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Landau–Devonshire thermodynamic potentials for displacive perovskite ferroelectrics from first principles

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Abstract

A general approach for fitting Landau–Devonshire thermodynamic potentials directly from first principles is developed for simple displacive ferroelectric perovskite materials. As the first step, a \(\hbox {PbTiO}_3\) potential is parameterized completely from density functional theory calculations as a test case, under the only assumption that the transition between the non-polar and polar phases is of first order. The utility of this approach is assessed by comparing quantities characterizing the phase transition, dielectric and piezoelectric properties and equibiaxial strain–temperature phase diagrams with the predictions of several thermodynamic potentials parameterized from experimental data. In the second step, a similar parameterization is generated for a fictitious polar perovskite \(\hbox {SnTiO}_{3}\), enabling us to predictively evaluate an approximate ‘equibiaxial strain–temperature–spontaneous polarization’ phase diagram for its thin films.

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Notes

  1. See also BESAC report “From Quanta to the Continuum: Opportunities for Mesoscale Science” available from http://science.energy.gov/ as well as the complete volume 40 of the MRS Bulletin from November 2015.

  2. There is no reason why this need be the case. If the Landau polynomial is convergent, the temperature-dependent terms play a minor role near the phase transition where the polynomial becomes asymptotically accurate. At lower temperatures, however, these terms may become important. This is the case, for example, in barium titanate.

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Acknowledgements

The authors acknowledge partial support from the National Science Foundation (DMR 1309114). KCP is grateful to Neha Gadigi for help with coding and to S. Pamir Alpay, and Valentino R. Cooper for useful discussions.

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  1. Krishna Chaitanya Pitike

    Present address: Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA

Authors and Affiliations

  1. Department of Materials Science & Engineering, and Institute of Materials Science, University of Connecticut, Storrs, CT, 06269, USA

    Krishna Chaitanya Pitike, Nasser Khakpash, George A. Rossetti Jr. & Serge M. Nakhmanson

  2. Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21, Prague 8, Czech Republic

    John Mangeri

  3. Department of Physics, University of Connecticut, Storrs, Connecticut, 06269, USA

    John Mangeri & Serge M. Nakhmanson

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  1. Krishna Chaitanya Pitike
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Pitike, K.C., Khakpash, N., Mangeri, J. et al. Landau–Devonshire thermodynamic potentials for displacive perovskite ferroelectrics from first principles. J Mater Sci 54, 8381–8400 (2019). https://doi.org/10.1007/s10853-019-03439-2

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