A family tree for hafnia

TL;DR

This paper uses first-principles calculations to establish a physically meaningful family tree of hafnia phases, revealing new phases and clarifying relationships among known polymorphs based on pressure criteria.

Contribution

It introduces a pressure-based criterion to connect hafnia phases and uncovers previously unknown structures, enhancing understanding of phase relationships.

Findings

Pressure distinguishes parent and daughter hafnia phases effectively.

Several new hafnia phases were identified, including potential common ancestors.

The study clarifies the phase transition pathways in hafnia.

Abstract

Several candidate reference phases have been proposed to discuss phase transitions and ferroelectricity in hafnia in recent years. Although these proposals comply with crystallographic requirements, a physically compelling rationale connecting parent and daughter phases is often lacking. This problem is aggravated by the absence of clearly dominant polarization switching pathways, making it difficult to formulate a robust physical criterion for identifying the relevant high-symmetry states. Here we use first-principles calculations to show that pressure provides a simple and robust criterion for establishing physically meaningful family relationships among many hafnia polymorphs, including the monoclinic ground state and the technologically relevant ferroelectric phase, and their respective parent structures. Our simulations also reveal several previously unreported phases, including higher-energy structures that act as common ancestors of the widely discussed cubic and orthorhombic reference phases.