Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals

Mariola O. Ramirez, Tom T.A. Lummen, Irene Carrasco, Eftihia Barnes, Ulrich Aschauer, Dagmara Stefanska, Arnab Sen Gupta, Carmen De Las Heras, Hirofumi Akamatsu, Martin Holt, Pablo Molina, Andrew Barnes, Ryan C. Haislmaier, Przemyslaw J. Deren, Carlos Prieto, Luisa E. Bausá, Nicola A. Spaldin, Venkatraman Gopalan

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

Original languageEnglish
Article number011103
JournalAPL Materials
Volume7
Issue number1
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Single crystals
Polarization
Nanoparticles
Powders
Nonlinear optics
Perovskite
Temperature
Density functional theory
Minerals
Electrostatics
Microscopic examination
Stabilization
Spectroscopy
Oxygen
X ray diffraction
perovskite

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Engineering(all)

Cite this

Ramirez, M. O., Lummen, T. T. A., Carrasco, I., Barnes, E., Aschauer, U., Stefanska, D., ... Gopalan, V. (2019). Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals APL Materials, 7(1), [011103]. https://doi.org/10.1063/1.5078706

Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals . / Ramirez, Mariola O.; Lummen, Tom T.A.; Carrasco, Irene; Barnes, Eftihia; Aschauer, Ulrich; Stefanska, Dagmara; Sen Gupta, Arnab; De Las Heras, Carmen; Akamatsu, Hirofumi; Holt, Martin; Molina, Pablo; Barnes, Andrew; Haislmaier, Ryan C.; Deren, Przemyslaw J.; Prieto, Carlos; Bausá, Luisa E.; Spaldin, Nicola A.; Gopalan, Venkatraman.

In: APL Materials, Vol. 7, No. 1, 011103, 01.01.2019.

Research output: Contribution to journalArticle

Ramirez, MO, Lummen, TTA, Carrasco, I, Barnes, E, Aschauer, U, Stefanska, D, Sen Gupta, A, De Las Heras, C, Akamatsu, H, Holt, M, Molina, P, Barnes, A, Haislmaier, RC, Deren, PJ, Prieto, C, Bausá, LE, Spaldin, NA & Gopalan, V 2019, ' Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals ', APL Materials, vol. 7, no. 1, 011103. https://doi.org/10.1063/1.5078706
Ramirez MO, Lummen TTA, Carrasco I, Barnes E, Aschauer U, Stefanska D et al. Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals APL Materials. 2019 Jan 1;7(1). 011103. https://doi.org/10.1063/1.5078706
Ramirez, Mariola O. ; Lummen, Tom T.A. ; Carrasco, Irene ; Barnes, Eftihia ; Aschauer, Ulrich ; Stefanska, Dagmara ; Sen Gupta, Arnab ; De Las Heras, Carmen ; Akamatsu, Hirofumi ; Holt, Martin ; Molina, Pablo ; Barnes, Andrew ; Haislmaier, Ryan C. ; Deren, Przemyslaw J. ; Prieto, Carlos ; Bausá, Luisa E. ; Spaldin, Nicola A. ; Gopalan, Venkatraman. / Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals In: APL Materials. 2019 ; Vol. 7, No. 1.
@article{1330e31fda8d46d7ad6e40151b5f512f,
title = "Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals",
abstract = "Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.",
author = "Ramirez, {Mariola O.} and Lummen, {Tom T.A.} and Irene Carrasco and Eftihia Barnes and Ulrich Aschauer and Dagmara Stefanska and {Sen Gupta}, Arnab and {De Las Heras}, Carmen and Hirofumi Akamatsu and Martin Holt and Pablo Molina and Andrew Barnes and Haislmaier, {Ryan C.} and Deren, {Przemyslaw J.} and Carlos Prieto and Baus{\'a}, {Luisa E.} and Spaldin, {Nicola A.} and Venkatraman Gopalan",
year = "2019",
month = "1",
day = "1",
doi = "10.1063/1.5078706",
language = "English",
volume = "7",
journal = "APL Materials",
issn = "2166-532X",
publisher = "American Institute of Physics Publising LLC",
number = "1",

}

TY - JOUR

T1 - Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals

AU - Ramirez, Mariola O.

AU - Lummen, Tom T.A.

AU - Carrasco, Irene

AU - Barnes, Eftihia

AU - Aschauer, Ulrich

AU - Stefanska, Dagmara

AU - Sen Gupta, Arnab

AU - De Las Heras, Carmen

AU - Akamatsu, Hirofumi

AU - Holt, Martin

AU - Molina, Pablo

AU - Barnes, Andrew

AU - Haislmaier, Ryan C.

AU - Deren, Przemyslaw J.

AU - Prieto, Carlos

AU - Bausá, Luisa E.

AU - Spaldin, Nicola A.

AU - Gopalan, Venkatraman

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

AB - Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

UR - http://www.scopus.com/inward/record.url?scp=85060483485&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85060483485&partnerID=8YFLogxK

U2 - 10.1063/1.5078706

DO - 10.1063/1.5078706

M3 - Article

VL - 7

JO - APL Materials

JF - APL Materials

SN - 2166-532X

IS - 1

M1 - 011103

ER -