Unlike metals where dislocations carry strain singularity but no charge, dislocations in oxide ceramics are characterized by both a strain field and a local charge with a compensating charge envelope. Oxide ceramics with their deliberate engineering and manipulation are pivotal in numerous modern technologies such as semiconductors, superconductors, solar cells, and ferroics. Dislocations facilitate plastic deformation in metals and lead to a monotonous increase in the strength of metallic materials in accordance with the widely recognized Taylor hardening law. However, achieving the objective of tailoring the functionality of oxide ceramics by dislocation density still remains elusive. Here a strategy to imprint dislocations with {100}<100> slip systems and a tenfold change in dislocation density of BaTiO₃ single crystals using high-temperature uniaxial compression are reported. Through a dislocation density-based approach, dielectric permittivity, converse piezoelectric coefficient, and alternating current conductivity are tailored, exhibiting a peak at medium dislocation density. Combined with phase-field simulations and domain wall potential energy analyses, the dislocation-density-based design in bulk ferroelectrics is mechanistically rationalized. These findings may provide a new dimension for employing plastic strain engineering to tune the electrical properties of ferroics, potentially paving the way for advancing dislocation technology in functional ceramics.

We report an intrinsic strain engineering, akin to thin filmlike approaches, via irreversible high-temperature plastic deformation of a tetragonal ferroelectric single-crystal BaTiO3. Dislocations well-aligned along the [001] axis and associated strain fields in plane defined by the [110]/[1¯10] plane are introduced into the volume, thus nucleating only in-plane domain variants. By combining direct experimental observations and theoretical analyses, we reveal that domain instability and extrinsic degradation processes can both be mitigated during the aging and fatigue processes, and demonstrate that this requires careful strain tuning of the ratio of in-plane and out-of-plane domain variants. Our findings advance the understanding of structural defects that drive domain nucleation and instabilities in ferroic materials and are essential for mitigating device degradation.

Dislocations are usually expected to degrade electrical, thermal and optical functionality and to tune mechanical properties of materials. Here, we demonstrate a general framework for the control of dislocation–domain wall interactions in ferroics, employing an imprinted dislocation network. Anisotropic dielectric and electromechanical properties are engineered in barium titanate crystals via well-controlled line-plane relationships, culminating in extraordinary and stable large-signal dielectric permittivity (≈23100) and piezoelectric coefficient (≈2470 pm V^–1). In contrast, a related increase in properties utilizing point-plane relation prompts a dramatic cyclic degradation. Observed dielectric and piezoelectric properties are rationalized using transmission electron microscopy and time- and cycle-dependent nuclear magnetic resonance paired with X-ray diffraction. Succinct mechanistic understanding is provided by phase-field simulations and driving force calculations of the described dislocation–domain wall interactions. Our 1D-2D defect approach offers a fertile ground for tailoring functionality in a wide range of functional material systems.

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 (e₃₃) ≈ 5800 and large-signal piezoelectric coefficient (d₃₃*) ≈ 1890 picometers/volt]. Dislocation-based anisotropy delivers a different suite of tools with which to tailor functional materials.