Hafnia: Energetics of thin films and nanoparticles

Crystallization energetics of amorphous hafnia powders and thin films on platinum substrates was studied by differential scanning calorimetry and time-resolved high temperature x-ray diffraction. For initially amorphous 25 and 20 nm films from atomic layer deposition, crystallization enthalpy decreases from -38 to -32 kJ/mol, and crystallization temperature increases from 388 to 417 °C as thickness decreases. Enthalpy of water vapor adsorption on the surface of monoclinic hafnia was measured for both bulk powder and nanoparticles and was found to vary from -110 to -130 kJ/mol for coverage of ∼5 H₂O/nm². The enthalpies of monoclinic hafnia with various surface areas, prepared by crystallization and annealing of an amorphous hafnia precursor, were measured by high temperature oxide melt solution calorimetry. Under the previously used assumption that the interfacial enthalpy is 20% of the surface enthalpy, the surface enthalpy was calculated from experimental data as 2.8±0.1 J/m² for the hydrated surface and 3.7±0.1 J/m² for the anhydrous hafnia surface. These values are similar to those measured previously for monoclinic zirconia.