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Low-temperature polarity in antiferroelectric PbZrO3 and PbHfO3 driven by dynamical covalency in the ZrO6 and HfO6 substructures

Annette Bussmann-Holder1, Marcin Fiajłkowski2, Andrzej Majchrowski3, A. Szewczyk4, J. Więckowski4, Iwona Lazar2, Andrzej Soszyński2, and Krystian Roleder2

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Phys. Rev. B 112, 174112 – Published 7 November, 2025

DOI: https://doi.org/10.1103/y5wr-lmyg

Abstract

At low temperatures, additional phase transitions have been detected in the antiferroelectric crystals PbZrO3 and PbHfO3 near 270 K. In this paper we investigate these transitions theoretically and experimentally and arrive at the conclusion that it is of first order, using the free energy expanded to a sixth order in the order parameter. In addition to recently published pyroelectric and dielectric properties, the presence of this transition has been proven by measuring the temperature dependence of the specific heat and natural absorbance, and compared with the literature data of the structural investigations by neutron scattering. Opposite to the previous articles, the origin of this transition is not connected with the Pb ion displacements, but it is solely caused by the p-d interaction in the transition metal-oxides ZrO6 and HfO6 substructures, typical for a broad number of ferroelectric oxide perovskites.

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Outline

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Phys. Rev. B 112, 174112– Published 7 November, 2025
  • Received 8 May 2025
  • Revised 21 September 2025
  • Accepted 15 October 2025
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Open access publication funded by Max Planck Society.

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