2023 journal article
Ferroelectricity in hafnia controlled via surface electrochemical state
Nature Materials.
arxiv.org (repository)
Source: ORCID
Added: February 1, 2024
Ferroelectricity in binary oxides including hafnia and zirconia has riveted the attention of the scientific community due to the highly unconventional physical mechanisms and the potential for the integration of these materials into semiconductor workflows. Over the last decade, it has been argued that behaviours such as wake-up phenomena and an extreme sensitivity to electrode and processing conditions suggest that ferroelectricity in these materials is strongly influenced by other factors, including electrochemical boundary conditions and strain. Here we argue that the properties of these materials emerge due to the interplay between the bulk competition between ferroelectric and structural instabilities, similar to that in classical antiferroelectrics, coupled with non-local screening mediated by the finite density of states at surfaces and internal interfaces. Via the decoupling of electrochemical and electrostatic controls, realized via environmental and ultra-high vacuum piezoresponse force microscopy, we show that these materials demonstrate a rich spectrum of ferroic behaviours including partial-pressure-induced and temperature-induced transitions between ferroelectric and antiferroelectric behaviours. These behaviours are consistent with an antiferroionic model and suggest strategies for hafnia-based device optimization. Ferroelectricity in hafnia-based systems seems to be correlated with oxygen vacancy dynamics, but the coupling of this and ferroelectric response is rarely studied. Here it is shown that Hf0.5Zr0.5O2 can be antiferroionic, with antiferroelectric behaviour coupled to surface electrochemistry.
