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, KNbO3,and PbTiO3ferroelectrics 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, KNbO3,and PbTiO3only. 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.
Spontaneous electric polarization of solid ferroelectrics follows aligning directions of crystallographic axes. Domains of differently oriented polarization are separated by domain walls (DWs), which are predominantly flat and run along directions dictated by the bulk translational order and the sample surfaces. Here we explore DWs in a ferroelectric nematic (NF) liquid crystal, which is a fluid with polar long-range orientational order but no crystallographic axes nor facets. We demonstrate that DWs in the absence of bulk and surface aligning axes are shaped as conic sections. The conics bisect the angle between two neighboring polarization fields to avoid electric charges. The remarkable bisecting properties of conic sections, known for millennia, play a central role as intrinsic features of liquid ferroelectrics. The findings could be helpful in designing patterns of electric polarization and space charge.
more » « less- Award ID(s):
- 2122399
- NSF-PAR ID:
- 10396471
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 14
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Nanoelectronic devices based on ferroelectric domain walls (DWs), such as memories, transistors, and rectifiers, have been demonstrated in recent years. Practical high‐speed electronics, on the other hand, usually demand operation frequencies in the gigahertz (GHz) regime, where the effect of dipolar oscillation is important. Herein, an unexpected giant GHz conductivity on the order of 103S m−1is observed in certain BiFeO3DWs, which is about 100 000 times greater than the carrier‐induced direct current (dc) conductivity of the same walls. Surprisingly, the nominal configuration of the DWs precludes the alternating current (ac) conduction under an excitation electric field perpendicular to the surface. Theoretical analysis shows that the inclined DWs are stressed asymmetrically near the film surface, whereas the vertical walls in a control sample are not. The resultant imbalanced polarization profile can then couple to the out‐of‐plane microwave fields and induce power dissipation, which is confirmed by the phase‐field modeling. Since the contributions from mobile‐carrier conduction and bound‐charge oscillation to the ac conductivity are equivalent in a microwave circuit, the research on local structural dynamics may open a new avenue to implement DW nano‐devices for radio‐frequency applications.
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Defects are essential to engineering the properties of functional materials ranging from semiconductors and superconductors to ferroics. Whereas point defects have been widely exploited, dislocations are commonly viewed as problematic for functional materials and not as a microstructural tool. We developed a method for mechanically imprinting dislocation networks that favorably skew the domain structure in bulk ferroelectrics and thereby tame the large switching polarization and make it available for functional harvesting. The resulting microstructure yields a strong mechanical restoring force to revert electric field–induced domain wall displacement on the macroscopic level and high pinning force on the local level. This induces a giant increase of the dielectric and electromechanical response at intermediate electric fields in barium titanate [electric field–dependent permittivity (ε33) ≈ 5800 and large-signal piezoelectric coefficient (
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