Origin of Ferroelectricity in Epitaxial Si-Doped HfO₂ Films

HfO2-based unconventional ferroelectric materials were recently discovered and have attracted a great deal of attention in both academia and industry. The growth of epitaxial Si-doped HfO2 films has opened up a route to understand the mechanism of ferroelectricity. Here, we used pulsed laser deposition to grow epitaxial Si-doped HfO2 films in different orientations of N-type SrTiO3 substrates. Polar nanodomains can be written and read using piezoforce microscopy, and these domains are reversibly switched with a phase change of 180°. Films with different thicknesses displayed a coercive field Ec and a remnant polarization Pr of approximately 4–5 MV/cm and 8–32 μC/cm2, respectively. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) results identified that the as-grown Si-doped HfO2 films have strained fluorite structures. The ABAB stacking mode of the Hf atomic grid observed by HRTEM clearly demonstrates that the ferroelectricity originates from the noncentrosymmetric Pca21 polar structure. Combined with soft X-ray absorption spectra, the results showed that the Pca21 ferroelectric crystal structure manifested as an O sublattice distortion by the effect of the interface strain and Si dopant interactions, resulting in a nanoscaled ferroelectric ordered state because of further crystal splitting.