The other model antiferroelectric: PbHfO3thin films from ALD precursors
B. Hanrahan, C. Milesi-Brault, A. Leff, A. Payne, S. Liu, M. Guennou, and N. Strnad
APL Materials, vol. 9, no. 2, art. no. 021108, 2021
Antiferroelectric PbHfO3 is grown from atomic layer deposition precursors lead bis(dimethylaminomethylpropanolate) and tetrakis dimethylamino hafnium with H2O and O3 oxidizers in thicknesses from 20 nm to 200 nm at a substrate temperature of 250 °C. X-ray analysis shows an as-grown crystalline PbO phase that diffuses into an amorphous HfO2 matrix upon annealing to form a randomly oriented, orthorhombic PbHfO3 thin film. Electrical characterization reveals characteristic double hysteresis loops with maximum polarizations of around 30 μC/cm2 and transition fields of 350 kV/cm-500 kV/cm depending on the thickness. Temperature-dependent permittivity and polarization testing show a phase transition at 185 °C, most probably to the paraelectric phase, but give no clear evidence for the intermediate phase known from bulk PbHfO3. The energy storage density for the films reaches 16 J/cm3 at 2 MV/cm. A dielectric tunability of 221% is available within 1 V for the thinnest film. These results highlight the unique spectrum of properties available for thin film perovskite antiferroelectrics.