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The local crystal phase and orientation of ferroelectric grains inside TiN/Hf0.5Zr0.5O2/TiN have been studied by the analysis of the local electron beam scattering Kikuchi patterns, recorded in transmission. Evidence was found that the ferroelectric phase of the layers is derived from an orthorhombic phase, most likely of space group Pca21. The orientation analysis reveals a strong out-of-plane texture of the polycrystalline film which is in accordance with a high remanent polarization Pr observed for P-V measurements. The results of this analysis help us to further optimize the ratio of ferroelectric grains and their orientation for many applications, e.g., in the field of emerging memory or infrared sensors.

Piezoelectric thin films are of current interest in science and industry for highly integrated nano-electro-mechanical-systems and sensor devices. In this study, the dependence of the piezoelectric properties on the doping concentration in Si:HfO2 thin films and their crystallographic origin are investigated. The Si:HfO2 films with a thickness of 20 nm and various Si doping concentrations in the range of 2.7–5.6 cat.% were examined. The relationship between the piezoelectric displacement and remanent polarization is studied during wake-up from the antiferroelectric-like pristine state until the cycled ferroelectric state, which reveals an application-dependent optimal doping concentration. Furthermore, the piezoelectric and ferroelectric properties, as well as the relative permittivity, were measured over wake-up, thus giving a glimpse at the underlying mechanism of the transition from a pristine antiferroelectric-like behavior to a ferroelectric/piezoelectric one, revealing a pre-existing polar phase that is reorienting during wake-up. The studied samples show a strong displacement and polarization dependence on the doping concentration. Hence, the stoichiometry is an excellent parameter for the application-specific adjustment of complementary metal–oxide–semiconductor compatible piezoelectric thin films.

The in‐plane piezoelectric response of 20 nm thick Si‐doped HfO2 is examined by exploiting thermal expansion of the substrate upon rapid temperature cycling. The sample is heated locally by a deposited metal film, and the subsequently registered pyroelectric current is found to be frequency dependent in the observed range of 5 Hz to 35 kHz. While the intrinsic response remains constant, the secondary contribution can be switched off in the high‐frequency limit due to substrate clamping. As this secondary response is generated by thermal expansion and the piezoelectric effect, this allows for extraction of the corresponding in‐plane response. By comparing pyroelectric measurements in low‐ and high‐frequency limits, a piezoelectric coefficient d31 of −11.5 pm V −1 is obtained, which is more than five times larger than that of AlN. The magnitude of piezoelectric response increases upon electric field cycling, which is associated with a transition from antiferroelectric‐like behavior to a purely ferroelectric polarization hysteresis. The hafnium oxide material system is proposed as a promising candidate for future CMOS compatible piezoelectric micro‐ and nano‐electromechanical systems (MEMS and NEMS).