Phase transformation behavior of ultrathin HfZrO films investigated through wide range annealing experiments

HfZrO thin films are not always ferroelectric. This work investigates the impact of annealing temperature and time on the crystalline structures and dielectric properties of 10 nm thick HfZrO thin films. It is found that the tetragonal phase crystal is formed from the amorphous film firstly, then transforms to the orthorhombic and monoclinic phases, in accordance with the annealing temperature and time. The volume fraction of the orthorhombic phase in the film, which is known as the origin of ferroelectricity, becomes dominant in a certain range of the annealing condition. Thus, the annealing temperature and time are responsible for the anti-ferroelectric, ferroelectric, and paraelectric characteristics of HfZrO thin films. This phase transformation behavior is discussed from the viewpoint of formation energies of the respective crystal phases, which accompanies the changes of unit cell volumes. The competition of transformation rates between the tetragonal to orthorhombic and the orthorhombic to monoclinic is key for the formation of ferroelectric films.