ti O 3
journal, December 1961


Anomalous Phase Diagram of Ferroelectric ( Ba , Ca ) TiO 3 Single Crystals with Giant Electromechanical Response
journal, June 2008


Effect of Sn 2+ Ion Substitution on Dielectric Properties of (Ba,Ca)TiO 3 Ferroelectric Ceramics
journal, September 2010

  • Suzuki, Shoichiro; Takeda, Toshikazu; Ando, Akira
  • Japanese Journal of Applied Physics, Vol. 49, Issue 9
  • DOI: 10.1143/JJAP.49.09MC04

Effects of Lattice Constant and Sintering Atmosphere on Substitution of Sn 2+ Ions at Ba Site in (Ba,Ca)TiO 3 Perovskites: Experimental and Theoretical Studies
journal, September 2011

  • Suzuki, Shoichiro; Honda, Atsushi; Higai, Shin'ichi
  • Japanese Journal of Applied Physics, Vol. 50, Issue 9S2
  • DOI: 10.7567/JJAP.50.09NC11

XAFS Study of Local Structure Change in Perovskite Titanates
journal, January 2005


Local Structural Origins of the Distinct Electronic Properties of Nb-Substituted SrTiO 3 and BaTiO 3
journal, November 2008


High-throughput screening of perovskite alloys for piezoelectric performance and thermodynamic stability
journal, April 2014


EXPGUI , a graphical user interface for GSAS
journal, April 2001


VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Cluster and domain-state dynamics of ferroelectric Sr 1 x Ca x TiO 3 ( x =0.007)
journal, April 1995


Origin of Composition Variation of Ferroelectric Phase Transition Temperature in (Ba,Ca)TiO 3 by Synchrotron Radiation Powder Diffraction
journal, September 2013

  • Moriyoshi, Chikako; Takeda, Shoichi; Magome, Eisuke
  • Japanese Journal of Applied Physics, Vol. 52, Issue 9S1
  • DOI: 10.7567/JJAP.52.09KF02

Local off-centering symmetry breaking in the high-temperature regime of SnTe
journal, January 2014


Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020


    Works referencing / citing this record:

    Local Structural Heterogeneity and Electromechanical Responses of Ferroelectrics: Learning from Relaxor Ferroelectrics
    journal, July 2018

    • Li, Fei; Zhang, Shujun; Damjanovic, Dragan
    • Advanced Functional Materials, Vol. 28, Issue 37
    • DOI: 10.1002/adfm.201801504

    Effect of A‐site substitutions on energy storage properties of BaTiO 3 ‐BiScO 3 weakly coupled relaxor ferroelectrics
    journal, April 2019

    • Nayak, Sanjib; Venkateshwarlu, Sarangi; Budisuharto, Anthony Setiadi
    • Journal of the American Ceramic Society, Vol. 102, Issue 10
    • DOI: 10.1111/jace.16449