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

doi:10.1063/1.5078706

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

Applied Fine Chemistry

Research output: Contribution to journal › Article

2 Citations (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 language	English
Article number	011103
Journal	APL Materials
Volume	7
Issue number	1
DOIs	https://doi.org/10.1063/1.5078706
Publication status	Published - Jan 1 2019

All Science Journal Classification (ASJC) codes

Materials Science(all)
Engineering(all)

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10.1063/1.5078706

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Ramirez, M. O., Lummen, T. T. A., Carrasco, I., Barnes, E., Aschauer, U., Stefanska, D., Sen Gupta, A., De Las Heras, C., Akamatsu, H., Holt, M., Molina, P., Barnes, A., Haislmaier, R. C., Deren, P. J., Prieto, C., Bausá, L. E., Spaldin, N. A., & 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 journal › Article

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, 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.

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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. ",

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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

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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.

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