Lead zirconate (PbZrO₃, PZ) is a prototype antiferroelectric (AFE) oxide from which state-of-the-art energy storage materials are derived by chemical substitutions. A thorough understanding of the structure-property relationships of PZ-based materials is essential for both performance improvement and the design of more environmentally friendly replacements. (Pb_1−xBa_x)ZrO₃ (PBZ) can serve as a model system for studying the effect of A-site substitution in the perovskite lattice, with barium destabilizing the AFE state. Here, the two-dimensional ²⁰⁷Pb solid-state NMR spectra of PZ and PBZ were recorded to analyze the local structural role of barium substitution. At low substitution levels, ²⁰⁷Pb NMR spectroscopy reveals the presence of Pb-O bond length disorder. Upon crossing the threshold value of x for the macroscopic phase transition into a ferroelectric (FE) state, the barium cations cause local-scale lattice expansions in their vicinity, resulting in the collapse of two lead lattice sites into one. The stabilization of the larger volume site coincides with the favoring of larger lead displacements. We also observed more covalent bonding environments which may originate from the lower polarizability of the barium cations, facilitating the formation of stronger Pb-O bonds in their vicinity. From the local structural point of view, we propose that the substitution-induced AFE → FE phase transition is therefore related to an increasing correlation of larger lead displacements in larger oxygen cavities as the barium content increases. Our results also highlight ²⁰⁷Pb NMR spectroscopy as a valuable method for the characterization of the structure-property relationships of PbZrO₃-based AFE and FE oxides.

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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.

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The irreversible field-induced phase transition between the antiferroelectric (P) and ferroelectric (Q) polymorphs of sodium niobate (NaNbO 3) ceramics constitutes a focal point in improving the material’s energy storage properties. The coexistence of P and Q phases can be verified by X-ray and electron diffraction methods, but its extent remains elusive. Two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy allows the quantification of relative amounts of the coexisting polymorphs, but the analysis of ceramic sample pieces requires a trade-off between sufficient sensitivity (at higher magnetic fields) and separation of the overlapping P and Q signals (at lower magnetic fields). In this contribution, we apply thesatellite transition magic angle spinning (STMAS) pulse sequence in a quantitative analysis of the antiferroelectric−ferroelectric phase transition in NaNbO3 ceramics. Both field- and grain size-induced transitions are investigated and the coexistence of the Q and P phases after the application of an electric field is quantified to be approximately 50%:50%. No indication is found that the local structure of the field-induced Q polymorph differs fundamentally from that induced in small-sized grains. Furthermore, the sensitivity and resolution of STMAS is compared to previously reported applications of the triple quantum magic angle spinning (3QMAS) sequence to the NaNbO3 system.@en

Antiferroelectric materials exhibit a unique electric-field-induced phase transition, which enables their use in energy storage, electrocaloric cooling, and nonvolatile memory applications. However, in many prototype antiferroelectrics this transition is irreversible, which prevents their implementation. In this work, we demonstrate a general approach to promote the reversibility of this phase transition by targeted modification of the material's local structure. A new NaNbO₃-based composition, namely (1− x)NaNbO₃−xSrSnO₃, was designed with a combination of first-principles calculations and experimental characterization. Our theoretical study predicts stabilization of the antiferroelectric state over the ferroelectric state with an energy difference of 1.4 meV/f.u. when 6.25 mol % of SrSnO₃ is incorporated into NaNbO₃. A series of samples was prepared using solid-state reactions, and the structural changes upon SrSnO₃ incorporation were investigated using X-ray diffraction and ²³Na solid-state nuclear magnetic resonance spectroscopy. The results revealed an increase in the unit cell volume and a more disordered, yet less distorted local Na environment, which were related to the stabilization of the antiferroelectric order. The SrSnO₃-modified compositions exhibited well-defined double polarization loops and an eight times higher energy storage density as compared to unmodified NaNbO₃. Our results indicate that this first-principles calculations based approach is of great potential for the design of new antiferroelectric compositions.

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