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.
