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Abstract Because of its compatibility with semiconductor-based technologies, hafnia (HfO 2 ) is today’s most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO 2 has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart from classic ferroelectrics (e.g., perovskite oxides like PbTiO 3 ) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by first-principles calculations and an experimental investigation of HfO 2 thin films using piezoresponse force microscopy. Further, the simulations show how the chemical coordination of the active oxygen atoms is responsible for the negative longitudinal piezoelectric effect. Building on these insights, it is predicted that, by controlling the environment of such active oxygens (e.g., by means of an epitaxial strain), it is possible to change the sign of the piezoelectric response of the material. 

Piezoresponse force microscopy (PFM) is widely used for characterization and exploration of the nanoscale properties of ferroelectrics. However, quantification of the PFM signal is challenging due to the convolution of various extrinsic and intrinsic contributions. Although quantification of the PFM amplitude signal has received considerable attention, quantification of the PFM phase signal has not been addressed. A properly calibrated PFM phase signal can provide valuable information on the sign of the local piezoelectric coefficient—an important and nontrivial issue for emerging ferroelectrics. In this work, two complementary methodologies to calibrate the PFM phase signal are discussed. The first approach is based on using a standard reference sample with well‐known independently measured piezoelectric coefficients, while the second approach exploits the electrostatic sample–cantilever interactions to determine the parasitic phase offset. Application of these methodologies to studies of the piezoelectric behavior in ferroelectric HfO₂‐based thin‐film capacitors reveals intriguing variations in the sign of the longitudinal piezoelectric coefficient,d_33,eff. It is shown that the piezoelectric properties of the HfO₂‐based capacitors are inherently sensitive to their thickness, electrodes, as well as deposition methods, and can exhibit wide variations including ad_33,effsign change within a single device.

 

Functional characterization of antiferroelectric (AFE) materials typically involves macroscopic testing of their nonlocal integrated information on their dielectric properties, such as polarization hysteresis loops, field‐dependent strain, and capacitance while the local AFE properties have been rarely addressed. Here, a new protocol is demonstrated for local probing of the antiferroelectric/ferroelectric (AFE/FE) phase transition in PbZrO₃capacitors by piezoresponse force microscopy (PFM). PFM spectroscopy of the local AFE/FE phase transition parameters is performed and their spatial variability via two‐dimensional mapping is investigated. It is shown that AFE hysteresis loops recorded by PFM in the bias‐on regime exhibit four characteristic amplitude peaks. Within the framework of Landau theory, these features are attributed to a considerable increase in the electromechanical strain response due to the dielectric constant divergence during AFE/FE phase transitions. The proposed approach can be used to differentiate between the antiferroelectric and nonpolar dielectric phases in functional devices using the electrically induced polarization.