The limits of integrating ferroelectric materials on commercial semiconductor chips were demolished the moment ferroelectricity in hafnia and zirconia films was reported in 2011. This breakthrough moment in the history of ferroelectric materials was made possible by the fortuitous interplay between advances in atomic layer processing and the strong surface energy dependence of crystal phases in HfO₂ and ZrO₂. Aided by commercial investment in using both materials as high-k gate and DRAM dielectric materials, atomic layer deposition (ALD) processes are beginning to take full advantage of the completely solid-soluble hafnia-zirconia (Hf_1-xZr_xO₂) ferroelectric system with new precursors and new insights obtained by systematically evaluating film growth conditions. The capability to precisely adjust the compositional profile and to alter oxidation conditions during atomic layer deposition film growth are giving an unprecedented level of control to engineer Hf_1-xZr_xO₂ and doped HfO₂ thin films for ferroelectric applications.

The latest advances in atomic layer processing of Hf_1-xZr_xO₂ and doped-HfO₂ are presented where the dynamic interaction between composition and film growth conditions provide an engineering roadmap to adjust the physical and structural properties of the dielectric films. Metal precursors play a crucial role in the ensuing film properties. The adjustability of the electrical and structural properties of Hf_1-xZr_xO₂ with ozone exposure during ALD film growth is discussed with respect to the important role oxygen and oxygen vacancies have in the overall phase stability of these novel ferroelectric materials, as well as C incorporation caused by ALD precursors. Just as atomic layer deposition has proven to be instrumental in the discovery and stabilization of the ferroelectric phase in HfO₂-based thin films, atomic layer etching (ALE) of HfO₂/ZrO₂-based layers is now being used to preserve ferroelectricity while pushing the thickness dimension to new limits, yielding high performance films for ferroelectric tunnel junction applications. Further innovations in atomic layer processing will continue to be a harbinger of high performance ferroelectrics in the coming years based on the current status and future outlook for ferroelectric Hf_1-xZr_xO₂ and other emerging ferroelectric materials.