Ferroelectric Effects Probed by in situ Transmission Electron Microscopy

Ferroelectric perovskite oxides are widely used in sensors, actuators and optical modulators and, at the same time, they show promise for implementation in future applications such as energy storage, memory and cooling devices. At the infancy of the discovery of polycrystalline ferroelectrics, BaTiO3 was considered as a candidate for various applications, but the breakthrough for the commercialization of ferroelectrics came in 1952 when the ferroelectric PbZrO3 - PbTiO3 (PZT) solid solution system was discovered. PZT and other lead containing perovskite oxides remained on the forefront of scientific and industrial interest. However, concerns over the environmental and health hazards posed by these toxic materials in the electronic and electrical equipment created a legislation change. Nowadays, all applicable products in the EU must pass RoHS (Restriction of Hazardous Substances also known as Directive 2002/95/EC) compliance. This change in the industrial standards fueled research in lead-free ferroelectric materials once again. Attention is currently placed on materials based on BaTiO3, BaZrO3, (Na/K)NbO3, Na1/2Bi1/2TiO3. Their widespread application is yet to be realized as their physical properties pale in comparison to PZT. Substantial challenges also lie in the miniaturization of polar perovskites where effects at nano and microscopic scales become dominant, which inhibit their performance.In this thesis one of the most prominent lead-free ferroelectric perovskites BaTiO3 is studied by transmission electron microscopy (TEM) techniques in combination with in situ temperature and electric field control. In detail, a reliable focused ion beam sample preparation for in situ TEM electrical biasing for ferroelectrics is established. The method is tested on BaTiO3 at room temperature, where the electrical response is observed at the expected field values, further confirmed by finite element calculations. Domain area (polarization) - applied bias loops are directly measured revealing strong pinning at lower fields, while higher fields depin domain walls allowing for more free movement following Rayleigh's law.Upon increasing the temperature, BaTiO3 exhibits morphological transformations in its domain structure from ferroelectric 180° (close to room temperature) to ferroelastic 90° state (below the Curie temperature). Electrical biasing experiments of ferroelastic needle domains show two different forward growth mechanisms. In one case, the needle domains are shown to move freely, influenced mainly by Peierls-like potentials, while when perpendicular domains meet, their movement is hindered by strong domain domain pinning mediated by electromechanical fields. The latter one produces square shaped P-E like loops with distinct steps, indicative of Barkhausen pulses.Finally, the effect of ferroelectric phase transition on the electronic structure is studied with in situ electron energy loss spectroscopy (EELS) and density functional theory (DFT) calculations. Core-loss EELS measurements show that changes in the Ti 3d states qualitatively agree with DFT calculations. Off-axis low-loss EELS allows precise bandgap measurements in both phases. Custom experimental and data treatment methodologies are developed to retrieve momentum resolved dielectric functions, which show excellent fit with DFT calculated ones at small momentum transfer. A pathway to study oxygen deficient perovskites with EELS is theoretically demonstrated with DFT.