Impact of monolayer engineering on ferroelectricity of sub-5 nm Hf0.5Zr0.5O2 thin films

The sub-5 nm Hf0.5Zr0.5O2 (HZO) thin films have been studied for years; however, they still suffer from challenges including poor ferroelectricity, wake-up effect, and the need for high-temperature annealing. In this paper, the concept and the method of "monolayer engineering" by atomic layer deposition (ALD) are proposed and implemented, which leads to dramatic improvements in the crystallinity and ferroelectricity of the HZO thin film with a thickness of only ∼4 nm at a low annealing temperature of only 370 °C. By substituting one ZrO2 for one HfO2 atomic layer, a high ferroelectric remnant polarization (Pr) ∼15 μC/cm2 is achieved in the HZO thin film. Moreover, the pronounced ferroelectric characteristics are demonstrated in the pristine state, indicating the nearly wake-up-free property of the HZO layer. This study manifests that the monolayer engineering by ALD enables atomic tailoring to enhance the material and physical properties of nanoscale thin films.