Structural Changes Underlying Field‐Cycling Phenomena in Ferroelectric HfO2 Thin Films

Since 2011, ferroelectric HfO 2 has attracted growing interest in both fundamental and application oriented groups. In this material, noteworthy wake‐up and fatigue effects alter the shape of the polarization hysteresis loop during field cycling. Such changes are problematic for application of HfO 2 to ferroelectric memories, which require stable polarization hystereses. Herein, electrical and structural techniques are implemented to unveil how cyclic switching changes nanoscale film structure, which modifies the polarization hysteresis. Impedance spectroscopy and scanning transmission electron microscopy identify regions with different dielectric and conductive properties in films at different cycling stages, enabling development of a structural model to explain the wake‐up and fatigue phenomena. The wake‐up regime arises due to changes in bulk and interfacial structuring: the bulk undergoes a phase transformation from monoclinic to orthorhombic grains, and the interfaces show changes in and diminishment of a nonuniform, defect rich, tetragonal HfO 2 layer near the electrodes. The evolution of these aspects of structuring contributes to the increase in P r and the opening of the constricted P – V hysteresis that are known to occur with wake‐up. The onset of the fatigue regime is correlated to an increasing concentration of bulk defects, which are proposed to pin domain walls.