Emergent room temperature polar phase in CaTiO3 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

doi:10.1063/1.5078706

Title: Emergent room temperature polar phase in CaTiO₃ nanoparticles and single crystals

Journal Article · Tue Jan 22 00:00:00 EST 2019 · APL Materials

DOI:https://doi.org/10.1063/1.5078706· OSTI ID:1492695

^[1];

^[2]; Carrasco, Irene ^[3];

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^[4]; Stefanska, Dagmara ^[5]; Sen Gupta, Arnab ^[2]; de las Heras, Carmen ^[1]; Akamatsu, Hirofumi ^[2]; Holt, Martin ^[6];

^[1]; Barnes, Andrew ^[2]; Haislmaier, Ryan C. ^[2];

^[5]; Prieto, Carlos ^[7];

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Univ. Autonoma de Madrid, Madrid (Spain). Dept. Fisica de Materiales, Inst. Nicolas Cabrera and Condensed Matter Physics Center (IFIMAC)
Pennsylvania State Univ., University Park, PA (United States). Dept. of Material Sciences and Engineering
Univ. of Surrey, Guildford (United Kingdom). Advanced Technology Inst., Dept. of Electrical and Electronic Engineering
Univ. of Bern, Bern (Switzerland). Dept. of Chemistry and Biochemistry
Polish Academy of Sciences (PAS), Warsaw (Poland). Inst. of Low Temperature and Structure Research
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Inst. de Ciencia de Materiales de Madrid, ICMM, (CSIC), Madrid (Spain)
Federal Inst. of Technology, Zurich (Switzerland). Materials Theory

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 CaTiO₃, 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 CaTiO₃ 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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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); Spanish Ministerio de Economia y Competitividad (MINECO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; DMR-1420620; DMR-1807768; SC0012375

OSTI ID:: 1492695

Journal Information:: APL Materials, Vol. 7, Issue 1; ISSN 2166-532X

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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Title: Emergent room temperature polar phase in CaTiO₃ nanoparticles and single crystals