Local structural distortions in Na0.5Bi0.5TiO3-based solid solutions have been proved to play a crucial role in understanding and tuning their enhanced piezoelectric properties near the morphotropic phase boundary. In this work all local structural disorders in a lead-free ternary system, namely 85% Na0.5Bi0.5TiO3-10% Bi0.5K0.5TiO3-5% BaTiO3, were mapped in reciprocal space by 3D electron diffraction. Furthermore, a comprehensive model of the local disorder was developed by analysing the intensity and morphology of the observed weak diffuse scattering. We found that the studied ceramics consists of plate-like in-phase oxygen octahedral nanoscale domains randomly distributed in an antiphase tilted matrix. In addition, A-site chemical short-range order of Na/Bi and polar displacements contribute to different kinds of diffuse scattering. The proposed model explains all the observed diffraction features and offers insight into the ongoing controversy over the nature of local structural distortions in Na0.5Bi0.5TiO3-based solid solutions.

A semi-quantitative comparison of 3D electron diffraction data revealed structural differences at the nanoscale for three (95-x)Na_0.5Bi_0.5TiO₃-xK_0.5Bi_0.5TiO₃-5BaTiO₃ solid solutions close to the morphotropic phase boundary, with x = 0, 5, 10. Using a novel rotation electron diffraction technique, diffuse scattering intensity was recorded in 3D as continuous rods along hk0.5 reciprocal-planes. By analyzing the different superstructure reflections and the intensity/morphology of diffuse scattering, a structural model of the local octahedral-tilt disorder for the different ceramics was developed. A good agreement was obtained between the experimental and simulated data with a model comprising of antiphase (a⁻a⁻a⁻) and plate-like in-phase (a⁰a⁰c⁺) nanodomains.

The temperature-dependence of superstructure reflections, diffuse scattering intensity and ferroelectric domains morphology for 95Na_0.5Bi_0.5TiO₃-5BaTiO₃ ceramic was investigated by in-situ transmission electron microscopy. A subtle local structural phase transition was observed around 110°C. This local phase transition is characterized by a transformation in the dominant octahedral-tilt system from antiphase to in-phase tilting and was correlated with the depolarization mechanism common in this type of materials. Simulations of octahedral-tilt disorder were developed at different temperatures which enabled us to provide a comprehensive structural model that explains the temperature-dependence of superstructure reflections and electron diffuse scattering intensity. This model revealed that plate-like in-phase nanodomains tilted about three orthogonal axes coexist with an antiphase tilted matrix, even at room temperature. With increasing temperature, the concentration of in-phase nanodomains is increased till a critical volume fraction is reached. We propose that these plate-like in-phase nanodomains are an inherent characteristic of NBT-based compounds and that the local phase transition observed around 110°C leads to a disruption in the long-range ferroelectric order and is responsible for the depolarization mechanism.

The local structural disorder in 0.6PbIn_½Nb_½O₃-0.4PbMg_⅓Nb_⅔O₃ ceramic was revealed by 3D electron diffraction. Rotation electron diffraction method was applied to reconstruct the 3D reciprocal space volume containing both diffuse scattering and Bragg reflections. The butterfly-shaped diffuse scattering in the vicinity of h00 type reflections and the ellipsoidal-shaped diffuse scattering in the vicinity of hk0 type reflections were detected. Moreover, sharp superstructure reflections and strong diffuse scattering sheets along <110>^* directions were observed in thin-volume sections centered along several zone axes cut from the 3D reciprocal space volume. This indicates that the local structure deviates significantly from the average one. By analyzing the intensity and morphology of diffraction features in 3D a model of structural disorder was developed comprising of 1:1 chemical short-range order of B-site cations and local displacements of Pb atoms. The final local structure is more akin to a spin glass state and no polar nanoregions were observed. This model was able to explain all significant diffraction features observed in volume-sections centered along three different zone axes.