Coupling of emergent octahedral rotations to polarization in (K,Na)NbO3 ferroelectrics

Levin, I.; Krayzman, V.; Cibin, G.; Tucker, M. G.; Eremenko, M.; Chapman, K.; Paul, R. L.

doi:10.1038/s41598-017-15937-x

Title: Coupling of emergent octahedral rotations to polarization in (K,Na)NbO₃ ferroelectrics

Journal Article · Wed Nov 15 00:00:00 EST 2017 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-017-15937-x· OSTI ID:1460084

Levin, I. ^[1]; Krayzman, V. ^[1];

^[2]; Tucker, M. G. ^[3]; Eremenko, M. ^[1];

^[4]; Paul, R. L. ^[1]

National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Diamond Light Source, Didcot (United Kingdom)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Perovskite potassium sodium niobates, K_1-xNa_xNbO₃, are promising lead-free piezoelectrics. Their dielectric and piezoelectric characteristics peak near x = 0.5, but the reasons for such property enhancement remain unclear. We addressed this uncertainty by analyzing changes in the local and average structures across the x = 0.5 composition, which have been determined using simultaneous Reverse Monte Carlo fitting of neutron and X-ray total-scattering data, potassium EXAFS, and diffuse-scattering patterns in electron diffraction. Within the A-sites, Na cations are found to be strongly off-centered along the polar axis as a result of oversized cube-octahedral cages determined by the larger K ions. These Na displacements promote off-centering of the neighboring Nb ions, so that the Curie temperature and spontaneous polarization remain largely unchanged with increasing x, despite the shrinking octahedral volumes. The enhancement of the properties near x = 0.5 is attributed to an abrupt increase in the magnitude and probability of the short-range ordered octahedral rotations, which resembles the pre-transition behavior. Lastly, these rotations reduce the bond tension around Na and effectively soften the short Na-O bond along the polar axis - an effect that is proposed to facilitate reorientation of the polarization as external electric field is applied.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1460084

Journal Information:: Scientific Reports, Vol. 7, Issue 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Title: Coupling of emergent octahedral rotations to polarization in (K,Na)NbO₃ ferroelectrics