The effect of growth temperature and postmetallization annealing on the electrical characteristics of atomic layer deposited HfO2 films has been studied. Trap distributions at the interface have been obtained by means of deep level transient spectroscopy, whereas conductance transient technique provided the energy and geometrical profiles of electrically active defects at the insulator bulk. Differences in the interface quality have been observed between films on n- and p-type substrates. The most suitable growth temperatures seem to be 300 °C for p-type and 500 °C for n-type substrates. In all cases, postmetallization annealing in forming gas causes displacements of defects from the insulator bulk to the interface.