Ta5+-substitution effects on crystal structure and ferroelectric property in HfO2-based films

To investigate the Ta5+-substitution effects on crystal structure and ferroelectric property in HfO2-based films, TaxHf1−xO2+δ films with various film thicknesses and Ta content were prepared. The ferroelectric orthorhombic phase was formed in a wide film thickness range of 20–100 nm while in a narrow composition range of x = 0.10–0.14. These thickness-insensitive and composition-sensitive characteristics of Ta5+-substituted HfO2 film are similar to Y3+ rather than Zr4+. The X-ray photoelectron spectroscopy measurement suggests that the ionic state of Ta is not reduced and TaxHf1−xO2+δ film has an excess oxygen state. The excess oxygen may consist of a combination of oxygen vacancies and more interstitial oxygens. These defects facilitate the formation of the ferroelectric phasebut also decrease the breakdown voltage and increase the leakage current in Ta5+-substituted HfO2 films. On the other hand, the generation of excess oxygen indicates the possibility of controlling oxygen vacancies which deteriorate fatigue and retention properties.