A Predictive Theory for Domain Walls in Oxide Ferroelectrics Based on Interatomic Interactions and its Implications for Collective Material Properties

Atanu Samanta; Suhas Yadav; Zongquan Gu; Cedric J G Meyers; Liyan Wu; Dongfang Chen; Shishir Pandya; Robert A York; Lane W Martin; Jonathan E Spanier; Ilya Grinberg

doi:10.1002/adma.202106021

A Predictive Theory for Domain Walls in Oxide Ferroelectrics Based on Interatomic Interactions and its Implications for Collective Material Properties

Adv Mater. 2022 Feb;34(7):e2106021. doi: 10.1002/adma.202106021. Epub 2021 Dec 14.

Authors

Atanu Samanta¹, Suhas Yadav¹, Zongquan Gu², Cedric J G Meyers^{2

3}, Liyan Wu², Dongfang Chen², Shishir Pandya⁴, Robert A York³, Lane W Martin^{4

5}, Jonathan E Spanier², Ilya Grinberg¹

Affiliations

¹ Department of Chemistry, Bar-Ilan University, Ramat Gan, 5290002, Israel.
² Department of Mechanical Engineering and Mechanics, Drexel University, Philadelphia, PA, 19104, USA.
³ Department of Electrical and Computer Engineering, University of California at Santa Barbara, Santa Barbara, CA, 93106, USA.
⁴ Department of Materials Science and Engineering, University of California at Berkeley, Berkeley, CA, 94720, USA.
⁵ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.

PMID: 34695263
DOI: 10.1002/adma.202106021

Abstract

Domain walls separating regions of ferroelectric material with polarization oriented in different directions are crucial for applications of ferroelectrics. Rational design of ferroelectric materials requires the development of a theory describing how compositional and environmental changes affect domain walls. To model domain wall systems, a discrete microscopic Landau-Ginzburg-Devonshire (dmLGD) approach with A- and B-site cation displacements serving as order parameters is developed. Application of dmLGD to the classic BaTiO₃ , KNbO_3, and PbTiO₃ ferroelectrics shows that A-B cation repulsion is the key interaction that couples the polarization in neighboring unit cells of the material. dmLGD decomposition of the total energy of the system into the contributions of the individual cations and their interactions enables the prediction of different properties for a wide range of ferroelectric perovskites based on the results obtained for BaTiO₃ , KNbO_3, and PbTiO₃ only. It is found that the information necessary to estimate the structure and energy of domain-wall "defects" can be extracted from single-domain 5-atom first-principles calculations, and that "defect-like" domain walls offer a simple model system that sheds light on the relative stabilities of the ferroelectric, antiferroelectric, and paraelectric bulk phases. The dmLGD approach provides a general theoretical framework for understanding and designing ferroelectric perovskite oxides.

Keywords: density functional theory (DFT); discrete microscopic Landau-Ginzburg-Devonshire (dmLGD) approach; ferroelectric domain walls, ferroelectric perovskites, order parameters.

Abstract

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